Oct 2012 Jolanta Karp in Ska PHD

Crystal Growth Using Low Temperature
Gradient Sublimation in Vacuo

Jolanta Karpinska M.Sc.
PhD Thesis
Supervisors: Dr. Andrea Erxleben, Prof. Patrick McArdle
National University of Ireland, Galway

OE Gaillimh
Thesis submitted to the School of Chemistry, National

University of Ireland, Galway.
October 2012
Declaration
I declare that the work included in this thesis is entirely my own work and has not
been previously submitted for a degree to this or any other academic institution.
Jolanta Karpinska
Table of Content
Aim of Thesis
vi
Abstract
vii
Acknowledgements
ix
List of Publications
Abbreviations
xii
Symbols and Terms Used in Crystallography
xiv
Chapter 1: Theory
Crystalline solids:
1
2
Polymorphism
Pseudo-polymorphism
Nucleation and Crystal Growth:
Nucleation
Nucleation in polymorphic systems
10
Crystal growth
10
Continuous growth
12
Surface nucleation
12
Spiral growth
13
Crystallization Methods:
15
Solution crystallization
15
Vapour crystallization
16
Melt crystallization
18
Chapter 2: Experimental Section
19
Materials
20
Instrumentation and Techniques:
20
Low temperature gradient sublimation in vacuo,

method A
20
Sublimation in a vacuum oven using an externally

i
Controlled heater, method B
23
X-Ray diffraction techniques
24
Thermal analysis
26
Microscopy
27
ATR-Infrared spectroscopy
28
Chapter 3: Crystal Growth of Pure Form not Available From

Solution: Application to Stanozolol
30
Introduction: Crystalline forms of stanozolol
31
Experimental Section:
32
Crystallization of polymorphic forms stanozolol
32
Crystallization of solvated forms of stanozolol
33
Results:
36
Structural analysis of polymorphism in stanozolol
36
Structural diversity of stanozolol solvates
44
Molecular packing and hydrogen bonding of stanozolol

solvates
55
Tautomerism in stanozolol solvates
63
Thermal analysis of stanozolol solvates: strength of

intermolecular interaction
Discussion
65
72
Chapter 4: Crystal Growth of Pure Form not Available From

Solution: Application to Ethinylstradiol
Introduction:
Crystalline forms of ethinylestradiol
73
74
74
75
Crystallization of ethinylestradiol
75
Crystallization of solvated forms of ethinylestradiol
76
Results:
78
Polymorphism in the crystal structures of ethinylestradiol 78

ii
Structural diversity of ethinylestradiol solvates
82
Molecular packing and hydrogen bonding of

ethinylestradiol solvates
89
Unused Hydrogen Bonding Capacity in Steroid Crystal

Structures
91
Discussion
92
Chapter 5: Detection of Bending Properties of Organic Crystals:

Application to Naftazone and 1,3-Dinitrobenzene
93
Introduction: Bending phenomena of molecular crystals
94
95
Synthesis of naftazone
95
Crystal growth of naftazone and 1,3-dinitrobenzene
95
Results:
97
Detection of bending properties of naftazone
97
Detection of bending properties of 1,3-dinitrobenzene
99
Discussion
101
Chapter 6: Combined Synthesis, by Thermal Transformation,

and Crystal Growth of
p-(phenylsulfonyl)biphenyls
102
Introduction
103
104
Synthesis of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)
hexa-1,3,5-trien-1-yl]-4-benzene, OMe and NO2
derivatives
104
Crystallization of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)
hexa-1,3,5-trien-1-yl]-4-benzene, OMe and NO2
derivatives
104
Synthesis and crystal growth of 4-(phenylsulfonyl)

biphenyl, OMe and NO2 derivatives
106
iii
Results:
108
Combined synthesis, by thermal transformation,

and crystal growth
108
Analysis of intra-molecular interactions
109
Discussion
115
Chapter 7: Using Driving Force to Control Crystal Morphology:

Application to Metal - Free Phthalocyanine,
1,4-Naphthaquinone and Benzoic Acid
116
Introduction
117
Experimental Section
118
Results:
119
Application to metal-free phthalocyanine
119
Application to 1,4-naphthaquinone
120
Application to benzoic acid
123
Application to tetraphenyltin
124
Discussion
Chapter 8: Crystallographic Data: Electronic Information
125
126
1) Stanozolol, polymorph 1 (stanozolol_1.cif):

17-hydroxy-17-methylandrostano[3, 2-c]pyrazole
127
2) Stanozolol, polymorph 2 (stanozolol_2.cif):

17-hydroxy-17-methylandrostano[3, 2-c]pyrazole
137
3) Stanozolol ethanol solvate (stanozolol_3.cif)
147
4) Stanozolol isopropanol solvate (stanozolol_4.cif)
153
5) Stanozolol butan-2-ol solvate (stanozolol_5.cif)
160
6) Stanozolol ethanol dihydrate solvate (stanozolol_6.cif)
167
7) Stanozolol isopropanol dihydrate solvate (stanozolol_7.cif)
177
8) Stanozolol monohydrate (stanozolol_8.cif)
184
9) Stanozolol acetic acid solvate (stanozolol_9.cif)
190
10) Stanozolol formamide solvate (stanozolol_10.cif)
197
iv
11) Stanozolol pyridine solvate (stanozolol_11.cif)
207
12) Stanozolol dimethylformamide solvate (stanozolol_12.cif)
217
13) Ethinylestradiol: (EE_1.cif)

19-Nor-17-pregna-1,3,5(10)-trien-20-yne-3,17-diol
227
14) Ethinylestradiol acetone solvate (EE_2.cif)
235
15) Ethinylestradiol pentan-2-ol solvate (EE_3.cif)
241
16) Ethinylestradiol DMSO solvate (EE_4.cif)
247
17) 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5trien-1-yl]-4-benzene (phsulf_1.cif)
254
18) 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5trien-1-yl]-4-methoxybenzene (phsulf_2.cif)
260
19) 1-[(1E,3E,5E)-4,6-bis(phenylylsulfonyl)hexa-1,3,5trien-1-yl]-4-nitrobenzene (phsulf_3.cif)
266
20) 4-(phenylsulfonyl)biphenyl (phsulf_11.cif)
273
21) 4-methoxybiphen-4-yl phenyl sulphone (phsulf_22.cif)
278
22) 4-nitrobiphen-4-yl phenyl sulphone (phsulf_33.cif)
283
23) 1,4-naphthaquinone (14naph.cif)
288
Bibliography
292
Publications
302
Aim of Thesis
Crystals of pure organic materials are often grown by methods fundamentally
based on crystallization from solution. A range of factors affect the process of
nucleation and crystal growth in solution. The solvent can influence the crystal habit
and impurities which are always present may cause crystallization difficulties by
acting as nucleation and crystal growth inhibitors. Indeed some compounds are
known to be difficult to crystallize in any other than a solvated form. Sometimes
crystallization from solution may even require the use of additives to induce crystal
growth. These additives and the concentration at which nucleation occurs can also
affect the nature of the product obtained. All of these problems are avoided when
crystals are grown from the gas phase.
It is estimated that approximately two-thirds of all organic compounds are
able to convert from the solid to the gaseous state on heating. However, sublimation
is not normally a first choice crystallization method despite the wide range of
experimental setups that has been developed for crystal growth from the vapour. The
aim of this thesis was to develop a convenient and rapid sublimation based technique
that can be easily implemented in any chemistry laboratory for crystal growth of
organic compounds.
vi
Abstract
A sublimation method based on the use of a conventional vacuum oven was
developed for growing high quality single crystals of organic compounds suitable for
structure determination. Key features of the method are the use of a low thermal
gradient which favours the growth of large crystals and the use of vacuum which is
ideal for air sensitive compounds. Crystals grown from the vapour are not affected
by solvent effects and impurities have far less influence than when crystals are grown
from solution. This low temperature gradient sublimation in vacuo technique was
successfully applied to: compounds which give only solvated crystals from solution
crystallization; fragile crystals which can be bent on the application of mechanical
stress and systems whose crystal habit is influenced by the crystallization driving
force. It was also possible to combine thermal transformation and crystal growth for
some 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzenes which
gave crystals of the corresponding 4-(phenylsulfonyl)biphenyls.
Stanozolol and ethinylestradiol are two important steroids which before this
work were known only as solvates but are shown here to have two polymorphs and
just one crystal form respectively when crystallized from the vapour. Solution
crystallization experiments run in parallel gave a wide range of solvated structures.
All crystalline forms of stanozolol and ethinylestradiol were analysed using
diffraction techniques (single crystal X-ray diffraction and powder X-ray diffraction)
and thermal methods (differential scanning calorimetry and thermogravimetric
analysis). Infrared spectroscopy was additionally used for the characterisation and
identification of polymorphic forms.
Crystal growth using the sublimation method also provides easy detection of
the bending properties of molecular crystals. Crystal faces of naftazone and 1,3dinitrobenzene when grown by sublimation tend to be curved in the bending
direction. This effect is not observed for solution grown crystals. These bent crystals
can be easily detected using optical microscopy.
Crystal growth of 1,4-naphthaquinone, metal-free phthalocyanine and
benzoic acid from the vapour was investigated under a range of crystallization
driving forces. The results show that the crystal habit of planar molecules, which
vii
have stacked structures and no directional intermolecular interactions, strongly

depends on crystallization driving force.
viii
Acknowledgements
Firstly I would like to express my gratitude to Prof. Patrick McArdle for his
expertise, guidance and for all stimulating discussions throughout the course of my
work. It was a great pleasure and privilege to work with you!
I am very grateful to Dr. Andrea Erxleben for all discussions, valuable
suggestions and help with my project.
I also wish to thank Prof. Paul V. Murphy and Dr. Fawaz Aldabbagh for their
assistance in explaining reaction mechanisms. To Dr. Liam Carroll for training and
providing his expertise in SEM.
Many thanks to the technical staff in NUI, Galway for their assistance. I
would especially like to thank Seamus Kellehan for all the help with setting up the
sublimation equipment and Dermot McGrath for running all the DSC-TG
experiments.
A big thanks to the SSPC group in NUIG, especially Michelle Hennigan and
Nicole Walsh for many motivating conversations, support and advice. It was a lot of
fun to work with you! Also, thanks to the Woods group for allowing me to marry
into their group.
Finally to my family, to my husband Oliver, thanks for the encouragement
and for making everything so much easier. Thanks to my Mum and Dad who always
believe in me. To Conor, Katie and Alanna for being so cute and Patricia, Colm,
Jenny, Rachel and Claire for your wonderful support over the last few years!
ix
List of Publications
17-Hydroxy-17-methylandrostano[3,2-c]pyrazole, Stanozolol: The Crystal
Structures of Polymorphs 1 and 2 and 10 Solvates; Jolanta Karpinska, Andrea
Erxleben, and Patrick McArdle; Crystal Growth & Design, 2011, 11 (7), pp 2829
2838;
Ethyl [2-(4-phenoxyphenoxy)ethyl]carbamate; Jolanta Karpinska, Manuel Kuhs,
Ake Rasmuson, Andrea Erxleben and Patrick McArdle; Acta Crystallographica,
2012, Section E68, o2834-o2835;
Manuscripts in Preparation
Applications of Low Temperature Gradient Sublimation in Vacuo: Rapid
Production of High Quality Crystals; The First Solvent Free Crystals of Ethinyl
Estradiol and Crystal Habit Control of Flat Molecule Systems which have
Stacked Structures; Jolanta Karpinska, Andrea Erxleben and Patrick McArdle; for
Cryst. Growth & Design;
Crystallization properties of Fenoxycarb; Manuel Kuhs, Jacek Zeglinski,
Michael Svard, Jolanta Karpinska, Patrick McArdle and Ake Rasmuson;
Additional Papers and Conference Contribution

Acetic anhydride mediated condensation of aromatic o-diacid dichlorides with
benzimidazoles to provide electro-reducible p-dione adducts; Eamonn Joyce, Paul
Kavanagh, Dnal Leech, Jolanta Karpinska, Patrick McArdle, Fawaz Aldabbagh;
Tetrahedron Letters, Volume 53, Issue 29, pp 37883791;

Crystal Growth by Low Thermal Gradient Sublimation; Oral presentation at
10th International Workshop on Crystal Growth of Organic Materials CGOM10;
University of Limerick, Limerick, Ireland;
x
Crystal Growth by Low Thermal Gradient Sublimation: Sublimation

Combines the Synthesis, by Thermal Transformation, and Crystal Growth of
Diphenyl Phenyl Sulfones; Poster presentation at CGOM10; University of
Limerick, Limerick, Ireland;
Using crystallization driving force to control crystal morphology; Poster
presentation at CGOM10; University of Limerick, Limerick, Ireland;
Crystal growth using low temperature gradient sublimation in vacuo; Oral
presentation at the 2011 Eli Lilly Chemistry Postgraduate symposium in Galway,
National University of Ireland, Galway, Ireland;
Crystal growth using low temperature gradient sublimation; Poster
presentation at XXII International Congress and General Assembly of the IUCr (Aug
2011) in Municipal Conference Centre, Madrid, Spain;
Unused hydrogen bonding capacity in the crystal structures of steroid
compounds; Poster presentation at 2011 Spring Meeting of the British
Crystallographic Association; University of Keele, England;
Crystal growth of steroid compounds via LTGSV; Oral presentation at SSPC
Technical meeting, University of Limerick, Limerick, Ireland;
17-hydroxy-17 methylandrostano[3,2-c]pyrazole, Stanozolol : the crystal
structures of polymorph I and ten solvates; Poster presentation at 9th International
Workshop on Crystal Growth of Organic Materials (CGOM9); School of Chemical
and Biomedical Engineering, Nanyang Technological University, Singapore;
xi
Abbreviations
Abbreviations
Description
0D, 1D, 2D, 3D
Zero, One, Two and Three-Dimensional
API
Active Pharmaceutical Ingredient
ATR-IR
Attenuated Total Reflectance-Infrared Spectroscopy
CCDC
Cambridge Crystallographic Data Centre
CSD
Cambridge Structural Database
DMF
N,n-Dimethylformamide
DMSO
Dimethyl Sulfoxide
DSC
Differential Scanning Calorimetry
EDX
Energy Dispersive X-ray
EE
Ethinylestradiol
FT-FIR
Fourier Transform Far Infrared Spectroscopy
FT-IR
Fourier Transform Infrared Spectroscopy
H-bond
Hydrogen Bond
IUCr
International Union of Crystallography
LTGSV
Low Temperature Gradient Sublimation in the Vacuum
NO2
Nitro
OMe
Methoxy
SEM
Scanning Electron Microscopy
Temperature
TPT
Tetraphenyltin
TGA
Thermal Gravimetric Analysis
THF
Tetrahydrofuran
xii
PhEur
Pharmacopoeia European
PXRD
X-Ray Powder Diffraction
ROY
5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile
xiii
Symbols and Terms used in Crystallography

Symbols
Description
a, b, c
Vectors of the edges of the unit cell
, ,
Angles between the edges of the unit cell
V / 3
Cell volume
x, y, z
Coordination of a point expressed in units of a, b, c
h, k, l
Crystal face indices, also known as Miller indices
Number of molecules in the unit cell
/ mm-1
Absorption coefficient
Wavelength
/ [Mg/m-3]
Density
U11, Uii, Uij
Anisotropic vibrational parameter
Mw / [g/mol]
Molecular weight
F(000)
Total number of electrons in the unit cell

It is a mathematical function describing the amplitude and
phase of a wave diffracted from crystal lattice planes
F(hkl)
characterised by Miller indices h, k, l
|F(hkl)|, |F|
Amplitude of structure factor without phase indication
|FO| and |FC|
Observed and calculated structure factors

A measure of agreement based on F between the calculated
and observed model
R1 (I > 2(I))
Reliability index
wR2
A measure of agreement based on F2 between the
xiv
calculated and observed model which takes into account

the errors in (r) during refinement
A measure of the extent to which calculated model

approaches the observed values. Ideally it is expected to be
close to unity.
GooF
xv
Chapter 1:
Theory
Crystalline solids
Crystalline solids can be described in terms of atoms, molecules or ions
which are arranged in regular systematic 3D patterns [1, 2]. They can exist in
different crystalline forms such as polymorphs and solvates (the latter are also known
as pseudo-polymorphs). Polymorphs are single component solid forms, while
solvates contain more than one constituent in the crystal structure, Fig. 1.1 [3].
Differences in the molecular arrangement of polymorphs, or the chemical
composition in the case of solvates, vary the inter- and intra-molecular interactions.
These differences lead to changes in the chemical and physical properties which are
especially important to the pharmaceutical industry.
Fig. 1.1 Crystalline forms of an API: (a) pure API, (b) polymorphic form of an API,
(c) clathrate or solvate of an API, (d) solvated form of an API.
The energy differences between polymorphic forms are usually quite small
making it easy to generate a new form unintentionally. The various steps of drug
processing and development in particular create a variety of opportunities for phase
transformation, solvate formation, solvate desolvatation or a change in the degree of
crystallinity. Since form conversion may also take place during storage or use, drug
stability is a major concern for the pharmaceutical industry. Appearance of a new,
more stable crystalline form during late stage of development can cause product
delay or even API withdrawal [4].
Every compound has different polymorphic forms, and that, in general, the number
of forms known for a given compound is proportional to the time and money spent in
research on that compound
McCrone, 1963 [5]
Insufficient understanding of solid-state properties has led to problematic

situations in the past. Sometimes it is not possible to continue the production of a
polymorph of interest due to the occurrence of a more stable form. In this situation
the less stable polymorphs are often referred to as disappearing polymorphs [6]. A
well-known example is the sudden occurrence of a new polymorphic form of
Ritonavir, once used to treat Acquired Immunodeficiency Syndrome (AIDS) [7]. The
lower solubility and bioavailability of the new stable form forced Abbott
Laboratories Ltd. to withdraw the drug from sale. It required a lot of time and effort
before they were able to reproduce the original polymorph [8]. Sometimes the
change in impurity profile can lead to disappearing polymorphs as in the case of the
female steroid hormone; progesterone [9]. After some time in production the
metastable polymorph of this compound could no longer be produced. The analysis
of a fifty-year old sample revealed the presence of eleven impurities, including
another steroid compound which had been added during the synthesis to enhance
crystal growth. Some of these factors were responsible for the stabilisation of
metastable form II. Appearance of a new crystalline forms or a phase change results
in differences in dissolution rate, oral absorption, bioavailability, toxicology and
ultimately clinical trial results. Therefore early isolation and characterisation of all
possible crystalline forms of a drug compound is a major concern for the
pharmaceutical industry.
In the chemistry of crystalline solids the main focus is to understand
polymorphism and pseudo-polymorphism at a molecular level. Knowledge of how
molecules interact with each other and how they arrange and pack to form 3D
structures helps in the prediction and preparation of the most stable form of a given
compound. Also, an understanding of the physicochemical properties of crystalline
solids is crucial to the selection of the most stable form for development of
successful pharmaceutical products.
Polymorphism
It is thought that Klaproth was the first to be aware of polymorphism when he
observed in 1788 that calcium carbonate can crystallize as calcite and aragonite [10].
In 1809 Humphrey Davy made a remark that diamond and graphite are both carbon
and they only differ in the arrangement of carbon atoms in the solid state. However,
the term polymorphism was first coined in 1822 by Eilhard Mitscherlich during his
work on the isomorphous sulphates of cobalt, copper, iron, magnesium, manganese,
nickel and zinc [11, 12]. In 1965 McCrone [5] defined polymorphism as:
A solid crystalline phase of a given compound resulting from the possibility of at
least two different arrangements of the molecule of that compound in the solid state.
In other words it is the ability of a compound to exist in two or more crystalline

phases with different conformations and/or crystal packing giving rise to a variety of
crystal structures. As a consequence, polymorphs have different chemical and
physical properties. These differences vanish in the liquid and vapour phase [13].
Structural diversity of polymorphic compounds which results in different
crystal lattices arises from packing polymorphism and conformational polymorphism.
Packing polymorphism takes place when relatively rigid molecules can pack into
different 3D structures [14-16]. Often organic molecules can exist in a variety of
different conformations. This also results in different 3D structures when molecules
pack to form a crystal. Conformational polymorphism can be therefore defined as the
existence of different conformers of the same molecule in different polymorphic
modifications [17-19]. To describe situations when organic molecules in
polymorphic systems can exist as geometric isomers or tautomers the term
configurational polymorphism was introduced [20]. In some cases it is not clear
whether a system should be recognised as having packing or conformational
polymorphism because the differences in packing influence the geometry of the
molecule and the different conformations make the molecules pack differently.
Therefore it is common that polymorphic systems have a mixed origin as they exhibit
both packing and conformational differences [21].
In 1888 terms such as monotropy and enantiotropy were introduced by

Lehmann to describe the relative thermodynamic stability of polymorphic systems
[22]. When one polymorph is stable at all temperatures below the melting point,
while all other polymorphs are unstable, the system is monotropic [23, 24]. This
means that the free energy curves for each of the polymorphs do no cross and
therefore no reversible transition can take place below the melting point. In contrary,
in other polymorphic systems these free energy curves cross, meaning that their
relative stabilities are reversed at a particular temperature. This is characteristic for
enantiotropic polymorphs [25].
It was estimated that in pharmaceuticals 70% of barbiturates, 60% of
sulphonamides and 23% of steroids exist in different polymorphic forms. 5-methyl2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY) is the top polymorphic
system with seven determined crystal structures and three other polymorphic forms
observed using Raman spectroscopy, Fig. 1.2 [26, 27].
Fig. 1.2 Polymorphism of 5-methyl-2-[(2-nitrophenyl)amino]-3thiophenecarbonitrile, also known as ROY for red, orange and yellow crystals.
The discovery of all the potential polymorphic forms requires extensive

crystallization studies. Many factors which influence the relative nucleation and
5
growth rates need to be examined. To obtain different forms of the same compound a
variety of methods are available, such as: crystallization from single or mixed
solvents, sublimation, cooling from the melt, thermal treatment, vapour diffusion,
grinding or desolvatation of crystalline solvates. Crystallization from solution may
involve pH adjustment, the presence of tailor-made additives and the adjustment of
experimental conditions like temperature, initial supersaturation and rate of agitation
[28]. Crystallization is a multi-step process which involves nucleation, crystal growth
and Ostwald ripening [29] of the crystals. Both nucleation and crystal growth
determine the nature of the polymorphic form that will be formed from solvent
crystallization.
Pseudo-polymorphism
Substances are often exposed to solvents or solvent vapour during different
stages of industrial processing. In the pharmaceutical industry the most common
solvent-based processes include: wet granulation, spray-drying, lyophilisation,
precipitation, crystallization and recrystallization. Solvent molecules are often found
to co-crystallize with the mother compound. They are likely to affect crystal packing
and molecular conformation and for these reasons are sometimes considered as
unwanted impurities [30]. However solvent molecules often play an important role in
the crystal structures. They can act as H-bond donors or acceptors contributing to the
formation of the H-bonding network. If either the molecule or the crystal structure
contains voids or empty channels due to the crystal packing, solvent molecules tend
to fill these empty spaces. Some solvent molecules have both hydrophobic and
hydrophilic parts and they can be used as bridges between polar and non-polar
regions. In coordination chemistry they frequently act as ligands, completing the
coordination sphere of the metal ion [30].
Solvates are defined as crystalline solids of a compound in which solvent
molecules are present as an integral part of the crystal structure [31]. If the
incorporated solvent is water then it is referred to as a hydrate. Some solvates of the
same substance have the ability to crystallize in identical crystal structures [32-34].
Molecules in these isostructural (isomorphous) solvates are arranged in the same
manner forming identical intermolecular interactions and crystallizing in the same
space group. Only relatively small differences can be observed in the unit cell
dimensions if the systems remain isomorphous. Often molecules of the same solvent
can be incorporated in the crystal lattice in different proportions forming solvates
with different stoichiometic ratios. Like other organic compounds some solvates may
exhibit
polymorphism
themselves.
They
have
identical
components
and
stoichiometry ratio but different packing arrangements. This was demonstrated for
three monohydrates of tranilast [35], two hydrates of succinyl sulfathiazole [36] and
two hydrates of oxazepam [37]. The case of indantrione 1,2-dioxime is particularly
interesting as the compound is capable of forming polymorphic solvates with
different stochiometic ratios: 1:1 and 1:2 with methanol and 1:1 with ethanol [38].
Sometimes crystallization from a wet solvent or a solvent mixture may lead to the
formation of a crystal with more than one type of solvent molecule included in the
structure. These types of solvates are also known as heterosolvates [39].
Solvates were once obtained unintentionally during various solvent based
crystallization or purification processes [40]. Nowadays to satisfy regulatory
authorities [41] it has become essential to find every possible crystalline form of an
API in systematic polymorph screenings. Although some organic solvents of
solvated crystals are classified as unsafe they can be ideal precursors for the
development of a desired polymorphic form [42, 43]. In contrast, solvates containing
non-toxic organic solvents may have a higher solubility than the pure form which
could improve the bioavailability and dissolution rate of an API [44].
CSD provides valuable information on the solvent-forming properties of
organic compounds [45]. An analysis of every entry containing solvent molecules
has been performed by many researchers [39, 46]. It was shown that water, with
more than 11,000 hits, is the most common solvent incorporated in the crystal
structures of solvated forms. Approximately 2,800 hits were found for
dichloromethane and about 1,000 to 1,400 hits for other solvents (methanol, benzene,
ethanol and acetone). Among pharmaceutically relevant organic compounds listed in
the 4.02 edition of Pharmacopoeia European (PhEur) it was found that 36% may
exist in different polymorphic forms, 29% occur as hydrates and 10% are known to
form solvates [47]. All statistics place water molecule as a top solvate forming
solvent. This can be attributed to some specific features of this molecule. Water can
easily fit into even small structural voids due to the small size. The multidirectional
H-bonding capability is also responsible for the inclusion of water molecule into the
crystal structures of APIs.
Many classification systems have been developed for hydrates in the past.
Most of them are based on the location of the water molecule in the crystal lattice
and were introduced by Jeffrey, Clark and Morris [48]. These include: isolated site
hydrates, channel hydrates and ion associated hydrates. The first category represents
hydrates where water molecules are isolated from direct contact with other water
molecules by intervening drug molecules. The second category describes hydrates
with water molecules arranged next to each other forming channels through the
crystal structure. This category is further subdivided into expanded channels and
planar hydrates. Expanded channels may increase or contract the lattice volume by
absorbing or desorbing moisture depending on the humidity conditions. In planar
hydrates water molecules are arranged in 2D order forming planes in the crystal
lattice. The ion-associated hydrates belong to the third category of crystalline
hydrates in which water molecules are coordinated to a metal ion. Another
classification which does not require knowledge of the crystal structure was given by
Gal, Kuhnert-Brandstatter and Grimm [49]. It is based on the thermal behaviour of
organic hydrates. The most recent model which takes into account the mechanism
and structural changes upon dehydration was proposed by Petit and Coquerel [50].
Nucleation and Crystal Growth

Nucleation
Crystal nucleation is a key factor in controlling many properties of the
appearing crystalline phase [51]. The ability to control this preliminary stage of
crystal growth allows control of polymorphism and the size and distribution of
crystals.
Nucleation is a process which leads to the creation of a new crystalline entity
[52]. It is defined as a series of atomic or molecular events which cause the
rearrangement of atoms or molecules into a cluster according to the scheme:
A + A = A2
A2 + A = A3
An-1 + A = An (cluster)
This cluster, also known as a nucleus or critical nuclei, must have the ability to grow
irreversibly to a macroscopically large size. The size and the frequency of critical
nuclei strongly depend on the conditions within the crystallization medium.
The absence of foreign particles or crystals in the crystallization media is
known as homogeneous nucleation. In contrast, heterogeneous nucleation takes place
in the presence of foreign particles or surfaces which can encourage the formation of
nuclei at supersaturations lower than required for homogeneous nucleation.
Heterogeneous nucleation is more likely to occur since it is practically impossible to
perform crystallization experiments free from foreign bodies. Both types of
mechanism are referred to as primary nucleation. Formations of new crystals can be
induced by the presence of the crystals, also referred to as seeds, of the same
substance. This mechanism, known as secondary nucleation, is more favourable than
both homogeneous and heterogeneous primary nucleation and thus it occurs at lower
supersaturation.
Nucleation in polymorphic systems: rule of stages

In 1897, for compounds which can crystallize in more than one form
(polymorphs or solvates), Ostwald developed the Rule of Stages [53, 54]:
When leaving a given state and in transforming to another state, the state which is
sought out is not the thermodynamically stable one, but the state nearest in stability
to the original state.
This means that the crystallizing system advances from the supersaturated state to
equilibrium in stages with the smallest possible change in free energy, Fig. 1.3.
Hence, before the crystals of the most stable form appear, a polymorphic compound
will form every possible metastable form. The Rule of stages is a general rule, based
on the observation of many polymorphic systems, thus there are many exceptions
known [55].
Fig. 1.3 Schematic representation of Ostwald Rule of Stages with form 1 being the
least stable and form 4 the most stable polymorph.
Crystal growth
Following the nucleation step, crystals continue to grow, reaching a visible
size. Growth occurs when the amount of atoms leaving the growth medium and
joining the crystal surface is greater than the amount of atoms leaving the crystal
10
surface and going back into the growth medium. For crystals to grow a driving force
is necessary. According to the law of thermodynamics during the crystallization
process a decrease in free energy is required to promote crystal growth. The
difference between the chemical potential m of the growth medium (solution, melt,
vapor) and the chemical potential c of the crystalline phase is defined as the driving
force:
= m - c
If the growth medium is vapour the level of supersaturation becomes the driving
force as the crystals grow when the vapour pressure is higher than the equilibrium or
saturated vapour pressure.
On an atomic scale the growth surface of a crystal is irregular. It contains
many kinks, free vacancies and unfinished atomic layers which may be used by
atoms joining the crystal surface, Fig. 1.4 [56]. Kinks and edges are more likely to be
occupied by an atom. This is due to the larger contact surface. Some atoms might be
placed directly in favoured positions but most of them will have to migrate through
the crystal surface to find such a site.
Fig. 1.4 Kossel model of a crystal surface.
Many attempts have been made to explain the mechanism and rate of crystal
growth. This includes the surface energy theory, diffusion theory, adsorption layer
theory and screw dislocation theory [57, 58]. Surface energy theories were originated
by Gibbs (1878) and Curie (1885) and according to their hypothesis the growing
crystal assumed that shape for which the surface energy is lowest. Noyes, Whitney
(1897) and Nernst (1904) gave rise to diffusion theories which presume that the
11
substance is deposited constantly on a crystal face at a rate proportional to the

difference in concentration between deposition point and the bulk of solution. In
1922 Volmer proposed that crystal growth is a discontinuous process where crystal
surfaces grow by adsorption in a layer by layer mode. This is known as adsorption
layer theory and modifications were suggested by Kossel and Stranski. The screw
dislocation theory, also known as BCF theory, was first developed by F. C. Frank
(1949) and further analysed by W. K. Burton, N. Cabrera and F. C. Frank. Growth on
a crystal surface can occur by one of the following mechanisms: continuous growth,
surface nucleation or spiral growth.
Continuous growth
In the continuous model the surface of the crystal is molecularly rough and
retains this form during the crystal growth [53]. The energy which is essential to
form a new step is low thus the crystal surface contains many growth sites such as
kink and step sites, Fig 1.5 [59]. These kinks and steps are randomly distributed over
the crystal surface and are used as growth positions for arriving units.
Fig. 1.5 Rough crystal surface during the continuous growth model.
Surface nucleation
Surface nucleation mechanisms originate from adsorption layer theory [60].
Growth patterns of surface nucleation can be classified into two mechanisms. The
first one is known as layer by layer growth or single nucleation growth, where one
2D nucleus spreading over the whole crystal surface is responsible for the growth of
12
a single layer. A modification of this mechanism occurs when the nucleation rate is
faster than the time needed to form one layer on the crystal surface. Many nuclei
which appear all over the surface spread and combine into a layer. This type of
mechanism is known as multinucleation growth. 2D nuclei can also form all over the
surface and on top of existing nuclei which already started to spread contributing to
the growth of multiple layers simultaneously. This growth pattern is known as
multinucleation multilayer growth or birth and spread, Fig. 1.6 [61].
Fig. 1.6 The creation of the nuclei on a surface during crystal growth by birth and
spread mode.
Spiral growth
An energy barrier associated with 2D nucleation has to be overcome for the
crystal growth to happen [57]. This means that the event should occur at relatively
high supersaturation. However, the growth of 2D nuclei was observed at a low level
of supersaturation and this could not be explained using Volmer, Kossel and Stranski
theory. Hence F. C. Frank proposed the presence of screw dislocations as a result of
a continuous source of steps which promote crystal growth [62].
A dislocation is a consequence of stress that arises during crystal growth [63].
Screw dislocation is a line defect which, when exposed to the crystal surface, creates
a step, giving a rise to the spiral growth pattern, Fig. 1.7 [64]. As the dislocation is a
source of a step, this growth mechanism requires less energy than continuous or
surface nucleation growth and thus it will occur at low supersaturation, generating
13
spiral patterns around the dislocation centre. As a result of spiral growth each crystal
can have a unique growth rate based on the specific dislocation structure.
Fig.1.7 Formation and progress of spiral growth by screw dislocation mechanism.
14
Crystallization Methods
In general crystal growth can take place from solution, melt or vapour [65].
The choice of crystallization technique has the most important influence on the
nature and form of the obtained material and is often limited by the small amount of
sample [13, 58]. Crystallization processes are sensitive to many factors [66]. These
include the type of solvent used, initial saturation, impurities, additives, rate of
cooling, temperature of crystallization and temperature gradient. If conditions such
as pressure, temperature or supersaturation within a medium are changing too rapidly
it might not be possible to obtain a crystalline material [67]. A formation of
amorphous or glassy matter will take place instead. In some cases under constant
crystallization conditions, even if the solid is formed, spontaneous nucleation will
only occur after seeding.
Many classical crystallization methods [68] such as slow evaporation from a
single
or
mixture
of
solvents,
rapid
cooling,
precipitation
(anti-solvent
crystallization), vapour diffusion, slurry ripening and lyophilization require the use
of solvent. Other methods which are often employed for crystal growth of organic
compounds include crystallization from melt, heat induced transformation,
sublimation and desolvatation of solvates. Newer techniques have also been
developed and successfully applied to generate metastable polymorphic forms:
capillary crystallization [69], epitaxial matching [70, 71], laser-induced nucleation
[72], supercritical fluid crystallization [73] and ultrasound [74]. The work included in
this thesis is focused on crystal growth from the vapour, therefore sublimation
methods will be reviewed in more detail.
Solvent crystallization
Crystallization from solution takes place below the melting point of
crystallized matter, therefore it is the method of choice for compounds which are not
thermally stable [58, 75]. Crystals grow freely in solution and their faces are not
affected by contact with foreign surfaces, which can often allow optical recognition
of crystallographic axes. However, sometimes the presence of solvent may lead to
15
the formation of an undesired solvate [30]. Also, specific solvent interaction may
have an effect on nucleation or the crystal morphology.
Some polymorphs are sensitive to the type of solvent used, as in the case of
sulfathiazole form I, which was found to be stabilized by the use of 1-propanol or 1butanol. Both solvents inhibit the formation of the -dimer which is required for
nucleation and transformation into forms II and IV [76].
Many methods have been developed for crystal growth from solution. The
simplest is slow evaporation of solvent from solution at room temperature.
Minimalization of nucleation sites results in larger crystals. This can be achieved by
initial filtration, the use of unscratched flasks and a constant temperature. Slow
evaporation of solvent may take several weeks depending on the type and scale of
the performed crystallization. Sometimes, to minimise the chances of solvent
inclusion, mixtures of solvents are used for slow evaporation or for cooling supersaturated solutions. This was demonstrated in the co-crystallization of carbamazepine
and nineteen co-crystal formers [77].
Cooling of hot super-saturated solutions is also a common approach in
solvent based crystallization methods [78]. The use of stirred vessels aids the
production of uniform crystals. Although larger amounts of compounds are required
(as not all of the compound will crystallize), this method is more suited for the
growth of single crystals because the level of super-saturation can be more closely
controlled than in a slow evaporation process [58].
Vapour diffusion requires the presence of two solvents. The solute solution in
an open container is placed in a larger sealed vessel which contains a miscible and
volatile anti-solvent (i.e. a solvent in which the compound has little or no solubility)
[79, 80]. As the anti-solvent diffuses into the solute solution, saturation is achieved
forcing the nucleation and crystal growth. This method is often used for growing
large single crystals for structure determination [80].
Vapour crystallization
Sublimation is defined as a direct transition of a solid to a vapour without
passing through the liquid phase [81]. Approximately two-thirds of all organic
compounds are able to convert from solid to gas state on heating [82]. Vapour
16
growth gives solvent free crystals with well-defined faces. The temperatures at which
compounds sublime and crystallize, the distance between the sublimed compound
and the condensation area, the pressure and the type of collecting surface all have a
great influence on the size, habit and form of the grown crystals [82, 83]. Also, slow
growth rates and clean surfaces with a low level of nucleation sites contribute to the
growth of large crystals with low dislocation content. Very slow growth rates which
favour high quality crystals can be achieved using small temperature gradients in the
sublimation equipment [84].
The type of polymorph formed depends on the sublimation temperature, with
high temperatures favouring stable forms and low temperatures yielding unstable or
metastable crystals. It is possible to adjust crystallization conditions in order to
obtain crystals of one polymorphic form however, mixtures of several polymorphs
are often found to crystallize together [85]. Concomitant sublimation takes place
when polymorphs have similar vapour pressures at a particular temperature. This
often happens near the temperature of polymorphic transition.
Generally sublimation methods can be classified into three groups [86]:
simple, vacuum and entrainer. Simple sublimation is the most common type of
crystal growth from the vapour phase. The compound changes phase from solid to
vapour upon heating and diffuses towards the condensation area. The difference in
partial pressures between the vaporised and condensed matter is the driving force for
diffusion. In vacuum sublimation the transport of vapour onto the condenser is
increased by reducing the pressure which further increases the partial pressure
driving force. Entrained sublimation is also known as carrier sublimation due to the
use of inert gases. They enhance the rate of flow of vapour and thus increase the
yield of condensed matter.
A wide variety of experimental apparatus types have been developed over the
years for growing crystals from the gas phase. The most common is the use of a cold
finger. A horizontal glass tube was applied for the crystallization and crystal habit
control of succinic acid polymorphs [87]. Sealed tubes are used for the preparation of
metals (zinc and cadmium) and non-metallic sulphides [88]. Silver halide crystals
can be grown in quartz tubes on copper and quartz substrates [89]. A train
sublimation system was developed and applied to the purification of organic
pigments [90]. Two and three zone furnaces were employed to control and maintain
17
a temperature gradient and to keep a constant rate of sublimation during the growth
of single crystals [91].
Crystals obtained by sublimation are often used as seeds in solution phase
crystallization on a larger scale.
Melt crystallization
Melt refers to a liquid state of matter close to its freezing point. Crystal
growth from the melt is only suitable for thermally stable compounds. Also, it is not
possible to grow mixed crystals of uniform composition [92].
Melt crystallization can be used to obtain meta-stable forms of polymorphic
systems [93]. Often, super-cooling of melts first give the least stable form which
afterwards transforms into a more stable polymorph. Sometimes quench cooling a
melt can result in the formation of an amorphous solid which undergoes glass
transition and then crystallization upon further heating [94, 95].
The most widely used melt crystallization techniques are divided into four
groups. These include: the pulling (Kyropoulos and Czochralski), crucible, zone
melting and flame fusion techniques. The Kyropoulos and Czochralski methods were
applied to the single crystal growth of many organic and inorganic compounds [96,
97]. These methods require the presence of a seed crystal which in the Kyropoulos
method is allowed to grow into the molten phase and in the Czochralski method is
slowly withdrawn from the molten phase pulling out a growing single crystal. In the
crucible technique a melt is placed in a crucible which is slowly transferred from a
hot to a cold zone. For this purpose a furnace can be used to control the rate of
cooling [98]. The zone refining method also requires presence of a seed and it is
applicable to materials having a large surface tension. Zone refining has the
advantage of producing high purity, dislocation free crystals of organic and inorganic
materials [99, 100]. The flame fusion technique was developed by Verneuil in 1904
for the production of artificial gemstones [101]. Nowadays it is used for the mass
production of jewels and scientific instruments [102, 103].
18
Chapter 2:
19
Materials
50g of Stanozolol (>98%), 1g of Methandrostenolone (>95%), 5g of
Ethynilestradiol (>98%) and 25g of metal-free phthalocyanine (>93%) were
purchased from TCI Europe. 25g of 1,3-dinitrobenzene (>97%), 5g of
nitrocinnamaldehyde (>97%) and 100g of methoxycinnamaldehyde (>98%) were
obtained from Sigma Aldrich.
Instrumentation and Techniques

Low temperature gradient sublimation in vacuo, method A
A sublimation method for growing high quality single crystals has been
developed. The combination of Low (and very low) Temperature Gradients with
Sublimation in Vacuum, LTGSV, has several important advantages over other
crystallization techniques. Sublimation (which is also a purification technique) gives
high quality single crystals in a few hours (or less) without the necessity of using
solvents. Working in vacuo protects compounds from oxidation and the use of a low
thermal gradient favors the growth of good quality large crystals, suitable for
structure determination. The crystalline form and morphology of the crystals grown
by this method are not affected by solvents and impurities are less important than
when crystals are grown from solution.
Method A which uses the vacuum ovens heater as a temperature source has
been successfully applied to several different classes of compounds. These include
systems for which: 1) crystals of pure forms are not available from solution due to
difficulties with crystal packing, 2) there is a problematic habit when grown from
solution 3) polymorphs are formed and 4) crystals grown from solution are of poor
quality.
20
a)
b)
Fig. 2.1 Containers for growing crystals by low temperature gradient sublimation in
the vacuum.
Crystals of the compounds listed in Table 2.1 were grown in almost closed
containers in a Heraeus VT025 vacutherm oven which was operated at 10-9 GPa
pressure. The two sample container types used for the compounds in Table 2.1 are
shown in Fig. 2.1. The glass sample bottle (25mm diameter), Fig. 2.1 (a), is covered
with aluminium foil (shiny side up) in which a pinhole has been made and crystals
grow on the smooth side of the bottle. In Fig. 2.1 (b) a Petri glass covering a clock
glass is used. The total weight losses observed for stanozolol after 48 hours in the
oven were 4% and 15% respectively. The Petri dish has the significant advantage of
allowing more accurate examination of any crystals grown under a microscope. The
use of smooth surfaces favours growth of large single crystals, whereas scratched
surfaces enhance the level of nucleation which leads to the production of larger
quantities of small crystals. This was demonstrated for methandrostenolone, Fig. 2.2.
Fig. 2.2 Crystals of methandrostenolone grown on scratched and smooth surface.

21
Table 2.1 List of compounds grown by LTGSV.
Compound name
Sublimation
Temp [C]
Benzoic acid***
89
Caffeine
170
Carbamazepine
110
o-chlorobenzoic acid
m-chlorobenzoic acid
p-chlorobenzoic acid
Cholesterol
Ethinyl estradiol
4-hydroxy-N-phenylbenzenesulfonamide
Methandrostenolone
Naftazone
1,4-naphthaquinone***
80
4-Nitro benzoic acid

Oxalic acid
Phenacetin
Phenathraquinone
monosemicarbazide
Phthalocyanine***
Progesterone
ROY
Salicylanilide
Approx. time
required to observe
first crystals*
30 min
100
110
160
115
135
Plates to needles
Needles +
hexagonal
blocks**
Blocks
(From III)
Plates
Plates
Plates
Needles
Needles
135
Plates
12 h
120
160
6h
6h
180
75
95
Blocks
Plates
Blocks to
needles
Plates
Needles
Plates
190
Blocks
8h
475
95
Plates to needles
Blocks
4h
1h
100
Yellow blocks +
Orange needles
4h
> 115
120
Orange needles
Plates
3h
30 min
140
Needles + blocks
(polymorph I +
polymorph II)
12 h
Stanozolol
> 150
Succinic acid
Sulfamerazine
Sulfapirydyne
Sulfathiazole
Crystal Habit
130
180
150
135
Needles
(polymorph I)
Plates
Blocks
Blocks
Blocks
8h
15 min
30 min
35 min
2h
12 h
8h
30 min
12 h
20 min
30 min
6h
5h
8h
6h
24 h
22
(Forms I + II)
Blocks
110
28 h
(Forms III)
* Crystals of suitable size for single crystal X-ray analysis
** Hexagonal crystals were not stable enough at atmospheric pressure for structure
determination
*** External heater was used to create a range of driving forces across the condensation
area
Sublimation in a vacuum oven using an externally controlled heater,

method B
The experimental setup which used two Petri dishes is shown in Fig. 2.3. This
was placed inside a Heraeus VT025 vacutherm oven. Six small holes were drilled in
the pressure relief valve on the rear of the oven. Insulated wires were cemented to the
pressure relief valve using epoxy resin. The six wires were used to connect two
thermocouples and a small heater. The heater was wound onto a 3 x 1 cm ceramic
rod using 70 cm of 0.4 mm nichrome which had a resistance of 4.2
. A variable
voltage transformer was used to control the temperature using voltages in the range
of 15 to 25 volts. The sample was placed in the centre of the Petri dish directly above
the heater. The sublimation temperature was measured using a thermocouple held on
the glass surface in place of the sample by a piece of high temperature tape. The
heater generated a radial temperature gradient illustrated by the colour gradient in
Fig. 2.3. Glass wool was placed around the setup to minimize heat loss and reduce
temperature gradients. The temperature at the walls of the oven did not exceed 100
C at the highest temperatures used.
Fig. 2.3 Sublimation equipment setup showing how the driving force changes across
the condensation area.
23
This setup was applied to the crystal growth of 1,4-naphthaquinone, metalfree phthalocyanine and benzoic acid. In each of the performed experiments it was
observed that the high driving force (in the centre of the Petri dish) promotes
nucleation at the expense of crystal growth. However, towards the edge of the Petri
dish, the nucleation rate is lower and the reduced driving force promotes the growth
of larger crystals.
X-Ray diffraction techniques

X-rays are scattered in all directions when they hit electrons passing through
the matter [104, 105]. However when the matter is crystalline the scattering of the Xrays occurs in specific directions which strictly depend on the nature of the repeating
pattern. This relationship applied in the X-ray diffraction methods provides a
comprehensive description of the arrangement of the atoms in the solid state
structure of crystalline solids.
Single Crystal X-Ray Diffraction

Single X-ray crystallographic studies give the most detailed characterisation
of solid state [106]. The determination of the unit cell reveals the periodicity of the
crystal and the assignment of the phases to the structure factors allows the generation
of the 3D electron density map of the crystal and this gives detailed information
about the structure of small molecules and macromolecules at the atomic level.
However, if it is not possible to grow high quality single crystals for structure
determination powder X-ray diffraction, PXRD, is the method of choice for
polymorph identification and characterisation [107].
An Oxford Diffraction Xcalibur system equipped with Sapphire CCD

detector was used to collect X-ray diffraction data at both ambient temperature and
150K. The crystal structures were solved by direct methods, Shelxs-97, and refined
by full matrix least squares using Shelxl-97 [108]. Both are included in the Oscail
package [109] which was also used for the analysis of crystal packing and
intermolecular interactions. The only twinned crystal structure of 1-[(1E,3E,5E)-4,6-
24
bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-methoxybenzene was resolved with the

program Rotax [110]. In all cases non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included in calculated positions except those of the water
molecules in the crystal structures of hydrates, where the hydrogens were refined
with a distance restraint of 0.89. Some of the packing diagrams were produced
using Mercury [111].
Powder X-Ray diffraction (PXRD)

Diffraction from a powder gives essentially the same information as single
crystal X-ray diffraction however the reflection data collapsed onto a line plot of 2
vs. intensity. Thus reflections with identical 2 values are on top of each other. It is
possible to obtain crystal structures from powder data using the Rietveld method but
the work is not trivial nor is it always successful [112]. It should also be pointed out
that PXRD examines more than one crystal and thus gives a better overview of a
sample than results based on just one crystal. Thanks to the specific fingerprints of
microcrystalline
powders
PXRD
is
the
preferred
method
for
routine
polymorph/solvates identification and characterisation. PXRD can also be employed

in quantitative analysis of polymorphic mixtures [113].
Powder diffraction patterns were collected using Inel Equinox 3000 and
Siemens D500 powder diffractometers between 4-90 and 4-40 (2) respectively
using CuK radiation with steps of 0.05. Powder patterns were also calculated using
the atom coordinates by programs within the Oscail package.
PatMatch
Calculated powder patterns were compared using program PatMatch included
in the Oscail package. To compare two PXRD patterns, A and B, program selects n
(usually twelve) peaks with the highest intensity. For those peaks their positions, 2,
and intensities, I, are compared within the errors of 0.85 and 0.70 respectively. The
program reports the number of matching peaks (m) for both PXRD patterns. For
matching peaks the difference in their intensities, I, is calculated: I=IA-IB. For
isomorphous structures this value will be close to zero. Match indices, Match, for
two PXRD patterns are calculated using following equation:
25
Match = 1-(I * Weight),

Weight =
Isomorphous compounds will have match indices > 0.85.
Thermal analysis
The role of thermal analysis is to monitor the properties of the sample against
time or temperature as compounds undergo both physical and chemical changes [12,
37, 114, 115]. These changes include; colour change, sublimation, melting and phase
changes. The factors which affect the kinetics of these processes include particle
size, impurities, crystal shape and presence of polymorphic nuclei. Also the mass and
heating rate of the sample have a direct effect on the resolution of thermal events. A
combination of DSC and TGA is often employed for distinguishing polymorphs and
solvates of pharmaceutical solids [37, 116, 117]. Thermal methods have been applied
in many other areas, such as: polymers, electronics, material science and in quality
control.
Thermogravimetric analysis (TGA)

Thermogravimetric analysis is an analytical technique used to determine the
thermal stability of a sample [107]. The principle is to measure weight changes as a
function of temperature. TGA measurements play an important role in
characterization of solvates and excipients. The main application of TGA is the
determination of solvate stoichiometry which can be calculated from the weight loss
per known amount of analyzed compound [106]. It is also useful in identifying
sublimation and decomposition processes [118, 119]. The key disadvantage of
thermogravimetric analysis is that it does not provide any information about the
nature of the compound and for this reason TGA is often coupled with another
analytical technique.
Differential scanning calorimetry (DSC)
26
DSC measures the amount of energy that is absorbed (endothermic event) and
released (exothermic event) by a sample during heating, cooling or at constant
temperature [71]. This technique provides information on melting point, heat
capacity and heat of fusion of examined material. The identification of different
polymorphs is often possible on the basis of differences of their melting points [106].
Phase transitions and stability relations between different polymorphic forms can
also be investigated using this technique [107, 120]. It is possible to analyse the
relative stability of different solvates by estimating the strength of the host-solvent
interaction using the enthalpy of desolvatation (HDSC) obtained from a DSC
thermogram. This can be compared with the enthalpy of vaporisation (Hvap) of the
pure solvent [121-123]. Because of the low sensitivity this method cannot detect
polymorphic impurities (<5%). In rare cases this method may not be sensitive to
polymorphic systems at all. For instance only one form of mannitol can be
distinguished by DSC [37]. The analysis of pseudo-polymorphic compounds may be
affected by the type of pan used in the experiment. Also the method is not suitable
for substances which decompose before melting [37].
Thermogravimetric analysis (TGA) and Differential scanning calorimetry

(DSC) were performed on a STA625 thermal analyzer from Rheometric Scientific.
The samples were scanned at a rate of 10C/min from 25 to 400 C under a nitrogen
purge at 50ml/min in open aluminium crucibles. The system was calibrated using an
indium standard. The enthalpy of vaporisation values were taken from Bunger
Riddick and Sakano [124].
Microscopy
Optical microscopy
Optical microscopy is often a primary choice in screening crystal morphology
or monitoring crystal growth or phase transformations of polymorphic systems [12].
Polymorphs differ in their crystal shape and somethimes colour and this can be
observed using optical or scanning electron microscopy. Visual differences in the
crystal morphology do not reflect polymorphism itself. Because there is no intrinsic
relationship between crystal morphology and crystal structure, microscopy alone is
not enough to study polymorphism. Changes in crystal morphology can be caused by
27
different solvents, impurities, additives, etc. Optical microscopy has been applied to
the study of the growth rates of individual faces of many polymorphic systems such
as sulfathiazole [125] and methylprednisolone [126].
Scanning Electron Microscopy

Scanning Electron Microscope (SEM) is routinely used to generate high
resolution images [127]. It can detect and analyse surface fractures, examine surface
contamination, crystal morphology, and the presence and location of crystal defects
[128]. When additionally equipped with an Energy Dispersive X-ray system (EDX)
it provides rapid determination of elemental composition. SEM work will usually
require the sample to be kept in a vacuum. This can be a limiting factor especially
when dealing with solvated crystals or compounds which are vulnerable to
sublimation at room temperature. SEM is widely used in many areas including:
metallurgy, life science, biology, gemology and medical and forensic science. It has
also been applied to the determination of crystal growth mechanisms [129, 130],
topographical control of crystal nucleation [131] and the investigation of the stability
of crystalline drugs[132, 133].
The Olympus SZX16 stereozoom microscope and a Hitachi S-4700 SEM

coupled with EDX were used to perform surface analysis of organic compounds in
this study.
ATR-Infrared spectroscopy
Infrared (IR) spectroscopy provides valuable information on structure and
molecular conformation in the solid state [134, 135]. Significantly changes arising
from intermolecular interactions such as H-bonding affect the observed spectrum.
This is particularly important when studying polymorphism [136]. Sometimes
however IR spectra of polymorphic systems do not differ significantly and this
indicates that the fingerprints of vibrational modes are not greatly affected by the
differences in the crystal structures. In general IR spectroscopic techniques are
robust, inexpensive, require only small quantities of a compound and very little
sample preparation [135]. Therefore they are highly suitable for preliminary
examination, identification and characterisation of pharmaceutical products. As the
28
older dispersive equipment has now been replaced by the more accurate Fourier
transform (FT) spectrometers IR has been successfully employed in the quantitative
analysis of polymorphic systems [137, 138].
Attenuated total reflectance (ATR) is a widely used and particularly
convenient sampling technique which allows for qualitative and quantitative analysis
of solid state pharmaceutical compounds with almost no sample preparation [1].
ATR-IR spectra were collected from 4000-650 cm-1 on a PerkinElmer FTIR/FT_FIR Spectrum 400 using 32 accumulations at a resolution of 4cm-1 using
Spectrum v6.3.2 software. The ATR was a DATR 1 bounce diamond/ZeSe universal
ATR sampling accessory.
29
Chapter 3:
Crystallization of Solvent Free Crystals not
Available from Solution: Study Case
Stanozolol
30
Introduction
Crystalline forms of stanozolol
Stanozolol is an anabolic steroid that was developed by Winthrop
Laboratories in 1962 [139]. It proved to be successful in treating anaemia,
osteoporosis and hereditary angioedema and it is also popularly used as a female
body builder [140-142]. It is commonly sold under the names Winstrol, Tenabol and
Winstrol Depot [143].
Stanozolol was described in the early literature as having three polymorphic
forms and several solvated forms. In 1993 W. L Rocco characterised polymorphs 1
and 2 and four solvates (monohydrate, methanol, ethanol and isopropanol) using
differential scanning calorimetry (DSC), X-ray powder diffraction (PXRD) and
infrared spectroscopy (FT-IR) [144]. PXRD studies revealed the diversity in crystal
structures among the crystalline forms of stanozolol and its pseudo-polymorphs. In
2003 the first and only crystal structure (before this work) of stanozolol in its ethanol
solvate was published by D. R. Lisgarten [145]. No crystal structures of pure
stanozolol polymorphs had been reported before this work.
Sublimation method A was applied to grow solvent free crystals of
stanozolol. Solution crystallization gave crystals of four already known and seven
new solvated forms. Thus the crystal structures of two polymorphs and ten solvates
were determined. Structural diversities among crystalline forms of stanozolol were
further investigated comparing experimental and calculated PXRD patterns using the
Patmatch program within the Oscail package. Thermal analysis was applied to
establish stoichiometry ratios of solvates and to investigate the strength of solventstanozolol interactions. This work provides an understanding of why no solvent free
crystal forms of stanozolol are available from solution in contrast to the ease with
which solvated forms may be crystallized.
31
Crystallization of stanozolol
Despite the wide range of organic solvents used, only crystals of solvated
forms were obtained. High quality single crystals of polymorphs 1 and 2 were grown
by sublimation, method A, described in the Chapter 2. The amount of sample used in
the experiments varied from 10 to 100 mg. The temperature range used for
stanozolol sublimation was from 135 to 170 C. Both polymorphs were observed at
150 C. However, at the lower end of the temperature range block shaped crystals
dominate whereas at 170 C only needles were produced. This temperature range
was chosen as DSC measurements indicated that there were no transformations in
this region, Fig. 3.1.
Fig. 3.1 DSC-TG curves for stanozolol, showing the solid-solid polymorphic
transformation of form 2 form 1 at 235 C and melting of form 1 at 242 C
followed by decomposition at 353 C.
32
Typical crystals are shown in Fig. 3.2. Crystals of pure polymorphs were used
as seeds but only transformation to one of already known solvated form was
observed.
Fig.3.2 Crystal habit of stanozolol polymorph 1 (left) and 2 (right).
Crystallization of solvated forms of stanozolol

The solvents listed in Table 3.1, were used in crystallization experiments but
all attempts led to crystalline solvates. Crystals of eleven solvates were grown and
pictures of all of these are shown in Fig. 3.3.
Table 3.1 Overview of the solvents used in crystallization experiment.

Overview of the solvents used
acetic acid B
diethyl ether C
propanol A
acetone C
DMF B
propan-2-ol B
acetonitrile C
1,4 - dioxane A
pyridine B
benzene B
ethanol B
THF C
butanol C
ethyl acetate A
toluene C
butan-2-ol B
formamide B
wet ethanol B
chloroform C
methanol B
wet isopropanol B
cyclohexan C
pentanol C
xylene A
Formation of monohydrate form, B solvate formation, C crystals were not observed
Solvated crystals containing methanol, ethanol, isopropanol, 2-butanol, acetic

acid and formamide were obtained by cooling hot saturated solutions. Crystals of the
ethanol dihydrate, the isopropanol dihydrate, the dimethylformamide hydrate and the
pyridine solvate were prepared by slow evaporation from wet solvent solutions. The
33
monohydrate was obtained from wet solvents which do not give solvates by slow
evaporation. These solvents were: propanol, 1,4-dioxane, ethyl acetate and xylene.
a) monohydrate
b) methanol solvate
c) ethanol solvate
d) isopropanol solvate
e) butan-2-ol solvate
f) ethanol dihydrate solvate

34
g) isopropanol dihydrate solvate
h) acetic acid solvate
i) formamide solvate
j) pyridine solvate
k) dimethylformamide hydrate solvate

Fig. 3.3 Crystal habit of stanozolol solvates.
35
Results
Structural analysis of polymorphism in stanozolol
Both needle and block shaped crystals were suitable for single crystal X-ray
analysis. Crystallographic results for both polymorphs are given in Table 3.2.
Table 3.2 Crystal data for polymorphs of stanozolol.

Crystalline form of
Polymorph 1
Polymorph 2
Empirical formula
C21 H32 N2 O1
C21 H32 N2 O1
Formula weight
328.49
328.49
Temperature / K
298(2)
298(2)
Wavelength /
0.7107
0.7107
Crystal system
Orthorhombic
Orthorhombic
Space group
P212121
P21212
a/
7.3164(4)
19.4540(7)
b/
21.562(2)
18.7009(8)
c/
24.0058(11)
10.8348(4)
V / 3
3787.1(5)
3941.8(3)
/ Mg/m-3 (calculated)
1.152
1.107
/ mm-1
0.070
0.068
Reflections collected
11756
12685
Independent reflections
6695
6908
[Rint = 0.0278]
[Rint = 0.0185]
Reflections observed (>2)
3213
5298
Goodness-of-fit on F2
0.756
1.026
Final R indices [I>2(I)]
R1 = 0.0380
R1 = 0.0487
wR2 = 0.0616
wR2 = 0.1023
R1 = 0.1056
R1 = 0.0718
wR2 = 0.0703
wR2 = 0.1138
stanozolol
R indices (all data)
36
calculated XPRD
of polymorph 1
observed XPRD
of polymorph 1
(needles)
5
10
15
20
25
30
35
40
2
Fig. 3.4 Observed and calculated PXRD patterns of polymorph 1.
calculated XPRD
of polymorph 2
observed XPRD
of polymorph 2
(blocks)
5
10
15
20
25
30
35
40
2
Fig. 3.5 Observed and calculated PXRD patterns of polymorphs 2.
37
The needles and blocks were identified as polymorphs 1 and 2 respectively

by comparing their PXRD patterns with those reported in the literature [144]. The
calculated PXRD patterns for the needles and the blocks are also in good agreement
with both the reported and observed patterns, Fig. 3.4-5.
Polymorph 1 crystallised in the orthorhombic space group P212121 with two
molecules per asymmetric unit. The molecules within the asymmetric unit are
tautomers A and B, Fig. 3.6. The tautomers were identified on the basis of the C-C
and C-N bond lengths in the heterocyclic ring and by the way in which the hydrogen
atoms of the N-H and O-H bonds fitted into the hydrogen bonded network. Thus the
C-C ring junction bonds were C2-C18, 1.381(6) and C23-C39, 1.352(6)
respectively and H1N1 and O1H1 were close to the intermolecular contact lines
joining the N1O1 and O1N4 respectively.
20
7
6
19
1
3
2
1 E
2
A
18
B
16
13
41
21
28
10
10
22
12
4
1
9
23
14
E
3
17
15
tautomer A
29
C
33
A
39
26
24
11
4
27
25
37
38
36
tautomer B
42
30
34
31
32
35
Fig. 3.6 Tautomers of polymorph 1 showing the numbering scheme for the non
hydrogen atoms.
There are two potential hydrogen bond donors and three potential hydrogen
bond acceptors in each of the tautomers. Hydrogen bonded chains form a spiral motif
in the a direction. The motif involves (N1-HO1-HN4-N3-HN2-)n, Table 3.3.
This is illustrated in Fig. 3.7 and 3.8 and in graph set notation this is described as
C33(8) chains [146]. The double ended nature of tautomer As hydrogen bonding
links the spiral motifs into a 3D network.
38
Fig. 3.7 View of hydrogen bonded spiral down a showing the C33(8) graph set of
polymorph 1.
Fig. 3.8 Spirals of polymorph 1 linked by tautomer A molecules.
39
Table 3.3 Hydrogen bonding interactions in the crystal structures of polymorph 1

and polymorph 2.
Orientation
Form of
of
stanozolol
stanozolol
Tautomer
head - tail
A and B
polymorph
1
head - head
DA
Dimensionality
H-bond
[]
of network
N1H1N1O1
2.817
2D
N4H1N4N2
2.978
O1H1O1N3
2.808
O1H1O1N3
2.833
polymorph
tail - tail
O2H1O2O1
2.743
head - tail
N2H1N2O2
2.778
N4H1N4N1
2.885
3D
However, the O-H group of tautomer B, O2, is not involved in hydrogen bonding.
This agrees with the reported analysis of IR spectra where a high frequency nonhydrogen bonded O-H band was observed at 3619 cm-1, Fig. 3.9. Unused hydrogen
bonding capacity is not common as it breaks the first rule of Etters analysis of
hydrogen bonding which states that All good proton donors and acceptors are used
in hydrogen bonding [146]. There are, however, several well established exceptions
to this rule. Alloxan for example has no hydrogen bonds in its crystal structure and
an analysis using crystal structure prediction methods of possible interactions
between alloxan molecules and those of related systems shows that some dipoledipole interactions, for example (C=O)(C=O), can compete with conventional
hydrogen bonding [147]. Since there are no dipoles in the stanozolol molecule other
than hydrogen bond donors and acceptors it is more likely that it belongs to the class
of rigid awkward shaped molecules which have packing difficulties of which
desloratadine is an example [148].
40
Fig. 3.9 FT-IR spectra of Stanozolol polymorph 1 (red) and 2 (green) showing high
3600
3200
2800
2400
2000
1800
cm-1
1600
1400
1200
1000
800
650.0
frequency non-hydrogen bonded O-H band at 3619 cm-1.
%T
4000.0
3619 cm-1
41
Polymorph 2 crystallized in space group P21212 with two molecules of

tautomer B per asymmetric unit. All potential H-bond donors and acceptors are
involved in the formation of a 3D H-bonding network which consists of two
identical, independent, interpenetrating 3D networks, Fig. 3.10.
Fig. 3.10 Colour coded two identical, independent 3D hydrogen bonded networks of
polymorph 2 down a.
Fig. 3.11 H-bonded ring of polymorph 2 down c displaying the R44(10) graph set.
42
All nitrogen atoms of two molecules and oxygen atoms of another two
molecules are involved in the formation of a ring motif, Fig. 3.11. This ring pattern,
R44(10), involves (O1-HN3-N4-HN1-N2-HO2-H).
A void search, which was performed with the PC void program within the
Oscail package [149], shows that both structures contain voids. One sphere of radius
1.6 can be fitted into the polymorph 1 structure and two spheres of 1.85 radius
can be fitted into polymorph 2. The void in polymorph 1 is adjacent to O2 which is
not involved in hydrogen bonding, Fig. 3.12, and the voids in polymorph 2 are at the
origin at 0.5, 0, 0, and 0.75 0, 0. The structure adopted by polymorph 1 is a
compromise between the loss of some hydrogen bonding and the generation of a
more dense structure. The calculated densities of polymorphs 1 and 2 are 1.152 and
1.107 mg/m3 respectively. The presence of voids in these structures is probably due
to the molecules packing difficulties. These packing problems may also explain why
it has not proved possible to obtain solvent free crystals from solution. The
observation of the less dense less stable polymorph is formed at lower temperature
and its conversion to the more stable form at higher temperature is in agreement with
Ostwalds rule of stages [54].
Fig. 3.12 Arrangement of voids in polymorph 1.

43
Structural diversity of stanozolol solvates

Crystals of eleven solvates were grown and the crystal structures of ten of
them were determined. The crystallographic data is given in Tables 3.4-8.
Table 3.4 Crystal data for monohydrate and ethanol solvate.
Crystalline form of
monohydrate
ethanol solvate
Empirical formula
C21 H34 N2 O2
C23 H38 N2 O2
Formula weight
346.50
374.55
Temperature / K
298(2)
150(2)
Wavelength /
0.7107
0.7107
Crystal system
Orthorhombic
Orthorhombic
Space group
P212121
P212121
a/
7.2098(5)
7.1392(5)
b/
10.4654(7)
10.9541(8)
c/
26.0313(13)
26.8891(16)
V / 3
1964.2(2)
2102.8(3)
1.172
1.183
/ mm-1
0.075
0.075
10407
6211
3552
3627
[Rint = 0.0345]
[Rint = 0.0460]
2182
2219
0.801
0.892
R1 = 0.0372
R1 = 0.0550
wR2 = 0.0631
wR2 = 0.0705
R1 = 0.0720
R1 = 0.0993
wR2 = 0.0676
wR2 = 0.0894
stanozolol
44
Table 3.5 Crystal data for isopropanol and butan-2-ol solvate.
Crystalline form of
isopropanol solvate
butan-2-ol solvate
Empirical formula
C24 H40 N2 O2
C25 H42 N2 O2
Formula weight
388.58
402.61
Temperature / K
150(2)
298(2)
Wavelength /
0.7107
0.7107
Crystal system
Monoclinic
Monoclinic
Space group
C2
C2
a/
24.5445(13)
25.321(2)
b/
7.2894(3)
7.421(2)
c/
15.2500(8)
15.393(2)
122.679(7)
123.40
V / 3
2296.56(19)
2414.6(7)
1.124
1.107
/ mm-1
0.071
0.069
5444
17882
3446
4402
[Rint = 0.0161]
[Rint = 0.0472]
3029
3388
0.980
1.039
R1 = 0.0318
R1 = 0.0503
wR2 = 0.0725
wR2 = 0.1290
R1 = 0.0375
R1 = 0.0691
wR2 = 0.0739
wR2 = 0.1418
stanozolol
45
Table 3.6 Crystal data for ethanol dihydrate and isopropanol dihydrate solvate.
Crystalline form of
ethanol
isopropanol
stanozolol
dihydrate solvate
dihydrate solvate
Empirical formula
C44 H74 N4 O5
C24 H44 N2 O4
Formula weight
739.07
424.61
Temperature / K
150(2)
150(2)
Wavelength /
0.7107
0.7107
Crystal system
Monoclinic
Monoclinic
Space group
P21
P21
a/
7.3934(2)
10.5093(3)
b/
27.5812(6)
7.2906(2)
c/
10.5964(3)
15.5622(5)
109.234(3)
94.812(3)
V / 3
2040.19(9)
1188.16(6)
1.203
1.187
/ mm-1
0.078
0.080
9236
5499
5277
3650
[Rint = 0.0197]
[Rint = 0.0169]
4629
3157
0.980
0.973
R1 = 0.0327
R1 = 0.0332
wR2 = 0.0701
wR2 = 0.0733
R1 = 0.0379
R1 = 0.0397
wR2 = 0.0711
wR2 = 0.0747
46
Table 3.7 Crystal data for acetic acid and formamide solvate.
Crystalline form of
acetic acid solvate
formamide solvate
Empirical formula
C25 H40 N2 O5
C43 H64 N5 O3
Formula weight
448.59
698.99
Temperature / K
298(2)
293(2)
Wavelength /
0.7107
0.7107
Crystal system
Monoclinic
Orthorhombic
Space group
P21
P212121
a/
10.3775(8)
7.5672(3)
b/
7.4347(6)
19.6475(9)
c/
15.5801(8)
26.3375(9)
91.895(6)
V / 3
1201.40(14)
3915.8(3)
1.240
1.186
/ mm-1
0.086
0.075
5253
14471
3275
6840
[Rint = 0.0395]
[Rint = 0.0264]
1872
4211
0.875
0.909
R1 = 0.0504
R1 = 0.0476
wR2 = 0.0824
wR2 = 0.1086
R1 = 0.0921
R1 = 0.0852
wR2 = 0.0900
wR2 = 0.1176
stanozolol
47
Table 3.8 Crystal data for pyridine and dimethylformamide hydrate solvate.
Crystalline form of
pyridine solvate
DMF hydrate solvate
Empirical formula
C47 H69 N5 O2
C45 H73 N5 O4
Formula weight
736.07
748.08
Temperature / K
298(2)
298(2)
Wavelength /
0.7107
0.7107
Crystal system
Orthorhombic
Monoclinic
Space group
P212121
P21
a/
7.233(2)
10.4243(10)
b/
11.850(2)
7.4432(5)
c/
48.672(2)
27.018(2)
stanozolol
94.069(9)
V / 3
4171.8(14)
2091.1(3)
1.172
1.188
/ mm-1
0.072
0.076
12520
9056
6556
5784
[Rint = 0.0251]
[Rint = 0.0169]
4847
4640
1.085
1.025
R1 = 0.0679
R1 = 0.0493
wR2 = 0.1132
wR2 = 0.1208
R1 = 0.0962
R1 = 0.0668
wR2 = 0.1223
wR2 = 0.1327
48
DMF hydrate
Formamide
Pyridine
Acetic acid
Isopropanol
dihydrate
Ethanol
dihydrate
Butan-2-ol
Isopropanol
Ethanol
Monohydrate
5
10
15
20
25
2
Fig. 3.13 Calculated PXRD patterns for ten pseudo-polymorphs of stanozolol.
49
The crystals of the methanol solvate which appeared to be of good optical

quality were not suitable for single crystal X-ray diffraction as less than 2% of the
reflections could be indexed. A possible explanation for the failure of the methanol
solvate to form crystals with long range order is that methanol is trying to crystallize
with a structure similar to polymorph 1 with the solvent molecules in the voids.
However, the void volume which is about the size of a water molecule is just too
small to properly accommodate a methanol molecule.
Visual inspection of Fig. 3.13 suggests that the isopropanol and butan-2-ol
solvates are isomorphous. There are several different powder pattern matching
methods available and most of them are in commercial software packages. The
generalized expression for the similarity of powder diffraction patterns shows that
the criteria described in literature all refer to the correlation function and are point by
point comparisons [150]. The Xmatch program was developed to include point
neighbourhoods and was claimed to be an improvement on traditional methods
[150]. Xmatch does not pick out this isomorphous pair of solvates. The PatMatch
program within the Oscail package was successfully used to analyse calculated
PXRD patterns of the crystalline forms of stanozolol, Fig. 3.13. A brief description
of the PatMatch method is given above in Chapter 2. A twelve peak comparison was
used and the selected peaks are given in Table 3.10. Table 3.9 contains a list of
identification numbers assigned to the analysed crystalline forms of stanozolol. The
PatMatch results are presented in Tables 3.11 and 3.12. Table 3.11 is the matrix of
the numbers of matching peaks and the diagonals which correspond to identities
show the expected 12 in Table 3.11 while the expected 1.0 along the diagonal of
Table 3.12 is set to 0 to make it easier to visualize the results using bar charts etc.
The program also lists the top matches and these are shown in Table 3.13 and clearly
only two solvates are isomorphous, Fig. 3.14-15.
50
Table 3.9 List of crystalline forms of stanozolol and their corresponding

identification numbers.
Identification
number
Crystalline form of stanozolol
Polymorph 1
Polymorph 2
Stanozolol ethanol dihydrate solvate
Stanozolol acetic acid solvate
Stanozolol butan-2-ol solvate
Stanozolol DMF hydrate solvate
Stanozolol ethanol solvate
Stanozolol formamide solvate
Stanozolol monohydrate
10
Stanozolol isopropanol dihydrate solvate
11
Stanozolol isopropanol solvate
12
Stanozolol pyridine solvate
Table 3.10 Position of the peaks with highest intensities chosen for PXRD analysis.
Identification
Position of the peaks [2]
number
1
6
7
12.75, 13.25, 14.15, 16.35, 16.55, 16.85,

18.35, 20.75, 33.25, 35.55, 38.25, 38.50;
12.20, 12.45, 13.10, 14.40, 15.45, 16.60,
17.00, 18.50, 20.50, 24.55, 26.75, 36.25;
12.80, 17.95, 18.80, 25.80, 26.25, 26.85,
29.70, 31.85, 33.30, 34.25, 36.00, 38.10;
14.60, 15.60, 17.80, 20.20, 20.85, 23.50,
24.10, 25.40, 26.15, 26.55, 30.35, 39.25;
12.60, 13.20, 14.65, 15.85, 17.30, 20.35,
21.00, 22.10, 23.10, 27.70, 28.25, 37.30;
14.60, 15.75, 17.00, 17.55, 17.80, 20.30,
21.25, 22.50, 25.65, 28.70, 34.85, 38.60;
13.95, 15.05, 15.95, 20.50, 21.25, 22.50,
51
24.25, 24.70, 27.10, 27.90, 34.80, 35.85;

14.75, 17.85, 18.00, 18.20, 19.10, 22.40,
22.85, 27.20, 27.40, 29.75, 38.40, 38.65;

14.00, 14.90, 15.25, 16.90, 17.25, 21.20,
22.00, 27.00, 28.25, 29.20, 34.40, 37.15;

14.75, 15.55, 16.90, 18.30, 22.00, 23.75,
10
25.45, 28.00, 28.30, 29.30, 36.45, 39.85;

12.85, 13.45, 15.10, 16.25, 17.65, 20.50,
11
21.65, 22.75, 23.65, 28.45, 29.15, 38.40;

14.40, 14.75, 15.35, 15.90, 16.05, 16.95,
12
17.50, 18.50, 20.65, 21.40, 22.25, 31.65;
Table 3.11 Number of peaks matched.

1
10
11
12
12
12
12
0 12
0 12
10
3 12
12
12
12
10
12
11
12
12
12
Ten out of twelve matching peaks were found for the isopropanol and butan2-ol solvates. For these peaks a match indices of 0.88 was calculated. The
isomorphous pair, isopropanol and butan-2-ol solvates, are both monoclinic (space
group C2) with one molecule per asymmetric unit. Although there is a significant
difference in their unit cell dimensions, for example the a dimensions differ by 0.776
, the observed and calculated PXRD patterns are very similar, Fig. 3.14-15. It is
interesting that there are considerable differences in observed and calculated
52
intensities. This is due to preferred orientation effects as both observed patterns are
dominated by their 4 0 2 reflections. Thus these solvates are isomorphus and also
have similar crystal morphologies.
Table 3.12 Pattern match indices.

4
5
6
7
8
9
10
11
12
1 0.00 0.00 0.00 0.00 0.16 0.00 0.00 0.00 0.00 0.00 0.38 0.00
2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
4 0.00 0.00 0.00 0.00 0.00 0.34 0.00 0.00 0.00 0.00 0.00 0.00
5 0.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.88 0.00
6 0.00 0.00 0.00 0.34 0.00 0.00 0.00 0.00 0.00 0.46 0.06 0.00
7 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
9 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
10 0.00 0.00 0.00 0.00 0.00 0.46 0.00 0.00 0.00 0.00 0.00 0.00
11 0.38 0.00 0.00 0.00 0.88 0.06 0.00 0.00 0.00 0.00 0.00 0.00
12 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Table 3.13 Top matches for the pairs of PXRD patterns of crystalline forms of
stanozolol.
Match Indices
Identification numbers of pairs of forms of stanozolol
0.88
5 and 11 Stanozolol butan-2-ol and isopropanol solvates
0.46
6 and 10 Stanozolol DMF hydrate and isopropanol

dihydrate solvates
0.38
1 and 11 Polymorph 1 and stanozolol isopropanol solvate
0.34
4 and 6 Stanozolol DMF hydrate and acetic acid solvates
0.16
1 and 5 Polymorph 1 and stanozolol butan-2-ol solvate
0.06
6 and 11 Stanozolol DMF hydrate and isopropanol solvates
53
calculated XPRD
butan-2-ol
calculated XPRD
isopropanol
5
10
15
20
25
30
35
40
2
Fig. 3.14 Calculated PXRD patterns of the isopropanol and butan-2-ol solvates.
.
observed XPRD
butan-2-ol
observed XPRD
isopropanol
5
10
15
20
25
30
35
40
2
Fig. 3.15 Observed PXRD patterns of the isopropanol and butan-2-ol solvates.
54
Molecular packing and hydrogen bonding of stanozolol solvates

Although stanozolol has the facility of co-crystallizing with many solvents
forming distinctly different structures some similarities in H-bonding patterns were
recognised. Stanozolol can form H-bonds with the solvent molecules through the
hydroxyl group located on one end of the molecule and both of the nitrogen atoms in
the pyrazole ring at the other end of the molecule. The solvent molecules act as Hbond donors and or acceptors and can form two and three dimensional H-bonded
networks. There is no unused H-bonding capacity in any of the solvated forms. The
list of all H-bonds in the crystal structures of the stanozolol solvates is in Table 3.14.
Table 3.14 H-bonding interactions in the crystal structures of stanozolol solvates.

Crystalline
Orientation
form of
of
stanozolol
stanozolol
ethanol
head - tail
Tautomer
H-bond
DA
Dimensionality
[]
of network
O1H1O1O2 2.790
2D
O2H1O2N2 2.808
solvate
N1H1N1O1 2.833
isopropanol
head - tail
N1H1N1O1 2.785
2D
O1H1O1O2 2.747
solvate
O2H1O2N2 2.857
butan-2-ol
head - tail
N1H1N1O1 2.816
2D
O1H1O1O2 2.774
solvate
O2H1O2N2 2.916
ethanol
head - head
dihydrate
tail - tail
solvate
A and B
O1H1O1O3 2.820
2D
O2H1O2O5 2.720
O3H1O3N2 2.759
O4H1O4O2 2.764
O4H2O4O3 2.911
O5H1O5O1 2.773
O5H2O5N3 3.086
N1H1N1N3 2.937
N4H1N4O4 2.747
55
isopropanol
head - tail
O1H1O1O2 2.722
dihydrate
O2H2O2O4 2.783
solvate
O3H1O3O1 2.798
2D
O3H2O3N2 2.873
O4H1O4O3 2.831
O4H2O4O3 2.848
N1H1N1O4 2.855
monohydrate
head - tail
O1H1O1O2 2.725
3D
O2H1O2N1 2.899
O2H2O2O1 2.916
N2H1N2O1 2.897
acetic acid
head - head
solvate
tail - tail
O1H1O1O2 2.608
2D
O3H1O3O1 2.795
O5H1O5N2 2.719
N1H1N1O4 2.876
formamide
head - head
solvate
tail - tail
A and B
O1H1O1O2 2.745
2D
O2H1O2O3 2.746
N1H1N1N3 3.063
N4H1N4N2 3.099
pyridine
head - tail
O1H1O1O2 2.830
3D
O2H1O2N2 2.865
solvate
N1H1N1N5 2.952
N3H1N3O1 2.830
DMF
head - head
hydrate
tail - tail
A and B
solvate
O1H1O1O3 2.744
2D
O2H1O2O1 2.831
O4H1O4N2 2.834
N1H1N1N3 2.954
N4H4O4
2.764
2D Hydrogen bonded layer structures

Isopropanol and butan-2-ol solvates, have stanozolol molecules hydrogen
bonded head to tail forming chains via N1H1N1O1 hydrogen bonds. Solvent
molecules link these chains into 2D sheets via the solvent oxygen O2 and
O1H1O1O2 and O2H1O2N2 hydrogen bonds. The hydrogen bonding chain
56
within the sheets can be classified as C33(7), Fig. 3.16-17. These 2D sheets are not
hydrogen bonded to each other. The ethanol solvate has a similar hydrogen bond
network but alternate molecules are rotated preventing the adoption of a sheet
structure, Fig. 3.18.
Fig. 3.16 The view of hydrogen bonding pattern in a direction of isopropanol

solvate.
Fig. 3.17 The view of hydrogen bonding pattern in a direction of butan-2-ol solvate.
57
Fig. 3.18 The view of hydrogen bonding pattern in a direction of ethanol solvate.
Solvates from wet ethanol, acetic acid, formamide and wet DMF, have layer
structures in which stanozolol molecules are oriented head to head and tail to tail,
Fig. 3.19-21. There are no H-bonds between stanozolol molecules in the structure of
the acetic acid solvate. Stanozolol is orientated in the headtohead, tailtotail
fashion with H-bonded acetic acid molecules in between.
Fig. 3.19 Layered nature of ethanol dihydrate solvate.
58
Fig. 3.20 Layered nature of acetic acid solvate.
Fig. 3.20 Layered nature of formamide solvate.
Fig. 3.21 Layered nature of DMF hydrate solvate.
The isopropanol dihydrate solvate has a double layer sheet structure with no
hydrogen bonding between the double layers, Fig. 3.22. These double layers are
connected by the water molecules via the O3O4 H-bond (2.848 ). Stanozolol
59
molecules are not H-bonded with each other. They are linked to the isopropanol and
two water molecules via O1H1O1O2 (2.722 ), N1H1N1O4 (2.855 ) and
O3H2O3N2 (2.873 ) respectively.
Fig. 3.22 Double layers of isopropanol dihydrate solvate.
3D Hydrogen bonded networks

The monohydrate and the pyridine solvate have 3D hydrogen bonded
networks. The structure of the monohydrated form consists of 2D sheets parallel to
the ac face, Fig. 3.23. These layers are connected via the water molecules into a 3D
arrangement. Fig. 3.24 shows a view down the a axis of the interconnected layers.
The structure of the pyridine solvate is unlike the other solvates where a layered
arrangement of the molecules can be observed. The pyridine molecule is H-bonded
to stanozolol via N1H1N1N5 (2.722 ). It is not involved in the propagation of
hydrogen bonds but it does force the stanozolol molecules to pack into a 3D network
in which there is no unused hydrogen bonding capacity, Fig. 3.25.
60
Fig. 3.23 View of interconnected layers of monohydrate solvate.
Fig. 3.24 View of 2D sheets and of monohydrate solvate.
61
Fig. 3.25 3D hydrogen bonding network of pyridine solvate.
62
Tautomerism in stanozolol solvates

The stanozolol tautomers A and B are observed both alone and together in the
crystal structures of polymorphs and solvates, Table 3.14. DFT gas phase
calculations performed using Gaussian 09 [151] show that the energies of both
tautomers are very close with tautomer A just 1.2 kJ/mol lower than tautomer B. A
value of 81kJ/mol was calculated for the lattice energy of polymorph 1 using the
Habit program within the Oscail package [109]. Thus differences in packing energies
can easily overcome the small energy difference between the tautomers. Both
tautomers were found in the crystal structures of the ethanol dihydrate, formamide
and the DMF hydrate solvates. The monohydrate has only tautomer B present. The
ethanol solvate has one stanozolol molecule per asymmetric unit but it appears that
the structure is disordered with both tautomers present in nearly equal amounts as the
bond lengths in the heterocyclic ring have values which are the mean of the
tautomers observed in the other structures. The rest of the solvates contain only
tautomer A.
(a)
63
(b)
(c)
Fig 3.26 Tautomers of (a) ethanol dihydrate (view down c), (b) formamide (view
down b) and (c) DMF hydrate (view down a) solvates.
64
Thermal analysis of stanozolol solvates: strength of intermolecular

interaction
Thermal analysis was used to check the stanozolol to solvent stoichiometric
ratio in bulk samples and to investigate the strength of solvent stanozolol
interactions. The TGA and DSC results for the monohydrate, methanol, ethanol and
isopropanol solvates were also in good agreement with the data found in the
literature [144]. Due to the complex nature of the ethanol dihydrate and the DMF
hydrate, total weight loss was calculated for all solvent molecules present.
Fig 3.27 DSC-TG curves for monohydrate, showing the weight loss of water
molecule, solid-solid polymorphic transformation of form 2 form 1 at 228 C,
melting of polymorph 1 at 242 C and decomposition.
65
Fig 3.28 DSC-TG curves for methanol solvate showing the solvent weight loss at
158 C, polymorphic transformation of form 3 form 2 form 1 at 208 C and
228 C respectively, followed by the melting peak of polymorph 1 at 245 C and
decomposition.
66
Fig 3.29 DSC-TG curves for ethanol solvate showing the solvent weight loss at 123
C, before the melting at 241 C and decomposition.
Fig 3.30 DSC-TG curves for isopropanol solvate showing the solvent weight loss at
128 C, before the melting at 242 C and decomposition.
67
Fig 3.31 DSC-TG curves for butan-2-ol solvate showing the solvent weight loss,
melting at 241 C and decomposition.
Fig 3.32 DSC-TG curves for ethanol dihydrate solvate showing the solvent weight
loss, melting at 242 C and decomposition.
68
Fig 3.33 DSC-TG curves for acetic acid solvate showing the solvent weight loss,
melting at 242 C and decomposition.
Fig 3.34 DSC-TG curves for pyridine solvate showing the solvent weight loss at 159
C, followed by the melting peak at 244 C and decomposition.
69
Fig 3.35 DSC-TG curves for dimethylformamide hydrate solvate showing the solvent
weight loss, melting at 242 C and decomposition.
Thermograms for some of the solvates are shown in Fig. 3.27-35 and Table
3.15 gives data for solvent weight loss and enthalpy changes. Solvent loss occurs as a
one step process in most cases but multi step processes are observed for solvates with
more than one solvent molecule in the lattice. There is excellent agreement between
the observed and calculated weight loss on heating.
The endotherms of desolvatation are followed by a sharp endotherm at 244C
which corresponds to the melting of polymorph 1. The extra peaks between 200 and
240 C which are observed for the methanol solvate and the monohydrate have also
been reported for the ethanol solvate and have been attributed the transformation
along polymorphs 3 2 1 [144]. The transformations and melting occur at
211.9C, 231.5C, 245.2C and 211.1C, 229.9C, 244.5C for the methanol solvate
and the monohydrate respectively. In sublimation experiments only forms 1 and 2
have been observed and it has not been possible to produce crystals for form 3.
Thermal analysis can be used to estimate the strength of the host-solvent
interaction by comparing the enthalpy of desolvatation (HDSC) obtained from DSC
thermogram with the enthalpy of vaporisation (Hvap) of the pure solvent. If the
70
solvent is strongly bound then the enthalpy of desolvatation will exceed the enthalpy
of vaporisation [121-123]. HDSC was calculated using the relationship: HDSC =
[(Hexp100)/Mcalc], where is the molecular weight of the solvent and Mcalc is the
theoretical loss of solvent weight.
Table 3.15 DSC-TG analysis of some stanozolol solvates.

Solvated form of
host/guest
Mcalc
Mexpa
Hexp
HDSC
stanozolol
ratio
[%]
[%]
[J/g]
[kJ/mol] [kJ/mol]
monohydrate
(1:1)
5.2
4.9
104.4
36.2
40.7
methanol
(1:1)
8.9
8.8
162.5
33.9
35.3
ethanol
(1:1)
12.3
12.1
195.5
73.2
38.7
isopropanol
(1:1)
15.5
14.7
164.6
63.8
39.9
butan-2-ol
(1:1)
18.4
17.8
157.1
63.3
40.8
acetic acid
(1:2)
26.8
25.2
295.2
66.2
24.4
pyridine
(2:1)
10.7
10.7
31.7
23.4
36.4
ethanol dihydrate
(2:1:2)
11.1
10.9
DMF hydrate
(2:1:1)
12.2
11.4
Hvap
Observed solvent weight obtained from TGA analysis.

For ethanol, butan-2-ol and acetic acid solvates HDSC values are greater than
Hvap. This suggests that in these cases the solvent molecules are tightly bound in the
crystal lattice. The lower value HDSC for the monohydrate is probably not an
indication of weak binding as the relative value of Hvap for water is expected to be
high since in water all atoms are involved in its hydrogen bonding. The data does
indicate weaker binding for methanol and pyridine and this is probably due to the
lack of long range order in the methanol solvate and the presence of just a single
hydrogen bonding interaction involving the pyridine.
71
Discussion
All attempts to crystallize stanozolol from solution gave solvated crystals.
Sublimation proved to be a successful method for the growth of the first high quality
solvent free crystals of stanozolol polymorphs 1 and 2. Their crystal structures
contain voids and in the case of polymorph 1 unused H-bonding capacity. Both
features are the consequence of packing difficulties due to the rigid awkward shape
of the molecule. The ready crystallization of solvates which have structures without
voids and their near maximal use of hydrogen bonding capacity is due to their greater
range of packing options.
DSC coupled with TG provided valuable information on the nature of
analyzed materials. It provides easy identification of the methanol solvate whose
crystal quality was not good enough for single crystal X-ray diffraction analysis.
Programs within the Oscail software provide a rapid analysis of the degree of
similarities between the calculated PXRD patterns. The results showed that only two
solvates of stanozolol are isomorphous. This isomorphous pair also had similar
experimental PXRD patterns and crystal morphologies.
72
Chapter 4:
Crystallization of Solvent Free Crystals not
Available from Solution: Study Case Ethynyl
Estradiol (EE)
73
Introduction
Crystalline forms of ethinylestradiol
Ethinylestradiol (EE) is a synthetic derivative of the natural estrogen
estradiol. It is one of the most widely prescribed medicines and is a component of the
combined oral contraceptive pill. It has also proved to be successful in the treatment
of breast cancer [152].
EE was reported to exist in two polymorphic forms with the following
melting points [153]: 146 C, 183 C. Although the polymorphism and pseudopolymorphism of EE was investigated by several research groups no solvent free
crystals have been reported before this work. Seven solvated crystal structures of EE
have been published and some of them have been analyzed by DSC, TGA, FT-IR
and PXRD. The first structure of the hemihydrate form (CSD refcode: FISWIN) was
reported in 1987 by van Geerestein [154]. In 1989 the hemihydrate was redetermined
and the structures of two new solvates, acetonitrile and methanolate, determined. C.
Guguta studied pseudo-polymorphic properties of EE in 2007 [155]. This resulted in
four new solvated forms (dimethylformamide, dioxin, ethanol and nitromethane) and
a detailed comparison of their crystal structures. In spite of these rather
comprehensive studies no crystals of pure form were obtained.
Sublimation method A was used to grow the first solvent free crystals of EE.
They were used as seeds in an attempt to obtain solvent free crystals from solution
but only crystals of new or known solvates were formed. The crystal structures of
solvent free EE and three new solvates were determined. Thermal analysis was
applied to investigate the polymorphism of EE and desolvatation of solvated crystals.
PXRD patterns were calculated and compared for all crystalline forms of EE and
used to analyze further if the reported structural diversity among the solvated forms
continues. A CSD search for non H-bonded carbonyl and hydroxyl groups was
performed to investigate this phenomenon among steroid compounds.
74
Crystallization of ethinylestradiol
100 mg of EE was used to obtain high quality single crystals by sublimation
method A suitable for structure determination. Colourless lath type crystals were
observed in the temperature range: 110 to 140 C, Fig. 4.2. This range of temperature
was chosen as no events were observed on this portion of the DSC curve, Fig. 4.1.
Below the lower end of that temperature range sublimation was still observed but no
crystal formation took place and only white powder was obtained.
The FT-IR
spectrum of this white powder was identical to spectra of crystals grown by

sublimation.
Fig. 4.1 DSC-TG curves for EE, showing melting at 183 C and decomposition at
310 C.
75
Fig. 4.2 Ethinylestradiol crystal grown by LTGSV via method A.
Crystallization of solvated forms of ethinylestradiol

Crystals of EE grown by sublimation were used as seeds in an attempt to
obtain solvent free crystals from solution. Despite the use of a wide range of
solvents, Table 4.1, no crystals of a pure form were obtained. Crystallization from
butan-2-ol and propanol gave the already known hemihydrate form. Crystallization
from acetone, DMSO and pentan-2-ol yield crystals of the corresponding new
solvates, Fig. 4.3.
Table 4.1 Overview of the solvents used in crystallization experiment.

Overview of the solvents used
acetic acid
diethyl ether
pentan-2-ol B
acetone B
DMF C
propanol A
acetonitrile C
DMSO B
propan-2-ol
benzene
1,4-dioxane C
Pyridine
butanol
ethanol C
THF
butan-2-ol A
ethyl acetate
Toluene
chloroform
Formamide
Xylene
cyclohexan
methanol
Formation of hemihydrate form, B New solvate formation, C Known
solvate formation
76
a) acetone solvate
b) pentan-2-ol solvate
c) DMSO solvate
Fig. 4.3 Crystals of EE acetone, pentan-2-ol and DMSO solvates.
77
Results
Polymorphism in crystal structures of ethinylestradiol
Suitable crystals of EE were analyzed using single crystal X-ray diffraction.
Table 4.2 contains crystallographic data for pure form of EE.
Table 4.2 Crystal data for pure form of EE.

Crystalline form of EE
Solvent free EE
Empirical formula
C20 H24 O2
Formula weight
296.39
Temperature / K
150.1
Wavelength /
0.7107
Crystal system
Orthorhombic
Space group
P212121
a/
6.8664(3)
b/
20.9003(11)
c/
22.0448(8)
V / 3
3163.6(2)
1.245
/ mm-1
0.078
9428
5434 [Rint = 0.0424]
3926
1.027
R1 = 0.0626, wR2 = 0.1001
R1 = 0.0991, wR2 = 0.1145
78
EE was found to crystallize in the orthorhombic space group P212121 with two
molecules per asymmetric unit. Fig. 4.4 shows the numbering scheme of non
hydrogen atoms.
C20
O2
C38
C18
C12
C13
C16
C17
O1
C2
C9
C36
C37
C8
C5
C3
C19
C33
C7
C6
C1
C10
C32
C11
C14
C15
C40
O4
C4
O3
C27
C29
C28
C25
C23
C22
C39
C31
C34
C35
C26
C21
C30
C24
Fig. 4.4 Numbering scheme of EE for the non hydrogen atoms.
The hydroxyl groups form 1D hydrogen bonded chains through two

moderately strong interactions O3H1O3O4 (2.755 ) and O4H1O4O2
(2.774 ), Fig. 4.5. Although each of the molecules has two hydroxy groups that can
act as potential hydrogen bond donors and acceptors the O1 hydroxyl does not
participate in hydrogen bonding.
Fig. 4.5 1D hydrogen bonded chain of EE extending in c direction.
79
Table 4.3 H-bonding interactions in the crystal structures of pure form of EE.
DHA
DH []
HA []
DA []
DHA []
O4H1O4O2
0.891
1.912
2.774
162.36
O3H1O3O4
0.901
1.862
2.755
170.65
O2H1O2
3.438
This observation is supported by the presence of a high frequency nonhydrogen bonded O-H band in the IR spectrum at 3607 cm-1, Fig. 4.6. The
intermolecular interactions in the structure of EE are listed in Table 4.3.
80
Fig. 4.6 FT-IR spectra of pure form of EE with high frequency non-hydrogen bonded
%T
4000.0
3607 cm-1
3600
3200
2800
2400
2000
1800
cm-1
1600
1400
1200
1000
800
650.0
O-H band at 3607 cm-1.
81
Structural diversity of ethinylestradiol solvates

It has been shown that EE forms a broad range of different crystal structures
with solvent molecules. The most recent report of EE structures presents a detailed
analysis of crystal packing and H-bonding networks which show a large diversity
among the seven solvated forms of EE. In this study an attempt was again made to
obtain solvent free crystals from solution using the crystals obtained by sublimation
as seeds. However, again only crystals of three new solvates (acetone, DMSO and
pentan-2-ol) were formed. The crystal structures of these new solvates were
determined to see if the diversity of solvate structures continued, Table 4.4-6.
Table 4.4 Crystal data for EE acetone solvate.

acetone solvate
Empirical formula
C23 H30 O3
Formula weight
354.47
Temperature / K
149.9
Wavelength /
0.7107
Crystal system
Monoclinic
Space group
P21
a/
6.8006(4)
b/
22.1731(9)
c/
7.3916(5)
117.031(7)
V / 3
992.83(9)
2
-3
/ Mg/m (calculated)
1.186
/ mm-1
0.077
3018
2106, Rint = 0.0216
1978
Goodness-of-fit on F
1.043
0.0315, R2 = 0.0735
0.0348, R2 = 0.0756
82
Table 4.5 Crystal data for EE DMSO solvate.
DMSO solvate
Empirical formula
C24 H36 O4 S2
Formula weight
452.65
Temperature / K
150.0
Wavelength /
0.7107
Crystal system
Orthorhombic
Space group
P21212
a/
6.9652 (3)
b/
10.9689 (3)
c/
31.2143 (11)
V / 3
2384.78(15)
1.261
/ mm-1
0.250
7212
4224, Rint = 0.0204
3945
1.119
0.432, R2 = 0.924
0.0476, R2 = 0.0982
83
Table 4.6 Crystal data for EE pentan-2-ol solvate.
Pentan-2-ol solvate
Empirical formula
C25 H36 O3
Formula weight
384.54
Temperature / K
149.9
Wavelength /
0.7107
Crystal system
Monoclinic
Space group
P21
a/
12.3596(6)
b/
6.9442(3)
c/
13.9837(8)
111.000(6)
V / 3
1120.47(9)
1.140
/ mm-1
0.073
5341
3508, Rint = 0.0324
2899
1.048
0.0578, R2 = 0.1400
0.0729, R2 = 0.1516
84
1,4-dioxan
nitromethan
DMSO
DMF
acetonitrile
acetone
penthan-2-ol
ethanol
methanol
hemihydrate
5
10
15
20
25
30
2
Fig. 4.7 Calculated PXRD patterns of ten solvates of EE.
85
The crystal structures of ten known EE solvates were analyzed by comparing

their calculated powder patterns, Fig. 4.7, using the PatMatch program. Identification
numbers assigned to the crystalline forms of EE are listed in Table 4.7. Table 4.8
gives the position of the peaks chosen for the analysis of calculated powder
diffraction patterns.
Table 4.7 List of crystalline forms of EE and their corresponding identification

numbers.
Identification
number
EE acetonitrile solvate
EE 1,4 - dioxan solvate
EE DMF solvate
EE ethanol solvate
EE hemihydrate
EE methanol solvate
EE nitromethane solvate
EE
EE acetone solvate
10
EE DMSO solvate
11
EE pentan-2-ol solvate
Table 4.8 Position of the peaks with highest intensities chosen for PXRD analysis.
Identification
number
1
Position of the peaks [2]

14.90, 17.10, 17.30, 19.35, 20.65, 21.20,
22.80, 22.95, 24.05, 26.05, 28.85 31.70;
14.80, 15.05, 15.85, 16.75, 17.40, 19.30,

19.55, 19.85, 21.35, 22.05, 23.25, 36.05;
14.80, 15.50, 15.70, 16.45, 25.40, 25.65,

26.00, 26.45, 26.85, 27.55, 28.10, 39.10;
13.70, 14.50, 15.35, 16.65, 18.45, 19.55

20.50, 21.95, 24.35, 25.35, 26.70, 37.00;
86
14.05,16.85, 18.45, 19.75, 22.60, 23.45
25.10, 26.25, 32.70, 37.95, 38.05, 39.40;

14.95, 15.05, 15.85, 17.50, 19.25, 22.00
22.45, 24.00, 24.50, 27.35, 29.00, 30.90;

15.30, 15.40, 16.05, 16.55, 18.00, 20.70
21.85, 22.50, 22.60, 23.00, 24.55, 31.60;

13.30, 14.10, 15.90, 17.40, 18.55, 19.80
21.60, 22.70, 22.80, 24.55, 24.90, 28.95;

14.00, 14.65, 15.10, 15.20, 15.60, 16.70,
24.00, 26.15, 26.45, 27.40, 31.55, 35.05;

15.30, 18.85, 20.70, 22.75, 24.15, 25.05,
10
25.50, 25.70, 26.80, 26.95, 28.80, 36.00

11.90, 13.50, 14.40, 15.15, 18.60, 19.00,
11
20.35, 20.65, 21.95, 22.80, 24.10, 25.50
Table 4.9 Number of peaks matched.

1
10
11
12
12
12
12
12
12
12
12
12
10
12
11
12
87
The number of matching peaks and calculated match indices are illustrated in
Tables 4.9-4.10. The results show that there are no isomorphous structures among all
known solvates of EE. The highest match index was just 0.57 and it was found for
1,4-dioxan and nitromethane which show a similar arrangement of EE molecules into
sheets. Other solvates of EE show a range of distinctly different structures, Table
4.11.
Table 4.10 Pattern match indices.

1
10
11
1 0.00 0.00 0.00 0.00 0.00 0.31 0.00 0.00 0.00 0.00 0.00
2 0.00 0.00 0.00 0.00 0.00 0.25 0.57 0.00 0.00 0.00 0.00
3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.17 0.00 0.00 0.00
5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
6 0.31 0.25 0.00 0.00 0.00 0.00 0.49 0.00 0.00 0.00 0.00
7 0.00 0.57 0.00 0.00 0.00 0.49 0.00 0.18 0.00 0.00 0.00
8 0.00 0.00 0.00 0.17 0.00 0.00 0.18 0.00 0.00 0.00 0.00
9 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
11 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Table 4.11 Top matches for the pairs of PXRD patterns of crystalline forms of EE.
Match indices
Identification numbers of pairs of forms of EE
0.57
2 and 7 EE 1,4-dioxan and nitromethane solvates
0.49
6 and 7 EE methanol and nitromethane solvates
0.31
1 and 6 EE acetonitrile and methanol solvates
0.25
2 and EE 1,4-dioxane and methanol solvates
0.18
7 and 8 EE nitromethane solvate and EE
0.17
4 and 8 EE ethanol solvate and EE
88
Molecular packing and H-bonding of ethinylestradiol solvates

The hydrogen bonding network of the EE acetone solvate is similar to the 1D
chain found in the pure form of EE with the solvent taking the place of the second
EE molecule. The EE molecules are orientated headtotail with O1H1O2
(2.703 ) interactions. The acetone carbonyl acts as an acceptor in the O2H2O3
(2.678 ) H-bond, Fig 4.8.
Fig. 4.8 1D H- bonded chain of EE acetone solvate extending in b direction.
The DMSO solvate has a DMSO:EE ratio of 2:1 and it is the only one with
zero-dimensional H-bonding. Both ends of the EE molecule are H-bonded to DMSO
molecules through O1H1O3 (2.673 ) and O2H2O4 (2.710 ) interactions,
Fig. 4.9.
Fig. 4.9 0D H-bonding network of EE DMSO solvate.
In the structure of EE pentan-2-ol solvate molecules of EE are orientated

headtotail way and linked through the O2H2O1 (2.801 ) H-bond. Pentan-2ol molecules participate in another two H-bonds: O1H1O3 (2.674 ) and
O3H3O2 (2.776 ). This forms 2D H-bonding network which is parallel to the
ab direction, Fig. 4.10.
89
Fig. 4.10 2D H-bonded sheets of EE pentan-2-ol solvate.
90
Unused Hydrogen Bonding Capacity in Steroid Crystal

Structures
Several well established examples of structures with non-hydrogen-bonded
donors or acceptors can be found in the literature. This has been explained by steric
hindrance, rigid, awkward shaped molecules or dipole-dipole interactions which
stabilize the crystal lattice and allow for molecules to pack into more favourable
structures than those with H-bonding motifs [148, 156]. Unused hydroxyl groups
were also analyzed by X-ray diffraction and IR spectroscopy in some carboxylic
acids [157].
To investigate lack of conventional hydrogen bonding among steroid
compounds two searches of the Cambridge Database (CSD, version 1.13) [45] were
performed for entries containing both C=O and O-H groups in the first case and only
O-H in the second case. The constraints in both searches were as follows: steroids:
no solvates and hydrates, 3D determined, no ions, no powders, no errors, no
polymeric, only organic structures, no(C=OH-O or O-HO-H). 85 hits for lack of
C=OH-O and 134 hits for no O-HO-H contact were found. The hits were
analysed manually and inappropriate entries were eliminated. Examining steroid
structures on the CSD reveals 14 related examples with unused O-H groups
(FNPEYO, FUFDAL, GAPGAF, KANYAA, LAKJAJ, LALXIF, MBRHES,
NPREYO, QEYBAX, QUMJOX, RAMYAG, SUQDUE, WATRIT, YAPZEU) and
10 with unused C=O groups (AFAWOU, CAZXAC10, EYHENO, HMESDP,
ISTEST, LOHVAF, NOTEST01, NPTYMO, PAMLUL, ZUKRUS).
Unused good proton donors and acceptors are rare in the crystal structures of
organic solids. However several entries which were found in CSD represent
examples of unused hydroxyl and carbonyl groups in steroids compound. It seems
that this feature is more likely to occur for steroids rather than any other classes of
compounds due to their rigid nature and molecular shape.
91
Discussion
It has been shown that shape of the molecule has a significant influence on
the crystal packing and nature of intramolecular interactions formed in the crystal
structures. Incorporation of solvent molecules into the crystal lattice can compensate
for the inefficiency with which rigid awkward shaped molecules pack during crystal
growth. The first high quality solvent free crystals of EE were grown by sublimation.
Solution crystallization of EE gave a wide variety of solvated structures. Seeding of
saturated solutions with crystals of the solvent free form also resulted in formation of
three new or already known solvates. This leads to the conclusion that crystals of the
pure form of EE can only be obtained from the vapour phase. No other solvent free
form of EE was observed during the crystallization experiments and DSC-TG
analysis of solvated forms. The low melting form, reported in the literature as well as
in the introduction to this chapter, is thus probably wrong.
The analysis of H-bonding shows similarities between EE and polymorph 1
of Stanozolol. The hydroxyl group of one of the molecules in the asymmetric unit is
not H-bonded. These features were attributed to the rigid awkward shape of the
molecule. All H-bonding donors and acceptors are used in the solvated structures
forming a range of different H-bonding patterns. No voids were found in the pure
form of EE.
Crystal structures of all of the crystalline forms of EE were compared and
analysed using their calculated powder patterns. No isomorphous structures were
found. Small similarities can be found for 1,4-dioxan and nitromethane EE solvates
which have the highest calculated match index of 0.57.
92
Chapter 5:
Detection of Bending Properties of Organic
Crystals: Application to Naftazone and 1,3Dinitrobenzene
93
Introduction
Bending phenomena of molecular crystals
Correlation between bending properties of molecular solids and crystal

packing was first described by C. M. Reddy and his co-workers [158]. His study
includes the investigation of 60 molecular crystals and he reports that 17 can be bent
without breaking on application of a mechanical stress. This phenomenon, although
now widespread for organic compounds is still rare among pharmaceuticals. Indeed,
venlafaxine hydrochloride is the only pharmaceutical that has been reported to have
bending properties.
The bending direction of molecular crystals is associated with anisotropy in
the intermolecular interactions [159, 160]. In the presence of interactions of
comparable strength in all directions, (i.e. a normal 3D H-bonding network), crystals
are hard and brittle. If the crystal structure contains strong and weak interactions in
nearly perpendicular directions the crystal is likely to bend on the application of
mechanical stress.
For reasons which will be clear below it was decided to examine the bending
properties of two compounds, naftazone and 1,3-dinitrobenzene. Crystals were
grown both by sublimation and from solution. SEM and optical microscopy were
used in the preliminary examination of morphology changes. In order to establish the
bending direction, crystal faces were indexed using Oxford program suite CrysAlis
Pro, version 171.34.36.
94
Synthesis of naftazone
0.11 g of semicarbazide hydrochloride was dissolved in 3ml of distilled water
and added to 30ml of an ethanol suspension of 0.32g of 1,2-naphtoquinone. The clear
brown solution was heated under reflux for 4 hours and the solution was left to cool
overnight. The orange needle shaped crystals of naftazone (meta-stable form II) were
filtered off, washed with ethanol and dried.
H2O
HCl
Scheme 5.1 Synthesis of naftazone.
Crystal growth of naftazone and 1,3-dinitrobenzene

When metastable form II was recrystallized from ethanol, orange crystals of
stable form I were collected, Fig. 5.1. Crystallization by sublimation, method A, in
the temperature range 140 to 160 C gave only the stable form I of naftazone, Fig.
5.2.
Fig. 5.1 Crystals of naftazone grown from ethanol (form II).

95
Fig. 5.2 Crystals of naftazone (form I) grown by LTGSV via method A.
1,3-dinitrobenzene crystals were grown by slow evaporation of saturated

solution from acetonitrile at room temperature and by vacuum sublimation at 75 C,
Fig. 5.3.
Fig. 5.3 Crystals of 1,3-dinitrobenzene grown by LTGSV via method A.
96
Results
Detection of bending properties of naftazone
Naftazone is an API which is a veinotonic and vasculoprotector drug. Two
polymorphic forms are known and it is quite difficult to ensure the crystallization of
one pure form from solution. It is an example of concomitant polymorphism and has
been examined in some detail [55]. Following the successful use of sublimation for
polymorph selection for stanozolol and EE it was decided to apply it to naftazone. In
the temperature range from 140 to 160 C, crystallization of naftazone by method A
sublimation gave good quality crystals of the stable form I only. No crystals of the
metastable form were detected.
Fig. 5.4 Bending nature of naftazone crystals grown from the gas phase.
Several different crystal habits were observed. Together with flattened rod
and plate like crystals there were also bent rods and some ultra-thin plates which
were curved, Fig. 5.4. The bent rods and curved plates were not observed for crystals
grown from solution. It was also noticed that the crystals bent without breaking in the
direction of the initially observed bend on application of a mechanical stress, like
shown on Fig. 5.5. This property, although established for a range of organic
compounds, is still rare among pharmaceuticals and naftazone is just the second
example. The only other reported case is venlafaxine hydrochloride. It was the
observation of curved plates on sublimation of the compound that suggested that this
97
might be a method for the detection of bending crystals. It was also decided to study
1,3-dinitrobenzene which had been described by C.M. Reddy but which was difficult
to crystallize from solution and could not be face indexed.
Fig. 5.5 Naftazone crystal mounted on a fibre (left and face indexation (right) of
crystal with plate habit.
In the naftazone structure molecules are connected via N3H2O2 (2.915
) into H-bonded chains which extend in the b direction. Apart from weak
C3H2O2 interactions no significant short contacts in the other two directions are
present in the crystal structure of naftazone. Face indexation showed that bending is
about the b-axis which is also the direction of the 1D H-bonding motif, Fig. 5.6-7.
Thus the 1D chains are not broken when the lattice bends.
Fig. 5.6 Molecular arrangements of naftazone, Form I, view down the c axis.
98
Fig. 5.7 Molecular arrangements of naftazone, Form I, view down the b axis.
Detection of bending properties of 1,3-dinitrobenzene

1,3-dinitrobenzene is known to bend on the application of mechanical stress
but the crystals grown from solution were of poor quality and it was not possible to
index their faces and to determine the bending direction. Crystals which were grown
by sublimation, method A, reveal their bending properties as among the rod shaped
crystals some bent crystals were observed, Fig 5.3. The crystal quality was suitable
for face indexation. To establish the bending face, one of these crystals was mounted
on a fibre, Fig. 5.8.
Fig. 5.8 Face indexation of 1,3-dinitrobenzene.
99
Face indexation established that the bending of 1,3-dinitrobenzene crystals is

about the b axis. This was predicted by C. M. Reddy from the crystal packing which
shows anisotropic distribution of intermolecular interaction [158]. The molecules are
stacked in a zigzag fashion along the c axis, Fig 5.9. There are also weak CHO
interactions are present in a and b directions.
Fig. 5.9 Molecular arrangement 1,3-dinitrobenzene.
100
Discussion
Sublimation especially when LTGSV is used provides easy optical detection
of molecular solids which have plastic behaviour. This phenomenon is unique for
crystals grown from the gaseous phase and it was not observed for crystals of the
same compound grown from solution.
The examples presented here of naftazone and 1,3-dinitrobenzene show that
compounds with bending properties tend to yield crystals with bent and curved faces
among normal crystals only when grown by sublimation. The ability to grow such
crystals is particularly important when experimental recognition of bending direction
is difficult. Deformed crystals grown by sublimation can be directly mounted on a
fibre and used for face indexation without the necessity of applying any mechanical
stress.
101
Chapter 6:
Combined Synthesis, by Thermal
Transformation, and Crystal Growth of p(phenylsulfonyl)biphenyls
102
Introduction
Organosulfones are very useful intermediates in many different fields such as
agrochemicals, pharmaceuticals [161] and polymers [162]. Aryl sulphones in
particular were reported as potential antifungal, antibacterial, antitummoral and antiHIV-1 agents [163].
Application of method A to 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5trien-1-yl]-4-benzene led to the production of crystals of the corresponding 4(phenylsulfonyl)biphenyl. Methoxy (OMe) and nitro (NO2) derivatives of 1[(1E,3E,5E)- 4,6-bis (phenylsulfonyl) hexa- 1,3,5- trien-1-yl]- 4-benzene were
synthesized and crystal formation of the corresponding 4-(phenylsulfonyl)biphenyls
was observed.
4-(phenylsulfonyl)biphenyl is usually prepared in Suzuki-Miyaura coupling
[164], Friedel-Crafts [165] and other multistep reactions which require use of both
solvents and catalysts [161]. Method A was applied as a combined process of
synthesis and crystal growth. The process is then a one-step synthesis which does not
require the presence of solvents, a catalyst or further purification. The product is
crystalline and suitable for structure determination.
Crystal structures of all compounds included in this study were determined
and the influence of para-substitution on the inter-molecular interactions have been
analysed.
103
Synthesis of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-benzene and OMe and NO2 derivatives
Equivalent amounts (1eq) of 1,3-bisphenylsulfonyl, trans-cinnamaldehyde
and 33eq. of aluminium oxide were used in the synthesis of (1). The suspension was
stirred for 4 hours at room temperature. The aluminium oxide was extracted with
CH2Cl2 and the resulting solution was concentrated to bright yellow oil. This oil was
dissolved in hot isopropyl alcohol and then chilled in a -20C freezer for one hour.
The resulting participate was readily filtered. Trans-nitrocinnamaldehyde and transmethoxycinnamaldehyde were used for the preparation of their corresponding
derivatives, scheme 6.1.
+
O
(1)
O
R= OCH3, NO2
Scheme 6.1 Synthesis of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-benzene, methoxy and nitro derivatives.
Crystallization of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5trien-1-yl]-4-benzene, OMe and NO2 derivatives

Crystallization from a range of organic solvents gave twinned crystals or noncrystalline matter. Crystallization by slow evaporation from acetonitrile at room
temperature gave yellow crystals of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-
104
1,3,5-trien-1-yl]-4-benzene and corresponding OMe and NO2 derivatives suitable for

single X-ray diffraction analysis, Fig. 6.1-3.
Fig. 6.1 Crystals of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4benzene grown from acetonitrile and corresponding numbering scheme.
Fig. 6.2 Crystals of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4methoxybenzene grown from acetonitrile and corresponding numbering scheme.
Fig. 6.3 Crystals of 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4nitrobenzene grown from acetonitrile and corresponding numbering scheme.
105
Synthesis and crystal growth of 4-(phenylsulfonyl)biphenyl, OMe

and NO2 derivatives
Preparation and crystal growth of p-(phenylsulfonyl)biphenyls took place on

a Petri dish in a Heraeus VT025 vacutherm oven maintained at a pressure of 10-9
GPa using sublimation temperatures of 115 C (R = H and OCH3) and 125 C (R =
NO2). After approximately five hours colourless crystals formed on the lid of the
Petri dish, Fig. 6.4-6, and a brown residue was observed on the bottom dish.
Fig. 6.4 Crystals of 4-(phenylsulfonyl)biphenyl grown by sublimation, method A, and

corresponding numbering scheme.
Fig. 6.5 Crystals of 4-methoxybiphen-4-yl phenyl sulphone

grown by sublimation, method A, and corresponding numbering scheme.
106
Fig. 6.6 Crystals of 4-nitrobiphen-4-yl phenyl sulphone grown by sublimation,

method A, and corresponding numbering scheme.
107
Results
Combined synthesis, by thermal transformation, and crystal growth
Method A, as a rapid technique for crystal growth, was applied to 1[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzene
and
para
substituted OCH3 and NO2 derivatives. Upon heating and in vacuum these
compounds undergo cyclization which leads to the formation and crystal growth of
4-(phenylsulfonyl)biphenyl and related OCH3 and NO2 compounds. Schemes 6.2 and
6.3 illustrate possible mechanisms for this thermal transformation. However because
the formation of a highly unstable vinyl radical shown in scheme 6.2 is problematical
and because the existence of a zwiterion form in the gas phase was reported for some
amino acids [166] and because gas phase reaction kinetics have suggested a gas
phase zwitterion mechanism [167] a zwitterion mechanism is presented as a
possibility in scheme 6.3.
SO 2Ph
R = H, NO 2, OCH 3
SO 2Ph
SO 2Ph
SO 2Ph
(1)
homolysis
SO 2Ph
PhSO 2H
SO 2Ph
SO 2Ph
radical
aromatisation
H
(2)
HC
R
SO 2Ph
Scheme 6.2 Possible mechanism of thermal transformation of 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzene via radical aromatisation.
108
R = H, NO 2, OCH 3
SO 2Ph
SO 2Ph
SO 2Ph
(1)
PhO 2S
SO 2Ph
SO 2Ph
PhSO 2H
Elimination of
PhSO2H
H
R
(2)
SO 2Ph
Elimination of PhSO2H:
H
O S O
Ph
O S O
H+
Ph
HO S O
Ph
B-
Scheme 6.3 Possible mechanism of thermal transformation of 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzene via formation of zwitterion.
Analysis of intra-molecular interactions

Crystal data for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]4-benzene, bis(phenylsulfonyl)-hexatrienes and corresponding NO2 and OCH3
derivatives are given in Tables 6.1-3.
109
Table 6.1 Crystal data for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-benzene I and bis(phenylsulfonyl)-hexatrienes II.
Identification number
(I)
(II)
Empirical formula
C24 H20 O4 S2
C18 H14 O2 S
Formula weight
436.52
294.35
Temperature / T
299.1
297.0
Wavelength /
0.7107
0.7107
Crystal system
Monoclinic
Monoclinic
Space group
P21
P21/c
a/
5.9436(3)
16.5020(12)
b/
14.0768(8)
7.8520(5)
c/
13.0684(8)
11.3748(9)
100.537(5)
101.480(8)
V / 3
1074.95(11)
1444.39(18)
1.349
1.354
/ mm-1
0.276
0.225
5206
6662
2704 [Rint = 0.0344]
2650 [Rint = 0.0331]
2287
1648
Data Completeness
0.999
0.999
1.059
1.066
R1 = 0.0540
R1 = 0.0519
wR2 = 0.1286
wR2 = 0.1115
R1 = 0.0666
R1 = 0.0970
wR2 = 0.1436
wR2 = 0.1506
110
Table 6.2 Crystal data for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-methoxybenzene III and 4-methoxybiphen-4-yl phenyl sulphone IV.
(III)
(IV)
Empirical formula
C25 H22 O5 S2
C19 H16 O3 S
Formula weight
466.55
324.38
Temperature / T
150.0
296.3
Wavelength /
0.7107
0.7107
Crystal system
Monoclinic
Monoclinic
Space group
P21/c
P21
a/
5.84331(18)
a = 6.7378(3)
b/
25.5606(8)
b = 7.9901(4)
c/
14.9540(5)
c = 15.1328(7)
90.258(3)
98.700(5)
Volume / 3
2233.49(12)
805.31(7)
1.387
1.338
/ mm-1
0.274
0.213
32900
3681
4078 [Rint = 0.0516]
2209 [Rint = 0.0255]
3615
1914
Data Completeness
0.999
0.998
1.018
1.055
R1 = 0.0384
R1 = 0.0384
wR2 = 0.0838
wR2 = 0.0854
R1 = 0.0463
R1 = 0.0482
wR2 = 0.0875
wR2 = 0.0909
111
Table 6.3 Crystal data for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-nitrobenzene V and 4-nitrobiphen-4-yl phenyl sulphone VI.
(V)
(VI)
Empirical formula
C24 H19 N O6 S2
C18 H13 N O4 S
Formula weight
481.52
339.35
Temperature / K
149.9
149.9
Wavelength /
0.7107
0.7107
Crystal system
Triclinic
Monoclinic
Space group
P1
P21/c
a/
5.86394(16)
13.1110(9)
b/
8.2153(3)
7.6752(5)
c/
11.8849(4)
15.2536(13)
87.204(3)
77.171(3)
86.386(2)
Volume / 3
556.78(3)
1513.47(19)
1.436
1.489
/ mm-1
0.281
0.237
4109
6953
2552 [Rint = 0.0125]
2766 [Rint = 0.0445]
2466
1772
Data Completeness
0.999
0.999
1.150
0.998
R1 = 0.0321
R1 = 0.0541
wR2 = 0.0961
wR2 = 0.870
R1 = 0.0335
R1 = 0.1014
wR2 = 0.0974
wR2 = 0.1021
99.600(7)
112
I and III crystallized in the monoclinic space groups P21 and P21/c, whereas
V was found in triclinic space group P1. The analysis of the inter-molecular
interactions shows phenyl rings are not involved in - stacking interactions. The
only phenyl which participates in C-H contact was found in the structure of III,
Fig. 6.7. In the crystal structures of I and V only weak C-HO contacts were found,
Fig. 6.8.
Fig. 6.7 Weak C-H interaction in the structure of1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-methoxybenzene, III.
Fig. 6.8 Weak C-HO interaction in the structure of 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-nitrobenzene, V.
II, IV and VI crystallized in the monoclinic space groups P21/c, P21 and
P21/c respectively. The biphenyl group in the crystal structure of II was found to be
113
almost planar, with the twist angle of just 3.85. This differs significantly from the
gas phase structure of biphenyl where the twist angle is approximately 40 [168].
This is also often found in the crystal structures of other biphenyls [169, 170]. For IV
and VI the values of the dihedral angles correspond to 11.48 and 18.73.
The analysis of the inter-molecular interactions shows that all the phenyl
rings in the crystal structure of II participate in - stacking interactions, Fig. 6.9.
These interactions are reduced in the crystal structure of IV where only para
substituted phenyl is involved, Fig. 6.10. No - stacking interactions were found in
the structure of VI where the para-phenyl position was substituted with a OMe
group.
Fig. 6.9 Crystal packing of 4-(phenylsulfonyl)biphenyl showing maximum capacity of

- stacking interaction.
Fig. 6.10 - stacking interaction in the structure of 4-nitrobiphen-4-yl phenyl

sulphone, VI.
114
Discussion
Application
of
method
to
some
1-[(1E,3E,5E)-4,6-
bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzenes led to the production of

crystals of the corresponding 4-(phenylsulfonyl)biphenyls. Method A can be an
alternative and effective method for preparation of 4-(phenylsulfonyl) biphenyl and
related derivatives. This approach allows rapid production of already crystalline
material without the necessity of using solvents and catalysts. Also due to the
formation of crystals by sublimation further purification of the product is also
unnecessary.
Crystals were analyzed using single crystal X-ray diffraction. The
intermolecular interactions in the crystal structures of the 4-(phenylsulfonyl)
biphenyls show that - stacking interactions are reduced by para-phenyl substitution
with NO2 and OMe groups.
115
Chapter 7:
Using the Crystallization Driving Force to
Control Crystal Morphology:
Application to 1,4-Naphthaquinone, MetalFree Phthalocyanine and Benzoic Acid
116
Introduction
The presence of a radial temperature gradient across the de-sublimation
surface, when crystals are grown via method B, suggested that there might also be a
driving force gradient present. To investigate any effect that a driving force gradient
might have on crystal habit compounds were chosen which are known to have a
tendency to give needle growth from solution and which have simple stacked
structures without any strong H-bonding networks [171, 172]. The compounds
chosen were metal-free phtalocyanine, 1,4-naphthoquinone and benzoic acid. The
same method was used to grow crystals of tetraphenyltin (TPT). TPT is similar to the
three compounds chosen for this study in that it does not have any strong directional
H-bonding but in contrast to the others it does not have a stacked structure due to its
near spherical shape.
The growth of crystals of metal free phthalocyanine by sublimation has been
reported using a horizontal two zone furnace by two groups with and without the use
of a carrier gas [90, 171]. It is difficult to compare the crystallization driving force
variations in those experiments with those observed here. It is suggested in both
studies that the driving force is lowest closest to the sublimation region. In the
second study a ring of amorphous material was reported closest to the heater with a
clear gap before any crystals were observed. This latter observation supports the
contrary idea that the driving force would be highest close to the heater. In this study
the highest driving force region was recognized on the basis of high nucleation level
and glass formation which was found close to the small heater. In contrast the edge
of the de-sublimation surface which displayed a significantly lower number of
nucleation sites was defined as the lowest driving force region.
The results for all compounds were analyzed using optical microscopy, SEM
and single crystal X-ray diffraction. The crystal structure of 1,4-naphthoquinone was
re-determined as the only one found in the CSD, which was reported in 1965 [173].
117
Experimental section
Metal-free phthalocyanine, 1,4-naphthaquinone, benzoic acid and TPT were
grown by sublimation, method B, described in chapter 2. The crystals obtained in
each experiment are shown in Fig. 7.1. Experimental conditions are listed in Table
7.1. Crystals of metal-free phthalocyanine were identified as the form by
comparing their FT-IR spectra with those reported in the literature [174].
Fig. 7.1 Left to right: 1,4-naphthaquinone, metal-free phthalocyanine and benzoic

acid crystals grown under different driving force conditions: 1) high driving force
and 4) low driving force region.
Table 7.1 Crystallization conditions during crystal growth of metal-free

phthalocyanine (1), 1,4-naphthaquinone (2), benzoic acid (3) and TPT (4).
Identification
number
Sublimation
T1 [C]*
T4 [C]**
T [C]
T [C]
(1)
474
328
314
14
(2)
81.5
67.4
63.6
3.8
(3)
89.0
64.1
56.1
4.0
(4)
157
123
117
T1 - temperature on the de-sublimation surface in the high crystallization driving

force region
**
T4 - temperature on the de-sublimation surface in the low crystallization driving

force region
118
Results
Application to metal-free phthalocyanine
Fig. 7.2 Crystal growth of metal-free phthalocyanine under a range of crystallization

driving forces.
The longest needles were observed close to the temperature region where the
driving force is relatively low, Fig. 7.2.2-.3. As the driving force increases a rapid
change in the crystal habit was observed, Fig. 7.3.
Fig. 7.3 SEM image of metal-free phthalocyanine crystals grown under high driving
force conditions.
Phthalocyanine has a highly anisotropic structure, where the intermolecular

interactions are only defined by - interactions and which extend in the b direction,
Fig. 7.4. Molecular packing shows that in the low driving force conditions
phthalocyanine forms needles parallel to the stacking direction. The stacking
direction was defined on the basis of the angles between the plane of the molecule
and the 100, 010 and 001 faces and they are -49.330 , -45.848 , -62.960 respectively.
119
Fig. 7.4 Face indexation and molecular packing of metal-free phthalocyanine.
Application to 1,4-naphthaquinone
Fig. 7.5 Crystal growth of 1,4-naphthaquinone under a range of crystallization

driving forces.
Crystal data for 1,4-naphthoquinone are given in Table 7.2. The observed
habit changes of 1,4-naphthoquinone crystals grown from the vapour are shown in
Fig 7.5. In the high driving force region the sublimed compound is glass like, Fig.
7.5.1, and no single crystals were observed. As the driving force decreases with the
distance from the heater, block shaped crystals are initially observed, Fig. 7.5.2.
However towards the edge of the Petri dish the blocks evolve into needles as shown
in Fig. 7.5.4. The aspect ratio (length/thickness) of the crystals was calculated and
found to be inversely proportional to the distance from the centre of the desublimation surface, Fig. 7.6.
120
Table 7.2 Crystal data and for 1,4-naphthaquinone.
Compound name
1,4-naphthoquinone
Empirical formula
C10 H6 O2
Formula weight
158.15
Temperature / T
150.0
Wavelength /
0.7107
Crystal system
Monoclinic
Space group
P21/c
a/
8.1933(3)
b/
7.7393(3)
c/
11.4405(4)
94.486(3)
Volume / 3
723.23(4)
1.452
/ mm-1
0.102
3141
1320 [Rint = 0.0120]
1184
Data Completeness
0.996
1.054
R1 = 0.0306, wR2 = 0.0834
R1 = 0.0347, wR2 = 0.0859
121
Fig. 7.6 Aspect ratio vs. distance from the centre of the Petri dish.
The crystal faces of the blocks and needles were indexed, Fig 7.7-8. The
molecular packing, Fig 7.7, shows that low driving force conditions, similar to
phthalocyanine, favours the growth of needles parallel to the stacking direction. The
angles between the plane of the molecules and 100 (38.479 ), 010 (-70.107 ) and 001
(-62.695) faces illustrate that under low driving force conditions growth along the a
direction is dominated by molecules attaching flat to the 100 face.
Fig. 7.7 Face indexation of needle shaped crystal grown at low driving forces and
molecular packing of 1,4-naphthaquinone.
122
Fig. 7.8 Face indexation of block shaped crystal grown at high driving forces.
Application to benzoic acid
Fig. 7.9 Crystal growth of benzoic acid under a range of crystallization driving
forces.
Fig. 7.9 represents the effect of a range of driving forces on the crystal habit
of benzoic acid. At a high driving force, Fig. 7.9.1, benzoic acid forms twinned
crystals. As the temperature decreases across the condensation area, plate like
crystals, Fig. 7.9.2, change into needles approximately 15 mm in length, Fig. 7.9.4.
Benzoic acid forms hydrogen bonded dimers which extend into ribbons with
weak C-HO interactions. There are also - stacking interactions parallel to the
needle growth direction. The angle between the plane of the molecule and the 100 (53.896 ), 010 (48.217 ) and 001 (-58.052 ) crystal faces show the same tendency
observed for the other two cases above of 1,4-naphthaquinone and metal-free
phthalocyanine.
123
Fig. 7.10 Crystal packing of benzoic acid view down b direction.
Application to tetraphenyltin
The crystallization driving force range provided by method B has no effect on
the crystal habit of TPT, Fig. 7.11, as crystals of the same size and shape were
observed across the de-sublimation surface. This leads to the conclusion that only the
crystal habit of planar molecules with stacked structures and no strong intermolecular
interactions are dependent on the crystallization driving force.
Fig. 7.11 Crystals of TPT grown by the sublimation, method B.
124
Discussion
Sublimation method B requires the use of a small heater in a conventional
vacuum oven which is only employed as a vacuum chamber. The use of a small
heater allows generation of a range of crystallization driving forces across the
condensation area and expands the sublimation temperature range up to 500 C. A
high driving force region, at the center of the Petri dish, favors the formation of new
nuclei at the expense of the growth of existing crystals. A decreasing driving force
towards the edge of the Petri dish results in a lower level of nucleation and growth of
the nuclei into larger crystals.
The crystal habit of the compounds studied was found to be highly dependent
on the crystallization driving force. A low crystallization driving force favors needle
growth. In the absence of directional hydrogen-bonds the crystal growth of planar
molecules in the stacking direction is intrinsically promoted by the low step
generation energies in that direction and if flat molecules initially attach flat to all
crystal faces when the crystallization driving force is low then growth in all other
directions will be disfavored and long needles will be observed. In contrast to the
behavior observed for flat molecules tetraphenyltin, which has a near spherical shape
and no directional intermolecular forces, gives isotropic crystals under the same
crystallization conditions.
125
Chapter 8:
Crystallographic Data Electronic
Information
126
1) Polymorph 1 of stanozolol
7
Table 8.1 Crystal data and structure refinement for polymorph 1 of stanozolol.
Identification code
stanozolol_1
Empirical formula
C21H32N2O
Formula weight
328.49
Temperature
298(2) K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P212121
Unit cell dimensions
a = 7.3164(4)
b = 21.562(2)
c = 24.0058(11)
Volume
3787.1(5) 3
Density (calculated)
1.152 Mg/m3
0.070 mm-1
F(000)
1440
Crystal size
0.80 x 0.10 x 0.10 mm

127
Theta range for data collection
2.9360 to 29.1583
Index ranges
-5<=h<=9; -28<=k<=17; -16<=l<=32
11756
6695 [Rint = 0.0278]
3213
Data Completeness
0.998
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
1.00000 and 0.97969
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
6695 / 0 / 440
0.756
R1 = 0.0380 wR2 = 0.0616
R1 = 0.1056 wR2 = 0.0703
Absolute structure parameter
-1.2(14)
Largest diff. peak and hole
0.163 and -0.129 e.-3
Table 8.2 Atomic coordinates ( x 104) and equivalent isotropic displacement

parameters (2 x 103) for polymorph 1 of stanozolol. U(eq) is defined as one third of
the trace of the orthogonalized Uij tensor.
Atom
U(eq)
O(1)
8683(2)
7743(1)
9076(1)
54(1)
O(2)
8633(3)
1717(1)
8157(1)
93(1)
N(1)
8533(3)
3450(1)
6427(1)
54(1)
N(2)
6725(3)
3530(1)
6533(1)
51(1)
N(3)
12265(3)
6178(1)
10432(1)
54(1)
N(4)
10585(3)
6003(1)
10601(1)
48(1)
C(1)
9599(4)
3854(1)
6709(1)
57(1)
C(2)
8447(3)
4222(1)
7019(1)
43(1)
C(3)
8815(3)
4748(1)
7409(1)
50(1)
C(4)
7093(3)
5152(1)
7498(1)
34(1)
C(5)
7403(3)
5585(1)
8003(1)
34(1)
C(6)
9089(3)
5999(1)
7948(1)
51(1)
C(7)
9389(3)
6423(1)
8456(1)
47(1)
128
C(8)
7710(3)
6810(1)
8576(1)
31(1)
C(9)
7677(3)
7175(1)
9129(1)
36(1)
C(10)
5610(3)
7291(1)
9220(1)
46(1)
C(11)
4569(3)
6804(1)
8867(1)
41(1)
C(12)
6079(3)
6372(1)
8655(1)
31(1)
C(13)
5677(3)
5952(1)
8163(1)
35(1)
C(14)
4136(3)
5500(1)
8299(1)
52(1)
C(15)
3753(3)
5054(1)
7813(1)
56(1)
C(16)
5477(3)
4712(1)
7629(1)
42(1)
C(17)
5006(3)
4272(1)
7144(1)
56(1)
C(18)
6716(3)
3999(1)
6901(1)
42(1)
C(19)
6710(4)
5528(1)
6962(1)
61(1)
C(20)
7391(3)
7273(1)
8096(1)
52(1)
C(21)
8486(4)
6823(1)
9622(1)
60(1)
C(22)
12647(4)
5782(1)
10016(1)
50(1)
C(23)
11212(4)
5365(1)
9920(1)
39(1)
C(24)
10961(3)
4847(1)
9518(1)
42(1)
C(25)
9495(3)
4382(1)
9722(1)
34(1)
C(26)
8944(3)
3939(1)
9239(1)
35(1)
C(27)
10571(3)
3586(1)
8978(1)
51(1)
C(28)
10007(3)
3138(1)
8515(1)
52(1)
C(29)
8525(3)
2689(1)
8719(1)
41(1)
C(30)
7606(4)
2269(1)
8273(1)
55(1)
C(31)
5754(4)
2109(1)
8541(1)
63(1)
C(32)
5376(4)
2598(1)
8990(1)
60(1)
C(33)
6904(3)
3075(1)
8917(1)
39(1)
C(34)
7346(3)
3507(1)
9400(1)
37(1)
C(35)
5688(3)
3893(1)
9570(1)
49(1)
C(36)
6142(3)
4341(1)
10038(1)
50(1)
C(37)
7772(3)
4757(1)
9899(1)
36(1)
C(38)
8132(3)
5205(1)
10385(1)
44(1)
C(39)
9918(4)
5522(1)
10302(1)
40(1)
C(40)
10287(3)
4025(1)
10222(1)
51(1)
129
C(41)
9306(4)
2270(1)
9177(1)
66(1)
C(42)
7357(4)
2579(1)
7712(1)
83(1)
Table 8.3 Bond lengths [] and angles [] for polymorph 1 of stanozolol.

Bond lengths []
O(1)-C(9)
1.435(2)
O(2)-C(30)
1.435(3)
N(1)-C(1)
1.351(3)
N(1)-N(2)
1.358(2)
N(2)-C(18)
1.342(3)
N(3)-C(22)
1.343(3)
N(3)-N(4)
1.348(2)
N(4)-C(39)
1.354(3)
C(1)-C(2)
1.376(3)
C(2)-C(18)
1.384(3)
C(2)-C(3)
1.496(3)
C(3)-C(4)
1.547(3)
C(4)-C(19)
1.545(3
C(4)-C(5)
1.547(3)
C(4)-C(16)
1.549(3
C(5)-C(6)
1.529(3)
C(5)-C(13)
1.539(3
C(6)-C(7)
1.539(3)
C(7)-C(8)
1.513(3)
C(8)-C(12)
1.535(3)
C(8)-C(20)
1.542(3
C(8)-C(9)
1.542(3)
C(9)-C(21)
1.524(3)
C(9)-C(10)
1.549(3)
C(10)-C(11)
1.549(3)
C(11)-C(12)
1.532(3)
C(12)-C(13)
1.517(3)
C(13)-C(14)
1.525(3)
C(14)-C(15)
1.537(3)
C(15)-C(16)
1.526(3)
C(16)-C(17)
1.542(3)
C(17)-C(18)
1.502(3)
C(22)-C(23)
1.402(3)
C(23)-C(39)
1.361(3)
C(23)-C(24)
1.487(3)
C(24)-C(25)
1.548(3)
C(25)-C(40)
1.540(3)
C(25)-C(26)
1.556(3)
C(25)-C(37)
1.558(3)
C(26)-C(34)
1.543(3)
C(26)-C(27)
1.545(3)
C(27)-C(28)
1.529(3)
C(28)-C(29)
1.534(3)
C(29)-C(33)
1.525(3)
C(29)-C(41)
1.532(3)
C(29)-C(30)
1.555(3)
C(30)-C(42)
1.515(3)
C(30)-C(31)
1.539(3)
C(31)-C(32)
1.533(3)
C(32)-C(33)
1.529(3)
C(33)-C(34)
1.521(3)
C(34)-C(35)
1.527(3)
C(35)-C(36)
1.519(3)
C(36)-C(37)
1.530(3)
C(37)-C(38)
1.537(3)
C(38)-C(39)
1.488(3)
130
Bond angles []
C(1)-N(1)-N(2)
112.8(2)
C(18)-N(2)-N(1)
102.86(19)
C(22)-N(3)-N(4)
103.7(2)
N(3)-N(4)-C(39)
112.5(2)
N(1)-C(1)-C(2)
106.8(2)
C(1)-C(2)-C(18)
104.4(2)
C(1)-C(2)-C(3)
131.7(2)
C(18)-C(2)-C(3)
123.8(2)
C(2)-C(3)-C(4)
111.56(19)
C(19)-C(4)-C(3)
109.11(19)
C(19)-C(4)-C(5)
111.3(2)
C(3)-C(4)-C(5)
109.17(18)
C(19)-C(4)-C(16)
110.7(2)
C(3)-C(4)-C(16)
107.76(19)
C(5)-C(4)-C(16)
108.76(18)
C(6)-C(5)-C(13)
112.52(17)
C(6)-C(5)-C(4)
113.76(18)
C(13)-C(5)-C(4)
112.67(18)
C(5)-C(6)-C(7)
113.20(19)
C(8)-C(7)-C(6)
111.3(2)
C(7)-C(8)-C(12)
108.35(18)
C(7)-C(8)-C(20)
109.61(19)
C(12)-C(8)-C(20)
111.93(19)
C(7)-C(8)-C(9)
117.3(2)
C(12)-C(8)-C(9)
101.27(17)
C(20)-C(8)-C(9)
108.23(18)
O(1)-C(9)-C(21)
107.15(19)
O(1)-C(9)-C(8)
110.51(19)
C(21)-C(9)-C(8)
114.06(18)
O(1)-C(9)-C(10)
112.02(18)
C(21)-C(9)-C(10)
110.5(2)
C(8)-C(9)-C(10)
102.65(18)
C(9)-C(10)-C(11)
107.02(19)
C(12)-C(11)-C(10)
103.87(18)
C(13)-C(12)-C(11)
118.81(18)
C(13)-C(12)-C(8)
114.97(18)
C(11)-C(12)-C(8)
103.08(18)
C(12)-C(13)-C(14)
111.01(18)
C(12)-C(13)-C(5)
110.03(17)
C(14)-C(13)-C(5)
109.32(18)
C(13)-C(14)-C(15)
111.92(19)
C(16)-C(15)-C(14)
111.76(19)
C(15)-C(16)-C(17)
109.32(19)
C(15)-C(16)-C(4)
113.18(19)
C(17)-C(16)-C(4)
113.2(2)
C(18)-C(17)-C(16)
110.4(2)
N(2)-C(18)-C(2)
113.1(2)
N(2)-C(18)-C(17)
123.7(2)
C(2)-C(18)-C(17)
123.1(2)
N(3)-C(22)-C(23)
112.0(2)
C(39)-C(23)-C(22)
104.5(2)
C(39)-C(23)-C(24)
122.6(2)
C(22)-C(23)-C(24)
132.9(2)
C(23)-C(24)-C(25)
111.50(19)
C(40)-C(25)-C(24)
108.01(19)
C(40)-C(25)-C(26)
111.85(17)
C(24)-C(25)-C(26)
110.00(18)
C(40)-C(25)-C(37)
110.55(19)
C(24)-C(25)-C(37)
108.10(17)
C(26)-C(25)-C(37)
108.26(18)
C(34)-C(26)-C(27)
112.84(19)
C(34)-C(26)-C(25)
112.32(18)
131
C(27)-C(26)-C(25)
113.84(18)
C(28)-C(27)-C(26)
113.40(19)
C(27)-C(28)-C(29)
110.92(19)
C(33)-C(29)-C(41)
112.8(2)
C(33)-C(29)-C(28)
107.8(2)
C(41)-C(29)-C(28)
109.7(2)
C(33)-C(29)-C(30)
101.3(2)
C(41)-C(29)-C(30)
108.1(2)
C(28)-C(29)-C(30)
117.0(2)
O(2)-C(30)-C(42)
104.9(2)
O(2)-C(30)-C(31)
110.8(2)
C(42)-C(30)-C(31)
111.4(2)
O(2)-C(30)-C(29)
113.0(2)
C(42)-C(30)-C(29)
114.0(2)
C(31)-C(30)-C(29)
102.9(2)
C(32)-C(31)-C(30)
107.3(2)
C(33)-C(32)-C(31)
104.6(2)
C(34)-C(33)-C(29)
114.00(19)
C(34)-C(33)-C(32)
118.74(19)
C(29)-C(33)-C(32)
103.7(2)
C(33)-C(34)-C(35)
111.65(19)
C(33)-C(34)-C(26)
109.83(18)
C(35)-C(34)-C(26)
109.87(18)
C(36)-C(35)-C(34)
111.79(19)
C(35)-C(36)-C(37)
112.4(2)
C(36)-C(37)-C(38)
109.67(19)
C(36)-C(37)-C(25)
112.68(18)
C(38)-C(37)-C(25)
113.26(19)
C(39)-C(38)-C(37)
109.74(19)
N(4)-C(39)-C(23)
107.3(2)
N(4)-C(39)-C(38)
126.8(2)
C(23)-C(39)-C(38)
125.9(2)
Table 8.4 Anisotropic displacement parameters (2 x 103) for polymorph 1 of

stanozolol. The anisotropic displacement factor exponent takes the form: -2 2 [h2 a*2
U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
59(1)
36(1)
68(1)
-18(1)
13(1)
-12(1)
O(2)
116(2)
64(2)
99(2)
-36(1)
-2(2)
12(1)
N(1)
59(2)
45(2)
57(2)
-18(1)
5(1)
11(1)
N(2)
55(2)
43(1)
55(2)
-19(1)
-3(1)
5(1)
N(3)
55(2)
40(1)
67(2)
-3(1)
-6(1)
-3(1)
N(4)
63(2)
37(1)
43(1)
-8(1)
-3(1)
3(1)
C(1)
49(2)
48(2)
75(2)
-25(2)
-4(2)
0(2)
C(2)
38(2)
39(2)
53(2)
-21(2)
-1(2)
5(1)
C(3)
36(2)
51(2)
62(2)
-21(2)
1(2)
4(1)
C(4)
27(1)
36(2)
40(2)
-11(1)
-4(1)
3(1)
C(5)
28(1)
34(1)
39(2)
-7(1)
-2(1)
0(1)
C(6)
36(2)
48(2)
70(2)
-26(2)
10(1)
-3(1)
132
C(7)
27(1)
46(2)
67(2)
-18(2)
1(1)
-2(1)
C(8)
35(1)
29(1)
30(1)
-2(1)
3(1)
4(1)
C(9)
43(2)
24(1)
41(2)
-2(1)
0(1)
-1(1)
C(10)
51(2)
37(2)
49(2)
-11(2)
10(2)
-1(1)
C(11)
40(1)
39(2)
43(2)
1(1)
10(1)
4(1)
C(12)
31(1)
32(1)
31(1)
-4(1)
-1(1)
5(1)
C(13)
28(1)
39(2)
39(2)
-10(1)
-1(1)
2(1)
C(14)
30(2)
61(2)
65(2)
-23(2)
8(1)
2(1)
C(15)
33(2)
62(2)
73(2)
-31(2)
6(2)
-5(2)
C(16)
32(2)
42(2)
51(2)
-16(2)
-3(1)
-2(1)
C(17)
41(2)
53(2)
75(2)
-29(2)
-2(2)
-3(2)
C(18)
39(2)
39(2)
49(2)
-12(2)
-2(2)
6(1)
C(19)
74(2)
63(2)
45(2)
-16(2)
-3(2)
3(2)
C(20)
59(2)
55(2)
42(2)
2(2)
8(2)
-3(2)
C(21)
85(2)
48(2)
47(2)
-10(2)
-27(2)
-3(2)
C(22)
50(2)
38(2)
64(2)
-13(2)
5(2)
3(2)
C(23)
41(2)
28(2)
47(2)
-4(1)
-5(2)
0(1)
C(24)
45(2)
36(2)
45(2)
-4(2)
3(1)
-4(1)
C(25)
38(2)
29(1)
34(1)
-1(1)
-5(1)
-1(1)
C(26)
37(1)
30(1)
37(2)
-4(1)
-3(1)
2(1)
C(27)
39(2)
51(2)
65(2)
-21(2)
12(1)
-7(1)
C(28)
47(2)
54(2)
55(2)
-20(2)
5(2)
2(2)
C(29)
45(2)
37(2)
40(2)
-8(2)
-1(1)
-1(2)
C(30)
67(2)
46(2)
52(2)
-16(2)
6(2)
-5(2)
C(31)
71(2)
57(2)
62(2)
-17(2)
5(2)
-20(2)
C(32)
57(2)
52(2)
70(2)
-18(2)
4(2)
-19(2)
C(33)
41(2)
34(2)
42(2)
-5(1)
-1(1)
1(1)
C(34)
38(2)
36(2)
39(2)
-5(1)
1(1)
-2(1)
C(35)
39(2)
43(2)
64(2)
-11(2)
10(2)
-1(1)
C(36)
47(2)
43(2)
59(2)
-13(2)
10(2)
2(1)
C(37)
43(2)
27(1)
38(2)
-2(1)
1(1)
4(1)
C(38)
52(2)
39(2)
40(2)
-6(2)
-1(2)
-1(1)
C(39)
55(2)
28(2)
37(2)
-6(1)
-11(2)
2(1)
133
C(40)
66(2)
36(2)
52(2)
-1(2)
-11(2)
5(1)
C(41)
78(2)
50(2)
69(2)
-11(2)
-9(2)
11(2)
C(42)
104(3)
100(3)
46(2)
-17(2)
-1(2)
-35(2)
Table 8.5 Hydrogen coordinates ( x 104) and isotropic displacement parameters (2 x

103) for polymorph 1 of stanozolol.
Atom
U(eq)
H(1O1)
8581
7945
9364
71
H(2O2)
8809
1526
8447
121
H(1N1)
8954
3172
6204
70
H(4)
10002
6179
10869
62
H(1)
10868
3879
6695
75
H(3A)
9789
5004
7259
64
H(3B)
9219
4585
7764
64
H(5)
7652
5310
8319
44
H(6A)
8962
6254
7618
66
H(6B)
10159
5739
7899
66
H(7A)
9677
6172
8779
61
H(7B)
10420
6695
8385
61
H(10A)
5286
7707
9103
59
H(10B)
5301
7246
9611
59
H(11A)
3692
6579
9093
53
H(11B)
3933
7000
8559
53
H(12)
6394
6098
8967
40
H(13)
5308
6209
7846
46
H(14A)
3034
5732
8383
68
H(14B)
4462
5262
8627
68
H(15A)
2837
4754
7926
73
H(15B)
3266
5286
7501
73
H(16)
5858
4451
7943
54
H(17A)
4219
3942
7277
73
H(17B)
4350
4499
6858
73
H(19A)
7680
5820
6903
79
134
H(19B)
5573
5745
7001
79
H(19C)
6641
5251
6650
79
H(20A)
7069
7049
7764
67
H(20B)
8489
7506
8031
67
H(20C)
6418
7551
8193
67
H(21A)
8321
7060
9956
78
H(21B)
9768
6756
9559
78
H(21C)
7881
6430
9659
78
H(22)
13734
5784
9815
65
H(24A)
12114
4631
9469
55
H(24B)
10598
5014
9160
55
H(26)
8470
4207
8942
45
H(27A)
11431
3884
8828
67
H(27B)
11192
3354
9269
67
H(28A)
11066
2904
8393
68
H(28B)
9549
3372
8199
68
H(31A)
4795
2114
8262
82
H(31B)
5799
1698
8706
82
H(32A)
4188
2788
8934
77
H(32B)
5415
2415
9358
77
H(33)
6548
3340
8604
50
H(34)
7724
3255
9719
49
H(35A)
5254
4125
9250
63
H(35B)
4714
3618
9689
63
H(36A)
6413
4106
10373
64
H(36B)
5083
4598
10114
64
H(37)
7414
5011
9579
47
H(38A)
7161
5510
10405
57
H(38B)
8149
4976
10733
57
H(40A)
11351
3798
10106
66
H(40B)
9387
3741
10362
66
H(40C)
10618
4313
10510
66
H(41A)
9671
2520
9489
85
135
H(41B)
10346
2050
9035
85
H(41C)
8389
1979
9293
85
H(42A)
6671
2311
7471
108
H(42B)
8532
2660
7550
108
H(42C)
6710
2963
7760
108
136
2) Polymorph 2 of stanozolol.
Table 8.6 Crystal data and structure refinement for polymorph 2 of stanozolol.
Identification code
stanozolol_2
Empirical formula
C21 H32 N2 O
Formula weight
328.49
Temperature
298(2) K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P21212
a = 19.4540(7)
b = 18.7009(8)
c = 10.8348(4)
Volume
3941.8(3) 3
1.107 Mg/m3
137
0.068 mm-1
F(000)
1440
Crystal size
0.40 x 0.30 x 0.25 mm
3.0117 to 29.2370
Index ranges
-15<=h<=24; -14<=k<=25; -13<=l<=7
12685
6908 [Rint = 0.0185]
5298
Data Completeness
0.997
1.00000 and 0.98866
Refinement method
6908 / 2 / 447
1.026
R1 = 0.0487 wR2 = 0.1023
R1 = 0.0718 wR2 = 0.1138
1.2(17)
0.189 and -0.157 e.-3

parameters (2 x 103) for polymorph 2 of stanozolol. U(eq) is defined as one third of
Atom
U(eq)
O(1)
7216(1)
3487(1)
9450(2)
53(1)
O(2)
11695(1)
7432(1)
-294(2)
62(1)
N(1)
8099(1)
6189(1)
127(2)
59(1)
N(2)
7442(1)
6304(1)
434(2)
59(1)
N(3)
8648(1)
7920(1)
8686(2)
55(1)
N(4)
8680(1)
7214(1)
8432(2)
54(1)
C(1)
8363(2)
5739(2)
963(3)
59(1)
C(2)
7867(1)
5561(1)
1829(2)
49(1)
C(3)
7867(1)
5101(2)
2965(2)
51(1)
C(4)
7294(1)
5320(1)
3870(2)
38(1)
138
C(5)
7200(1)
4729(1)
4864(2)
38(1)
C(6)
7839(1)
4572(2)
5647(2)
51(1)
C(7)
7733(1)
3983(2)
6610(2)
48(1)
C(8)
7124(1)
4139(1)
7454(2)
38(1)
C(9)
6857(1)
3520(2)
8288(2)
47(1)
C(10)
6104(1)
3743(2)
8527(3)
80(1)
C(11)
5889(1)
4260(2)
7496(3)
79(1)
C(12)
6499(1)
4255(2)
6611(2)
45(1)
C(13)
6572(1)
4865(1)
5699(2)
42(1)
C(14)
5924(1)
4938(2)
4938(3)
69(1)
C(15)
5993(1)
5501(2)
3937(3)
60(1)
C(16)
6616(1)
5375(1)
3122(2)
45(1)
C(17)
6629(1)
5947(2)
2114(3)
58(1)
C(18)
7293(1)
5931(1)
1444(2)
50(1)
C(19)
7478(1)
6046(1)
4452(3)
56(1)
C(20)
7282(2)
4791(2)
8255(3)
62(1)
C(21)
6902(2)
2783(2)
7707(3)
73(1)
C(22)
8995(1)
8265(2)
7808(2)
52(1)
C(23)
9249(1)
7782(1)
6959(2)
40(1)
C(24)
9655(1)
7876(1)
5783(2)
43(1)
C(25)
9957(1)
7168(1)
5309(2)
35(1)
C(26)
10144(1)
7256(1)
3921(2)
35(1)
C(27)
10695(1)
7827(1)
3675(2)
46(1)
C(28)
10843(1)
7935(1)
2297(2)
45(1)
C(29)
11029(1)
7236(1)
1660(2)
37(1)
C(30)
11041(1)
7231(1)
212(2)
47(1)
C(31)
10901(2)
6438(2)
-112(3)
65(1)
C(32)
10607(2)
6078(2)
1049(2)
58(1)
C(33)
10447(1)
6701(1)
1907(2)
40(1)
C(34)
10318(1)
6549(1)
3268(2)
39(1)
C(35)
9735(2)
6011(1)
3431(2)
54(1)
C(36)
9594(2)
5882(1)
4800(3)
56(1)
C(37)
9396(1)
6581(1)
5433(2)
40(1)
139
C(38)
9181(1)
6439(1)
6768(2)
50(1)
C(39)
9041(1)
7129(1)
7393(2)
43(1)
C(40)
10594(1)
6974(2)
6077(2)
56(1)
C(41)
11728(1)
6966(2)
2137(3)
58(1)
C(42)
10520(2)
7730(2)
-362(2)
64(1)
Table 8.8 Bond lengths [] and angles [] for polymorph 2 of stanozolol.

Bond lengths []
O(1)-C(9)
1.440(3)
O(2)-C(30)
1.436(3)
N(1)-C(1)
1.338(3)
N(1)-N(2)
1.339(3)
N(2)-C(18)
1.330(3)
N(3)-C(22)
1.334(3)
N(3)-N(4)
1.350(3)
N(4)-C(39)
1.336(3)
C(1)-C(2)
1.387(4)
C(2)-C(18)
1.379(4)
C(2)-C(3)
1.501(3)
C(3)-C(4)
1.541(3)
C(4)-C(19)
1.540(4)
C(4)-C(16)
1.552(3)
C(4)-C(5)
1.554(3)
C(5)-C(6)
1.533(3)
C(5)-C(13)
1.540(3
C(6)-C(7)
1.532(3)
C(7)-C(8)
1.525(3)
C(8)-C(20)
1.528(4)
C(8)-C(12)
1.535(3
C(8)-C(9)
1.558(3)
C(9)-C(21)
1.517(4)
C(9)-C(10)
1.546(4)
C(10)-C(11)
1.535(4)
C(11)-C(12)
1.525(3)
C(12)-C(13)
1.516(3)
C(13)-C(14)
1.513(3)
C(14)-C(15)
1.518(4)
C(15)-C(16)
1.517(4)
C(16)-C(17)
1.529(3)
C(17)-C(18)
1.482(4)
C(22)-C(23)
1.380(3)
C(23)-C(39)
1.370(3)
C(23)-C(24)
1.510(3)
C(24)-C(25)
1.537(3)
C(25)-C(40)
1.536(3)
C(25)-C(37)
1.555(3)
C(25)-C(26)
1.556(3)
C(26)-C(27)
1.537(3)
C(26)-C(34)
1.538(3)
C(27)-C(28)
1.534(3)
C(28)-C(29)
1.522(3)
C(29)-C(33)
1.534(3)
C(29)-C(41)
1.540(3)
C(29)-C(30)
1.570(3)
C(30)-C(42)
1.512(4)
C(30)-C(31)
1.548(4)
C(31)-C(32)
1.537(4)
C(32)-C(33)
1.523(3)
140
C(33)-C(34)
1.523(3)
C(34)-C(35)
1.527(3)
C(35)-C(36)
1.527(4)
C(36)-C(37)
1.525(3)
C(37)-C(38)
1.529(3)
C(38)-C(39)
1.483(3)
Bond angles []
C(1)-N(1)-N(2)
107.5(2)
C(18)-N(2)-N(1)
109.1(2)
C(22)-N(3)-N(4)
107.7(2)
C(39)-N(4)-N(3)
108.2(2)
N(1)-C(1)-C(2)
110.0(3)
C(18)-C(2)-C(1)
103.8(2)
C(18)-C(2)-C(3)
122.4(2)
C(1)-C(2)-C(3)
133.8(3)
C(2)-C(3)-C(4)
111.7(2)
C(19)-C(4)-C(3)
109.0(2)
C(19)-C(4)-C(16)
110.7(2)
C(3)-C(4)-C(16)
107.5(2)
C(19)-C(4)-C(5)
111.8(2)
C(3)-C(4)-C(5)
109.74(19)
C(16)-C(4)-C(5)
108.03(19)
C(6)-C(5)-C(13)
110.42(19)
C(6)-C(5)-C(4)
115.10(19)
C(13)-C(5)-C(4)
112.54(19)
C(7)-C(6)-C(5)
113.9(2)
C(8)-C(7)-C(6)
112.0(2)
C(7)-C(8)-C(20)
109.7(2)
C(7)-C(8)-C(12)
106.62(19)
C(20)-C(8)-C(12)
112.6(2)
C(7)-C(8)-C(9)
117.7(2)
C(20)-C(8)-C(9)
109.3(2)
C(12)-C(8)-C(9)
100.76(18)
O(1)-C(9)-C(21)
107.3(2)
O(1)-C(9)-C(10)
108.9(2)
C(21)-C(9)-C(10)
111.7(3)
O(1)-C(9)-C(8)
112.2(2)
C(21)-C(9)-C(8)
114.5(2)
C(10)-C(9)-C(8)
102.2(2)
C(11)-C(10)-C(9)
107.8(2)
C(12)-C(11)-C(10)
104.0(2)
C(13)-C(12)-C(11)
118.6(2)
C(13)-C(12)-C(8)
114.76(19)
C(11)-C(12)-C(8)
104.1(2)
C(14)-C(13)-C(12)
110.2(2)
C(14)-C(13)-C(5)
110.8(2)
C(12)-C(13)-C(5)
109.51(19)
C(13)-C(14)-C(15)
112.3(2)
C(16)-C(15)-C(14)
112.2(2)
C(15)-C(16)-C(17)
108.7(2)
C(15)-C(16)-C(4)
112.7(2)
C(17)-C(16)-C(4)
113.9(2)
C(18)-C(17)-C(16)
110.5(2)
N(2)-C(18)-C(2)
109.7(2)
N(2)-C(18)-C(17)
125.6(3)
C(2)-C(18)-C(17)
124.6(2)
N(3)-C(22)-C(23)
109.8(2)
C(39)-C(23)-C(22)
104.4(2)
C(39)-C(23)-C(24)
123.2(2)
C(22)-C(23)-C(24)
132.4(2)
C(23)-C(24)-C(25)
112.5(2)
C(40)-C(25)-C(24)
109.4(2)
C(40)-C(25)-C(37)
110.7(2)
141
C(24)-C(25)-C(37)
108.09(18)
C(40)-C(25)-C(26)
111.15(19)
C(24)-C(25)-C(26)
108.74(19)
C(37)-C(25)-C(26)
108.75(18)
C(27)-C(26)-C(34)
111.31(18)
C(27)-C(26)-C(25)
113.76(19)
C(34)-C(26)-C(25)
113.92(19)
C(28)-C(27)-C(26)
113.0(2)
C(29)-C(28)-C(27)
111.8(2)
C(28)-C(29)-C(33)
107.79(18)
C(28)-C(29)-C(41)
109.9(2)
C(33)-C(29)-C(41)
112.3(2)
C(28)-C(29)-C(30)
117.5(2)
C(33)-C(29)-C(30)
100.43(19)
C(41)-C(29)-C(30)
108.7(2)
O(2)-C(30)-C(42)
106.0(2)
O(2)-C(30)-C(31)
108.7(2)
C(42)-C(30)-C(31)
112.4(2)
O(2)-C(30)-C(29)
113.2(2)
C(42)-C(30)-C(29)
113.4(2)
C(31)-C(30)-C(29)
103.3(2)
C(32)-C(31)-C(30)
107.4(2)
C(33)-C(32)-C(31)
103.9(2)
C(34)-C(33)-C(32)
118.7(2)
C(34)-C(33)-C(29)
114.3(2)
C(32)-C(33)-C(29)
104.00(19)
C(33)-C(34)-C(35)
111.0(2)
C(33)-C(34)-C(26)
108.70(19)
C(35)-C(34)-C(26)
110.40(19)
C(36)-C(35)-C(34)
110.5(2)
C(37)-C(36)-C(35)
110.3(2)
C(36)-C(37)-C(38)
110.3(2)
C(36)-C(37)-C(25)
112.93(19)
C(38)-C(37)-C(25)
113.4(2)
C(39)-C(38)-C(37)
109.4(2)
N(4)-C(39)-C(23)
109.8(2)
N(4)-C(39)-C(38)
125.8(2)
C(23)-C(39)-C(38)
124.4(2)
Table 8.9 Anisotropic displacement parameters (2 x 103) for polymorph 2 of

stanozolol. The anisotropic displacement factor exponent takes the form: -2 2 [h2 a*2
U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
50(1)
73(1)
36(1)
17(1)
2(1)
-2(1)
O(2)
52(1)
77(1)
57(1)
9(1)
25(1)
4(1)
N(1)
83(2)
54(2)
40(1)
3(1)
13(1)
-2(1)
N(2)
90(2)
48(1)
40(1)
9(1)
5(1)
-1(1)
N(3)
60(1)
60(2)
45(1)
-2(1)
13(1)
5(1)
N(4)
61(1)
61(2)
40(1)
8(1)
19(1)
-3(1)
C(1)
67(2)
64(2)
46(2)
6(2)
14(1)
6(2)
C(2)
62(2)
45(2)
41(2)
5(1)
13(1)
5(1)
C(3)
54(2)
55(2)
46(2)
12(1)
14(1)
10(1)
142
C(4)
38(1)
37(1)
39(1)
5(1)
6(1)
2(1)
C(5)
36(1)
38(1)
40(1)
4(1)
4(1)
2(1)
C(6)
32(1)
71(2)
49(2)
18(2)
8(1)
5(1)
C(7)
35(1)
62(2)
46(1)
19(1)
4(1)
10(1)
C(8)
32(1)
44(1)
37(1)
7(1)
3(1)
-1(1)
C(9)
37(1)
60(2)
43(2)
16(1)
-2(1)
-6(1)
C(10)
38(2)
122(3)
79(2)
52(2)
9(2)
-1(2)
C(11)
35(2)
125(3)
78(2)
60(2)
14(1)
5(2)
C(12)
29(1)
58(2)
49(2)
18(1)
4(1)
-3(1)
C(13)
32(1)
47(2)
47(2)
14(1)
7(1)
3(1)
C(14)
34(1)
97(2)
75(2)
48(2)
0(1)
4(1)
C(15)
40(1)
76(2)
64(2)
32(2)
2(1)
9(1)
C(16)
48(1)
43(1)
45(1)
11(1)
-1(1)
0(1)
C(17)
59(2)
58(2)
57(2)
21(2)
2(1)
6(2)
C(18)
66(2)
42(2)
42(2)
8(1)
9(1)
0(1)
C(19)
66(2)
45(2)
56(2)
6(1)
9(1)
-9(1)
C(20)
76(2)
57(2)
53(2)
4(2)
-2(2)
-4(2)
C(21)
98(2)
56(2)
66(2)
25(2)
-28(2)
-21(2)
C(22)
64(2)
51(2)
40(2)
-4(1)
12(1)
3(1)
C(23)
46(1)
44(2)
31(1)
-1(1)
8(1)
2(1)
C(24)
56(2)
37(1)
36(1)
-4(1)
13(1)
-6(1)
C(25)
41(1)
36(1)
28(1)
2(1)
3(1)
1(1)
C(26)
36(1)
36(1)
32(1)
1(1)
6(1)
1(1)
C(27)
53(2)
47(2)
37(1)
-8(1)
8(1)
-11(1)
C(28)
50(1)
42(1)
42(1)
1(1)
12(1)
-7(1)
C(29)
35(1)
42(1)
35(1)
0(1)
7(1)
2(1)
C(30)
47(1)
54(2)
39(1)
-1(1)
14(1)
0(1)
C(31)
78(2)
68(2)
48(2)
-15(2)
20(2)
-9(2)
C(32)
72(2)
53(2)
49(2)
-13(1)
23(1)
-6(2)
C(33)
44(1)
39(1)
37(1)
-4(1)
9(1)
1(1)
C(34)
47(1)
35(1)
37(1)
-1(1)
8(1)
4(1)
C(35)
82(2)
33(1)
48(2)
-9(1)
24(1)
-9(1)
C(36)
78(2)
34(1)
55(2)
1(1)
25(2)
-7(1)
143
C(37)
48(1)
33(1)
39(1)
0(1)
9(1)
0(1)
C(38)
64(2)
43(2)
42(2)
6(1)
15(1)
-2(1)
C(39)
46(1)
49(2)
33(1)
1(1)
9(1)
0(1)
C(40)
53(2)
82(2)
33(1)
5(2)
0(1)
4(2)
C(41)
42(2)
74(2)
56(2)
6(2)
7(1)
6(1)
Table 8.10 Hydrogen coordinates ( x 104) and isotropic displacement parameters (2

x 103) for polymorph 2 of stanozolol.
Atom
U(eq)
H(1N2)
7160
6576
41
77
H(1N4)
8500
6877
8864
70
H(1)
8813
5571
963
77
H(3A)
8309
5142
3375
67
H(3B)
7804
4606
2729
67
H(5)
7100
4287
4412
49
H(6A)
8212
4434
5103
66
H(6B)
7976
5008
6066
66
H(7A)
7658
3531
6192
62
H(7B)
8146
3937
7105
62
H(10A)
5808
3325
8525
104
H(10B)
6064
3975
9324
104
H(11A)
5475
4095
7088
103
H(11B)
5809
4736
7821
103
H(12)
6454
3818
6117
59
H(13)
6646
5309
6159
54
H(14A)
5545
5064
5477
89
H(14B)
5818
4481
4560
89
H(15A)
5582
5498
3430
78
H(15B)
6030
5969
4318
78
H(16)
6548
4914
2711
59
H(17A)
6256
5864
1538
75
H(17B)
6563
6415
2482
75
H(19A)
7563
6389
3811
72
144
H(19B)
7883
5995
4951
72
H(19C)
7103
6207
4956
72
H(20A)
7361
5198
7736
81
H(20B)
7684
4698
8742
81
H(20C)
6899
4884
8791
81
H(21A)
6688
2439
8240
95
H(21B)
7376
2657
7589
95
H(21C)
6672
2787
6924
95
H(22)
9057
8758
7773
68
H(24A)
10025
8212
5928
56
H(24B)
9357
8077
5153
56
H(26)
9725
7432
3521
45
H(27A)
10545
8277
4028
59
H(27B)
11117
7688
4088
59
H(28A)
10440
8139
1902
58
H(28B)
11219
8271
2202
58
H(31A)
10574
6406
-786
84
H(31B)
11323
6204
-362
84
H(32A)
10194
5809
857
76
H(32B)
10942
5758
1418
76
H(33)
10026
6923
1590
52
H(34)
10738
6351
3632
51
H(35A)
9322
6192
3037
70
H(35B)
9857
5563
3038
70
H(36A)
9224
5538
4891
72
H(36B)
10002
5686
5189
72
H(37)
8988
6760
5004
52
H(38A)
8772
6143
6782
65
H(38B)
9545
6187
7198
65
H(40A)
10461
6894
6919
73
H(40B)
10920
7359
6041
73
H(40C)
10800
6548
5751
73
H(41A)
11691
6849
2997
75
145
H(41B)
12068
7332
2028
75
H(41C)
11861
6547
1682
75
H(42A)
10547
7698
-1244
83
H(42B)
10615
8212
-107
83
H(42C)
10067
7598
-96
83
H(1O1)
6960(20)
3290(20)
10050(30)
160(20)
H(1O2)
12084(14)
7210(20)
-140(50)
180(20)
146
3) Stanozolol ethanol solvate.
Table 8.11 Crystal data and structure refinement for stanozolol ethanol solvate.
Identification code
stanozolol_3
Empirical formula
C23 H38 N2 O2
Formula weight
374.55
Temperature
150(2) K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P212121
a = 7.1392(5)
b = 10.9541(8)
c = 26.8891(16)
Volume
2102.8(3) 3
1.183 Mg/m3
0.075 mm-1
F(000)
824
Crystal size
0.80 x 0.35 x 0.15 mm
2.9306 to 28.8699
Index ranges
-9<=h<=4; -13<=k<=11; -35<=l<=33
6211
3627 [Rint = 0.0460]

147
2219
Data Completeness
0.999
1.00000 and 0.92877
Refinement method
3627 / 3 / 260
0.892
R1 = 0.0550 wR2 = 0.0705
R1 = 0.0993 wR2 = 0.0894
0(2)
0.198 and -0.182 e.-3

parameters (2 x 103) for stanozolol ethanol solvate. U(eq) is defined as one third of
Atom
U(eq)
O(1)
5486(4)
-475(3)
12128(1)
24(1)
O(2)
4027(4)
6468(3)
7702(1)
43(1)
N(1)
1641(5)
290(3)
8015(1)
25(1)
N(2)
3466(4)
642(3)
8029(1)
22(1)
C(1)
1005(5)
-43(3)
8468(1)
27(1)
C(2)
2462(5)
120(3)
8803(1)
22(1)
C(3)
2586(5)
-40(3)
9360(1)
22(1)
C(4)
4636(5)
-91(3)
9543(1)
17(1)
C(5)
4665(5)
184(3)
10113(1)
18(1)
C(6)
3502(5)
-707(3)
10431(1)
30(1)
C(7)
3445(5)
-335(4)
10983(1)
27(1)
C(8)
5428(5)
-218(3)
11196(1)
18(1)
C(9)
5640(5)
392(3)
11723(1)
22(1)
C(10)
7613(6)
981(3)
11708(1)
28(1)
C(11)
8318(5)
922(3)
11166(1)
28(1)
C(12)
6509(5)
684(3)
10872(1)
18(1)
C(13)
6664(5)
327(3)
10323(1)
17(1)
148
C(14)
7762(5)
1290(3)
10037(1)
29(1)
C(15)
7749(5)
1054(4)
9477(1)
28(1)
C(16)
5760(5)
932(3)
9279(1)
20(1)
C(17)
5830(5)
813(3)
8709(1)
24(1)
C(18)
3938(5)
542(3)
8516(1)
19(1)
C(19)
5429(6)
-1368(3)
9423(1)
27(1)
C(20)
6366(6)
-1496(3)
11217(1)
28(1)
C(21)
4113(6)
1337(3)
11833(1)
42(1)
C(22)
4545(6)
7712(3)
7754(1)
31(1)
C(23)
6506(6)
7853(3)
7953(1)
37(1)
Table 8.13 Bond lengths [] and angles [] for stanozolol ethanol solvate.
Bond lengths []
O(1)-C(9)
1.450(4)
O(2)-C(22)
1.419(4)
N(1)-C(1)
1.352(4)
N(1)-N(2)
1.359(4)
N(2)-C(18)
1.354(4
C(1)-C(2)
1.387(5)
C(2)-C(18)
1.386(5
C(2)-C(3)
1.511(4)
C(3)-C(4)
1.545(5)
C(4)-C(19)
1.543(4)
C(4)-C(16)
1.551(4
C(4)-C(5)
1.562(4)
C(5)-C(6)
1.541(4)
C(5)-C(13)
1.543(5)
C(6)-C(7)
1.539(4)
C(7)-C(8)
1.533(5)
C(8)-C(12)
1.527(4)
C(8)-C(20)
1.552(4)
C(8)-C(9)
1.573(4)
C(9)-C(21)
1.532(5)
C(9)-C(10)
1.550(5)
C(10)-C(11)
1.542(4)
C(11)-C(12)
1.536(5)
C(12)-C(13)
1.532(4)
C(13)-C(14)
1.523(4)
C(14)-C(15)
1.527(4)
C(15)-C(16)
1.522(5)
C(16)-C(17)
1.539(4)
C(17)-C(18)
1.478(5)
C(22)-C(23)
1.507(5)
Bond angles []
C(1)-N(1)-N(2)
111.8(3)
C(18)-N(2)-N(1)
104.1(3)
N(1)-C(1)-C(2)
107.4(3)
C(18)-C(2)-C(1)
104.6(3)
C(18)-C(2)-C(3)
123.2(3)
C(1)-C(2)-C(3)
132.2(4)
149
C(2)-C(3)-C(4)
112.1(3)
C(19)-C(4)-C(3)
108.3(3)
C(19)-C(4)-C(16)
111.7(3)
C(3)-C(4)-C(16)
108.5(3)
C(19)-C(4)-C(5)
112.1(3)
C(3)-C(4)-C(5)
108.6(3)
C(16)-C(4)-C(5)
107.6(3)
C(6)-C(5)-C(13)
111.1(3)
C(6)-C(5)-C(4)
114.5(3)
C(13)-C(5)-C(4)
113.0(3)
C(7)-C(6)-C(5)
112.5(3)
C(8)-C(7)-C(6)
111.0(3)
C(12)-C(8)-C(7)
107.9(3)
C(12)-C(8)-C(20)
112.7(3)
C(7)-C(8)-C(20)
109.6(3)
C(12)-C(8)-C(9)
100.9(3)
C(7)-C(8)-C(9)
117.4(3)
C(20)-C(8)-C(9)
108.1(3)
O(1)-C(9)-C(21)
104.1(3)
O(1)-C(9)-C(10)
111.2(3)
C(21)-C(9)-C(10)
111.7(3)
O(1)-C(9)-C(8)
113.0(3)
C(21)-C(9)-C(8)
113.1(3)
C(10)-C(9)-C(8)
103.9(3)
C(11)-C(10)-C(9)
107.7(3)
C(12)-C(11)-C(10)
102.6(3)
C(8)-C(12)-C(13)
114.9(3)
C(8)-C(12)-C(11)
104.0(3)
C(13)-C(12)-C(11)
118.6(3)
C(14)-C(13)-C(12)
110.3(3)
C(14)-C(13)-C(5)
111.2(3)
C(12)-C(13)-C(5)
108.2(3)
C(13)-C(14)-C(15)
112.2(3)
C(16)-C(15)-C(14)
111.4(3)
C(15)-C(16)-C(17)
109.0(3)
C(15)-C(16)-C(4)
112.7(3)
C(17)-C(16)-C(4)
114.3(3)
C(18)-C(17)-C(16)
109.8(3)
N(2)-C(18)-C(2)
112.0(3)
N(2)-C(18)-C(17)
123.5(3)
C(2)-C(18)-C(17)
124.4(3)
O(2)-C(22)-C(23)
112.1(3)
Table 8.14 Anisotropic displacement parameters (2 x 103) for stanozolol ethanol

solvate. The anisotropic displacement factor exponent takes the form: -2 2 [h2 a*2
U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
27(2)
31(2)
14(1)
8(1)
1(1)
4(2)
O(2)
45(2)
32(2)
52(2)
-6(2)
26(2)
-13(2)
N(1)
27(2)
31(2)
16(2)
4(2)
-7(2)
2(2)
N(2)
24(2)
23(2)
20(2)
-1(1)
1(2)
5(2)
C(1)
18(2)
40(2)
22(2)
3(2)
0(2)
3(2)
C(2)
16(2)
23(2)
25(2)
0(2)
-2(2)
0(2)
C(3)
18(2)
30(2)
19(2)
4(2)
-1(2)
-4(2)
150
C(4)
17(2)
19(2)
15(2)
1(2)
2(2)
-2(2)
C(5)
20(2)
19(2)
15(2)
1(2)
1(2)
-2(2)
C(6)
21(2)
49(3)
21(2)
7(2)
-4(2)
-8(2)
C(7)
21(2)
46(3)
13(2)
6(2)
1(2)
-9(2)
C(8)
24(2)
19(2)
13(2)
0(2)
4(2)
-5(2)
C(9)
23(2)
30(2)
12(2)
-5(2)
1(2)
4(2)
C(10)
43(3)
21(2)
21(2)
-3(2)
-7(2)
-7(2)
C(11)
31(2)
37(2)
17(2)
3(2)
-7(2)
-17(2)
C(12)
21(2)
17(2)
15(2)
1(2)
-2(2)
0(2)
C(13)
16(2)
21(2)
15(2)
-1(2)
-2(2)
-1(2)
C(14)
27(2)
41(3)
19(2)
1(2)
-3(2)
-16(2)
C(15)
26(2)
45(3)
14(2)
1(2)
-1(2)
-12(2)
C(16)
26(2)
22(2)
12(2)
1(2)
-1(2)
-6(2)
C(17)
24(2)
29(2)
18(2)
1(2)
-5(2)
-2(2)
C(18)
25(2)
17(2)
15(2)
-4(2)
-5(2)
8(2)
C(19)
34(2)
23(2)
25(2)
-3(2)
-6(2)
5(2)
C(20)
44(3)
21(2)
19(2)
-2(2)
-4(2)
6(2)
C(21)
52(3)
51(3)
23(2)
-2(2)
-1(2)
27(3)
C(22)
35(2)
26(2)
32(2)
8(2)
6(2)
3(2)
C(23)
47(3)
36(2)
27(2)
-5(2)
-5(2)
8(3)

x 103) for stanozolol ethanol solvate.
Atom
U(eq)
H(1O1)
6430(40)
-820(40)
12203(15)
66(17)
H(1O2)
4710(50)
6150(30)
7477(10)
34(14)
H(1N1)
1070(50)
300(40)
7728(9)
60(15)
H(1)
-215
-336
8544
35
H(3A)
1938
-804
9456
29
H(3B)
1935
648
9525
29
H(5)
4056
1000
10153
23
H(6A)
2207
-738
10300
39
H(6B)
4044
-1536
10403
39
151
H(7A)
2783
455
11017
35
H(7B)
2739
-956
11174
35
H(10A)
7547
1840
11821
37
H(10B)
8479
532
11930
37
H(11A)
8908
1701
11065
37
H(11B)
9228
249
11121
37
H(12)
5784
1465
10881
23
H(13)
7332
-473
10297
22
H(14A)
9072
1298
10157
38
H(14B)
7212
2103
10103
38
H(15A)
8387
1735
9305
36
H(15B)
8452
295
9405
36
H(16)
5107
1719
9354
26
H(17A)
6296
1583
8562
31
H(17B)
6702
149
8615
31
H(19A)
6761
-1395
9510
36
H(19B)
5282
-1534
9067
36
H(19C)
4749
-1986
9615
36
H(20A)
7652
-1413
11339
36
H(20B)
6383
-1853
10882
36
H(20C)
5654
-2027
11441
36
H(21A)
4374
1733
12152
55
H(21B)
2892
929
11849
55
H(21C)
4096
1952
11568
55
H(22A)
3656
8120
7982
40
H(22B)
4458
8119
7426
40
H(23A)
7367
7350
7757
48
H(23B)
6540
7589
8301
48
H(23C)
6885
8711
7931
48
152
4) Stanozolol isopropanol solvate.
Table 8.16 Crystal data and structure refinement for stanozolol isopropanol solvate.
Identification code
stanozolol_4
Empirical formula
C24 H40 N2 O2
Formula weight
388.58
Temperature
150(2) K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
C2
a = 24.5445(13)
b = 7.2894(3), = 122.679(7)
c = 15.2500(8)
Volume
2296.56(19) 3
1.124 Mg/m3
0.071 mm-1
F(000)
856
Crystal size
0.51 x 0.32 x 0.26 mm
2.9565 to 29.1381 .
Index ranges
-24<=h<=31; -6<=k<=9; -20<=l<=20
5444
3446 [Rint = 0.0161]

153
3029
Data Completeness
0.996
1.00000 and 0.99757
Refinement method
3446 / 1 / 266
0.980
R1 = 0.0318 wR2 = 0.0725
R1 = 0.0375 wR2 = 0.0739
1.2(11)
0.164 and -0.183 e.-3

parameters (2 x 103) for stanozolol isopropanol solvate. U(eq) is defined as one
third of the trace of the orthogonalized Uij tensor.
Atom
U(eq)
O(1)
10475(1)
2553(2)
13827(1)
28(1)
O(2)
5862(1)
4010(2)
3842(1)
31(1)
N(1)
6403(1)
-321(2)
5483(1)
21(1)
N(2)
6378(1)
1520(2)
5556(1)
23(1)
C(1)
6871(1)
-1086(3)
6379(1)
20(1)
C(2)
7179(1)
318(2)
7082(1)
18(1)
C(3)
7735(1)
318(2)
8208(1)
19(1)
C(4)
8009(1)
2264(2)
8588(1)
16(1)
C(5)
8407(1)
2270(2)
9804(1)
17(1)
C(6)
8983(1)
924(3)
10294(1)
25(1)
C(7)
9336(1)
841(2)
11486(1)
24(1)
C(8)
9548(1)
2737(2)
11969(1)
19(1)
C(9)
9792(1)
2927(3)
13144(1)
23(1)
C(10)
9684(1)
4976(3)
13258(1)
33(1)
C(11)
9189(1)
5711(3)
12158(1)
30(1)
C(12)
8953(1)
3992(2)
11474(1)
18(1)
C(13)
8614(1)
4195(2)
10294(1)
17(1)
154
C(14)
8030(1)
5457(3)
9857(1)
23(1)
C(15)
7649(1)
5529(2)
8671(1)
23(1)
C(16)
7435(1)
3628(2)
8197(1)
18(1)
C(17)
7019(1)
3763(2)
7001(1)
23(1)
C(18)
6854(1)
1892(2)
6538(1)
19(1)
C(19)
8433(1)
2789(2)
8169(1)
23(1)
C(20)
10072(1)
3489(3)
11805(1)
28(1)
C(21)
9434(1)
1686(3)
13469(1)
33(1)
C(22)
6961(1)
4973(3)
4466(2)
42(1)
C(23)
6342(1)
4163(3)
3581(1)
30(1)
C(24)
6449(1)
2355(3)
3227(2)
47(1)
Table 8.18 Bond lengths [] and angles [] for stanozolol isopropanol solvate.
Bond lengths []
O(1)-C(9)
1.4438(18)
O(2)-C(23)
1.438(2)
N(1)-C(1)
1.343(2)
N(1)-N(2)
1.351(2)
N(2)-C(18)
1.3386(
C(1)-C(2)
1.376(2)
C(2)-C(18)
1.388(2
C(2)-C(3)
1.510(2)
C(3)-C(4)
1.542(2)
C(4)-C(19)
1.533(2)
C(4)-C(16)
1.556(2)
C(4)-C(5)
1.5602(19)
C(5)-C(13)
1.542(2
C(5)-C(6)
1.542(2)
C(6)-C(7)
1.536(2)
C(7)-C(8)
1.520(2)
C(8)-C(12)
1.533(2)
C(8)-C(20)
1.538(2)
C(8)-C(9)
1.559(2)
C(9)-C(21)
1.517(3)
C(9)-C(10)
1.543(3)
C(10)-C(11)
1.542(2)
C(11)-C(12)
1.530(2)
C(12)-C(13)
1.527(2)
C(13)-C(14)
1.522(2)
C(14)-C(15)
1.523(2)
C(15)-C(16)
1.520(2)
C(16)-C(17)
1.539(2)
C(17)-C(18)
1.488(2)
C(22)-C(23)
1.504(2)
C(23)-C(24)
1.499(3)
Bond angles []
C(1)-N(1)-N(2)
112.39(15)
C(18)-N(2)-N(1)
104.02(13)
155
N(1)-C(1)-C(2)
106.99(16)
C(1)-C(2)-C(18)
104.63(13)
C(1)-C(2)-C(3)
131.72(15)
C(18)-C(2)-C(3)
123.64(14)
C(2)-C(3)-C(4)
111.76(13)
C(19)-C(4)-C(3)
109.27(13)
C(19)-C(4)-C(16)
110.93(13)
C(3)-C(4)-C(16)
108.76(12)
C(19)-C(4)-C(5)
111.37(12)
C(3)-C(4)-C(5)
108.37(13)
C(16)-C(4)-C(5)
108.07(12)
C(13)-C(5)-C(6)
111.57(12)
C(13)-C(5)-C(4)
114.22(13)
C(6)-C(5)-C(4)
113.33(13)
C(7)-C(6)-C(5)
112.49(14)
C(8)-C(7)-C(6)
111.38(14)
C(7)-C(8)-C(12)
108.52(12)
C(7)-C(8)-C(20)
110.08(14)
C(12)-C(8)-C(20)
111.44(14)
C(7)-C(8)-C(9)
117.13(14)
C(12)-C(8)-C(9)
100.73(12)
C(20)-C(8)-C(9)
108.62(12)
O(1)-C(9)-C(21)
107.67(14)
O(1)-C(9)-C(10)
107.76(14)
C(21)-C(9)-C(10)
112.08(16)
O(1)-C(9)-C(8)
112.79(13)
C(21)-C(9)-C(8)
113.05(13)
C(10)-C(9)-C(8)
103.41(14)
C(11)-C(10)-C(9)
107.27(14)
C(12)-C(11)-C(10)
104.08(15)
C(13)-C(12)-C(11)
119.28(15)
C(13)-C(12)-C(8)
113.90(12)
C(11)-C(12)-C(8)
104.08(12)
C(14)-C(13)-C(12)
111.02(13)
C(14)-C(13)-C(5)
110.57(12)
C(12)-C(13)-C(5)
108.12(13)
C(13)-C(14)-C(15)
111.73(13)
C(16)-C(15)-C(14)
111.50(14)
C(15)-C(16)-C(17)
110.10(13)
C(15)-C(16)-C(4)
113.05(12)
C(17)-C(16)-C(4)
112.36(13)
C(18)-C(17)-C(16)
109.87(14)
N(2)-C(18)-C(2)
111.97(14)
N(2)-C(18)-C(17)
124.44(14)
C(2)-C(18)-C(17)
123.60(13)
O(2)-C(23)-C(24)
111.09(16)
O(2)-C(23)-C(22)
111.34(15)
C(24)-C(23)-C(22)
112.35(16)
Table 8.19 Anisotropic displacement parameters (2 x 103) for stanozolol

isopropanol solvate. The anisotropic displacement factor exponent takes the form: -2
2 [h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
16(1)
28(1)
22(1)
-6(1)
-1(1)
2(1)
O(2)
25(1)
34(1)
35(1)
14(1)
17(1)
7(1)
N(1)
22(1)
21(1)
14(1)
-3(1)
5(1)
-4(1)
N(2)
24(1)
22(1)
18(1)
-2(1)
7(1)
-2(1)
156
C(1)
19(1)
20(1)
17(1)
2(1)
7(1)
0(1)
C(2)
18(1)
18(1)
16(1)
-2(1)
9(1)
-3(1)
C(3)
20(1)
18(1)
15(1)
2(1)
7(1)
2(1)
C(4)
19(1)
14(1)
15(1)
0(1)
8(1)
1(1)
C(5)
17(1)
16(1)
17(1)
-1(1)
9(1)
0(1)
C(6)
26(1)
21(1)
19(1)
-5(1)
5(1)
4(1)
C(7)
24(1)
19(1)
18(1)
-2(1)
4(1)
2(1)
C(8)
15(1)
18(1)
19(1)
-4(1)
6(1)
-1(1)
C(9)
13(1)
30(1)
16(1)
-4(1)
1(1)
0(1)
C(10)
25(1)
37(1)
23(1)
-10(1)
4(1)
5(1)
C(11)
27(1)
27(1)
24(1)
-9(1)
5(1)
5(1)
C(12)
16(1)
20(1)
18(1)
-3(1)
9(1)
0(1)
C(13)
16(1)
17(1)
18(1)
-2(1)
9(1)
-2(1)
C(14)
23(1)
20(1)
21(1)
-5(1)
9(1)
1(1)
C(15)
23(1)
17(1)
22(1)
-1(1)
8(1)
5(1)
C(16)
17(1)
17(1)
17(1)
0(1)
8(1)
0(1)
C(17)
24(1)
19(1)
19(1)
1(1)
7(1)
3(1)
C(18)
18(1)
20(1)
16(1)
-1(1)
7(1)
0(1)
C(19)
24(1)
25(1)
21(1)
-3(1)
13(1)
-2(1)
C(20)
17(1)
35(1)
30(1)
2(1)
11(1)
1(1)
C(21)
25(1)
50(1)
17(1)
4(1)
7(1)
1(1)
C(22)
42(1)
49(2)
45(1)
-16(1)
31(1)
-15(1)
C(23)
31(1)
33(1)
29(1)
5(1)
18(1)
0(1)
C(24)
51(1)
47(2)
55(1)
-16(1)
36(1)
-13(1)

x 103) for stanozolol isopropanol solvate.
Atom
U(eq)
H(1N1)
6141
-948
4913
28
H(1)
6971
-2356
6503
25
H(3A)
8083
-493
8290
25
H(3B)
7584
-178
8646
25
H(5)
8106
1799
10003
22
157
H(6A)
8823
-317
10004
33
H(6B)
9293
1306
10103
33
H(7A)
9044
301
11679
31
H(7B)
9720
38
11767
31
H(10A)
9517
5123
13716
43
H(10B)
10097
5658
13567
43
H(11A)
8826
6338
12142
39
H(11B)
9395
6580
11924
39
H(12)
8633
3389
11596
24
H(13)
8927
4722
10133
22
H(14A)
8177
6708
10139
29
H(14B)
7743
5017
10084
29
H(15A)
7263
6318
8416
30
H(15B)
7922
6084
8445
30
H(16)
7151
3130
8424
23
H(17A)
6616
4448
6781
30
H(17B)
7259
4437
6749
30
H(19A)
8177
2696
7407
30
H(19B)
8804
1955
8457
30
H(19C)
8587
4051
8375
30
H(20A)
10203
4715
12114
36
H(20B)
9899
3561
11058
36
H(20C)
10448
2670
12140
36
H(21A)
9559
1995
14180
43
H(21B)
9546
404
13445
43
H(21C)
8967
1858
12992
43
H(22A)
7155
4127
5059
54
H(22B)
6868
6146
4672
54
H(22C)
7263
5173
4242
54
H(23)
6170
5031
2980
39
H(24A)
6039
1918
2624
61
H(24B)
6611
1461
3794
61
H(24C)
6767
2506
3031
61
158
H(1O2)
6009(10)
3260(30)
4353(17)
53(7)
H(1O1)
10538(10)
1470(30)
13822(16)
45(7)
159
5) Stanozolol butan-2-ol solvate.
Table 8.21 Crystal data and structure refinement for stanozolol butan-2-ol solvate.
Identification code
stanozolol_5
Empirical formula
C25 H42 N2 O2
Formula weight
402.61
Temperature
298(2) K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
C2
a = 25.321(2)
b = 7.421(2), = 123.40
c = 15.393(2)
Volume
2414.6(7) 3
1.107 Mg/m3
0.069 mm-1
F(000)
888
Crystal size
0.50 x 0.40 x 0.15 mm
3.0427 to 29.1956
Index ranges
-33<=h<=34; -10<=k<=9; -20<=l<=20
17882
4402 [Rint = 0.0472]

160
3388
Data Completeness
0.998
1.00000 and 0.69278
Refinement method
4402 / 1 / 267
1.039
R1 = 0.0503 wR2 = 0.1290
R1 = 0.0691 wR2 = 0.1418
0.7(19)
0.166 and -0.156 e.-3

parameters (2 x 103) for stanozolol butan-2-ol solvate. U(eq) is defined as one third
of the trace of the orthogonalized Uij tensor.
Atom
U(eq)
N(1)
8688(1)
3919(3)
14631(2)
56(1)
N(2)
8732(1)
5712(3)
14551(2)
61(1)
O(1)
4536(1)
6851(3)
6397(1)
67(1)
O(2)
4115(1)
13333(4)
6207(2)
94(1)
C(1)
8225(1)
3178(4)
13739(2)
47(1)
C(2)
7940(1)
4517(3)
13025(2)
42(1)
C(3)
7398(1)
4539(3)
11897(2)
43(1)
C(4)
7115(1)
6441(3)
11527(2)
37(1)
C(5)
6695(1)
6457(3)
10319(2)
37(1)
C(6)
6148(1)
5092(3)
9849(2)
52(1)
C(7)
5757(1)
5069(3)
8648(2)
52(1)
C(8)
5509(1)
6949(3)
8209(2)
43(1)
C(9)
5206(1)
7218(4)
7016(2)
57(1)
C(10)
5292(2)
9245(5)
6927(2)
80(1)
C(11)
5803(1)
9940(4)
8021(2)
67(1)
C(12)
6082(1)
8219(3)
8669(2)
43(1)
161
C(13)
6464(1)
8355(3)
9855(2)
39(1)
C(14)
7028(1)
9615(3)
10262(2)
50(1)
C(15)
7441(1)
9655(3)
11435(2)
51(1)
C(16)
7672(1)
7779(3)
11897(2)
41(1)
C(17)
8115(1)
7898(3)
13089(2)
58(1)
C(18)
8272(1)
6066(3)
13562(2)
47(1)
C(19)
6738(1)
6921(4)
11995(2)
53(1)
C(20)
5036(1)
7550(4)
8473(2)
61(1)
C(21)
5513(2)
6078(6)
6592(2)
89(1)
C(22)
4164(2)
11956(8)
8106(5)
145(2)
C(23)
3634(3)
11934(8)
7062(5)
135(2)
C(24)
3618(2)
13459(7)
6400(4)
119(2)
C(25)
2993(2)
13829(11)
5448(4)
142(2)
Table 8.23 Bond lengths [] and angles [] for stanozolol butan-2-ol solvate.
Bond lengths []
N(1)-C(1)
1.337(3)
N(1)-N(2)
1.346(3)
N(2)-C(18)
1.339(3
O(1)-C(9)
1.441(3)
O(2)-C(24)
1.446(5
C(1)-C(2)
1.358(3)
C(2)-C(18)
1.395(4
C(2)-C(3)
1.507(3)
C(3)-C(4)
1.544(3)
C(4)-C(19)
1.520(3)
C(4)-C(5)
1.553(3)
C(4)-C(16)
1.554(3)
C(5)-C(6)
1.539(3)
C(5)-C(13)
1.541(3)
C(6)-C(7)
1.544(4)
C(7)-C(8)
1.526(3)
C(8)-C(20)
1.529(3)
C(8)-C(12)
1.536(3)
C(8)-C(9)
1.565(3)
C(9)-C(21)
1.519(5)
C(9)-C(10)
1.536(4)
C(10)-C(11)
1.542(4)
C(11)-C(12)
1.533(3)
C(12)-C(13)
1.527(3)
C(13)-C(14)
1.523(3)
C(14)-C(15)
1.509(3)
C(15)-C(16)
1.525(3)
C(16)-C(17)
1.539(3)
C(17)-C(18)
1.489(3)
C(22)-C(23)
1.417(6)
C(23)-C(24)
1.508(7)
C(24)-C(25)
1.475(6)
162
Bond angles []
C(1)-N(1)-N(2)
112.5(2)
C(18)-N(2)-N(1)
103.6(2)
N(1)-C(1)-C(2)
107.8(2)
C(1)-C(2)-C(18)
104.2(2)
C(1)-C(2)-C(3)
133.0(2)
C(18)-C(2)-C(3)
122.9(2)
C(2)-C(3)-C(4)
112.24(18)
C(19)-C(4)-C(3)
108.96(19)
C(19)-C(4)-C(5)
111.81(18)
C(3)-C(4)-C(5)
108.77(17)
C(19)-C(4)-C(16)
110.91(19)
C(3)-C(4)-C(16)
107.74(17)
C(5)-C(4)-C(16)
108.55(17)
C(6)-C(5)-C(13)
111.75(17)
C(6)-C(5)-C(4)
113.78(18)
C(13)-C(5)-C(4)
113.38(17)
C(5)-C(6)-C(7)
112.8(2)
C(8)-C(7)-C(6)
110.9(2)
C(7)-C(8)-C(20)
109.9(2)
C(7)-C(8)-C(12)
107.64(18)
C(20)-C(8)-C(12)
112.2(2)
C(7)-C(8)-C(9)
116.9(2)
C(20)-C(8)-C(9)
108.95(19)
C(12)-C(8)-C(9)
101.06(19)
O(1)-C(9)-C(21)
107.7(2)
O(1)-C(9)-C(10)
107.4(2)
C(21)-C(9)-C(10)
112.1(3)
O(1)-C(9)-C(8)
113.0(2)
C(21)-C(9)-C(8)
113.4(2)
C(10)-C(9)-C(8)
103.1(2)
C(9)-C(10)-C(11)
107.8(2)
C(12)-C(11)-C(10)
103.9(2)
C(13)-C(12)-C(11)
119.0(2)
C(13)-C(12)-C(8)
114.12(18)
C(11)-C(12)-C(8)
103.42(17)
C(14)-C(13)-C(12)
111.51(18)
C(14)-C(13)-C(5)
109.92(18)
C(12)-C(13)-C(5)
108.83(19)
C(15)-C(14)-C(13)
112.35(19)
C(14)-C(15)-C(16)
112.0(2)
C(15)-C(16)-C(17)
110.11(19)
C(15)-C(16)-C(4)
112.03(17)
C(17)-C(16)-C(4)
113.07(19)
C(18)-C(17)-C(16)
110.7(2)
N(2)-C(18)-C(2)
112.0(2)
N(2)-C(18)-C(17)
124.5(2)
C(2)-C(18)-C(17)
123.4(2)
C(22)-C(23)-C(24)
114.5(5)
O(2)-C(24)-C(25)
112.8(4)
O(2)-C(24)-C(23)
112.8(4)
C(25)-C(24)-C(23)
115.2(5)
163
Table 8.24 Anisotropic displacement parameters (2 x 103) for stanozolol butan-2-ol

U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
N(1)
56(1)
51(1)
35(1)
10(1)
8(1)
10(1)
N(2)
55(1)
52(2)
40(1)
5(1)
4(1)
-1(1)
O(1)
43(1)
58(1)
53(1)
16(1)
-3(1)
-2(1)
O(2)
90(2)
86(2)
122(2)
-36(2)
69(2)
-25(1)
C(1)
48(1)
38(1)
37(1)
2(1)
11(1)
4(1)
C(2)
42(1)
39(1)
32(1)
4(1)
13(1)
5(1)
C(3)
46(1)
31(1)
32(1)
2(1)
10(1)
1(1)
C(4)
40(1)
30(1)
30(1)
4(1)
14(1)
1(1)
C(5)
37(1)
29(1)
34(1)
5(1)
13(1)
2(1)
C(6)
53(1)
36(1)
38(1)
7(1)
7(1)
-7(1)
C(7)
48(1)
35(1)
40(1)
3(1)
5(1)
1(1)
C(8)
38(1)
36(1)
38(1)
5(1)
10(1)
0(1)
C(9)
41(1)
63(2)
39(1)
13(1)
5(1)
4(1)
C(10)
61(2)
76(2)
54(2)
30(2)
0(1)
-10(2)
C(11)
53(2)
57(2)
55(2)
24(1)
6(1)
-9(1)
C(12)
36(1)
42(1)
37(1)
14(1)
12(1)
4(1)
C(13)
38(1)
33(1)
38(1)
6(1)
16(1)
0(1)
C(14)
48(1)
37(1)
47(1)
10(1)
15(1)
-6(1)
C(15)
48(1)
33(1)
49(2)
4(1)
12(1)
-11(1)
C(16)
38(1)
33(1)
38(1)
4(1)
12(1)
-2(1)
C(17)
59(2)
42(2)
43(2)
0(1)
9(1)
-10(1)
C(18)
44(1)
43(1)
37(1)
4(1)
11(1)
1(1)
C(19)
55(1)
54(2)
43(1)
2(1)
24(1)
2(1)
C(20)
41(1)
58(2)
69(2)
2(1)
22(1)
-2(1)
C(21)
73(2)
133(3)
34(2)
-1(2)
13(2)
8(2)
C(22)
150(4)
111(4)
164(5)
-8(4)
80(5)
24(4)
C(23)
136(4)
126(4)
146(5)
-9(4)
79(4)
-8(4)
C(24)
149(4)
102(3)
150(4)
-10(3)
109(4)
-19(3)
C(25)
109(3)
211(6)
129(4)
-2(4)
81(3)
11(4)
164

x 103) for stanozolol butan-2-ol solvate.
Atom
U(eq)
H(1N1)
8930
3317
15193
73
H(1O1)
4477
5774
6431
87
H(1O2)
3963
13454
5582
122
H(1)
8118
1963
13628
61
H(3A)
7071
3725
11802
55
H(3B)
7546
4106
11473
55
H(5)
6971
6064
10093
48
H(6A)
5871
5384
10080
67
H(6B)
6319
3897
10105
67
H(7A)
6019
4639
8411
67
H(7B)
5403
4246
8392
67
H(10A)
4896
9875
6668
104
H(10B)
5422
9449
6449
104
H(11A)
6125
10619
8004
87
H(11B)
5619
10701
8300
87
H(12)
6365
7706
8487
55
H(13)
6190
8818
10068
51
H(14A)
7278
9229
9995
65
H(14B)
6875
10823
10005
65
H(15A)
7205
10169
11700
67
H(15B)
7804
10425
11655
67
H(16)
7924
7323
11638
53
H(17A)
8501
8517
13275
75
H(17B)
7911
8589
13361
75
H(19A)
6581
8131
11803
68
H(19B)
7006
6831
12739
68
H(19C)
6388
6104
11738
68
H(20A)
5249
7676
9214
79
H(20B)
4707
6664
8228
79
165
H(20C)
4854
8685
8145
79
H(21A)
5345
6412
5883
115
H(21B)
5426
4828
6621
115
H(21C)
5962
6273
7003
115
H(22A)
4546
12021
8115
189
H(22B)
4167
10876
8452
189
H(22C)
4138
12986
8458
189
H(23A)
3252
11980
7064
176
H(23B)
3632
10802
6746
176
H(24)
3720
14540
6830
155
H(25A)
2876
12855
4964
184
H(25B)
3011
14930
5138
184
H(25C)
2684
13944
5621
184
166
6) Stanozolol ethanol dihydrate solvate.
Table 8.26 Crystal data and structure refinement for stanozolol ethanol dihydrate
solvate.
Identification code
stanozolol_6
Empirical formula
C44 H74 N4 O5
Formula weight
739.07
Temperature
150(2) K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 7.3934(2)
b = 27.5812(6), = 109.234(3)
c = 10.5964(3)
Volume
2040.19(9) 3
1.203 Mg/m3
0.078 mm-1
F(000)
812
Crystal size
0.50 x 0.30 x 0.15 mm
2.9481 to 29.0073
Index ranges
-9<=h<=8; -34<=k<=21; -8<=l<=14
167
9236
5277 [Rint = 0.0197]
4629
Data Completeness
0.997
1.00000 and 0.98656
Refinement method
5277 / 7 / 505
0.980
R1 = 0.0327 wR2 = 0.0701
R1 = 0.0379 wR2 = 0.0711
0.7(8)
0.174 and -0.209 e.-3

parameters (2 x 103) for stanozolol ethanol dihydrate solvate. U(eq) is defined as
one third of the trace of the orthogonalized Uij tensor.
Atom
U(eq)
O(1)
1709(2)
823(1)
3003(1)
26(1)
O(2)
1501(2)
4871(1)
10164(1)
22(1)
O(3)
-4186(2)
5290(1)
4847(1)
26(1)
O(4)
6696(2)
524(1)
7838(2)
30(1)
O(5)
1978(2)
309(1)
823(2)
28(1)
N(1)
-1537(2)
4830(1)
2753(2)
21(1)
N(2)
-2212(3)
4670(1)
3724(2)
22(1)
N(3)
2045(3)
829(1)
8260(2)
26(1)
N(4)
3743(3)
1023(1)
8276(2)
25(1)
C(1)
-807(3)
4468(1)
2224(2)
20(1)
C(2)
-1004(3)
4049(1)
2869(2)
18(1)
C(3)
-498(3)
3531(1)
2687(2)
18(1)
C(4)
-451(3)
3215(1)
3901(2)
16(1)
C(5)
-495(3)
2672(1)
3501(2)
17(1)
C(6)
1222(3)
2518(1)
3078(2)
27(1)
168
C(7)
1023(4)
1996(1)
2538(2)
27(1)
C(8)
738(3)
1639(1)
3559(2)
19(1)
C(9)
130(3)
1115(1)
3064(2)
23(1)
C(10)
-778(4)
928(1)
4091(2)
29(1)
C(11)
-1386(3)
1376(1)
4732(2)
27(1)
C(12)
-999(3)
1802(1)
3945(2)
19(1)
C(13)
-822(3)
2314(1)
4527(2)
17(1)
C(14)
-2598(3)
2452(1)
4871(2)
23(1)
C(15)
-2555(3)
2977(1)
5306(2)
23(1)
C(16)
-2292(3)
3324(1)
4261(2)
18(1)
C(17)
-2400(3)
3853(1)
4698(2)
23(1)
C(18)
-1881(3)
4196(1)
3783(2)
18(1)
C(19)
1361(3)
3337(1)
5062(2)
22(1)
C(20)
2566(3)
1613(1)
4775(2)
27(1)
C(21)
-1294(3)
1091(1)
1644(2)
32(1)
C(22)
1025(3)
1211(1)
8421(2)
24(1)
C(23)
2050(3)
1642(1)
8547(2)
18(1)
C(24)
1584(3)
2160(1)
8737(2)
18(1)
C(25)
3407(3)
2480(1)
9197(2)
15(1)
C(26)
2822(3)
3022(1)
8990(2)
16(1)
C(27)
1500(3)
3187(1)
9766(2)
17(1)
C(28)
816(3)
3710(1)
9453(2)
18(1)
C(29)
2511(3)
4056(1)
9721(2)
15(1)
C(30)
2067(3)
4585(1)
9219(2)
18(1)
C(31)
4017(3)
4763(1)
9149(2)
24(1)
C(32)
5160(3)
4308(1)
9011(2)
22(1)
C(33)
3755(3)
3887(1)
8895(2)
17(1)
C(34)
4521(3)
3376(1)
9213(2)
15(1)
C(35)
5737(3)
3231(1)
8347(2)
19(1)
C(36)
6354(3)
2705(1)
8555(2)
20(1)
C(37)
4672(3)
2361(1)
8320(2)
17(1)
C(38)
5381(3)
1836(1)
8465(2)
22(1)
C(39)
3771(3)
1504(1)
8429(2)
20(1)
169
C(40)
4509(3)
2371(1)
10676(2)
21(1)
C(41)
3652(3)
4071(1)
11226(2)
21(1)
C(42)
499(3)
4627(1)
7865(2)
24(1)
C(43)
-4861(3)
5007(1)
5731(2)
31(1)
C(44)
-6672(4)
4740(1)
5030(2)
40(1)
Table 8.28 Bond lengths [] and angles [] for stanozolol ethanol dihydrate solvate.
Bond lengths []
O(1)-C(9)
1.438(3)
O(2)-C(30)
1.442(2)
O(3)-C(43)
1.431(3
N(1)-C(1)
1.341(3)
N(1)-N(2)
1.357(2)
N(2)-C(18)
1.330(2)
N(3)-C(22)
1.337(3
N(3)-N(4)
1.360(2)
N(4)-C(39)
1.334(3
C(1)-C(2)
1.375(3)
C(2)-C(18)
1.391(3
C(2)-C(3)
1.505(3)
C(3)-C(4)
1.544(3)
C(4)-C(19)
1.528(3)
C(4)-C(5)
1.553(3)
C(4)-C(16)
1.559(3)
C(5)-C(6)
1.539(3)
C(5)-C(13)
1.546(3)
C(6)-C(7)
1.537(3)
C(7)-C(8)
1.529(3)
C(8)-C(20)
1.531(3)
C(8)-C(12)
1.538(3)
C(8)-C(9)
1.551(3)
C(9)-C(21)
1.527(3)
C(9)-C(10)
1.544(3)
C(10)-C(11)
1.546(3)
C(11)-C(12)
1.522(3)
C(12)-C(13)
1.529(3)
C(13)-C(14)
1.522(3)
C(14)-C(15)
1.517(3)
C(15)-C(16)
1.524(3)
C(16)-C(17)
1.539(3)
C(17)-C(18)
1.493(3)
C(22)-C(23)
1.393(3)
C(23)-C(39)
1.373(3)
C(23)-C(24)
1.498(3)
C(24)-C(25)
1.550(3)
C(25)-C(40)
1.539(3)
C(25)-C(26)
1.551(3)
C(25)-C(37)
1.555(3)
C(26)-C(27)
1.539(3)
C(26)-C(34)
1.546(3)
C(27)-C(28)
1.528(3)
C(28)-C(29)
1.526(3)
C(29)-C(33)
1.535(3)
C(29)-C(41)
1.540(3)
C(29)-C(30)
1.552(3)
C(30)-C(42)
1.523(3)
C(30)-C(31)
1.548(3)
C(31)-C(32)
1.547(3)
170
C(32)-C(33)
1.536(3)
C(33)-C(34)
1.516(3)
C(34)-C(35)
1.533(3)
C(35)-C(36)
1.514(3)
C(36)-C(37)
1.518(3)
C(37)-C(38)
1.531(3)
C(38)-C(39)
1.493(3)
C(43)-C(44)
1.494(3)
Bond angles []
C(1)-N(1)-N(2)
111.95(16)
C(18)-N(2)-N(1)
104.32(16)
C(22)-N(3)-N(4)
104.22(17)
C(39)-N(4)-N(3)
111.69(18)
N(1)-C(1)-C(2)
107.20(18)
C(1)-C(2)-C(18)
104.55(18)
C(1)-C(2)-C(3)
131.57(18)
C(18)-C(2)-C(3)
123.85(18)
C(2)-C(3)-C(4)
111.59(16)
C(19)-C(4)-C(3)
108.63(17)
C(19)-C(4)-C(5)
111.45(16)
C(3)-C(4)-C(5)
108.91(15)
C(19)-C(4)-C(16)
111.39(16)
C(3)-C(4)-C(16)
108.25(16)
C(5)-C(4)-C(16)
108.13(16)
C(6)-C(5)-C(13)
111.27(16)
C(6)-C(5)-C(4)
113.68(17)
C(13)-C(5)-C(4)
114.71(16)
C(7)-C(6)-C(5)
112.38(18)
C(8)-C(7)-C(6)
111.04(17)
C(7)-C(8)-C(20)
109.66(19)
C(7)-C(8)-C(12)
108.72(16)
C(20)-C(8)-C(12)
111.89(17)
C(7)-C(8)-C(9)
116.91(17)
C(20)-C(8)-C(9)
108.58(17)
C(12)-C(8)-C(9)
100.86(17)
O(1)-C(9)-C(21)
103.78(16)
O(1)-C(9)-C(10)
113.04(17)
C(21)-C(9)-C(10)
111.2(2)
O(1)-C(9)-C(8)
112.84(17)
C(21)-C(9)-C(8)
113.75(17)
C(10)-C(9)-C(8)
102.58(17)
C(9)-C(10)-C(11)
107.38(17)
C(12)-C(11)-C(10)
104.06(17)
C(11)-C(12)-C(13)
120.00(17)
C(11)-C(12)-C(8)
104.06(16)
C(13)-C(12)-C(8)
114.20(17)
C(14)-C(13)-C(12)
111.14(17)
C(14)-C(13)-C(5)
110.92(16)
C(12)-C(13)-C(5)
108.63(15)
C(15)-C(14)-C(13)
112.15(17)
C(14)-C(15)-C(16)
111.98(16)
C(15)-C(16)-C(17)
110.17(16)
C(15)-C(16)-C(4)
112.82(16)
C(17)-C(16)-C(4)
113.09(17)
C(18)-C(17)-C(16)
110.79(16)
N(2)-C(18)-C(2)
111.98(18)
N(2)-C(18)-C(17)
124.87(18)
C(2)-C(18)-C(17)
123.14(18)
N(3)-C(22)-C(23)
111.9(2)
C(39)-C(23)-C(22)
104.21(18)
C(39)-C(23)-C(24)
122.52(18)
C(22)-C(23)-C(24)
133.3(2)
C(23)-C(24)-C(25)
111.80(17)
171
C(40)-C(25)-C(24)
108.75(16)
C(40)-C(25)-C(26)
111.27(16)
C(24)-C(25)-C(26)
109.37(16)
C(40)-C(25)-C(37)
110.27(16)
C(24)-C(25)-C(37)
108.87(15)
C(26)-C(25)-C(37)
108.26(15)
C(27)-C(26)-C(34)
111.00(16)
C(27)-C(26)-C(25)
113.95(15)
C(34)-C(26)-C(25)
114.32(16)
C(28)-C(27)-C(26)
112.71(16)
C(29)-C(28)-C(27)
110.88(17)
C(28)-C(29)-C(33)
108.32(16)
C(28)-C(29)-C(41)
110.22(16)
C(33)-C(29)-C(41)
111.84(17)
C(28)-C(29)-C(30)
117.14(17)
C(33)-C(29)-C(30)
100.86(16)
C(41)-C(29)-C(30)
108.17(16)
O(2)-C(30)-C(42)
107.95(17)
O(2)-C(30)-C(31)
110.32(16)
C(42)-C(30)-C(31)
111.28(17)
O(2)-C(30)-C(29)
110.73(16)
C(42)-C(30)-C(29)
113.85(17)
C(31)-C(30)-C(29)
102.67(17)
C(32)-C(31)-C(30)
107.07(16)
C(33)-C(32)-C(31)
104.14(16)
C(34)-C(33)-C(29)
113.92(16)
C(34)-C(33)-C(32)
119.45(17)
C(29)-C(33)-C(32)
104.03(15)
C(33)-C(34)-C(35)
111.10(16)
C(33)-C(34)-C(26)
109.13(16)
C(35)-C(34)-C(26)
110.52(16)
C(36)-C(35)-C(34)
111.75(16)
C(35)-C(36)-C(37)
112.53(17)
C(36)-C(37)-C(38)
109.87(16)
C(36)-C(37)-C(25)
113.02(16)
C(38)-C(37)-C(25)
113.15(16)
C(39)-C(38)-C(37)
109.52(17)
N(4)-C(39)-C(23)
107.99(19)
N(4)-C(39)-C(38)
126.4(2)
C(23)-C(39)-C(38)
125.65(18)
O(3)-C(43)-C(44)
113.08(19)
Table 8.29 Anisotropic displacement parameters (2 x 103) for stanozolol ethanol

dihydrate solvate. The anisotropic displacement factor exponent takes the form: -2 2
[h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
34(1)
19(1)
24(1)
-1(1)
7(1)
9(1)
O(2)
24(1)
18(1)
22(1)
-4(1)
7(1)
4(1)
O(3)
32(1)
23(1)
27(1)
-5(1)
16(1)
-2(1)
O(4)
34(1)
26(1)
30(1)
3(1)
9(1)
8(1)
O(5)
32(1)
26(1)
28(1)
-1(1)
13(1)
-2(1)
N(1)
27(1)
12(1)
25(1)
4(1)
10(1)
1(1)
N(2)
26(1)
18(1)
23(1)
0(1)
10(1)
1(1)
172
N(3)
31(1)
18(1)
32(1)
-1(1)
13(1)
-4(1)
N(4)
27(1)
16(1)
33(1)
0(1)
13(1)
3(1)
C(1)
22(1)
16(1)
21(1)
0(1)
7(1)
1(1)
C(2)
18(1)
15(1)
18(1)
-1(1)
3(1)
-1(1)
C(3)
22(1)
18(1)
16(1)
0(1)
7(1)
1(1)
C(4)
18(1)
13(1)
15(1)
1(1)
5(1)
1(1)
C(5)
18(1)
16(1)
18(1)
-1(1)
6(1)
0(1)
C(6)
39(2)
14(1)
35(1)
4(1)
25(1)
3(1)
C(7)
41(2)
17(1)
29(1)
2(1)
21(1)
4(1)
C(8)
24(1)
14(1)
20(1)
1(1)
7(1)
3(1)
C(9)
26(1)
18(1)
24(1)
3(1)
6(1)
5(1)
C(10)
35(1)
15(1)
37(1)
3(1)
13(1)
1(1)
C(11)
32(1)
18(1)
36(1)
6(1)
17(1)
0(1)
C(12)
21(1)
16(1)
20(1)
3(1)
7(1)
1(1)
C(13)
21(1)
15(1)
16(1)
2(1)
7(1)
2(1)
C(14)
26(1)
19(1)
27(1)
5(1)
15(1)
-1(1)
C(15)
28(1)
20(1)
25(1)
2(1)
16(1)
2(1)
C(16)
19(1)
17(1)
17(1)
0(1)
6(1)
0(1)
C(17)
27(1)
20(1)
24(1)
1(1)
14(1)
5(1)
C(18)
20(1)
15(1)
17(1)
0(1)
4(1)
2(1)
C(19)
23(1)
19(1)
21(1)
-1(1)
5(1)
0(1)
C(20)
24(1)
25(1)
31(1)
-2(1)
7(1)
4(1)
C(21)
37(1)
21(1)
31(1)
-5(1)
2(1)
5(1)
C(22)
24(1)
22(1)
28(1)
-1(1)
10(1)
-1(1)
C(23)
22(1)
15(1)
17(1)
0(1)
5(1)
-1(1)
C(24)
19(1)
15(1)
21(1)
0(1)
7(1)
-1(1)
C(25)
14(1)
15(1)
14(1)
2(1)
4(1)
0(1)
C(26)
15(1)
16(1)
15(1)
1(1)
4(1)
-1(1)
C(27)
16(1)
14(1)
24(1)
0(1)
10(1)
-2(1)
C(28)
17(1)
18(1)
20(1)
-1(1)
8(1)
-2(1)
C(29)
16(1)
14(1)
17(1)
0(1)
6(1)
0(1)
C(30)
22(1)
15(1)
20(1)
-1(1)
9(1)
-2(1)
C(31)
27(1)
18(1)
31(1)
0(1)
12(1)
-4(1)
173
C(32)
21(1)
20(1)
26(1)
-2(1)
10(1)
-3(1)
C(33)
18(1)
14(1)
17(1)
1(1)
5(1)
-1(1)
C(34)
14(1)
16(1)
16(1)
1(1)
6(1)
-1(1)
C(35)
14(1)
18(1)
27(1)
-1(1)
9(1)
-3(1)
C(36)
17(1)
21(1)
24(1)
1(1)
10(1)
2(1)
C(37)
16(1)
18(1)
17(1)
0(1)
4(1)
-1(1)
C(38)
22(1)
18(1)
26(1)
2(1)
9(1)
5(1)
C(39)
25(1)
15(1)
20(1)
0(1)
6(1)
1(1)
C(40)
23(1)
19(1)
19(1)
0(1)
5(1)
1(1)
C(41)
22(1)
20(1)
20(1)
-2(1)
6(1)
-1(1)
C(42)
32(1)
20(1)
19(1)
1(1)
7(1)
3(1)
C(43)
31(1)
38(1)
25(1)
0(1)
10(1)
-8(1)
C(44)
35(2)
45(2)
42(1)
-10(1)
15(1)
-12(1)

x 103) for stanozolol ethanol dihydrate solvate.
Atom
U(eq)
H(1O1)
2565
819
3757
34
H(1O2)
400(40)
5013(9)
9820(20)
36(7)
H(1O3)
-3971
5108
4277
33
H(1O4)
7280(50)
287(10)
8450(30)
86(12)
H(2O4)
6420(30)
457(11)
6981(18)
86(12)
H(1O5)
1930(40)
525(8)
1510(20)
57(9)
H(2O5)
2140(50)
487(11)
110(30)
92(12)
H(1N1)
-1573
5135
2499
27
H(1N4)
4706
853
8196
32
H(1)
-258
4496
1534
26
H(3A)
772
3521
2565
24
H(3B)
-1452
3397
1871
24
H(5)
-1643
2638
2680
23
H(6A)
1338
2742
2379
34
H(6B)
2410
2544
3857
34
H(7A)
-84
1977
1702
35
174
H(7B)
2189
1907
2328
35
H(10A)
160
731
4785
37
H(10B)
-1907
723
3642
37
H(11A)
-2760
1358
4643
35
H(11B)
-617
1402
5691
35
H(12)
-2104
1813
3092
25
H(13)
315
2326
5361
22
H(14A)
-3750
2397
4080
30
H(14B)
-2694
2239
5599
30
H(15A)
-1493
3023
6157
29
H(15B)
-3768
3055
5467
29
H(16)
-3407
3273
3427
23
H(17A)
-3715
3923
4693
29
H(17B)
-1513
3898
5621
29
H(19A)
2486
3292
4779
29
H(19B)
1458
3122
5817
29
H(19C)
1302
3675
5333
29
H(20A)
3641
1511
4489
35
H(20B)
2390
1378
5419
35
H(20C)
2839
1933
5197
35
H(21A)
-689
1217
1015
42
H(21B)
-2423
1288
1587
42
H(21C)
-1685
754
1419
42
H(22)
-245
1190
8446
31
H(24A)
927
2176
9413
23
H(24B)
697
2288
7885
23
H(26)
2041
3053
8023
20
H(27A)
373
2970
9543
23
H(27B)
2196
3157
10737
23
H(28A)
3735
8503
23
H(28B)
31
3803
10011
23
H(31A)
3820
4980
8371
32
H(31B)
4722
4944
9971
32
175
H(32A)
5549
4329
8203
29
H(32B)
6320
4268
9805
29
H(33)
2895
3882
7942
22
H(34)
5342
3361
10174
20
H(35A)
4986
3283
7394
25
H(35B)
6886
3440
8571
25
H(36A)
7239
2663
9480
26
H(36B)
7061
2621
7938
26
H(37)
3843
2404
7368
23
H(38A)
5874
1755
7728
28
H(38B)
6439
1796
9322
28
H(40A)
5722
2549
10955
27
H(40B)
4768
2022
10788
27
H(40C)
3736
2471
11225
27
H(41A)
2816
4182
11718
27
H(41B)
4734
4295
11386
27
H(41C)
4133
3745
11532
27
H(42A)
-709
4504
7933
31
H(42B)
855
4436
7202
31
H(42C)
344
4968
7588
31
H(43A)
-5078
5223
6413
40
H(43B)
-3859
4770
6201
40
H(44A)
-7670
4972
4559
52
H(44B)
-7083
4560
5685
52
H(44C)
-6450
4513
4384
52
176
7) Stanozolol isopropanol dihydrate solvate.
Table 8.31 Crystal data and structure refinement for stanozolol isopropanol dihydrate
solvate.
Identification code
stanozolol_7
Empirical formula
C24 H44 N2 O4
Formula weight
424.61
Temperature
150(2) K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 10.5093(3)
b = 7.2906(2), = 94.812(3)
c = 15.5622(5)
Volume
1188.16(6) 3
1.187 Mg/m3
0.080 mm-1
F(000)
468
Crystal size
0.80 x 0.35 x 0.15 mm
3.0803 to 29.0461
Index ranges
-9<=h<=14; -8<=k<=9; -17<=l<=20
5499
3650 [Rint = 0.0169]
3157
177
Data Completeness
0.997
1.00000 and 0.99491
Refinement method
3650 / 5 / 294
0.973
R1 = 0.0332 wR2 = 0.0733
R1 = 0.0397 wR2 = 0.0747
0.5(9)
0.196 and -0.207 e.-3

parameters (2 x 103) for stanozolol isopropanol dihydrate solvate. U(eq) is defined
as one third of the trace of the orthogonalized Uij tensor.
Atom
U(eq)
O(1)
2688(1)
528(2)
6431(1)
22(1)
O(2)
3156(1)
4152(2)
6180(1)
31(1)
O(3)
8724(1)
4522(2)
5100(1)
25(1)
O(4)
8698(1)
645(2)
4999(1)
25(1)
N(1)
2165(2)
3638(2)
13585(1)
23(1)
N(2)
1924(2)
1824(2)
13503(1)
21(1)
C(1)
2432(2)
4291(3)
12821(1)
21(1)
C(2)
2366(2)
2883(2)
12218(1)
18(1)
C(3)
2517(2)
2844(2)
11264(1)
18(1)
C(4)
2672(2)
875(2)
10917(1)
16(1)
C(5)
2331(2)
874(2)
9926(1)
16(1)
C(6)
3155(2)
2161(2)
9422(1)
21(1)
C(7)
2689(2)
2279(2)
8462(1)
21(1)
C(8)
2623(2)
376(2)
8041(1)
17(1)
C(9)
1890(2)
203(2)
7128(1)
19(1)
C(10)
1495(2)
-1839(3)
7084(1)
24(1)
C(11)
1591(2)
-2587(3)
8011(1)
25(1)
C(12)
1799(2)
-858(2)
8566(1)
18(1)
178
C(13)
2266(2)
-1057(2)
9515(1)
17(1)
C(14)
1369(2)
-2301(3)
9975(1)
22(1)
C(15)
1679(2)
-2334(3)
10942(1)
23(1)
C(16)
1699(2)
-409(2)
11325(1)
17(1)
C(17)
1896(2)
-514(2)
12312(1)
23(1)
C(18)
2055(2)
1355(2)
12679(1)
18(1)
C(19)
4048(2)
241(3)
11161(1)
22(1)
C(20)
3980(2)
-380(3)
8002(1)
24(1)
C(21)
750(2)
1480(3)
6999(1)
25(1)
C(22)
4762(2)
6465(3)
6057(1)
35(1)
C(23)
4335(2)
4550(3)
5810(1)
26(1)
C(24)
5288(2)
3117(3)
6130(1)
33(1)
Table 8.33 Bond lengths [] and angles [] for stanozolol isopropanol dihydrate
solvate.
Bond lengths []
O(1)-C(9)
1.445(2)
O(2)-C(23)
1.438(2)
N(1)-C(1)
1.332(2)
N(1)-N(2)
1.351(2)
N(2)-C(18)
1.345(2
C(1)-C(2)
1.388(3)
C(2)-C(18)
1.379(2
C(2)-C(3)
1.506(2)
C(3)-C(4)
1.547(2)
C(4)-C(19)
1.536(2)
C(4)-C(5)
1.554(2)
C(4)-C(16)
1.560(2)
C(5)-C(6)
1.536(2)
C(5)-C(13)
1.545(2)
C(6)-C(7)
1.535(2)
C(7)-C(8)
1.534(2)
C(8)-C(12)
1.532(2)
C(8)-C(20)
1.534(2)
C(8)-C(9)
1.564(2)
C(9)-C(21)
1.517(3)
C(9)-C(10)
1.545(3)
C(10)-C(11)
1.539(3)
C(11)-C(12)
1.534(2)
C(12)-C(13)
1.523(2)
C(13)-C(14)
1.529(2)
C(14)-C(15)
1.514(2)
C(15)-C(16)
1.524(2)
C(16)-C(17)
1.534(2)
C(17)-C(18)
1.482(2)
C(22)-C(23)
1.507(3)
C(23)-C(24)
1.504(3)
179
Bond angles []
C(1)-N(1)-N(2)
108.49(15)
C(18)-N(2)-N(1)
107.79(15)
N(1)-C(1)-C(2)
109.68(17)
C(18)-C(2)-C(1)
104.28(15)
C(18)-C(2)-C(3)
123.11(15)
C(1)-C(2)-C(3)
132.57(17)
C(2)-C(3)-C(4)
112.61(14)
C(19)-C(4)-C(3)
108.51(14)
C(19)-C(4)-C(5)
112.25(14)
C(3)-C(4)-C(5)
108.95(13)
C(19)-C(4)-C(16)
110.77(15)
C(3)-C(4)-C(16)
108.84(14)
C(5)-C(4)-C(16)
107.46(14)
C(6)-C(5)-C(13)
110.66(13)
C(6)-C(5)-C(4)
114.43(14)
C(13)-C(5)-C(4)
114.19(13)
C(7)-C(6)-C(5)
112.56(15)
C(8)-C(7)-C(6)
111.39(14)
C(12)-C(8)-C(7)
108.08(14)
C(12)-C(8)-C(20)
112.29(15)
C(7)-C(8)-C(20)
109.44(15)
C(12)-C(8)-C(9)
100.36(14)
C(7)-C(8)-C(9)
117.56(14)
C(20)-C(8)-C(9)
108.90(14)
O(1)-C(9)-C(21)
107.61(14)
O(1)-C(9)-C(10)
107.19(14)
C(21)-C(9)-C(10)
112.30(16)
O(1)-C(9)-C(8)
113.27(14)
C(21)-C(9)-C(8)
113.17(14)
C(10)-C(9)-C(8)
103.19(14)
C(11)-C(10)-C(9)
107.68(15)
C(12)-C(11)-C(10)
103.40(15)
C(13)-C(12)-C(8)
114.99(14)
C(13)-C(12)-C(11)
119.09(15)
C(8)-C(12)-C(11)
104.02(14)
C(12)-C(13)-C(14)
110.43(14)
C(12)-C(13)-C(5)
108.28(13)
C(14)-C(13)-C(5)
110.73(14)
C(15)-C(14)-C(13)
112.69(15)
C(14)-C(15)-C(16)
111.64(15)
C(15)-C(16)-C(17)
109.96(14)
C(15)-C(16)-C(4)
112.44(14)
C(17)-C(16)-C(4)
113.58(14)
C(18)-C(17)-C(16)
109.95(14)
N(2)-C(18)-C(2)
109.76(16)
N(2)-C(18)-C(17)
125.71(15)
C(2)-C(18)-C(17)
124.53(16)
O(2)-C(23)-C(24)
107.41(16)
O(2)-C(23)-C(22)
109.46(16)
C(24)-C(23)-C(22)
112.55(17)
180

isopropanol dihydrate solvate. The anisotropic displacement factor exponent takes
the form: -2 2 [h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
26(1)
22(1)
18(1)
2(1)
6(1)
-2(1)
O(2)
23(1)
32(1)
36(1)
10(1)
2(1)
1(1)
O(3)
31(1)
29(1)
16(1)
0(1)
3(1)
3(1)
O(4)
27(1)
24(1)
23(1)
3(1)
0(1)
-1(1)
N(1)
28(1)
23(1)
18(1)
-3(1)
3(1)
3(1)
N(2)
22(1)
22(1)
19(1)
-2(1)
1(1)
3(1)
C(1)
27(1)
18(1)
19(1)
1(1)
1(1)
0(1)
C(2)
18(1)
18(1)
17(1)
-1(1)
0(1)
1(1)
C(3)
22(1)
15(1)
16(1)
2(1)
1(1)
-4(1)
C(4)
19(1)
15(1)
15(1)
0(1)
1(1)
-1(1)
C(5)
16(1)
16(1)
17(1)
1(1)
1(1)
-2(1)
C(6)
27(1)
17(1)
17(1)
-2(1)
3(1)
-6(1)
C(7)
27(1)
18(1)
18(1)
2(1)
4(1)
-2(1)
C(8)
19(1)
16(1)
15(1)
0(1)
1(1)
0(1)
C(9)
18(1)
23(1)
17(1)
-2(1)
3(1)
1(1)
C(10)
26(1)
25(1)
21(1)
-4(1)
3(1)
-6(1)
C(11)
37(1)
19(1)
18(1)
-2(1)
3(1)
-7(1)
C(12)
19(1)
16(1)
19(1)
0(1)
3(1)
0(1)
C(13)
20(1)
15(1)
16(1)
-1(1)
2(1)
-1(1)
C(14)
30(1)
15(1)
21(1)
-2(1)
3(1)
-6(1)
C(15)
32(1)
16(1)
22(1)
2(1)
4(1)
-6(1)
C(16)
19(1)
15(1)
17(1)
1(1)
2(1)
-2(1)
C(17)
29(1)
19(1)
21(1)
0(1)
5(1)
-3(1)
C(18)
18(1)
21(1)
15(1)
0(1)
1(1)
1(1)
C(19)
22(1)
24(1)
19(1)
-1(1)
-1(1)
-1(1)
C(20)
20(1)
30(1)
21(1)
0(1)
2(1)
3(1)
C(21)
25(1)
33(1)
17(1)
-1(1)
-1(1)
4(1)
C(22)
33(1)
34(1)
39(1)
1(1)
2(1)
-3(1)
C(23)
24(1)
29(1)
24(1)
3(1)
2(1)
-2(1)
181
C(24)
27(1)
37(1)
37(1)
-1(1)
4(1)
3(1)

x 103) for stanozolol isopropanol dihydrate solvate.
Atom
U(eq)
H(1O1)
2782
1662
6366
32
H(2O2)
2542
4578
5861
46
H(1O3)
8370(30)
5230(40)
4619(16)
108(12)
H(2O3)
8530(40)
5420(40)
5546(18)
126(13)
H(1O4)
8640(30)
1930(30)
5070(20)
118(14)
H(2O4)
9600(20)
280(60)
4980(30)
165(17)
H(1N1)
2148
4281
14062
30
H(1)
2637
5531
12706
27
H(3A)
3274
3578
11145
21
H(3B)
1759
3420
10953
21
H(5)
1444
1373
9839
19
H(6A)
3143
3403
9678
25
H(6B)
4049
1719
9478
25
H(7A)
1832
2851
8400
25
H(7B)
3278
3068
8162
25
H(10A)
609
-1961
6818
28
H(10B)
2068
-2535
6730
28
H(11A)
796
-3227
8136
30
H(11B)
2319
-3445
8111
30
H(12)
947
-243
8556
21
H(13)
3141
-1608
9561
21
H(14A)
480
-1871
9846
26
H(14B)
1425
-3563
9747
26
H(15A)
2523
-2918
11076
28
H(15B)
1033
-3082
11211
28
H(16)
832
127
11180
20
H(17A)
1150
-1116
12540
27
H(17B)
2663
-1258
12484
27
182
H(19A)
4232
309
11788
32
H(19B)
4642
1037
10881
32
H(19C)
4150
-1027
10969
32
H(20A)
3938
-1595
7732
35
H(20B)
4396
-478
8587
35
H(20C)
4471
451
7661
35
H(21A)
286
1234
6439
38
H(21B)
1047
2755
7018
38
H(21C)
183
1276
7459
38
H(22A)
4939
6540
6684
53
H(22B)
4086
7339
5869
53
H(22C)
5538
6763
5778
53
H(23)
4194
4467
5168
31
H(24A)
4977
1902
5943
50
H(24B)
5401
3156
6761
50
H(24C)
6108
3358
5894
50
183
8) Stanozolol monohydrate.
Table 8.36 Crystal data and structure refinement for stanozolol monohydrate.
Identification code
stanozolol_8
Empirical formula
C21 H34 N2 O2
Formula weight
346.50
Temperature
298(2) K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P212121
a = 7.2098(5)
b = 10.4654(7)
c = 26.0313(13)
Volume
1964.2(2) 3
1.172 Mg/m3
0.075 mm-1
F(000)
760
Crystal size
0.85 x 0.15 x 0.15 mm
2.9258 to 29.1472
Index ranges
-9<=h<=7; -14<=k<=13; -32<=l<=28
10407
184
3552 [Rint = 0.0345]
2182
Data Completeness
0.998
1.00000 and 0.98416
Refinement method
3552 / 2 / 237
0.801
R1 = 0.0372 wR2 = 0.0631
R1 = 0.0720 wR2 = 0.0676
1.2(15)
0.115 and -0.159 e.-3

parameters (2 x 103) for stanozolol monohydrate. U(eq) is defined as one third of
Atom
U(eq)
O(1)
7201(2)
4126(1)
5082(1)
41(1)
O(2)
10839(3)
3497(2)
4951(1)
60(1)
N(1)
11901(3)
5089(2)
9226(1)
47(1)
N(2)
10170(3)
5583(2)
9191(1)
44(1)
C(1)
12414(3)
4919(2)
8741(1)
41(1)
C(2)
11022(3)
5290(2)
8395(1)
32(1)
C(3)
10862(3)
5256(2)
7822(1)
34(1)
C(4)
8825(3)
5255(2)
7648(1)
27(1)
C(5)
8700(3)
5538(2)
7064(1)
28(1)
C(6)
9864(3)
4624(2)
6730(1)
41(1)
C(7)
9647(3)
4853(2)
6151(1)
40(1)
C(8)
7616(3)
4811(2)
5999(1)
28(1)
C(9)
7101(3)
5188(2)
5438(1)
36(1)
C(10)
5058(3)
5575(2)
5482(1)
52(1)
C(11)
4712(3)
5968(2)
6047(1)
54(1)
C(12)
6615(3)
5866(2)
6302(1)
32(1)
185
C(13)
6690(3)
5653(2)
6879(1)
28(1)
C(14)
5725(3)
6736(2)
7166(1)
45(1)
C(15)
5823(3)
6538(2)
7745(1)
49(1)
C(16)
7795(3)
6339(2)
7937(1)
35(1)
C(17)
7780(3)
6167(2)
8524(1)
46(1)
C(18)
9610(3)
5707(2)
8701(1)
35(1)
C(19)
7982(3)
3950(2)
7780(1)
41(1)
C(20)
6814(3)
3487(2)
6107(1)
46(1)
C(21)
8279(3)
6261(2)
5218(1)
57(1)
Table 8.38 Bond lengths [] and angles [] for stanozolol monohydrate.

Bond lengths []
O(1)-C(9)
1.449(2)
N(1)-C(1)
1.329(2)
N(1)-N(2)
1.354(2)
N(2)-C(18)
1.346(2)
C(1)-C(2)
1.403(3)
C(2)-C(18)
1.364(3)
C(2)-C(3)
1.495(2)
C(3)-C(4)
1.537(2)
C(4)-C(19)
1.534(3
C(4)-C(5)
1.549(2)
C(4)-C(16)
1.551(3)
C(5)-C(13)
1.533(3)
C(5)-C(6)
1.543(2)
C(6)-C(7)
1.534(2)
C(7)-C(8)
1.518(2)
C(8)-C(20)
1.527(3)
C(8)-C(12)
1.537(3
C(8)-C(9)
1.558(2)
C(9)-C(21)
1.519(3)
C(9)-C(10)
1.532(2)
C(10)-C(11)
1.549(3)
C(11)-C(12)
1.528(3)
C(12)-C(13)
1.519(2)
C(13)-C(14)
1.526(2)
C(14)-C(15)
1.523(2)
C(15)-C(16)
1.521(2)
C(16)-C(17)
1.538(2)
C(17)-C(18)
1.477(3)
Bond angles []
C(1)-N(1)-N(2)
104.10(16)
C(18)-N(2)-N(1)
112.19(16)
N(1)-C(1)-C(2)
111.98(19)
C(18)-C(2)-C(1)
104.36(15)
C(18)-C(2)-C(3)
122.09(19)
C(1)-C(2)-C(3)
133.51(19)
C(2)-C(3)-C(4)
111.63(15)
C(19)-C(4)-C(3)
108.21(18)
C(19)-C(4)-C(5)
111.58(15)
C(3)-C(4)-C(5)
110.18(15)
186
C(19)-C(4)-C(16)
110.61(15)
C(3)-C(4)-C(16)
108.25(16)
C(5)-C(4)-C(16)
107.96(15)
C(13)-C(5)-C(6)
112.63(14)
C(13)-C(5)-C(4)
112.28(14)
C(6)-C(5)-C(4)
113.77(15)
C(7)-C(6)-C(5)
113.70(17)
C(8)-C(7)-C(6)
110.51(15)
C(7)-C(8)-C(20)
110.10(19)
C(7)-C(8)-C(12)
107.33(16)
C(20)-C(8)-C(12)
112.32(16)
C(7)-C(8)-C(9)
117.85(16)
C(20)-C(8)-C(9)
108.20(15)
C(12)-C(8)-C(9)
100.79(15)
O(1)-C(9)-C(21)
107.43(15)
O(1)-C(9)-C(10)
107.38(16)
C(21)-C(9)-C(10)
111.74(19)
O(1)-C(9)-C(8)
113.09(16)
C(21)-C(9)-C(8)
113.97(17)
C(10)-C(9)-C(8)
103.07(15)
C(9)-C(10)-C(11)
107.22(16)
C(12)-C(11)-C(10)
104.45(16)
C(13)-C(12)-C(11)
118.10(15)
C(13)-C(12)-C(8)
112.68(16)
C(11)-C(12)-C(8)
104.39(15)
C(12)-C(13)-C(14)
111.11(16)
C(12)-C(13)-C(5)
110.91(14)
C(14)-C(13)-C(5)
109.54(15)
C(15)-C(14)-C(13)
111.33(17)
C(16)-C(15)-C(14)
112.77(17)
C(15)-C(16)-C(17)
109.60(15)
C(15)-C(16)-C(4)
112.86(16)
C(17)-C(16)-C(4)
113.60(16)
C(18)-C(17)-C(16)
109.92(15)
N(2)-C(18)-C(2)
107.37(18)
N(2)-C(18)-C(17)
126.50(18)
C(2)-C(18)-C(17)
126.10(16)

monohydrate. The anisotropic displacement factor exponent takes the form: -2 2 [h2
a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
40(1)
52(1)
31(1)
-8(1)
-3(1)
1(1)
O(2)
63(1)
57(1)
60(1)
-2(1)
28(1)
4(1)
N(1)
46(1)
61(1)
33(1)
2(1)
-4(1)
-1(1)
N(2)
43(1)
61(2)
27(1)
-4(1)
5(1)
-2(1)
C(1)
37(2)
57(2)
30(1)
-2(1)
4(1)
1(1)
C(2)
28(1)
41(1)
28(1)
-1(1)
0(1)
-4(1)
C(3)
33(1)
45(1)
26(1)
-1(1)
2(1)
2(1)
C(4)
29(1)
27(1)
25(1)
-3(1)
0(1)
-2(1)
C(5)
27(1)
29(1)
27(1)
-3(1)
2(1)
-2(1)
187
C(6)
34(1)
62(2)
27(1)
-10(1)
-4(1)
11(1)
C(7)
33(1)
60(2)
28(1)
-8(1)
1(1)
7(1)
C(8)
31(1)
32(1)
22(1)
1(1)
1(1)
1(1)
C(9)
43(2)
39(1)
27(1)
-1(1)
-1(1)
3(1)
C(10)
49(2)
74(2)
34(1)
-5(1)
-8(1)
19(1)
C(11)
45(2)
78(2)
38(1)
-7(1)
-10(1)
21(2)
C(12)
35(2)
33(1)
29(1)
-2(1)
-2(1)
7(1)
C(13)
25(1)
33(1)
27(1)
-4(1)
1(1)
3(1)
C(14)
41(2)
57(2)
38(1)
-10(1)
-6(1)
23(1)
C(15)
37(2)
68(2)
40(1)
-15(1)
-1(1)
19(1)
C(16)
34(2)
39(1)
30(1)
-8(1)
1(1)
3(1)
C(17)
38(2)
68(2)
31(1)
-11(1)
1(1)
6(1)
C(18)
35(2)
47(2)
23(1)
-2(1)
-4(1)
-7(1)
C(19)
47(2)
41(1)
36(1)
2(1)
0(1)
-8(1)
C(20)
67(2)
40(1)
32(1)
-1(1)
-2(1)
-4(1)
C(21)
87(2)
49(2)
35(1)
10(1)
0(1)
-7(2)

x 103) for stanozolol monohydrate.
Atom
U(eq)
H(1O1)
8282
3892
5054
53
H(1O2)
11450(40)
4080(30)
4744(9)
126(13)
H(2O2)
11040(40)
2630(20)
4870(12)
144(15)
H(2N2)
9506
5792
9452
57
H(1)
13560
4593
8642
54
H(3A)
11473
4496
7693
45
H(3B)
11487
5995
7678
45
H(5)
9250
6387
7018
36
H(6A)
11161
4719
6821
53
H(6B)
9505
3751
6807
53
H(7A)
10164
5680
6062
52
H(7B)
10325
4204
5963
52
H(10A)
4263
4864
5388
68
188
H(10B)
4792
6285
5254
68
H(11A)
4241
6834
6067
70
H(11B)
3831
5396
6209
70
H(12)
7271
6667
6232
42
H(13)
6045
4853
6957
37
H(14A)
6309
7541
7078
59
H(14B)
4437
6778
7060
59
H(15A)
5295
7278
7916
63
H(15B)
5080
5800
7837
63
H(16)
8474
7131
7867
45
H(17A)
7494
6975
8688
59
H(17B)
6829
5556
8619
59
H(19A)
8256
3743
8132
53
H(19B)
8501
3309
7559
53
H(19C)
6663
3981
7733
53
H(20A)
7543
2853
5933
60
H(20B)
5558
3450
5985
60
H(20C)
6837
3326
6470
60
H(21A)
9552
5994
5204
74
H(21B)
8174
7002
5434
74
H(21C)
7856
6466
4878
74
189
9) Stanozolol acetic acid solvate.
Table 8.41 Crystal data and structure refinement for stanozolol acetic acid solvate.
Identification code
stanozolol_9
Empirical formula
C25 H40 N2 O5
Formula weight
448.59
Temperature
298(2) K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 10.3775(8)
b = 7.4347(6), = 91.895(6)
c = 15.5801(8)
Volume
1201.40(14) 3
1.240 Mg/m3
0.086 mm-1
F(000)
488
Crystal size
0.45 x 0.10 x 0.05 mm
3.2136 to 29.1114
Index ranges
-13<=h<=13; -7<=k<=10; -19<=l<=12
5253
3275 [Rint = 0.0395]
1872
Data Completeness
0.971
190
1.00000 and 0.98722
Refinement method
3275 / 1 / 294
0.875
R1 = 0.0504 wR2 = 0.0824
R1 = 0.0921 wR2 = 0.0900
1.0(17)
0.196 and -0.179 e.-3

parameters (2 x 103) for stanozolol acetic acid solvate. U(eq) is defined as one third
Atom
U(eq)
O(1)
403(2)
1581(4)
1416(1)
50(1)
O(2)
-676(3)
-1558(4)
1598(2)
63(1)
O(3)
-464(3)
-1867(4)
217(2)
66(1)
O(4)
5681(3)
-874(4)
9848(2)
59(1)
O(5)
6047(3)
3(4)
11177(1)
65(1)
N(1)
4650(3)
108(5)
8176(2)
47(1)
N(2)
4681(3)
1914(5)
8041(2)
43(1)
C(1)
4123(4)
-788(6)
7510(2)
41(1)
C(2)
3788(3)
467(6)
6896(2)
36(1)
C(3)
3181(4)
284(5)
6005(2)
34(1)
C(4)
2658(3)
2109(5)
5660(2)
28(1)
C(5)
2522(3)
1975(5)
4653(2)
28(1)
C(6)
1601(4)
496(5)
4336(2)
36(1)
C(7)
1599(4)
284(5)
3350(2)
37(1)
C(8)
1266(4)
2045(6)
2898(2)
31(1)
C(9)
1532(4)
2157(6)
1924(2)
37(1)
C(10)
1743(4)
4194(5)
1761(2)
42(1)
C(11)
1985(4)
5086(5)
2648(2)
44(1)
C(12)
2210(3)
3475(5)
3243(2)
31(1)
191
C(13)
2193(4)
3783(5)
4215(2)
29(1)
C(14)
3152(4)
5232(5)
4476(2)
38(1)
C(15)
3329(4)
5391(5)
5447(2)
39(1)
C(16)
3674(4)
3592(5)
5861(2)
32(1)
C(17)
3940(4)
3874(5)
6831(2)
44(1)
C(18)
4146(3)
2119(6)
7252(2)
37(1)
C(19)
1376(3)
2524(5)
6067(2)
40(1)
C(20)
-149(3)
2558(6)
3048(2)
45(1)
C(21)
2666(4)
1059(6)
1640(2)
59(1)
C(22)
-889(4)
-2408(6)
882(2)
43(1)
C(23)
-1670(4)
-4078(6)
937(3)
55(1)
C(24)
6952(4)
1764(6)
10114(2)
61(1)
C(25)
6166(4)
183(6)
10344(2)
42(1)
Table 8.43 Bond lengths [] and angles [] for stanozolol acetic acid solvate.
Bond lengths []
O(1)-C(9)
1.456(4)
O(2)-C(22)
1.293(4)
O(3)-C(22)
1.209(4)
O(4)-C(25)
1.202(4)
O(5)-C(25)
1.313(4
N(1)-C(1)
1.335(4)
N(1)-N(2)
1.359(4)
N(2)-C(18)
1.342(4)
C(1)-C(2)
1.374(5)
C(2)-C(18)
1.393(5)
C(2)-C(3)
1.512(4)
C(3)-C(4)
1.551(5)
C(4)-C(19)
1.525(4)
C(4)-C(16)
1.550(5)
C(4)-C(5)
1.573(4)
C(5)-C(6)
1.528(5)
C(5)-C(13)
1.541(5
C(6)-C(7)
1.544(4)
C(7)-C(8)
1.522(5)
C(8)-C(12)
1.531(5)
C(8)-C(20)
1.542(5
C(8)-C(9)
1.553(4)
C(9)-C(21)
1.511(5)
C(9)-C(10)
1.553(5)
C(10)-C(11)
1.547(4)
C(11)-C(12)
1.527(5)
C(12)-C(13)
1.534(4)
C(13)-C(14)
1.512(5)
C(14)-C(15)
1.523(4)
C(15)-C(16)
1.522(5)
C(16)-C(17)
1.542(4)
C(17)-C(18)
1.472(5)
C(22)-C(23)
1.487(5)
C(24)-C(25)
1.482(5)
192
Bond angles []
C(1)-N(1)-N(2)
112.6(3)
C(18)-N(2)-N(1)
104.1(3)
N(1)-C(1)-C(2)
106.9(4)
C(1)-C(2)-C(18)
105.3(3)
C(1)-C(2)-C(3)
131.9(4)
C(18)-C(2)-C(3)
122.9(4)
C(2)-C(3)-C(4)
111.7(3)
C(19)-C(4)-C(16)
111.7(3)
C(19)-C(4)-C(3)
109.4(3)
C(16)-C(4)-C(3)
108.9(3)
C(19)-C(4)-C(5)
112.1(3)
C(16)-C(4)-C(5)
106.5(3)
C(3)-C(4)-C(5)
108.0(3)
C(6)-C(5)-C(13)
111.0(3)
C(6)-C(5)-C(4)
113.8(3)
C(13)-C(5)-C(4)
113.4(3)
C(5)-C(6)-C(7)
112.1(3)
C(8)-C(7)-C(6)
111.5(3)
C(7)-C(8)-C(12)
107.5(3)
C(7)-C(8)-C(20)
110.2(3)
C(12)-C(8)-C(20)
112.1(3)
C(7)-C(8)-C(9)
117.0(3)
C(12)-C(8)-C(9)
100.0(3)
C(20)-C(8)-C(9)
109.6(3)
O(1)-C(9)-C(21)
107.6(3)
O(1)-C(9)-C(10)
108.3(3)
C(21)-C(9)-C(10)
111.4(4)
O(1)-C(9)-C(8)
110.5(3)
C(21)-C(9)-C(8)
114.9(3)
C(10)-C(9)-C(8)
104.0(3)
C(11)-C(10)-C(9)
106.9(3)
C(12)-C(11)-C(10)
102.9(3)
C(11)-C(12)-C(8)
104.4(3)
C(11)-C(12)-C(13)
118.4(3)
C(8)-C(12)-C(13)
115.0(3)
C(14)-C(13)-C(12)
110.1(3)
C(14)-C(13)-C(5)
111.6(3)
C(12)-C(13)-C(5)
107.3(3)
C(13)-C(14)-C(15)
112.3(3)
C(16)-C(15)-C(14)
111.8(3)
C(15)-C(16)-C(17)
109.1(3)
C(15)-C(16)-C(4)
113.0(3)
C(17)-C(16)-C(4)
113.1(3)
C(18)-C(17)-C(16)
109.5(3)
N(2)-C(18)-C(2)
111.2(4)
N(2)-C(18)-C(17)
124.0(4)
C(2)-C(18)-C(17)
124.8(3)
O(3)-C(22)-O(2)
121.3(4)
O(3)-C(22)-C(23)
122.8(4)
O(2)-C(22)-C(23)
115.8(3)
O(4)-C(25)-O(5)
121.2(4)
O(4)-C(25)-C(24)
125.8(3)
O(5)-C(25)-C(24)
113.0(4)
193
Table 8.44 Anisotropic displacement parameters (2 x 103) for stanozolol acetic acid
U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
56(2)
51(2)
42(1)
3(2)
-13(1)
-15(2)
O(2)
85(2)
76(2)
28(1)
-8(2)
3(1)
-22(2)
O(3)
94(3)
69(2)
34(2)
-13(2)
1(2)
-28(2)
O(4)
76(2)
65(2)
35(2)
5(2)
-6(1)
-15(2)
O(5)
97(3)
66(2)
30(2)
1(2)
-1(1)
-24(2)
N(1)
50(2)
63(3)
28(2)
3(2)
-6(2)
6(2)
N(2)
50(2)
48(2)
31(2)
-3(2)
-3(2)
-1(2)
C(1)
50(3)
39(3)
33(2)
-1(2)
-1(2)
6(2)
C(2)
33(3)
42(3)
33(2)
-2(2)
2(2)
5(2)
C(3)
39(3)
30(2)
31(2)
-4(2)
2(2)
3(2)
C(4)
30(2)
27(2)
26(2)
-1(2)
0(2)
-2(2)
C(5)
33(2)
25(2)
26(2)
-1(2)
3(2)
-2(2)
C(6)
45(3)
34(3)
29(2)
2(2)
-3(2)
-4(2)
C(7)
46(3)
31(3)
33(2)
-6(2)
-3(2)
-7(2)
C(8)
34(2)
30(2)
28(2)
3(2)
1(2)
-4(2)
C(9)
33(3)
49(3)
30(2)
0(2)
0(2)
-4(2)
C(10)
41(3)
50(3)
34(2)
6(2)
-1(2)
-8(2)
C(11)
55(3)
36(3)
40(2)
7(2)
-2(2)
-8(2)
C(12)
33(2)
33(3)
26(2)
-1(2)
0(2)
-2(2)
C(13)
28(2)
27(3)
32(2)
-1(2)
2(2)
1(2)
C(14)
42(3)
31(2)
40(2)
2(2)
-1(2)
-5(2)
C(15)
54(3)
28(3)
36(2)
-5(2)
-2(2)
-4(2)
C(16)
30(2)
31(3)
34(2)
-9(2)
-2(2)
1(2)
C(17)
57(3)
43(3)
32(2)
-3(2)
-10(2)
-2(2)
C(18)
42(3)
46(3)
23(2)
-4(2)
0(2)
-1(2)
C(19)
43(3)
45(3)
33(2)
-1(2)
5(2)
7(2)
C(20)
44(3)
56(3)
34(2)
-1(2)
-2(2)
-4(2)
C(21)
71(4)
70(4)
37(2)
-5(2)
6(2)
11(3)
C(22)
45(3)
54(3)
30(2)
2(2)
1(2)
5(2)
194
C(23)
49(3)
48(3)
70(3)
1(2)
8(2)
-10(3)
C(24)
67(3)
54(3)
63(3)
6(3)
14(2)
-9(3)
C(25)
43(3)
46(3)
36(2)
4(3)
-4(2)
8(3)

x 103) for stanozolol acetic acid solvate.
Atom
U(eq)
H(1O1)
273
508
1499
65
H(1O3)
-708
-2525
-178
86
H(1O5)
5621
-899
11273
84
H(1N1)
4939
-401
8640
61
H(1)
4005
-2026
7470
53
H(3A)
2480
-577
6018
44
H(3B)
3818
-175
5618
44
H(5)
3375
1636
4457
36
H(6A)
735
779
4510
47
H(6B)
1853
-635
4603
47
H(7A)
2444
-116
3180
48
H(7B)
976
-628
3174
48
H(10A)
2478
4376
1402
54
H(10B)
987
4713
1473
54
H(11A)
2735
5864
2648
57
H(11B)
1242
5780
2816
57
H(12)
3074
3025
3125
40
H(13)
1327
4160
4372
38
H(14A)
2856
6377
4245
49
H(14B)
3977
4962
4231
49
H(15A)
4008
6252
5582
51
H(15B)
2539
5838
5685
51
H(16)
4485
3194
5616
41
H(17A)
4699
4621
6922
57
H(17B)
3214
4481
7079
57
H(19A)
1480
2456
6681
52
195
H(19B)
741
1664
5872
52
H(19C)
1100
3712
5905
52
H(20A)
-352
3662
2753
58
H(20B)
-269
2712
3652
58
H(20C)
-707
1620
2832
58
H(21A)
2819
1305
1048
77
H(21B)
2482
-197
1709
77
H(21C)
3418
1371
1984
77
H(23A)
-1349
-4961
549
72
H(23B)
-2554
-3814
786
72
H(23C)
-1612
-4538
1513
72
H(24A)
6663
2212
9562
80
H(24B)
7841
1417
10091
80
H(24C)
6862
2688
10538
80
196
10) Stanozolol formamide solvate.
Table 8.46 Crystal data and structure refinement for stanozolol formamide solvate.
Identification code
stanozolol_10
Empirical formula
C43 H64 N5 O3
Formula weight
698.99
Temperature
293(2) K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P212121
a = 7.5672(3)
b = 19.6475(9)
c = 26.3375(9)
Volume
3915.8(3) 3
4
197
1.186 Mg/m3
0.075 mm-1
F(000)
1524
Crystal size
0.50 x 0.40 x 0.20 mm
2.9805 to 28.9672
Index ranges
-8<=h<=10; -26<=k<=19; -32<=l<=32
14471
6840 [Rint = 0.0264]
4211
Data Completeness
0.998
1.00000 and 0.99372
Refinement method
6840 / 0 / 466
0.909
R1 = 0.0476 wR2 = 0.1086
R1 = 0.0852 wR2 = 0.1176
1.3(17)
0.395 and -0.206 e.-3

parameters (2 x 103) for stanozolol formamide solvate. U(eq) is defined as one third
Atom
U(eq)
O(1)
5892(3)
5744(1)
-203(1)
59(1)
O(2)
774(3)
4012(1)
3889(1)
55(1)
O(3)
6025(5)
-330(2)
1107(2)
148(2)
N(1)
8413(3)
6434(2)
3976(1)
58(1)
N(2)
6625(3)
6476(1)
3957(1)
50(1)
N(3)
3272(4)
3412(2)
-367(1)
65(1)
N(4)
1503(3)
3376(1)
-291(1)
54(1)
N(5)
3831(5)
-41(2)
609(1)
96(1)
C(1)
9162(4)
6355(2)
3518(1)
51(1)
198
C(2)
7801(4)
6342(2)
3170(1)
42(1)
C(3)
7801(3)
6280(2)
2603(1)
40(1)
C(4)
5984(3)
6057(1)
2399(1)
30(1)
C(5)
5908(3)
6209(1)
1820(1)
31(1)
C(6)
7362(3)
5842(2)
1513(1)
44(1)
C(7)
7357(3)
6033(2)
944(1)
44(1)
C(8)
5538(3)
5907(2)
712(1)
33(1)
C(9)
5202(4)
6205(2)
171(1)
47(1)
C(10)
3173(4)
6245(2)
150(1)
53(1)
C(11)
2495(4)
6255(2)
700(1)
46(1)
C(12)
4162(3)
6297(1)
1023(1)
32(1)
C(13)
4080(3)
6094(1)
1580(1)
30(1)
C(14)
2689(3)
6503(2)
1862(1)
40(1)
C(15)
2701(3)
6373(2)
2433(1)
41(1)
C(16)
4528(3)
6491(2)
2663(1)
32(1)
C(17)
4466(3)
6382(2)
3243(1)
41(1)
C(18)
6286(3)
6407(2)
3461(1)
40(1)
C(19)
5704(4)
5297(1)
2513(1)
42(1)
C(20)
5170(3)
5135(2)
699(1)
43(1)
C(21)
6033(5)
6898(2)
86(1)
77(1)
C(22)
3919(4)
3421(2)
100(1)
56(1)
C(23)
2640(4)
3399(2)
473(1)
43(1)
C(24)
2689(3)
3417(2)
1041(1)
40(1)
C(25)
894(3)
3646(1)
1267(1)
32(1)
C(26)
895(3)
3481(2)
1845(1)
34(1)
C(27)
2372(3)
3835(2)
2138(1)
47(1)
C(28)
2386(3)
3649(2)
2705(1)
47(1)
C(29)
608(3)
3801(2)
2951(1)
35(1)
C(30)
296(3)
3529(2)
3499(1)
42(1)
C(31)
-1733(3)
3447(2)
3532(1)
48(1)
C(32)
-2465(4)
3478(2)
2987(1)
41(1)
C(33)
-811(3)
3410(1)
2655(1)
33(1)
C(34)
-926(3)
3596(1)
2096(1)
31(1)
199
C(35)
-2326(3)
3182(2)
1824(1)
42(1)
C(36)
-2390(3)
3330(2)
1258(1)
43(1)
C(37)
-599(3)
3233(1)
1004(1)
37(1)
C(38)
-704(4)
3370(2)
432(1)
45(1)
C(39)
1073(4)
3375(2)
208(1)
41(1)
C(40)
648(4)
4412(1)
1169(1)
45(1)
C(41)
266(4)
4574(2)
2943(1)
48(1)
C(42)
1240(5)
2865(2)
3614(1)
66(1)
C(43)
5062(7)
-496(4)
813(2)
143(3)
Table 8.48 Bond lengths [] and angles [] for stanozolol formamide solvate.
Bond lengths []
O(1)-C(9)
1.437(4)
O(2)-C(30)
1.444(3)
O(3)-C(43)
1.113(5
N(1)-C(1)
1.341(4)
N(1)-N(2)
1.356(3)
N(2)-C(18)
1.338(3)
N(3)-C(22)
1.324(4
N(3)-N(4)
1.355(3)
N(4)-C(39)
1.355(3)
N(5)-C(43)
1.398(8)
C(1)-C(2)
1.378(4)
C(2)-C(18)
1.385(4)
C(2)-C(3)
1.500(3)
C(3)-C(4)
1.540(4)
C(4)-C(19)
1.537(4
C(4)-C(5)
1.555(3)
C(4)-C(16)
1.556(3)
C(5)-C(13)
1.537(3)
C(5)-C(6)
1.544(3)
C(6)-C(7)
1.543(3)
C(7)-C(8)
1.526(3)
C(8)-C(12)
1.531(4)
C(8)-C(20)
1.543(4
C(8)-C(9)
1.561(4)
C(9)-C(21)
1.516(4)
C(9)-C(10)
1.538(4)
C(10)-C(11)
1.536(4)
C(11)-C(12)
1.524(4)
C(12)-C(13)
1.521(3)
C(13)-C(14)
1.517(3)
C(14)-C(15)
1.525(3)
C(15)-C(16)
1.527(4)
C(16)-C(17)
1.545(3)
C(17)-C(18)
1.494(4)
C(22)-C(23)
1.379(4)
C(23)-C(39)
1.376(4)
C(23)-C(24)
1.498(4)
C(24)-C(25)
1.549(3)
C(25)-C(40)
1.537(4)
C(25)-C(37)
1.553(4)
C(25)-C(26)
1.557(3)
C(26)-C(27)
1.527(4)
200
C(26)-C(34)
1.545(3)
C(27)-C(28)
1.536(4)
C(28)-C(29)
1.522(4)
C(29)-C(33)
1.533(4)
C(29)-C(41)
1.541(4)
C(29)-C(30)
1.559(4)
C(30)-C(42)
1.517(4)
C(30)-C(31)
1.546(4)
C(31)-C(32)
1.541(4)
C(32)-C(33)
1.532(4)
C(33)-C(34)
1.519(3)
C(34)-C(35)
1.516(4)
C(35)-C(36)
1.520(3)
C(36)-C(37)
1.523(4)
C(37)-C(38)
1.532(3)
C(38)-C(39)
1.469(4)
Bond angles []
C(1)-N(1)-N(2)
113.3(2)
C(18)-N(2)-N(1)
102.7(2)
C(22)-N(3)-N(4)
103.3(3)
C(39)-N(4)-N(3)
112.3(2)
N(1)-C(1)-C(2)
106.5(3)
C(1)-C(2)-C(18)
104.4(2)
C(1)-C(2)-C(3)
131.6(3)
C(18)-C(2)-C(3)
124.0(2)
C(2)-C(3)-C(4)
111.8(2)
C(19)-C(4)-C(3)
109.3(2)
C(19)-C(4)-C(5)
111.9(2)
C(3)-C(4)-C(5)
108.7(2)
C(19)-C(4)-C(16)
110.3(2)
C(3)-C(4)-C(16)
108.7(2)
C(5)-C(4)-C(16)
107.9(2)
C(13)-C(5)-C(6)
110.97(19)
C(13)-C(5)-C(4)
114.06(19)
C(6)-C(5)-C(4)
113.4(2)
C(7)-C(6)-C(5)
113.1(2)
C(8)-C(7)-C(6)
110.6(2)
C(7)-C(8)-C(12)
108.5(2)
C(7)-C(8)-C(20)
109.4(2)
C(12)-C(8)-C(20)
112.4(2)
C(7)-C(8)-C(9)
116.9(2)
C(12)-C(8)-C(9)
101.0(2)
C(20)-C(8)-C(9)
108.6(2)
O(1)-C(9)-C(21)
108.3(3)
O(1)-C(9)-C(10)
111.8(3)
C(21)-C(9)-C(10)
111.3(3)
O(1)-C(9)-C(8)
109.2(2)
C(21)-C(9)-C(8)
113.8(3)
C(10)-C(9)-C(8)
102.3(2)
C(11)-C(10)-C(9)
107.5(2)
C(12)-C(11)-C(10)
104.6(2)
C(13)-C(12)-C(11)
119.4(2)
C(13)-C(12)-C(8)
114.4(2)
C(11)-C(12)-C(8)
103.68(19)
C(14)-C(13)-C(12)
111.2(2)
C(14)-C(13)-C(5)
110.2(2)
C(12)-C(13)-C(5)
108.68(19)
C(13)-C(14)-C(15)
112.9(2)
C(14)-C(15)-C(16)
111.8(2)
C(15)-C(16)-C(17)
110.1(2)
C(15)-C(16)-C(4)
112.4(2)
C(17)-C(16)-C(4)
112.8(2)
C(18)-C(17)-C(16)
110.4(2)
201
N(2)-C(18)-C(2)
113.0(2)
N(2)-C(18)-C(17)
123.8(2)
C(2)-C(18)-C(17)
123.2(2)
N(3)-C(22)-C(23)
113.6(3)
C(39)-C(23)-C(22)
104.2(2)
C(39)-C(23)-C(24)
121.9(2)
C(22)-C(23)-C(24)
133.9(3)
C(23)-C(24)-C(25)
111.6(2)
C(40)-C(25)-C(24)
109.1(2)
C(40)-C(25)-C(37)
110.4(2)
C(24)-C(25)-C(37)
108.4(2)
C(40)-C(25)-C(26)
111.6(2)
C(24)-C(25)-C(26)
108.3(2)
C(37)-C(25)-C(26)
109.0(2)
C(27)-C(26)-C(34)
111.7(2)
C(27)-C(26)-C(25)
113.6(2)
C(34)-C(26)-C(25)
112.8(2)
C(26)-C(27)-C(28)
112.8(2)
C(29)-C(28)-C(27)
111.1(2)
C(28)-C(29)-C(33)
107.8(2)
C(28)-C(29)-C(41)
109.6(2)
C(33)-C(29)-C(41)
111.6(2)
C(28)-C(29)-C(30)
117.5(2)
C(33)-C(29)-C(30)
101.2(2)
C(41)-C(29)-C(30)
109.0(2)
O(2)-C(30)-C(42)
107.8(2)
O(2)-C(30)-C(31)
106.1(2)
C(42)-C(30)-C(31)
111.5(3)
O(2)-C(30)-C(29)
113.3(2)
C(42)-C(30)-C(29)
114.0(2)
C(31)-C(30)-C(29)
103.8(2)
C(32)-C(31)-C(30)
107.5(2)
C(33)-C(32)-C(31)
103.6(2)
C(34)-C(33)-C(32)
119.0(2)
C(34)-C(33)-C(29)
114.4(2)
C(32)-C(33)-C(29)
103.8(2)
C(35)-C(34)-C(33)
111.7(2)
C(35)-C(34)-C(26)
110.0(2)
C(33)-C(34)-C(26)
109.2(2)
C(34)-C(35)-C(36)
112.5(2)
C(35)-C(36)-C(37)
112.2(2)
C(36)-C(37)-C(38)
111.2(2)
C(36)-C(37)-C(25)
112.7(2)
C(38)-C(37)-C(25)
112.6(2)
C(39)-C(38)-C(37)
110.4(2)
N(4)-C(39)-C(23)
106.5(2)
N(4)-C(39)-C(38)
127.6(2)
C(23)-C(39)-C(38)
125.8(2)
O(3)-C(43)-N(5)
121.1(8)
Table 8.49 Anisotropic displacement parameters (2 x 103) for stanozolol formamide

U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
67(1)
81(2)
30(1)
-4(1)
1(1)
15(1)
O(2)
59(1)
75(2)
33(1)
-14(1)
1(1)
-12(1)
O(3)
109(3)
204(5)
132(3)
15(3)
13(2)
35(3)
202
N(1)
64(2)
77(2)
34(2)
6(2)
-21(1)
-17(2)
N(2)
57(2)
66(2)
27(1)
-2(1)
-11(1)
-5(1)
N(3)
67(2)
83(2)
44(2)
2(2)
19(1)
6(2)
N(4)
59(2)
68(2)
35(2)
-1(1)
0(1)
7(1)
N(5)
80(2)
98(3)
110(3)
-2(2)
-36(2)
-1(2)
C(1)
51(2)
63(2)
40(2)
3(2)
-10(2)
-11(2)
C(2)
42(2)
49(2)
34(2)
2(1)
-10(1)
-8(1)
C(3)
34(2)
57(2)
28(2)
-2(1)
-4(1)
0(1)
C(4)
29(1)
35(2)
26(1)
-3(1)
-6(1)
2(1)
C(5)
29(1)
35(2)
27(1)
0(1)
-2(1)
-2(1)
C(6)
29(1)
67(2)
35(2)
-9(2)
-2(1)
3(2)
C(7)
37(2)
62(2)
33(2)
-4(2)
5(1)
-8(2)
C(8)
31(1)
43(2)
26(2)
-1(1)
-2(1)
-1(1)
C(9)
56(2)
52(2)
34(2)
1(2)
0(1)
-2(2)
C(10)
57(2)
70(3)
32(2)
-1(2)
-11(1)
13(2)
C(11)
45(2)
57(2)
37(2)
-4(2)
-3(1)
12(2)
C(12)
36(1)
31(2)
29(1)
0(1)
-3(1)
2(1)
C(13)
27(1)
34(2)
30(1)
-1(1)
-1(1)
-1(1)
C(14)
32(2)
52(2)
35(2)
-4(1)
-7(1)
10(2)
C(15)
33(1)
58(2)
32(2)
-5(1)
-4(1)
8(1)
C(16)
34(1)
37(2)
27(2)
0(1)
-2(1)
6(1)
C(17)
46(2)
49(2)
28(2)
-3(1)
3(1)
7(2)
C(18)
45(2)
45(2)
29(2)
1(1)
-6(1)
-2(1)
C(19)
49(2)
40(2)
36(2)
-1(1)
-7(1)
6(2)
C(20)
49(2)
45(2)
36(2)
-5(1)
-2(1)
3(1)
C(21)
120(3)
65(3)
46(2)
18(2)
3(2)
-22(2)
C(22)
46(2)
83(3)
39(2)
-5(2)
12(2)
12(2)
C(23)
40(2)
51(2)
37(2)
-3(1)
5(2)
8(2)
C(24)
37(2)
53(2)
30(2)
-5(1)
6(1)
1(2)
C(25)
28(1)
36(2)
32(1)
1(1)
4(1)
0(1)
C(26)
34(1)
39(2)
28(1)
0(1)
-1(1)
-1(1)
C(27)
26(1)
79(2)
37(2)
-5(2)
3(1)
-8(2)
C(28)
32(1)
73(2)
35(2)
-7(2)
-2(1)
-1(2)
203
C(29)
36(2)
41(2)
30(2)
1(1)
1(1)
0(1)
C(30)
50(2)
43(2)
32(2)
-4(2)
3(1)
7(2)
C(31)
52(2)
54(2)
38(2)
-7(2)
13(1)
-10(2)
C(32)
39(2)
45(2)
40(2)
3(1)
8(1)
-2(2)
C(33)
34(1)
34(2)
32(2)
6(1)
2(1)
4(1)
C(34)
26(1)
36(2)
31(1)
1(1)
5(1)
-1(1)
C(35)
29(1)
61(2)
36(2)
7(1)
1(1)
-4(2)
C(36)
32(1)
59(2)
36(2)
3(2)
-2(1)
-4(2)
C(37)
32(2)
44(2)
34(2)
4(1)
-3(1)
-1(1)
C(38)
47(2)
57(2)
30(2)
3(1)
-4(2)
2(2)
C(39)
51(2)
46(2)
25(2)
2(1)
8(1)
9(2)
C(40)
49(2)
43(2)
42(2)
0(1)
8(2)
2(1)
C(41)
50(2)
45(2)
49(2)
-4(2)
4(2)
-6(1)
C(42)
89(2)
69(3)
41(2)
12(2)
3(2)
26(2)
C(43)
76(4)
311(10)
41(3)
-41(4)
12(2)
-72(5)

x 103) for stanozolol formamide solvate.
Atom
U(eq)
H(1O1)
5648
5884
-488
77
H(1O2)
1848
4069
3887
72
H(1N1)
9008
6456
4254
76
H(1N4)
740
3355
-533
70
H(1)
10363
6317
3449
67
H(3A)
8686
5950
2501
52
H(3B)
8116
6716
2455
52
H(5)
6150
6697
1784
40
H(6A)
8505
5955
1656
57
H(6B)
7199
5354
1545
57
H(7A)
7669
6509
906
57
H(7B)
8234
5764
766
57
H(10A)
2805
6654
-26
68
H(10B)
2699
5854
-29
68
204
H(11A)
1741
6647
758
60
H(11B)
1835
5844
776
60
H(12)
4530
6775
1018
41
H(13)
3782
5610
1603
39
H(14A)
1533
6389
1728
51
H(14B)
2890
6983
1801
51
H(15A)
2337
5908
2498
53
H(15B)
1856
6674
2596
53
H(16)
4827
6970
2605
42
H(17A)
3742
6733
3398
53
H(17B)
3933
5944
3317
53
H(19A)
6606
5036
2346
58
H(19B)
4565
5159
2390
58
H(19C)
5768
5223
2872
58
H(20A)
6111
4908
523
60
H(20B)
4073
5052
526
60
H(20C)
5095
4965
1040
60
H(21A)
7297
6855
90
108
H(21B)
5668
7202
351
108
H(21C)
5661
7074
-237
108
H(22)
5122
3439
170
73
H(24A)
3607
3728
1151
52
H(24B)
2980
2968
1169
52
H(26)
1133
2992
1872
44
H(27A)
2233
4324
2104
62
H(27B)
3500
3712
1990
62
H(28A)
2655
3169
2743
61
H(28B)
3303
3907
2876
61
H(31A)
-2030
3014
3688
62
H(31B)
-2237
3809
3736
62
H(32A)
-3284
3108
2924
53
H(32B)
-3061
3907
2925
53
H(33)
-469
2930
2668
43
205
H(34)
-1231
4079
2068
40
H(35A)
-3472
3281
1972
55
H(35B)
-2087
2701
1874
55
H(36A)
-2781
3795
1206
55
H(36B)
-3245
3031
1099
55
H(37)
-292
2751
1043
48
H(38A)
-1412
3020
271
58
H(38B)
-1272
3805
374
58
H(40A)
1535
4662
1351
62
H(40B)
-502
4550
1283
62
H(40C)
759
4502
812
62
H(41A)
1243
4806
3098
67
H(41B)
-797
4673
3127
67
H(41C)
140
4725
2598
67
H(42A)
2491
2944
3629
93
H(42B)
989
2541
3350
93
H(42C)
838
2689
3933
93
206
11) Stanozolol pyridine solvate.
Table 8.51 Crystal data and structure refinement for stanozolol pyridine solvate.
Identification code
stanozolol_11
Empirical formula
C47 H69 N5 O2
Formula weight
736.07
Temperature
298(2) K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P212121
a = 7.233(2)
b = 11.850(2)
c = 48.672(2)
Volume
4171.8(14) 3
1.172 Mg/m3
0.072 mm-1
F(000)
1608
Crystal size
0.55 x 0.45 x 0.25 mm
2.9237 to 27.8887
Index ranges
-8<=h<=9; -15<=k<=15; -42<=l<=62
12520
6556 [Rint = 0.0251]

207
4847
Data Completeness
0.998
1.00000 and 0.79858
Refinement method
6556 / 0 / 493
1.085
R1 = 0.0679 wR2 = 0.1132
R1 = 0.0962 wR2 = 0.1223
0(2)
0.153 and -0.157 e.-3

parameters (2 x 103) for stanozolol pyridine solvate. U(eq) is defined as one third of
Atom
U(eq)
O(1)
6053(3)
4273(2)
1245(1)
49(1)
O(2)
11405(4)
1088(2)
3770(1)
60(1)
N(1)
12852(5)
3472(3)
3317(1)
66(1)
N(2)
11462(4)
2710(3)
3334(1)
53(1)
N(3)
8534(6)
-2510(3)
5857(1)
68(1)
N(4)
7064(6)
-1832(3)
5814(1)
67(1)
C(1)
12703(6)
4069(4)
3085(1)
61(1)
C(2)
11169(5)
3694(3)
2946(1)
44(1)
C(3)
10349(5)
4029(3)
2675(1)
48(1)
C(4)
9134(4)
3082(2)
2555(1)
32(1)
C(5)
8018(5)
3560(3)
2310(1)
34(1)
C(6)
9212(5)
4111(3)
2087(1)
43(1)
C(7)
8074(5)
4611(3)
1851(1)
44(1)
C(8)
6823(4)
3716(3)
1728(1)
36(1)
C(9)
5328(5)
4129(3)
1519(1)
41(1)
C(10)
3923(5)
3161(3)
1521(1)
56(1)
C(11)
4180(5)
2516(4)
1795(1)
56(1)
208
C(12)
5596(4)
3229(3)
1953(1)
37(1)
C(13)
6646(4)
2696(3)
2191(1)
35(1)
C(14)
5352(5)
2283(4)
2418(1)
50(1)
C(15)
6372(5)
1848(3)
2668(1)
50(1)
C(16)
7787(5)
2678(3)
2779(1)
38(1)
C(17)
8766(5)
2186(3)
3033(1)
46(1)
C(18)
10437(5)
2847(3)
3107(1)
44(1)
C(19)
10385(5)
2114(3)
2462(1)
45(1)
C(20)
8006(5)
2809(3)
1588(1)
47(1)
C(21)
4441(6)
5253(3)
1594(1)
65(1)
C(22)
9843(7)
-2324(3)
5671(1)
59(1)
C(23)
9250(6)
-1490(3)
5498(1)
48(1)
C(24)
10092(5)
-921(3)
5251(1)
46(1)
C(25)
8587(5)
-493(3)
5057(1)
35(1)
C(26)
9465(5)
242(3)
4825(1)
36(1)
C(27)
10951(5)
-388(3)
4659(1)
49(1)
C(28)
11755(5)
316(3)
4422(1)
47(1)
C(29)
10231(5)
770(3)
4237(1)
37(1)
C(30)
10783(5)
1648(3)
4015(1)
44(1)
C(31)
8989(5)
2286(3)
3958(1)
59(1)
C(32)
7714(6)
2106(4)
4209(1)
67(1)
C(33)
8932(5)
1486(3)
4417(1)
43(1)
C(34)
7997(5)
821(3)
4645(1)
39(1)
C(35)
6742(5)
1551(3)
4820(1)
58(1)
C(36)
5843(5)
876(3)
5048(1)
57(1)
C(37)
7247(5)
252(3)
5225(1)
43(1)
C(38)
6234(5)
-400(3)
5456(1)
56(1)
C(39)
7505(6)
-1217(3)
5592(1)
51(1)
C(40)
7576(6)
-1515(3)
4937(1)
57(1)
C(41)
9221(6)
-212(3)
4098(1)
59(1)
C(42)
12309(6)
2441(4)
4102(1)
72(1)
C(43)
2316(8)
352(4)
6528(1)
80(1)
C(44)
3879(8)
-206(5)
6457(1)
96(2)
209
N(5)
869(6)
505(4)
6360(1)
83(1)
C(46)
1071(7)
48(4)
6109(1)
80(1)
C(45)
4044(7)
-653(4)
6200(1)
79(1)
C(47)
2643(8)
-520(4)
6031(1)
81(1)
Table 8.53 Bond lengths [] and angles [] for stanozolol pyridine solvate.
Bond lengths []
O(1)-C(9)
1.441(4)
O(2)-C(30)
1.438(4)
N(1)-C(1)
1.336(4)
N(1)-N(2)
1.354(4)
N(2)-C(18)
1.339(4)
N(3)-C(22)
1.329(5)
N(3)-N(4)
1.350(5)
N(4)-C(39)
1.339(4)
C(1)-C(2)
1.374(5)
C(2)-C(18)
1.380(5)
C(2)-C(3)
1.500(4)
C(3)-C(4)
1.541(4)
C(4)-C(19)
1.530(4)
C(4)-C(16)
1.539(4)
C(4)-C(5)
1.547(4)
C(5)-C(6)
1.533(4)
C(5)-C(13)
1.539(4
C(6)-C(7)
1.533(4)
C(7)-C(8)
1.517(4)
C(8)-C(12)
1.525(4)
C(8)-C(20)
1.532(4
C(8)-C(9)
1.564(4)
C(9)-C(21)
1.523(5)
C(9)-C(10)
1.532(5)
C(10)-C(11)
1.547(5)
C(11)-C(12)
1.535(4)
C(12)-C(13)
1.520(4)
C(13)-C(14)
1.528(4)
C(14)-C(15)
1.516(5)
C(15)-C(16)
1.519(5)
C(16)-C(17)
1.540(4)
C(17)-C(18)
1.484(5)
C(22)-C(23)
1.369(5)
C(23)-C(39)
1.382(5)
C(23)-C(24)
1.505(4)
C(24)-C(25)
1.529(4)
C(25)-C(40)
1.531(4)
C(25)-C(37)
1.545(4)
C(25)-C(26)
1.559(4)
C(26)-C(34)
1.540(4)
C(26)-C(27)
1.540(4)
C(27)-C(28)
1.536(4)
C(28)-C(29)
1.521(4)
C(29)-C(41)
1.531(5)
C(29)-C(33)
1.539(5)
C(29)-C(30)
1.552(4)
C(30)-C(42)
1.510(5)
C(30)-C(31)
1.528(5)
C(31)-C(32)
1.545(5)
C(32)-C(33)
1.530(5)
C(33)-C(34)
1.518(4)
C(34)-C(35)
1.518(5)
210
C(35)-C(36)
1.516(5)
C(36)-C(37)
1.522(5)
C(37)-C(38)
1.547(5)
C(38)-C(39)
1.492(5)
C(43)-N(5)
1.339(6)
C(43)-C(44)
1.354(7)
C(44)-C(45)
1.362(7
N(5)-C(46)
1.344(6)
C(46)-C(47)
1.375(6)
C(45)-C(47)
1.316(6)
Bond angles []
C(1)-N(1)-N(2)
110.2(3)
C(18)-N(2)-N(1)
106.2(3)
C(22)-N(3)-N(4)
110.8(3)
C(39)-N(4)-N(3)
105.3(3)
N(1)-C(1)-C(2)
108.0(3)
C(1)-C(2)-C(18)
105.4(3)
C(1)-C(2)-C(3)
131.8(3)
C(18)-C(2)-C(3)
122.7(3)
C(2)-C(3)-C(4)
111.5(3)
C(19)-C(4)-C(16)
110.6(2)
C(19)-C(4)-C(3)
108.7(3)
C(16)-C(4)-C(3)
108.6(3)
C(19)-C(4)-C(5)
110.8(3)
C(16)-C(4)-C(5)
109.3(3)
C(3)-C(4)-C(5)
108.9(2)
C(6)-C(5)-C(13)
112.3(2)
C(6)-C(5)-C(4)
114.1(3)
C(13)-C(5)-C(4)
112.5(3)
C(5)-C(6)-C(7)
113.2(3)
C(8)-C(7)-C(6)
110.2(3)
C(7)-C(8)-C(12)
109.1(3)
C(7)-C(8)-C(20)
109.4(3)
C(12)-C(8)-C(20)
112.3(3)
C(7)-C(8)-C(9)
116.8(3)
C(12)-C(8)-C(9)
100.7(2)
C(20)-C(8)-C(9)
108.5(3)
O(1)-C(9)-C(21)
105.7(3)
O(1)-C(9)-C(10)
109.8(3)
C(21)-C(9)-C(10)
111.9(3)
O(1)-C(9)-C(8)
112.8(3)
C(21)-C(9)-C(8)
114.1(3)
C(10)-C(9)-C(8)
102.6(3)
C(9)-C(10)-C(11)
107.3(3)
C(12)-C(11)-C(10)
104.0(3)
C(13)-C(12)-C(8)
114.4(3)
C(13)-C(12)-C(11)
119.1(3)
C(8)-C(12)-C(11)
103.6(2)
C(12)-C(13)-C(14)
112.1(3)
C(12)-C(13)-C(5)
109.4(3)
C(14)-C(13)-C(5)
109.6(3)
C(15)-C(14)-C(13)
113.1(3)
C(14)-C(15)-C(16)
113.2(3)
C(15)-C(16)-C(4)
112.0(3)
C(15)-C(16)-C(17)
110.5(3)
C(4)-C(16)-C(17)
113.4(3)
C(18)-C(17)-C(16)
111.7(3)
N(2)-C(18)-C(2)
110.1(3)
N(2)-C(18)-C(17)
125.9(3)
C(2)-C(18)-C(17)
123.9(3)
N(3)-C(22)-C(23)
108.5(4)
C(22)-C(23)-C(39)
104.5(3)
C(22)-C(23)-C(24)
133.5(4)
211
C(39)-C(23)-C(24)
122.0(3)
C(23)-C(24)-C(25)
110.7(3)
C(24)-C(25)-C(40)
108.3(3)
C(24)-C(25)-C(37)
108.0(3)
C(40)-C(25)-C(37)
110.8(3)
C(24)-C(25)-C(26)
110.0(3)
C(40)-C(25)-C(26)
111.1(2)
C(37)-C(25)-C(26)
108.6(2)
C(34)-C(26)-C(27)
113.3(2)
C(34)-C(26)-C(25)
112.4(3)
C(27)-C(26)-C(25)
113.3(3)
C(28)-C(27)-C(26)
113.4(3)
C(29)-C(28)-C(27)
111.1(3)
C(28)-C(29)-C(41)
109.8(3)
C(28)-C(29)-C(33)
107.6(3)
C(41)-C(29)-C(33)
112.2(3)
C(28)-C(29)-C(30)
117.5(3)
C(41)-C(29)-C(30)
109.0(3)
C(33)-C(29)-C(30)
100.6(3)
O(2)-C(30)-C(42)
106.9(3)
O(2)-C(30)-C(31)
110.0(3)
C(42)-C(30)-C(31)
111.4(3)
O(2)-C(30)-C(29)
110.4(3)
C(42)-C(30)-C(29)
114.2(3)
C(31)-C(30)-C(29)
103.9(3)
C(30)-C(31)-C(32)
107.1(3)
C(33)-C(32)-C(31)
104.3(3)
C(34)-C(33)-C(32)
118.4(3)
C(34)-C(33)-C(29)
113.7(3)
C(32)-C(33)-C(29)
103.9(3)
C(33)-C(34)-C(35)
112.4(3)
C(33)-C(34)-C(26)
110.0(3)
C(35)-C(34)-C(26)
110.2(3)
C(36)-C(35)-C(34)
111.6(3)
C(35)-C(36)-C(37)
112.6(3)
C(36)-C(37)-C(25)
113.4(3)
C(36)-C(37)-C(38)
109.7(3)
C(25)-C(37)-C(38)
113.3(3)
C(39)-C(38)-C(37)
110.8(3)
N(4)-C(39)-C(23)
111.0(4)
N(4)-C(39)-C(38)
124.4(4)
C(23)-C(39)-C(38)
124.5(3)
N(5)-C(43)-C(44)
124.3(5)
C(43)-C(44)-C(45)
119.8(5)
C(43)-N(5)-C(46)
114.5(4)
N(5)-C(46)-C(47)
122.6(5)
C(47)-C(45)-C(44)
117.4(5)
C(45)-C(47)-C(46)
121.5(5)
Table 8.54 Anisotropic displacement parameters (2 x 103) for stanozolol pyridine

U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
64(2)
54(1)
30(1)
-10(1)
-2(1)
-5(1)
O(2)
93(2)
55(2)
32(1)
17(1)
14(2)
15(2)
N(1)
60(2)
92(3)
44(2)
17(2)
-22(2)
-19(2)
N(2)
54(2)
60(2)
46(2)
18(2)
-9(2)
-7(2)
212
N(3)
103(3)
58(2)
44(2)
21(2)
8(2)
5(2)
N(4)
85(3)
66(2)
49(2)
19(2)
15(2)
10(2)
C(1)
60(3)
76(3)
46(2)
24(2)
-16(2)
-20(2)
C(2)
50(2)
43(2)
40(2)
10(2)
-12(2)
-5(2)
C(3)
58(2)
41(2)
44(2)
16(2)
-15(2)
-11(2)
C(4)
36(2)
27(2)
34(2)
5(2)
-2(2)
-2(2)
C(5)
36(2)
32(2)
34(2)
0(2)
-4(2)
-1(2)
C(6)
45(2)
46(2)
39(2)
10(2)
-8(2)
-18(2)
C(7)
55(2)
43(2)
34(2)
5(2)
-11(2)
-6(2)
C(8)
36(2)
38(2)
34(2)
-8(2)
-2(2)
2(2)
C(9)
48(2)
51(2)
25(2)
-9(2)
-5(2)
8(2)
C(10)
41(2)
81(3)
46(2)
-12(2)
-9(2)
-7(2)
C(11)
42(2)
84(3)
42(2)
-10(2)
0(2)
-18(2)
C(12)
29(2)
45(2)
38(2)
-9(2)
-1(2)
3(2)
C(13)
32(2)
36(2)
38(2)
-5(2)
2(2)
-2(2)
C(14)
32(2)
68(3)
49(2)
8(2)
0(2)
-11(2)
C(15)
45(2)
57(2)
47(2)
7(2)
8(2)
-11(2)
C(16)
41(2)
37(2)
35(2)
4(2)
4(2)
2(2)
C(17)
58(2)
42(2)
38(2)
9(2)
6(2)
2(2)
C(18)
46(2)
45(2)
42(2)
11(2)
-4(2)
2(2)
C(19)
38(2)
47(2)
49(2)
7(2)
1(2)
9(2)
C(20)
44(2)
51(2)
46(2)
-3(2)
6(2)
2(2)
C(21)
73(3)
77(3)
44(2)
-11(2)
-14(2)
37(3)
C(22)
82(3)
59(2)
37(2)
8(2)
8(2)
13(2)
C(23)
66(3)
47(2)
30(2)
5(2)
3(2)
6(2)
C(24)
56(2)
50(2)
30(2)
9(2)
6(2)
8(2)
C(25)
46(2)
32(2)
29(2)
-3(2)
1(2)
0(2)
C(26)
43(2)
35(2)
29(2)
-1(2)
-2(2)
2(2)
C(27)
55(2)
59(2)
34(2)
11(2)
1(2)
20(2)
C(28)
47(2)
59(2)
34(2)
11(2)
8(2)
13(2)
C(29)
43(2)
39(2)
29(2)
8(2)
-4(2)
2(2)
C(30)
49(2)
49(2)
35(2)
6(2)
0(2)
3(2)
C(31)
61(2)
61(2)
54(2)
25(2)
-1(2)
12(2)
213
C(32)
61(3)
81(3)
60(2)
40(2)
8(2)
28(3)
C(33)
43(2)
43(2)
43(2)
11(2)
-1(2)
4(2)
C(34)
38(2)
41(2)
39(2)
7(2)
-3(2)
3(2)
C(35)
56(2)
60(2)
57(2)
18(2)
12(2)
18(2)
C(36)
49(2)
64(2)
58(2)
17(2)
15(2)
13(2)
C(37)
44(2)
43(2)
41(2)
4(2)
8(2)
0(2)
C(38)
54(2)
65(2)
47(2)
8(2)
17(2)
5(2)
C(39)
67(3)
49(2)
37(2)
11(2)
8(2)
5(2)
C(40)
83(3)
46(2)
40(2)
-1(2)
2(2)
-13(2)
C(41)
87(3)
56(2)
36(2)
4(2)
-6(2)
-11(2)
C(42)
71(3)
85(3)
59(2)
18(3)
4(2)
-23(3)
C(43)
95(4)
85(4)
58(3)
-4(3)
7(3)
-25(3)
C(44)
77(4)
101(4)
110(5)
46(4)
-15(4)
-14(4)
N(5)
75(3)
100(3)
74(3)
-7(3)
18(2)
-9(3)
C(46)
63(3)
106(4)
72(3)
10(3)
2(3)
-10(3)
C(45)
58(3)
67(3)
112(4)
18(3)
22(3)
6(3)
C(47)
80(4)
86(3)
78(3)
-11(3)
22(3)
-9(3)

x 103) for stanozolol pyridine solvate.
Atom
U(eq)
H(1O1)
6816
4785
1245
64
H(1O2)
11604
1558
3650
78
H(1N1)
13708
3558
3437
85
H(1N3)
8612
-2997
5988
89
H(1)
13499
4640
3028
79
H(3A)
11336
4203
2547
62
H(3B)
9608
4704
2699
62
H(5)
7258
4168
2386
44
H(6A)
10056
3552
2013
56
H(6B)
9947
4706
2170
56
H(7A)
7332
5233
1918
57
H(7B)
8898
4900
1710
57
214
H(10A)
4135
2660
1367
73
H(10B)
2675
3456
1508
73
H(11A)
3022
2466
1895
73
H(11B)
4647
1760
1763
73
H(12)
4910
3867
2031
49
H(13)
7346
2049
2120
46
H(14A)
4550
2899
2473
64
H(14B)
4578
1685
2345
64
H(15A)
6995
1150
2621
65
H(15B)
5481
1680
2811
65
H(16)
7100
3344
2841
49
H(17A)
7915
2185
3187
60
H(17B)
9118
1411
2996
60
H(19A)
9640
1505
2394
58
H(19B)
11110
1855
2614
58
H(19C)
11192
2375
2318
58
H(20A)
8699
2406
1725
61
H(20B)
8841
3160
1461
61
H(20C)
7218
2292
1491
61
H(21A)
5355
5839
1586
84
H(21B)
3943
5210
1776
84
H(21C)
3465
5418
1466
84
H(22)
10972
-2697
5661
77
H(24A)
10880
-1451
5155
59
H(24B)
10851
-292
5311
59
H(26)
10117
854
4920
46
H(27A)
11947
-607
4781
64
H(27B)
10414
-1072
4584
64
H(28A)
12460
941
4497
61
H(28B)
12589
-148
4314
61
H(31A)
8406
1999
3793
76
H(31B)
9239
3084
3933
76
H(32A)
7294
2822
4282
88
215
H(32B)
6646
1654
4160
88
H(33)
9701
2059
4506
56
H(34)
7239
232
4559
51
H(35A)
7457
2162
4900
75
H(35B)
5788
1881
4705
75
H(36A)
4995
333
4968
74
H(36B)
5131
1381
5164
74
H(37)
8002
829
5315
55
H(38A)
5767
130
5591
72
H(38B)
5189
-803
5378
72
H(40A)
6559
-1262
4826
73
H(40B)
7120
-1979
5084
73
H(40C)
8415
-1945
4826
73
H(41A)
10070
-618
3984
77
H(41B)
8227
77
3988
77
H(41C)
8733
-709
4236
77
H(42A)
13440
2025
4123
93
H(42B)
11989
2787
4274
93
H(42C)
12470
3013
3965
93
H(43)
2243
649
6704
104
H(44)
4837
-283
6583
125
H(46)
111
120
5983
104
H(45)
5106
-1038
6147
102
H(47)
2718
-816
5854
106
216
12) Stanozolol DMF hydrate solvate.
Table 8.56 Crystal data and structure refinement for stanozolol DMF hydrate solvate.
Identification code
stanozolol_12
Empirical formula
C45 H73 N5 O4
Formula weight
748.08
Temperature
298(2) K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 10.4243(10)
b = 7.4432(5), = 94.069(9)
c = 27.018(2)
Volume
2091.1(3) 3
1.188 Mg/m3
0.076 mm-1
F(000)
820
Crystal size
0.20 x 0.06 x 0.06 mm
3.0189 to 29.0783
Index ranges
-14<=h<=12; -5<=k<=9; -36<=l<=20
9056
217
5784 [Rint = 0.0169]
4640
Data Completeness
0.998
1.00000 and 0.97696
Refinement method
5784 / 1 / 503
1.025
R1 = 0.0493 wR2 = 0.1208
R1 = 0.0668 wR2 = 0.1327
0.2(17)
0.351 and -0.318 e.-3

parameters (2 x 103) for stanozolol DMF hydrate solvate. U(eq) is defined as one
Atom
U(eq)
O(1)
1843(2)
1864(4)
1985(1)
56(1)
O(2)
1359(2)
521(3)
2935(1)
51(1)
O(3)
11709(5)
5502(5)
2138(2)
141(2)
O(4)
5199(5)
1126(5)
7493(1)
79(1)
N(1)
3096(3)
4978(4)
-2059(1)
53(1)
N(2)
3377(3)
3219(4)
-2032(1)
55(1)
N(3)
3341(3)
-3065(4)
7001(1)
48(1)
N(4)
3682(3)
-1326(4)
6952(1)
47(1)
N(5)
9869(4)
5863(5)
2541(1)
68(1)
C(1)
2745(4)
5654(5)
-1631(1)
48(1)
C(2)
2810(3)
4273(5)
-1292(1)
40(1)
C(3)
2612(3)
4202(4)
-745(1)
37(1)
C(4)
2422(3)
2263(4)
-558(1)
33(1)
C(5)
2682(3)
2242(4)
15(1)
31(1)
C(6)
1854(3)
3564(5)
289(1)
43(1)
C(7)
2225(3)
3598(4)
853(1)
42(1)
218
C(8)
2150(3)
1725(4)
1078(1)
34(1)
C(9)
2730(3)
1454(5)
1619(1)
45(1)
C(10)
3011(4)
-574(5)
1643(1)
61(1)
C(11)
3054(4)
-1265(5)
1107(1)
55(1)
C(12)
3005(3)
453(4)
795(1)
35(1)
C(13)
2662(3)
339(4)
240(1)
34(1)
C(14)
3604(4)
-887(5)
-7(1)
46(1)
C(15)
3410(4)
-886(5)
-570(1)
46(1)
C(16)
3437(3)
1015(4)
-782(1)
38(1)
C(17)
3335(4)
951(5)
-1349(1)
53(1)
C(18)
3200(3)
2804(5)
-1559(1)
45(1)
C(19)
1044(3)
1651(5)
-724(1)
46(1)
C(20)
745(3)
1108(5)
1049(1)
52(1)
C(21)
3945(4)
2541(7)
1744(1)
67(1)
C(22)
2918(3)
-3569(5)
6549(1)
44(1)
C(23)
2988(3)
-2175(5)
6203(1)
37(1)
C(24)
2703(3)
-2066(4)
5652(1)
37(1)
C(25)
2533(3)
-101(4)
5468(1)
32(1)
C(26)
2675(3)
-35(4)
4897(1)
33(1)
C(27)
1767(4)
-1277(5)
4590(1)
45(1)
C(28)
2003(4)
-1260(5)
4035(1)
46(1)
C(29)
1902(3)
654(4)
3824(1)
34(1)
C(30)
2371(3)
960(5)
3297(1)
43(1)
C(31)
2689(4)
2994(6)
3300(1)
59(1)
C(32)
2890(4)
3588(5)
3846(1)
59(1)
C(33)
2869(3)
1834(4)
4139(1)
36(1)
C(34)
2642(3)
1899(4)
4690(1)
34(1)
C(35)
3655(4)
3067(5)
4967(1)
46(1)
C(36)
3590(4)
2985(5)
5527(1)
47(1)
C(37)
3627(3)
1080(4)
5720(1)
38(1)
C(38)
3677(4)
1094(5)
6292(1)
46(1)
C(39)
3472(3)
-767(5)
6477(1)
39(1)
C(40)
1201(3)
557(5)
5601(1)
45(1)
219
C(41)
529(3)
1336(6)
3833(1)
51(1)
C(42)
3547(4)
-142(7)
3185(1)
70(1)
C(43)
9204(5)
6970(8)
2888(2)
91(2)
C(44)
9299(5)
4169(8)
2403(2)
95(2)
C(45)
10995(7)
6376(7)
2396(2)
115(2)
Table 8.58 Bond lengths [] and angles [] for stanozolol DMF hydrate solvate.
Bond lengths []
O(1)-C(9)
1.434(4)
O(2)-C(30)
1.425(4)
O(3)-C(45)
1.239(6
N(1)-C(1)
1.336(4)
N(1)-N(2)
1.343(4)
N(2)-C(18)
1.339(4)
N(3)-C(22)
1.324(4
N(3)-N(4)
1.351(4)
N(4)-C(39)
1.354(4)
N(5)-C(45)
1.321(6)
N(5)-C(44)
1.432(6)
N(5)-C(43)
1.459(6)
C(1)-C(2)
1.376(4)
C(2)-C(18)
1.387(5)
C(2)-C(3)
1.505(4)
C(3)-C(4)
1.547(4)
C(4)-C(19)
1.543(4
C(4)-C(5)
1.553(4)
C(4)-C(16)
1.561(4
C(5)-C(6)
1.535(4)
C(5)-C(13)
1.543(4
C(6)-C(7)
1.545(4)
C(7)-C(8)
1.525(4)
C(8)-C(20)
1.532(4)
C(8)-C(12)
1.539(4
C(8)-C(9)
1.556(4)
C(9)-C(21)
1.521(5)
C(9)-C(10)
1.538(5)
C(10)-C(11)
1.540(5)
C(11)-C(12)
1.531(5)
C(12)-C(13)
1.520(4)
C(13)-C(14)
1.529(4)
C(14)-C(15)
1.521(4)
C(15)-C(16)
1.526(4)
C(16)-C(17)
1.528(4)
C(17)-C(18)
1.495(5)
C(22)-C(23)
1.403(4)
C(23)-C(39)
1.360(5)
C(23)-C(24)
1.499(4)
C(24)-C(25)
1.550(4)
C(25)-C(40)
1.539(4)
C(25)-C(37)
1.557(4)
C(25)-C(26)
1.563(4)
C(26)-C(27)
1.525(4)
C(26)-C(34)
1.543(4)
C(27)-C(28)
1.536(4)
C(28)-C(29)
1.535(5)
C(29)-C(41)
1.520(4)
C(29)-C(33)
1.546(4)
C(29)-C(30)
1.556(4)
220
C(30)-C(42)
1.523(5)
C(30)-C(31)
1.549(5)
C(31)-C(32)
1.541(5)
C(32)-C(33)
1.527(5)
C(33)-C(34)
1.525(4)
C(34)-C(35)
1.523(4)
C(35)-C(36)
1.521(4)
C(36)-C(37)
1.510(5)
C(37)-C(38)
1.542(4)
C(38)-C(39)
1.493(5)
Bond angles []
C(1)-N(1)-N(2)
113.1(3)
C(18)-N(2)-N(1)
103.5(3)
C(22)-N(3)-N(4)
104.7(3)
N(3)-N(4)-C(39)
111.2(3)
C(45)-N(5)-C(44)
122.5(4)
C(45)-N(5)-C(43)
120.1(4)
C(44)-N(5)-C(43)
117.2(4)
N(1)-C(1)-C(2)
107.0(3)
C(1)-C(2)-C(18)
104.1(3)
C(1)-C(2)-C(3)
132.5(3)
C(18)-C(2)-C(3)
123.3(3)
C(2)-C(3)-C(4)
112.5(3)
C(19)-C(4)-C(3)
108.6(2)
C(19)-C(4)-C(5)
112.3(2)
C(3)-C(4)-C(5)
108.5(2)
C(19)-C(4)-C(16)
110.8(3)
C(3)-C(4)-C(16)
108.9(2)
C(5)-C(4)-C(16)
107.7(2)
C(6)-C(5)-C(13)
112.0(2)
C(6)-C(5)-C(4)
114.3(2)
C(13)-C(5)-C(4)
113.4(2)
C(5)-C(6)-C(7)
112.2(3)
C(8)-C(7)-C(6)
111.2(3)
C(7)-C(8)-C(20)
109.2(3)
C(7)-C(8)-C(12)
108.5(2)
C(20)-C(8)-C(12)
112.1(3)
C(7)-C(8)-C(9)
117.7(3)
C(20)-C(8)-C(9)
108.4(2)
C(12)-C(8)-C(9)
100.8(3)
O(1)-C(9)-C(21)
107.5(3)
O(1)-C(9)-C(10)
108.1(3)
C(21)-C(9)-C(10)
111.1(3)
O(1)-C(9)-C(8)
113.2(3)
C(21)-C(9)-C(8)
113.7(3)
C(10)-C(9)-C(8)
103.1(3)
C(9)-C(10)-C(11)
107.9(3)
C(12)-C(11)-C(10)
103.7(3)
C(13)-C(12)-C(11)
119.5(3)
C(13)-C(12)-C(8)
114.8(2)
C(11)-C(12)-C(8)
103.8(2)
C(12)-C(13)-C(14)
110.6(3)
C(12)-C(13)-C(5)
109.2(2)
C(14)-C(13)-C(5)
110.4(2)
C(15)-C(14)-C(13)
113.1(3)
C(14)-C(15)-C(16)
111.7(3)
C(15)-C(16)-C(17)
110.1(3)
C(15)-C(16)-C(4)
112.1(3)
C(17)-C(16)-C(4)
113.9(3)
C(18)-C(17)-C(16)
110.6(3)
N(2)-C(18)-C(2)
112.4(3)
N(2)-C(18)-C(17)
124.1(3)
C(2)-C(18)-C(17)
123.5(3)
221
N(3)-C(22)-C(23)
112.1(3)
C(39)-C(23)-C(22)
104.0(3)
C(39)-C(23)-C(24)
122.6(3)
C(22)-C(23)-C(24)
133.3(3)
C(23)-C(24)-C(25)
112.2(3)
C(40)-C(25)-C(24)
108.0(3)
C(40)-C(25)-C(37)
111.3(3)
C(24)-C(25)-C(37)
109.3(2)
C(40)-C(25)-C(26)
111.8(2)
C(24)-C(25)-C(26)
109.2(2)
C(37)-C(25)-C(26)
107.3(2)
C(27)-C(26)-C(34)
111.8(2)
C(27)-C(26)-C(25)
114.8(2)
C(34)-C(26)-C(25)
112.7(2)
C(26)-C(27)-C(28)
112.9(3)
C(29)-C(28)-C(27)
111.0(3)
C(41)-C(29)-C(28)
110.2(3)
C(41)-C(29)-C(33)
112.3(3)
C(28)-C(29)-C(33)
107.3(2)
C(41)-C(29)-C(30)
108.8(2)
C(28)-C(29)-C(30)
117.3(3)
C(33)-C(29)-C(30)
100.7(2)
O(2)-C(30)-C(42)
107.9(3)
O(2)-C(30)-C(31)
112.1(3)
C(42)-C(30)-C(31)
110.7(3)
O(2)-C(30)-C(29)
109.2(3)
C(42)-C(30)-C(29)
114.4(3)
C(31)-C(30)-C(29)
102.6(3)
C(32)-C(31)-C(30)
107.5(3)
C(33)-C(32)-C(31)
104.1(3)
C(34)-C(33)-C(32)
119.2(3)
C(34)-C(33)-C(29)
114.5(2)
C(32)-C(33)-C(29)
103.5(2)
C(35)-C(34)-C(33)
110.3(2)
C(35)-C(34)-C(26)
111.0(3)
C(33)-C(34)-C(26)
108.8(2)
C(36)-C(35)-C(34)
112.8(3)
C(37)-C(36)-C(35)
112.4(3)
C(36)-C(37)-C(38)
109.8(3)
C(36)-C(37)-C(25)
112.3(3)
C(38)-C(37)-C(25)
114.4(3)
C(39)-C(38)-C(37)
109.5(3)
N(4)-C(39)-C(23)
108.0(3)
N(4)-C(39)-C(38)
125.9(3)
C(23)-C(39)-C(38)
126.1(3)
O(3)-C(45)-N(5)
126.7(5)
Table 8.59 Anisotropic displacement parameters (2 x 103) for stanozolol DMF

hydrate solvate. The anisotropic displacement factor exponent takes the form: -2 2
[h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
76(2)
63(2)
32(1)
3(1)
20(1)
-9(1)
O(2)
56(1)
67(2)
29(1)
5(1)
-2(1)
-10(1)
O(3)
209(5)
63(2)
168(4)
-14(3)
138(4)
-18(3)
O(4)
106(3)
68(2)
63(2)
-18(2)
0(2)
4(2)
N(1)
81(2)
50(2)
28(2)
13(1)
-1(1)
-1(2)
222
N(2)
80(2)
51(2)
33(2)
6(1)
9(1)
5(2)
N(3)
61(2)
45(2)
39(2)
13(1)
10(1)
1(2)
N(4)
61(2)
52(2)
29(2)
5(1)
4(1)
0(2)
N(5)
85(2)
70(3)
50(2)
-4(2)
15(2)
-5(2)
C(1)
69(2)
40(2)
36(2)
7(2)
4(2)
2(2)
C(2)
49(2)
40(2)
31(2)
6(2)
0(1)
-1(2)
C(3)
45(2)
34(2)
30(2)
5(1)
2(1)
7(2)
C(4)
39(2)
31(2)
28(2)
2(1)
0(1)
2(1)
C(5)
36(2)
29(2)
29(2)
4(1)
3(1)
1(1)
C(6)
57(2)
36(2)
36(2)
4(2)
10(2)
13(2)
C(7)
55(2)
37(2)
35(2)
-3(2)
10(2)
-2(2)
C(8)
39(2)
37(2)
28(2)
-1(1)
4(1)
-6(2)
C(9)
53(2)
54(2)
27(2)
3(2)
8(1)
-11(2)
C(10)
84(3)
65(3)
34(2)
18(2)
6(2)
6(2)
C(11)
82(3)
42(2)
43(2)
13(2)
10(2)
10(2)
C(12)
43(2)
34(2)
29(2)
6(1)
3(1)
0(2)
C(13)
40(2)
30(2)
33(2)
4(1)
5(1)
2(2)
C(14)
65(2)
36(2)
37(2)
7(2)
7(2)
18(2)
C(15)
66(2)
35(2)
39(2)
-1(2)
11(2)
14(2)
C(16)
48(2)
34(2)
31(2)
2(1)
4(1)
5(2)
C(17)
82(3)
42(2)
34(2)
3(2)
11(2)
13(2)
C(18)
56(2)
47(2)
31(2)
8(2)
2(2)
3(2)
C(19)
46(2)
47(2)
44(2)
6(2)
-7(2)
-2(2)
C(20)
47(2)
64(3)
46(2)
-3(2)
9(2)
-13(2)
C(21)
65(3)
96(3)
39(2)
-6(2)
-3(2)
-20(2)
C(22)
55(2)
41(2)
37(2)
10(2)
6(2)
2(2)
C(23)
36(2)
40(2)
34(2)
4(2)
7(1)
0(2)
C(24)
46(2)
33(2)
33(2)
5(1)
7(1)
-4(2)
C(25)
36(2)
33(2)
29(2)
5(1)
6(1)
-2(2)
C(26)
36(2)
35(2)
27(2)
2(1)
3(1)
-1(2)
C(27)
63(2)
39(2)
33(2)
6(2)
-2(2)
-17(2)
C(28)
63(2)
41(2)
34(2)
-1(2)
-1(2)
-4(2)
C(29)
33(2)
39(2)
31(2)
4(2)
4(1)
1(2)
223
C(30)
43(2)
56(2)
31(2)
2(2)
1(1)
-2(2)
C(31)
76(3)
68(3)
32(2)
14(2)
-1(2)
-20(2)
C(32)
86(3)
50(2)
40(2)
11(2)
0(2)
-23(2)
C(33)
40(2)
38(2)
32(2)
3(2)
5(1)
-4(2)
C(34)
40(2)
32(2)
31(2)
4(1)
5(1)
-3(2)
C(35)
66(2)
41(2)
31(2)
5(2)
4(2)
-17(2)
C(36)
67(2)
37(2)
35(2)
2(2)
1(2)
-16(2)
C(37)
46(2)
41(2)
28(2)
2(1)
3(1)
-6(2)
C(38)
63(2)
46(2)
29(2)
1(2)
0(1)
-11(2)
C(39)
44(2)
44(2)
31(2)
9(2)
7(1)
0(2)
C(40)
43(2)
53(2)
38(2)
7(2)
8(1)
0(2)
C(41)
40(2)
71(3)
42(2)
0(2)
3(1)
7(2)
C(42)
56(2)
120(4)
37(2)
-5(2)
13(2)
13(3)
C(43)
77(3)
126(4)
73(3)
-23(3)
19(2)
-11(3)
C(44)
72(3)
86(4)
125(5)
-2(3)
-12(3)
-11(3)
C(45)
170(6)
59(3)
129(5)
-17(3)
102(5)
-32(4)

x 103) for stanozolol DMF hydrate solvate.
Atom
U(eq)
H(1O1)
1684
2943
1979
73
H(1O2)
1581
766
2657
66
H(1O4)
4620(50)
1890(80)
7596(18)
96(19)
H(2O4)
5990(70)
930(100)
7650(20)
150(30)
H(1N1)
3138
5606
-2325
69
H(4)
3992
-662
7192
61
H(1)
2502
6834
-1573
62
H(3A)
1863
4914
-680
48
H(3B)
3352
4731
-562
48
H(5)
3569
2665
78
41
H(6A)
956
3227
234
56
H(6B)
1953
4760
155
56
H(7A)
3093
4060
912
54
224
H(7B)
1649
4398
1014
54
H(10A)
2343
-1192
1809
79
H(10B)
3829
-793
1828
79
H(11A)
3839
-1930
1066
72
H(11B)
2322
-2032
1017
72
H(12)
3873
964
832
46
H(13)
1793
-157
184
44
H(14A)
4475
-503
89
60
H(14B)
3505
-2104
113
60
H(15A)
2590
-1440
-670
60
H(15B)
4081
-1595
-706
60
H(16)
4285
1515
-680
49
H(17A)
4098
387
-1464
68
H(17B)
2595
235
-1463
68
H(19A)
436
2372
-562
60
H(19B)
938
412
-637
60
H(19C)
901
1787
-1077
60
H(20A)
443
951
708
68
H(20B)
230
1998
1199
68
H(20C)
682
-11
1222
68
H(21A)
3756
3798
1705
88
H(21B)
4590
2205
1525
88
H(21C)
4256
2308
2081
88
H(22)
2611
-4715
6470
57
H(24A)
1923
-2734
5560
48
H(24B)
3400
-2621
5488
48
H(26)
3542
-482
4851
42
H(27A)
887
-914
4630
59
H(27B)
1873
-2493
4715
59
H(28A)
2852
-1738
3989
60
H(28B)
1376
-2024
3856
60
H(31A)
3462
3213
3130
76
H(31B)
1987
3664
3133
76
225
H(32A)
3708
4200
3908
76
H(32B)
2205
4384
3934
76
H(33)
3716
1280
4115
47
H(34)
1791
2416
4730
44
H(35A)
4501
2680
4883
60
H(35B)
3540
4302
4858
60
H(36A)
4309
3650
5684
60
H(36B)
2804
3558
5616
60
H(37)
4440
559
5629
50
H(38A)
4506
1539
6425
60
H(38B)
3016
1886
6403
60
H(40A)
545
-117
5416
58
H(40B)
1109
1809
5521
58
H(40C)
1118
388
5950
58
H(41A)
279
1336
4168
66
H(41B)
-36
567
3633
66
H(41C)
478
2536
3703
66
H(42A)
3344
-1398
3201
91
H(42B)
4243
130
3425
91
H(42C)
3794
147
2859
91
H(43A)
9187
6354
3200
118
H(43B)
8340
7192
2756
118
H(43C)
9650
8092
2937
118
H(44A)
9587
3799
2089
124
H(44B)
8380
4285
2377
124
H(44C)
9550
3287
2651
124
H(45)
11282
7509
2497
150
226
13) Ethinylestradiol.
Table 8.61 Crystal data and structure refinement for ethinylestradiol.

Identification code
EE_1
Empirical formula
C20 H24 O2
Formula weight
296.39
Temperature
150.1 K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P212121
a = 6.8664(3)
b = 20.9003(11)
c = 22.0448(8)
Volume
3163.6(2) 3
1.245 Mg/m3
0.078 mm-1
F(000)
1280
Crystal size
0.50 x 0.40 x 0.20 mm
2.9325 to 29.1217
Index ranges
-9<=h<=5; -26<=k<=10; -29<=l<=14
9428
5434 [Rint = 0.0424]
3926
Data Completeness
0.998
1.00000 and 0.88116

227
Refinement method
5434 / 4 / 415
1.027
R1 = 0.0626 wR2 = 0.1001
R1 = 0.0991 wR2 = 0.1145
0.7(17)
0.198 and -0.209 e.-3

parameters (2 x 103) for ethinylestradiol. U(eq) is defined as one third of the trace
of the orthogonalized Uij tensor.
Atom
U(eq)
O(1)
9500(4)
3751(2)
5850(1)
33(1)
O(2)
8083(4)
1034(1)
1572(1)
26(1)
O(3)
2555(4)
-213(1)
-4252(1)
29(1)
O(4)
6256(3)
565(1)
544(1)
23(1)
C(1)
9419(6)
3506(2)
5268(2)
25(1)
C(2)
7871(5)
3621(2)
4885(1)
23(1)
C(3)
7802(5)
3355(2)
4304(1)
20(1)
C(4)
6030(5)
3492(2)
3918(1)
25(1)
C(5)
6336(5)
3334(2)
3253(1)
22(1)
C(6)
7260(5)
2676(2)
3192(1)
18(1)
C(7)
7457(5)
2453(2)
2535(1)
17(1)
C(8)
5664(5)
2466(2)
2123(2)
28(1)
C(9)
6205(5)
2007(2)
1599(1)
26(1)
C(10)
8160(5)
1686(2)
1777(1)
21(1)
C(11)
8240(5)
1769(2)
2483(1)
19(1)
C(12)
10247(5)
1739(2)
2782(1)
25(1)
C(13)
10206(5)
1996(2)
3434(1)
27(1)
C(14)
9308(5)
2671(2)
3474(1)
20(1)
C(15)
9315(5)
2963(2)
4110(1)
19(1)
C(16)
10877(5)
2861(2)
4503(2)
26(1)
C(17)
10941(6)
3128(2)
5076(2)
28(1)
228
C(18)
6871(6)
1268(2)
2763(2)
30(1)
C(19)
9829(5)
2009(2)
1481(1)
24(1)
C(20)
11164(6)
2255(2)
1245(2)
36(1)
C(21)
2953(5)
-75(2)
-3660(1)
20(1)
C(22)
4672(5)
235(2)
-3530(1)
19(1)
C(23)
5183(5)
398(2)
-2934(1)
18(1)
C(24)
7113(5)
717(2)
-2829(1)
23(1)
C(25)
7319(5)
1029(2)
-2207(1)
21(1)
C(26)
6517(5)
596(2)
-1709(1)
17(1)
C(27)
6763(5)
890(2)
-1079(1)
16(1)
C(28)
8804(5)
1087(2)
-853(1)
23(1)
C(29)
8596(5)
1111(2)
-149(1)
24(1)
C(30)
6460(5)
909(2)
-14(1)
20(1)
C(31)
5959(5)
471(2)
-565(1)
16(1)
C(32)
3798(5)
341(2)
-677(1)
20(1)
C(33)
3480(5)
51(2)
-1312(1)
20(1)
C(34)
4346(5)
479(2)
-1815(1)
17(1)
C(35)
3912(5)
247(2)
-2458(1)
16(1)
C(36)
2199(5)
-70(2)
-2599(1)
20(1)
C(37)
1697(5)
-239(2)
-3189(1)
21(1)
C(38)
7061(5)
-166(2)
-493(2)
26(1)
C(39)
5174(6)
1480(2)
-5(2)
24(1)
C(40)
4131(6)
1927(2)
-17(2)
36(1)
Table 8.63 Bond lengths [] and angles [] for ethinylestradiol.

Bond lengths []
O(1)-C(1)
1.382(4)
O(2)-C(10)
1.438(4)
O(3)-C(21)
1.364(4)
O(4)-C(30)
1.432(4)
C(1)-C(17)
1.377(5)
C(1)-C(2)
1.379(5)
C(2)-C(3)
1.397(4)
C(3)-C(15)
1.391(5)
C(3)-C(4)
1.512(5)
C(4)-C(5)
1.519(4)
C(5)-C(6)
1.520(4)
C(6)-C(7)
1.527(4)
C(6)-C(14)
1.538(5)
C(7)-C(8)
1.530(4)
229
C(7)-C(11)
1.532(5)
C(8)-C(9)
1.546(5)
C(9)-C(10)
1.551(5)
C(10)-C(19)
1.481(5)
C(10)-C(11)
1.567(4)
C(11)-C(12)
1.529(5)
C(11)-C(18)
1.537(5)
C(12)-C(13)
1.536(4)
C(13)-C(14)
1.542(5)
C(14)-C(15)
1.529(4)
C(15)-C(16)
1.395(5)
C(16)-C(17)
1.382(4)
C(19)-C(20)
1.173(5)
C(21)-C(22)
1.377(5)
C(21)-C(37)
1.393(4)
C(22)-C(23)
1.401(4)
C(23)-C(35)
1.400(4)
C(23)-C(24)
1.501(4)
C(24)-C(25)
1.524(4)
C(25)-C(26)
1.525(4)
C(26)-C(34)
1.528(4)
C(26)-C(27)
1.529(4)
C(27)-C(31)
1.533(4)
C(27)-C(28)
1.543(4)
C(28)-C(29)
1.560(4)
C(29)-C(30)
1.555(5)
C(30)-C(39)
1.485(5)
C(30)-C(31)
1.560(4)
C(31)-C(32)
1.529(4)
C(31)-C(38)
1.539(5)
C(32)-C(33)
1.541(4)
C(33)-C(34)
1.542(4)
C(34)-C(35)
1.528(4)
C(35)-C(36)
1.385(5)
C(36)-C(37)
1.390(4)
C(39)-C(40)
1.178(5)
Bond angles []
C(17)-C(1)-C(2)
119.8(3)
C(17)-C(1)-O(1)
117.9(3)
C(2)-C(1)-O(1)
122.3(4)
C(1)-C(2)-C(3)
121.1(3)
C(15)-C(3)-C(2)
119.5(3)
C(15)-C(3)-C(4)
122.6(3)
C(2)-C(3)-C(4)
117.9(3)
C(3)-C(4)-C(5)
113.0(3)
C(4)-C(5)-C(6)
109.9(3)
C(5)-C(6)-C(7)
113.3(3)
C(5)-C(6)-C(14)
110.6(3)
C(7)-C(6)-C(14)
107.5(3)
C(6)-C(7)-C(8)
119.1(3)
C(6)-C(7)-C(11)
112.8(3)
C(8)-C(7)-C(11)
104.7(3)
C(7)-C(8)-C(9)
103.9(3)
C(8)-C(9)-C(10)
106.7(3)
O(2)-C(10)-C(19)
108.8(3)
O(2)-C(10)-C(9)
107.4(3)
C(19)-C(10)-C(9)
111.2(3)
O(2)-C(10)-C(11)
114.7(3)
C(19)-C(10)-C(11)
111.1(3)
C(9)-C(10)-C(11)
103.5(3)
C(12)-C(11)-C(7)
108.8(3)
C(12)-C(11)-C(18)
110.5(3)
C(7)-C(11)-C(18)
113.0(3)
230
C(12)-C(11)-C(10)
117.1(3)
C(7)-C(11)-C(10)
99.5(3)
C(18)-C(11)-C(10)
107.7(3)
C(11)-C(12)-C(13)
111.9(3)
C(12)-C(13)-C(14)
112.4(3)
C(15)-C(14)-C(6)
111.8(3)
C(15)-C(14)-C(13)
114.6(3)
C(6)-C(14)-C(13)
110.4(3)
C(3)-C(15)-C(16)
118.3(3)
C(3)-C(15)-C(14)
121.0(3)
C(16)-C(15)-C(14)
120.7(3)
C(17)-C(16)-C(15)
122.0(4)
C(1)-C(17)-C(16)
119.3(3)
C(20)-C(19)-C(10)
178.9(4)
O(3)-C(21)-C(22)
118.1(3)
O(3)-C(21)-C(37)
122.6(3)
C(22)-C(21)-C(37)
119.3(3)
C(21)-C(22)-C(23)
121.7(3)
C(35)-C(23)-C(22)
119.4(3)
C(35)-C(23)-C(24)
122.3(3)
C(22)-C(23)-C(24)
118.3(3)
C(23)-C(24)-C(25)
114.2(3)
C(24)-C(25)-C(26)
111.1(3)
C(25)-C(26)-C(34)
109.7(3)
C(25)-C(26)-C(27)
112.1(3)
C(34)-C(26)-C(27)
108.1(3)
C(26)-C(27)-C(31)
113.7(3)
C(26)-C(27)-C(28)
120.1(3)
C(31)-C(27)-C(28)
104.0(2)
C(27)-C(28)-C(29)
104.3(3)
C(30)-C(29)-C(28)
105.5(3)
O(4)-C(30)-C(39)
109.5(3)
O(4)-C(30)-C(29)
113.1(3)
C(39)-C(30)-C(29)
110.2(3)
O(4)-C(30)-C(31)
110.7(3)
C(39)-C(30)-C(31)
110.6(3)
C(29)-C(30)-C(31)
102.6(3)
C(32)-C(31)-C(27)
109.4(3)
C(32)-C(31)-C(38)
109.9(3)
C(27)-C(31)-C(38)
113.2(3)
C(32)-C(31)-C(30)
116.3(3)
C(27)-C(31)-C(30)
99.3(3)
C(38)-C(31)-C(30)
108.5(3)
C(31)-C(32)-C(33)
110.7(3)
C(32)-C(33)-C(34)
111.7(3)
C(35)-C(34)-C(26)
112.5(3)
C(35)-C(34)-C(33)
114.1(3)
C(26)-C(34)-C(33)
111.1(3)
C(36)-C(35)-C(23)
118.0(3)
C(36)-C(35)-C(34)
121.7(3)
C(23)-C(35)-C(34)
120.2(3)
C(35)-C(36)-C(37)
122.8(3)
C(36)-C(37)-C(21)
118.8(3)
C(40)-C(39)-C(30)
177.7(4)
231
Table 8.64 Anisotropic displacement parameters (2 x 103) for ethinylestradiol. The

anisotropic displacement factor exponent takes the form: -2 2 [h2 a*2 U11 + ... + 2 h
k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
44(2)
34(2)
21(1)
-10(1)
-2(1)
-5(2)
O(2)
33(2)
21(2)
26(1)
-7(1)
-4(1)
6(1)
O(3)
32(2)
38(2)
16(1)
-5(1)
-4(1)
-6(2)
O(4)
32(2)
26(2)
12(1)
2(1)
-2(1)
-4(1)
C(1)
30(2)
23(2)
22(2)
0(2)
0(2)
-9(2)
C(2)
25(2)
18(2)
26(2)
-4(2)
3(2)
0(2)
C(3)
25(2)
16(2)
18(2)
2(2)
0(2)
-1(2)
C(4)
23(2)
24(2)
27(2)
-4(2)
-3(2)
5(2)
C(5)
22(2)
20(2)
24(2)
-2(2)
-4(2)
6(2)
C(6)
19(2)
15(2)
18(2)
2(2)
0(2)
0(2)
C(7)
17(2)
16(2)
17(2)
0(2)
-2(2)
1(2)
C(8)
25(2)
34(3)
25(2)
-6(2)
-12(2)
11(2)
C(9)
28(2)
28(2)
23(2)
-2(2)
-10(2)
5(2)
C(10)
26(2)
19(2)
19(2)
-4(2)
-1(2)
1(2)
C(11)
20(2)
19(2)
17(2)
3(2)
3(2)
3(2)
C(12)
29(2)
23(2)
22(2)
-3(2)
-2(2)
8(2)
C(13)
33(2)
25(2)
21(2)
-3(2)
-9(2)
11(2)
C(14)
19(2)
20(2)
20(2)
1(2)
1(2)
0(2)
C(15)
21(2)
18(2)
19(2)
2(2)
-3(2)
-3(2)
C(16)
24(2)
24(2)
30(2)
-1(2)
-2(2)
3(2)
C(17)
30(2)
28(2)
25(2)
0(2)
-12(2)
-6(2)
C(18)
44(3)
23(2)
25(2)
-2(2)
4(2)
-3(2)
C(19)
24(2)
30(2)
17(2)
1(2)
1(2)
5(2)
C(20)
32(2)
47(3)
27(2)
4(2)
8(2)
2(2)
C(21)
23(2)
21(2)
16(2)
-2(2)
-2(2)
6(2)
C(22)
19(2)
20(2)
18(2)
1(2)
2(2)
2(2)
C(23)
20(2)
15(2)
20(2)
-2(2)
-2(2)
3(2)
C(24)
24(2)
28(2)
17(2)
-2(2)
2(2)
-3(2)
C(25)
17(2)
27(2)
19(2)
-1(2)
-1(2)
-7(2)
232
C(26)
17(2)
18(2)
16(2)
-2(2)
2(1)
2(2)
C(27)
19(2)
13(2)
16(2)
0(2)
0(2)
-3(2)
C(28)
18(2)
28(2)
22(2)
1(2)
0(2)
-7(2)
C(29)
23(2)
29(2)
19(2)
-2(2)
-4(2)
-7(2)
C(30)
20(2)
23(2)
15(2)
2(2)
0(2)
-3(2)
C(31)
17(2)
17(2)
14(2)
0(2)
1(2)
0(2)
C(32)
23(2)
23(2)
14(2)
-1(2)
2(2)
-4(2)
C(33)
19(2)
20(2)
20(2)
-1(2)
3(2)
-4(2)
C(34)
16(2)
17(2)
18(2)
-2(2)
2(1)
-1(2)
C(35)
17(2)
12(2)
19(2)
3(2)
1(2)
2(2)
C(36)
21(2)
20(2)
19(2)
3(2)
2(2)
-2(2)
C(37)
18(2)
24(2)
21(2)
-1(2)
-3(2)
-4(2)
C(38)
30(2)
24(2)
23(2)
-2(2)
-2(2)
-1(2)
C(39)
33(2)
26(2)
11(2)
-4(2)
1(2)
-3(2)
C(40)
50(3)
29(3)
29(2)
-4(2)
4(2)
13(2)
Table 8.65 Hydrogen coordinates ( x 104) and isotropic displacement (2 x 103) for
ethinylestradiol.
Atom
U(eq)
H(2)
6854
3881
5016
30
H(4A)
5698
3941
3955
32
H(4B)
4940
3245
4071
32
H(5A)
7175
3653
3068
28
H(5B)
5096
3340
3042
28
H(6)
6449
2367
3411
23
H(7)
8429
2732
2345
22
H(8A)
5420
2894
1972
36
H(8B)
4518
2316
2337
36
H(9A)
6346
2242
1223
34
H(9B)
5199
1686
1546
34
H(12A)
11163
1988
2544
32
H(12B)
10697
1299
2785
32
H(13A)
11524
2009
3592
35
H(13B)
9457
1706
3686
35
233
H(14)
10118
2949
3221
25
H(16)
11906
2605
4375
34
H(17)
12001
3054
5328
36
H(18A)
7398
848
2700
39
H(18B)
5613
1297
2574
39
H(18C)
6744
1347
3190
39
H(20)
12223
2450
1058
46
H(22)
5516
338
-3845
25
H(24A)
7302
1041
-3138
30
H(24B)
8136
401
-2877
30
H(25A)
6622
1432
-2204
27
H(25B)
8683
1117
-2128
27
H(26)
7204
185
-1722
22
H(27)
5977
1281
-1078
21
H(28A)
9169
1502
-1013
30
H(28B)
9776
775
-974
30
H(29A)
9505
818
42
31
H(29B)
8846
1539
31
H(32A)
3073
738
-643
26
H(32B)
3312
48
-372
26
H(33A)
2095
-3
-1383
26
H(33B)
4084
-368
-1329
26
H(34)
3709
896
-1775
22
H(36)
1348
-174
-2286
26
H(37)
544
-457
-3267
27
H(38A)
6523
-401
-158
33
H(38B)
8413
-81
-417
33
H(38C)
6932
-413
-858
33
H(40)
3306
2279
-27
47
H(1O1)
8430(40)
3979(19)
5932(18)
73(18)
H(2O2)
9290(30)
860(20)
1590(20)
85(18)
H(3O3)
1330(30)
-364(19)
-4288(16)
56(15)
H(4O4)
6740(50)
791(15)
851(11)
41(12)
234
14) Ethinylestradiol acetone solvate.
Table 8.66 Crystal data and structure refinement for ethinylestradiol acetone solvate.
Identification code
EE_2
Empirical formula
C23 H30 O3
Formula weight
354.47
Temperature
149.9 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 6.8006(4)
b = 22.1731(9), = 117.031(7)
c = 7.3916(5)
Volume
992.83(9) 3
1.186 Mg/m3
0.077 mm-1
F(000)
384
Crystal size
0.50 x 0.40 x 0.20 mm
3.0877 to 28.9937
Index ranges
-8<=h<=8; -30<=k<=14; -9<=l<=8
3018
2106 [Rint = 0.0216]
235
1978
Data Completeness
0.889
1.00000 and 0.89846
Refinement method
2106 / 1 / 238
1.043
R1 = 0.0315 wR2 = 0.0735
R1 = 0.0348 wR2 = 0.0756
0.0(12)
0.108 and -0.172 e.-3

parameters (2 x 103) for ethinylestradiol acetone solvate. U(eq) is defined as one
Atom
U(eq)
O(1)
3292(3)
4167(1)
10678(2)
33(1)
O(2)
4115(2)
8735(1)
5559(2)
27(1)
O(3)
3545(3)
9779(1)
3558(2)
37(1)
C(16)
3583(3)
5826(1)
10801(3)
22(1)
C(17)
3892(3)
5238(1)
11534(3)
24(1)
C(1)
3110(3)
4764(1)
10153(3)
24(1)
C(2)
2011(3)
4893(1)
8100(3)
24(1)
C(3)
1709(3)
5479(1)
7366(3)
22(1)
C(4)
478(4)
5566(1)
5096(3)
29(1)
C(5)
-165(4)
6216(1)
4476(3)
28(1)
C(6)
1750(3)
6631(1)
5718(3)
21(1)
C(14)
2217(3)
6612(1)
7969(3)
21(1)
C(15)
2525(3)
5962(1)
8735(3)
20(1)
C(13)
4100(4)
7036(1)
9286(3)
24(1)
C(12)
3728(4)
7689(1)
8448(3)
25(1)
C(11)
3308(3)
7699(1)
6234(3)
21(1)
C(10)
2396(3)
8296(1)
5043(3)
23(1)
236
C(9)
1430(4)
8090(1)
2796(3)
28(1)
C(8)
796(4)
7419(1)
2766(3)
30(1)
C(7)
1361(3)
7279(1)
4992(3)
22(1)
C(18)
5443(3)
7528(1)
6112(3)
29(1)
C(19)
601(4)
8543(1)
5429(3)
26(1)
C(20)
-900(4)
8716(1)
5667(4)
37(1)
C(21)
2434(4)
10568(1)
1167(4)
35(1)
C(22)
2784(3)
9923(1)
1773(3)
29(1)
C(23)
2147(4)
9463(1)
134(4)
38(1)
Table 8.68 Bond lengths [] and angles [] for ethinylestradiol acetone solvate.
Bond lengths []
O(1)-C(1)
1.369(3)
O(2)-C(10)
1.434(3)
O(3)-C(22)
1.221(2)
C(16)-C(17)
1.392(3)
C(16)-C(15)
1.394(3)
C(17)-C(1)
1.390(3)
C(1)-C(2)
1.383(3)
C(2)-C(3)
1.385(3)
C(3)-C(15)
1.404(3)
C(3)-C(4)
1.509(3)
C(4)-C(5)
1.515(3)
C(5)-C(6)
1.517(3)
C(6)-C(7)
1.513(3)
C(6)-C(14)
1.546(3)
C(14)-C(15)
1.526(3)
C(14)-C(13)
1.529(3)
C(13)-C(12)
1.550(3)
C(12)-C(11)
1.528(3)
C(11)-C(7)
1.536(3)
C(11)-C(18)
1.542(3)
C(11)-C(10)
1.554(3)
C(10)-C(19)
1.479(3)
C(10)-C(9)
1.552(3)
C(9)-C(8)
1.545(3)
C(8)-C(7)
1.541(3)
C(19)-C(20)
1.176(3)
C(21)-C(22)
1.486(3)
C(22)-C(23)
1.489(3)
Bond angles []
C(17)-C(16)-C(15)
122.8(2)
C(1)-C(17)-C(16)
118.83(19)
O(1)-C(1)-C(2)
116.5(2)
O(1)-C(1)-C(17)
124.50(19)
C(2)-C(1)-C(17)
119.0(2)
C(1)-C(2)-C(3)
122.2(2)
C(2)-C(3)-C(15)
119.61(19)
C(2)-C(3)-C(4)
117.7(2)
C(15)-C(3)-C(4)
122.7(2)
C(3)-C(4)-C(5)
113.35(18)
237
C(4)-C(5)-C(6)
110.14(18)
C(7)-C(6)-C(5)
113.46(17)
C(7)-C(6)-C(14)
109.04(18)
C(5)-C(6)-C(14)
109.53(17)
C(15)-C(14)-C(13)
114.21(17)
C(15)-C(14)-C(6)
110.65(18)
C(13)-C(14)-C(6)
111.78(17)
C(16)-C(15)-C(3)
117.5(2)
C(16)-C(15)-C(14)
121.76(19)
C(3)-C(15)-C(14)
120.72(17)
C(14)-C(13)-C(12)
112.51(18)
C(11)-C(12)-C(13)
111.04(18)
C(12)-C(11)-C(7)
108.78(17)
C(12)-C(11)-C(18)
109.66(17)
C(7)-C(11)-C(18)
113.21(17)
C(12)-C(11)-C(10)
116.86(18)
C(7)-C(11)-C(10)
99.45(16)
C(18)-C(11)-C(10)
108.67(17)
O(2)-C(10)-C(19)
109.97(18)
O(2)-C(10)-C(9)
112.48(16)
C(19)-C(10)-C(9)
109.33(18)
O(2)-C(10)-C(11)
111.13(16)
C(19)-C(10)-C(11)
110.96(17)
C(9)-C(10)-C(11)
102.79(17)
C(8)-C(9)-C(10)
106.14(18)
C(7)-C(8)-C(9)
104.31(18)
C(6)-C(7)-C(11)
113.54(17)
C(6)-C(7)-C(8)
119.29(18)
C(11)-C(7)-C(8)
104.15(17)
C(20)-C(19)-C(10)
176.4(2)
O(3)-C(22)-C(21)
120.6(2)
O(3)-C(22)-C(23)
121.5(2)
C(21)-C(22)-C(23)
117.8(2)
Table 8.69 Anisotropic displacement parameters (2 x 103) for ethinylestradiol

acetone solvate. The anisotropic displacement factor exponent takes the form: -2 2
[h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
36(1)
23(1)
33(1)
6(1)
10(1)
1(1)
O(2)
25(1)
21(1)
31(1)
5(1)
10(1)
-2(1)
O(3)
44(1)
34(1)
27(1)
6(1)
11(1)
-3(1)
C(16)
20(1)
24(1)
24(1)
-1(1)
10(1)
-3(1)
C(17)
23(1)
28(1)
20(1)
2(1)
9(1)
0(1)
C(1)
22(1)
22(1)
30(1)
5(1)
13(1)
4(1)
C(2)
21(1)
23(1)
30(1)
-6(1)
12(1)
-4(1)
C(3)
20(1)
25(1)
23(1)
0(1)
10(1)
1(1)
C(4)
35(1)
24(1)
23(1)
-4(1)
8(1)
-7(1)
C(5)
31(1)
28(1)
17(1)
0(1)
5(1)
-7(1)
C(6)
23(1)
20(1)
21(1)
-1(1)
9(1)
-1(1)
238
C(14)
19(1)
22(1)
20(1)
-1(1)
8(1)
1(1)
C(15)
17(1)
22(1)
23(1)
-1(1)
11(1)
-1(1)
C(13)
27(1)
22(1)
20(1)
-1(1)
7(1)
-3(1)
C(12)
30(1)
20(1)
22(1)
0(1)
8(1)
-2(1)
C(11)
19(1)
19(1)
25(1)
0(1)
9(1)
-2(1)
C(10)
22(1)
21(1)
25(1)
2(1)
11(1)
-1(1)
C(9)
31(1)
28(1)
24(1)
3(1)
11(1)
-2(1)
C(8)
35(1)
30(1)
22(1)
-1(1)
10(1)
-5(1)
C(7)
22(1)
23(1)
19(1)
1(1)
7(1)
1(1)
C(18)
24(1)
28(1)
37(1)
5(1)
15(1)
3(1)
C(19)
27(1)
19(1)
28(1)
4(1)
10(1)
-1(1)
C(20)
37(1)
32(1)
49(2)
5(1)
27(1)
7(1)
C(21)
29(1)
37(2)
41(1)
13(1)
18(1)
3(1)
C(22)
21(1)
34(1)
31(1)
4(1)
12(1)
-4(1)
C(23)
38(1)
45(2)
35(1)
-2(1)
19(1)
-8(1)

x 103) for ethinylestradiol acetone solvate.
Atom
U(eq)
H(1O1)
3917
4136
11919
43
H(2O2)
3613
9038
4864
35
H(16)
4105
6142
11729
29
H(17)
4610
5162
12923
31
H(2)
1456
4577
7180
32
H(4A)
-847
5320
4561
38
H(4B)
1395
5425
4490
38
H(5A)
-1430
6321
4687
36
H(5B)
-577
6264
3044
36
H(6)
3062
6483
5631
28
H(14)
887
6764
8014
27
H(13A)
5472
6883
9362
32
H(13B)
4240
7040
10652
32
H(12A)
2473
7864
8548
33
239
H(12B)
5017
7931
9263
33
H(9A)
142
8328
1947
36
H(9B)
2520
8135
2299
36
H(8A)
-764
7358
1882
39
H(8B)
1641
7166
2306
39
H(7)
112
7424
5191
29
H(18A)
5892
7129
6648
38
H(18B)
6588
7810
6890
38
H(18C)
5177
7538
4721
38
H(20)
-2087
8852
5855
48
H(21A)
2914
10816
2358
45
H(21B)
894
10638
299
45
H(21C)
3269
10668
453
45
H(23A)
764
9284
-108
50
H(23B)
3263
9157
541
50
H(23C)
2002
9653
-1088
50
240
15) Ethinylestradiol pentan-2-ol solvate.
Table 8.71 Crystal data and structure refinement for ethinylestradiol pentan-2-ol
solvate.
Identification code
EE_3
Empirical formula
C25 H36 O3
Formula weight
384.54
Temperature
149.9 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 12.3596(6)
b = 6.9442(3), = 111.000(6)
c = 13.9837(8)
Volume
1120.47(9) 3
1.140 Mg/m3
0.073 mm-1
F(000)
420
Crystal size
0.50 x 0.40 x 0.20 mm
2.9274 to 29.0582
Index ranges
-16<=h<=8; -8<=k<=7; -18<=l<=18
5341
3508 [Rint = 0.0324]

241
2899
Data Completeness
0.998
1.00000 and 0.89590
Refinement method
3508 / 1 / 257
1.048
R1 = 0.0578 wR2 = 0.1400
R1 = 0.0729 wR2 = 0.1516
-0.2(19)
0.611 and -0.284 e.-3

parameters (2 x 103) for ethinylestradiol pentan-2-ol solvate.U(eq) is defined as
Atom
U(eq)
O(1)
267(2)
2131(3)
7534(2)
37(1)
O(2)
-8681(2)
5422(3)
7101(2)
35(1)
O(3)
1121(2)
-1358(4)
8203(2)
41(1)
C(24)
1511(4)
-1881(7)
9265(3)
54(1)
C(22)
2880(4)
936(8)
9793(3)
73(2)
C(21)
3069(6)
2762(9)
10362(5)
103(2)
C(23)
1879(5)
-176(8)
9906(4)
70(2)
C(16)
-2709(3)
1343(5)
7442(3)
31(1)
C(17)
-1547(3)
969(5)
7608(3)
32(1)
C(1)
-887(3)
2379(5)
7390(2)
28(1)
C(2)
-1384(3)
4125(5)
7017(3)
29(1)
C(3)
-2544(3)
4491(5)
6833(2)
27(1)
C(4)
-3032(3)
6425(5)
6386(3)
38(1)
C(5)
-4346(3)
6427(5)
5909(3)
33(1)
C(6)
-4859(3)
5531(4)
6643(2)
24(1)
C(14)
-4523(3)
3408(4)
6828(2)
23(1)
C(15)
-3231(3)
3086(5)
7063(2)
22(1)
242
C(13)
-5003(3)
2509(5)
7600(3)
30(1)
C(12)
-6329(3)
2772(5)
7257(3)
31(1)
C(11)
-6681(3)
4892(5)
7046(2)
26(1)
C(7)
-6178(3)
5666(5)
6265(2)
26(1)
C(8)
-6761(3)
7629(5)
5947(3)
36(1)
C(9)
-7982(3)
7350(6)
5999(3)
39(1)
C(10)
-7996(3)
5324(5)
6458(3)
28(1)
C(18)
-6297(3)
6048(5)
8051(3)
36(1)
C(19)
-8536(3)
3881(6)
5649(3)
41(1)
C(20)
-9001(3)
2744(8)
5028(4)
68(2)
C(25)
621(4)
-3170(7)
9450(4)
63(1)
Table 8.73 Bond lengths [] and angles [] for ethinylestradiol pentan-2-ol solvate.
Bond lengths []
O(1)-C(1)
1.379(4)
O(2)-C(10)
1.440(4)
O(3)-C(24)
1.434(4)
C(24)-C(23)
1.455(7)
C(24)-C(25)
1.510(6)
C(22)-C(21)
1.470(8)
C(22)-C(23)
1.514(7)
C(16)-C(15)
1.384(5)
C(16)-C(17)
1.395(4)
C(17)-C(1)
1.376(5)
C(1)-C(2)
1.375(5)
C(2)-C(3)
1.386(4)
C(3)-C(15)
1.403(4)
C(3)-C(4)
1.513(5)
C(4)-C(5)
1.518(4)
C(5)-C(6)
1.520(4)
C(6)-C(7)
1.525(4)
C(6)-C(14)
1.528(4)
C(14)-C(15)
1.527(4)
C(14)-C(13)
1.538(4)
C(13)-C(12)
1.546(4)
C(12)-C(11)
1.534(5)
C(11)-C(7)
1.534(4)
C(11)-C(18)
1.538(5)
C(11)-C(10)
1.566(4)
C(7)-C(8)
1.531(5)
C(8)-C(9)
1.549(5)
C(9)-C(10)
1.549(5)
C(10)-C(19)
1.479(5)
C(19)-C(20)
1.162(6)
Bond angles []
O(3)-C(24)-C(23)
110.3(4)
O(3)-C(24)-C(25)
109.4(4)
C(23)-C(24)-C(25)
117.6(4)
C(21)-C(22)-C(23)
111.1(5)
243
C(24)-C(23)-C(22)
116.0(4)
C(15)-C(16)-C(17)
122.5(3)
C(1)-C(17)-C(16)
119.1(3)
C(2)-C(1)-C(17)
119.5(3)
C(2)-C(1)-O(1)
117.6(3)
C(17)-C(1)-O(1)
122.9(3)
C(1)-C(2)-C(3)
121.6(3)
C(2)-C(3)-C(15)
120.0(3)
C(2)-C(3)-C(4)
118.2(3)
C(15)-C(3)-C(4)
121.8(3)
C(3)-C(4)-C(5)
112.8(3)
C(4)-C(5)-C(6)
110.0(3)
C(5)-C(6)-C(7)
113.2(3)
C(5)-C(6)-C(14)
110.8(3)
C(7)-C(6)-C(14)
108.1(2)
C(15)-C(14)-C(6)
112.2(2)
C(15)-C(14)-C(13)
115.2(2)
C(6)-C(14)-C(13)
111.1(3)
C(16)-C(15)-C(3)
117.3(3)
C(16)-C(15)-C(14)
121.2(3)
C(3)-C(15)-C(14)
121.4(3)
C(14)-C(13)-C(12)
111.6(3)
C(11)-C(12)-C(13)
111.6(3)
C(7)-C(11)-C(12)
108.4(3)
C(7)-C(11)-C(18)
113.4(3)
C(12)-C(11)-C(18)
110.5(3)
C(7)-C(11)-C(10)
99.7(2)
C(12)-C(11)-C(10)
117.0(3)
C(18)-C(11)-C(10)
107.6(2)
C(6)-C(7)-C(8)
119.2(3)
C(6)-C(7)-C(11)
112.8(3)
C(8)-C(7)-C(11)
104.5(3)
C(7)-C(8)-C(9)
103.9(3)
C(10)-C(9)-C(8)
106.8(3)
O(2)-C(10)-C(19)
107.7(3)
O(2)-C(10)-C(9)
108.2(3)
C(19)-C(10)-C(9)
111.6(3)
O(2)-C(10)-C(11)
114.4(3)
C(19)-C(10)-C(11)
111.7(3)
C(9)-C(10)-C(11)
103.2(3)
C(20)-C(19)-C(10)
176.9(4)

pentan-2-ol solvate. The anisotropic displacement factor exponent takes the form: -2
2 [h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
15(1)
34(1)
64(2)
11(1)
16(1)
6(1)
O(2)
24(1)
32(1)
59(2)
0(1)
27(1)
2(1)
O(3)
52(2)
36(1)
40(1)
2(1)
22(1)
10(1)
C(24)
75(3)
54(3)
41(2)
5(2)
29(2)
-4(2)
C(22)
52(3)
106(5)
45(3)
17(3)
-1(2)
-30(3)
C(21)
105(5)
86(4)
90(4)
19(4)
1(4)
41(4)
C(23)
83(4)
77(3)
47(2)
5(2)
21(3)
17(3)
244
C(16)
19(2)
28(2)
48(2)
4(2)
16(2)
0(2)
C(17)
22(2)
27(2)
48(2)
8(2)
13(2)
7(2)
C(1)
16(2)
32(2)
38(2)
2(2)
11(1)
2(2)
C(2)
20(2)
29(2)
43(2)
3(2)
17(2)
-2(1)
C(3)
20(2)
29(2)
34(2)
2(1)
11(1)
4(1)
C(4)
24(2)
29(2)
68(3)
14(2)
24(2)
4(2)
C(5)
23(2)
32(2)
48(2)
15(2)
18(2)
7(2)
C(6)
12(2)
25(2)
33(2)
-2(1)
8(1)
1(1)
C(14)
14(2)
24(2)
32(2)
-1(1)
10(1)
0(1)
C(15)
15(2)
24(2)
29(2)
-2(1)
9(1)
1(1)
C(13)
20(2)
32(2)
44(2)
8(2)
17(2)
6(2)
C(12)
21(2)
30(2)
50(2)
4(2)
21(2)
-1(2)
C(11)
16(2)
28(2)
37(2)
-1(1)
12(1)
2(1)
C(7)
14(2)
28(2)
37(2)
1(2)
10(1)
2(1)
C(8)
20(2)
34(2)
53(2)
9(2)
14(2)
3(2)
C(9)
21(2)
44(2)
56(2)
12(2)
18(2)
10(2)
C(10)
14(2)
32(2)
41(2)
-3(2)
13(1)
-1(1)
C(18)
23(2)
45(2)
39(2)
-7(2)
12(2)
3(2)
C(19)
14(2)
55(2)
56(2)
-6(2)
16(2)
-2(2)
C(20)
20(2)
103(4)
82(3)
-50(3)
20(2)
-19(2)
C(25)
56(3)
77(4)
59(3)
18(3)
24(2)
-3(3)

x 103) for ethinylestradiol pentan-2-ol solvate.
Atom
U(eq)
H(1O1)
475
1050
7763
48
H(2O2)
-8691
4362
7356
45
H(3O3)
1105
-2319
7857
53
H(24)
2206
-2671
9395
71
H(22A)
3579
162
10046
95
H(22B)
2719
1200
9073
95
H(21A)
3146
2513
11059
134
H(21B)
2422
3603
10050
134
245
H(21C)
3764
3361
10349
134
H(23A)
2095
-566
10616
91
H(23B)
1221
686
9753
91
H(16)
-3150
385
7590
40
H(17)
-1221
-217
7864
42
H(2)
-931
5083
6885
38
H(4A)
-2716
6780
5869
49
H(4B)
-2789
7389
6923
49
H(5A)
-4592
5703
5274
43
H(5B)
-4623
7738
5753
43
H(6)
-4543
6210
7300
31
H(14)
-4923
2755
6175
30
H(13A)
-4632
3107
8264
40
H(13B)
-4819
1147
7669
40
H(12A)
-6706
2023
6642
41
H(12B)
-6591
2290
7789
41
H(7)
-6474
4832
5662
34
H(8A)
-6812
7963
5259
46
H(8B)
-6337
8631
6415
46
H(9A)
-8133
8331
6428
51
H(9B)
-8571
7439
5319
51
H(18A)
-6533
7425
7898
46
H(18B)
-5436
5968
8391
46
H(18C)
-6674
5501
8516
46
H(20)
-9374
1834
4531
88
H(25A)
543
-4386
9047
82
H(25B)
-143
-2493
9228
82
H(25C)
874
-3486
10196
82
246
16) Ethinylestradiol DMSO solvate.
Table 8.76 Crystal data and structure refinement for ethinylestradiol DMSO solvate.
Identification code
EE_4
Empirical formula
C24 H36 O4 S2
Formula weight
452.65
Temperature
150.0 K
Wavelength
0.7107
Crystal system
Orthorhombic
Space group
P212121
a = 6.9652(3)
b = 10.9689(3)
c = 31.2143(11)
Volume
2384.78(15) 3
1.261 Mg/m3
0.250 mm-1
F(000)
976
Crystal size
0.50 x 0.40 x 0.20 mm
2.9905 to 29.0380
Index ranges
-9<=h<=5; -8<=k<=13; -21<=l<=42
7212
247
4224 [Rint = 0.0204]
3945
Data Completeness
0.998
1.00000 and 0.93708
Refinement method
4224 / 0 / 277
1.119
R1 = 0.0432 wR2 = 0.0924
R1 = 0.0476 wR2 = 0.0981
0.03(9)
0.249 and -0.303 e.-3

parameters (2 x 103) for ethinylestradiol DMSO solvate.U(eq) is defined as one
Atom
U(eq)
S(1)
7675(1)
9230(1)
8995(1)
24(1)
O(4)
9370(3)
10076(2)
8985(1)
29(1)
S(2)
8734(2)
5225(1)
9794(1)
41(1)
O(3)
8878(4)
6056(2)
10173(1)
45(1)
O(2)
9367(3)
2547(2)
8970(1)
24(1)
O(1)
6713(3)
1723(2)
5499(1)
29(1)
C(1)
6782(4)
1895(2)
5931(1)
19(1)
C(2)
6855(4)
3042(2)
6118(1)
19(1)
C(3)
6894(4)
3183(2)
6564(1)
15(1)
C(4)
6954(4)
4464(2)
6740(1)
20(1)
C(5)
6484(4)
4530(2)
7218(1)
20(1)
C(6)
7582(4)
3556(2)
7462(1)
15(1)
C(7)
7380(4)
3644(2)
7945(1)
16(1)
C(8)
7941(4)
4818(2)
8176(1)
20(1)
C(9)
8206(4)
4431(2)
8651(1)
21(1)
C(10)
8046(4)
3013(2)
8663(1)
18(1)
248
C(11)
8504(4)
2656(2)
8188(1)
16(1)
C(12)
7823(4)
1401(2)
8040(1)
19(1)
C(13)
7999(4)
1282(2)
7550(1)
18(1)
C(14)
6887(4)
2285(2)
7317(1)
16(1)
C(15)
6900(4)
2155(2)
6832(1)
16(1)
C(16)
6797(4)
1014(2)
6634(1)
18(1)
C(17)
6737(4)
869(2)
6195(1)
21(1)
C(18)
10701(4)
2767(3)
8124(1)
22(1)
C(19)
6067(4)
2660(2)
8785(1)
20(1)
C(20)
4492(5)
2409(3)
8888(1)
28(1)
C(21)
10539(7)
4118(4)
9867(1)
62(1)
C(22)
6705(7)
4300(4)
9884(2)
73(1)
C(23)
8017(5)
8141(3)
8573(1)
32(1)
C(24)
8116(6)
8219(3)
9429(1)
38(1)
Table 8.78 Bond lengths [] and angles [] for ethinylestradiol DMSO solvate.
Bond lengths []
S(1)-O(4)
1.502(2)
S(1)-C(24)
1.777(3)
S(1)-C(23)
1.795(3)
S(2)-O(3)
1.497(2)
S(2)-C(22)
1.762(5)
S(2)-C(21)
1.763(4)
O(2)-C(10)
1.423(3)
O(1)-C(1)
1.363(3)
C(1)-C(2)
1.389(4)
C(1)-C(17)
1.394(4)
C(2)-C(3)
1.401(4)
C(3)-C(15)
1.403(3)
C(3)-C(4)
1.509(3)
C(4)-C(5)
1.529(4)
C(5)-C(6)
1.519(4)
C(6)-C(7)
1.518(4)
C(6)-C(14)
1.544(3)
C(7)-C(8)
1.527(4)
C(7)-C(11)
1.537(4)
C(8)-C(9)
1.553(4)
C(9)-C(10)
1.559(3)
C(10)-C(19)
1.481(4)
C(10)-C(11)
1.568(4)
C(11)-C(12)
1.527(3)
C(11)-C(18)
1.548(4)
C(12)-C(13)
1.539(3)
C(13)-C(14)
1.531(3)
C(14)-C(15)
1.520(3)
C(15)-C(16)
1.398(4)
C(16)-C(17)
1.382(4)
C(19)-C(20)
1.176(4)
249
Bond angles []
O(4)-S(1)-C(24)
105.42(15)
O(4)-S(1)-C(23)
106.95(14)
C(24)-S(1)-C(23)
96.94(15)
O(3)-S(2)-C(22)
106.21(19)
O(3)-S(2)-C(21)
105.68(17)
C(22)-S(2)-C(21)
98.9(2)
O(1)-C(1)-C(2)
122.9(2)
O(1)-C(1)-C(17)
118.2(2)
C(2)-C(1)-C(17)
118.9(2)
C(1)-C(2)-C(3)
121.2(2)
C(2)-C(3)-C(15)
120.2(2)
C(2)-C(3)-C(4)
117.6(2)
C(15)-C(3)-C(4)
122.1(2)
C(3)-C(4)-C(5)
113.1(2)
C(6)-C(5)-C(4)
110.4(2)
C(7)-C(6)-C(5)
114.0(2)
C(7)-C(6)-C(14)
108.6(2)
C(5)-C(6)-C(14)
109.3(2)
C(6)-C(7)-C(8)
120.0(2)
C(6)-C(7)-C(11)
113.4(2)
C(8)-C(7)-C(11)
103.4(2)
C(7)-C(8)-C(9)
104.6(2)
C(8)-C(9)-C(10)
106.7(2)
O(2)-C(10)-C(19)
109.6(2)
O(2)-C(10)-C(9)
109.1(2)
C(19)-C(10)-C(9)
109.5(2)
O(2)-C(10)-C(11)
114.5(2)
C(19)-C(10)-C(11)
111.5(2)
C(9)-C(10)-C(11)
102.3(2)
C(12)-C(11)-C(7)
109.2(2)
C(12)-C(11)-C(18)
109.9(2)
C(7)-C(11)-C(18)
112.6(2)
C(12)-C(11)-C(10)
116.6(2)
C(7)-C(11)-C(10)
100.8(2)
C(18)-C(11)-C(10)
107.7(2)
C(11)-C(12)-C(13)
110.6(2)
C(14)-C(13)-C(12)
111.9(2)
C(15)-C(14)-C(13)
113.9(2)
C(15)-C(14)-C(6)
112.0(2)
C(13)-C(14)-C(6)
110.5(2)
C(16)-C(15)-C(3)
117.2(2)
C(16)-C(15)-C(14)
121.5(2)
C(3)-C(15)-C(14)
121.2(2)
C(17)-C(16)-C(15)
122.8(2)
C(16)-C(17)-C(1)
119.5(2)
C(20)-C(19)-C(10)
178.2(3)

DMSO solvate. The anisotropic displacement factor exponent takes the form: -2 2
[h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
S(1)
26(1)
22(1)
24(1)
4(1)
1(1)
4(1)
O(4)
33(1)
22(1)
32(1)
2(1)
-2(1)
-1(1)
S(2)
78(1)
26(1)
19(1)
-5(1)
-6(1)
1(1)
250
O(3)
85(2)
29(1)
22(1)
-10(1)
-2(1)
2(1)
O(2)
30(1)
22(1)
19(1)
2(1)
-9(1)
-4(1)
O(1)
49(2)
24(1)
13(1)
0(1)
0(1)
0(1)
C(1)
21(2)
24(1)
13(1)
-1(1)
0(1)
0(1)
C(2)
20(2)
19(1)
17(1)
6(1)
3(1)
1(1)
C(3)
11(1)
17(1)
17(1)
2(1)
3(1)
0(1)
C(4)
26(2)
14(1)
18(1)
2(1)
-2(1)
0(1)
C(5)
22(2)
16(1)
20(1)
-1(1)
0(1)
2(1)
C(6)
13(1)
16(1)
17(1)
0(1)
0(1)
1(1)
C(7)
15(1)
16(1)
16(1)
1(1)
3(1)
-1(1)
C(8)
24(2)
17(1)
19(1)
0(1)
1(1)
-2(1)
C(9)
28(2)
19(1)
15(1)
-4(1)
-1(1)
-4(1)
C(10)
22(2)
19(1)
14(1)
1(1)
-3(1)
-4(1)
C(11)
18(2)
15(1)
14(1)
1(1)
1(1)
-1(1)
C(12)
22(2)
18(1)
16(1)
3(1)
-2(1)
0(1)
C(13)
23(2)
14(1)
16(1)
0(1)
1(1)
-1(1)
C(14)
15(1)
15(1)
17(1)
0(1)
2(1)
0(1)
C(15)
13(1)
19(1)
15(1)
2(1)
0(1)
1(1)
C(16)
19(2)
16(1)
20(1)
3(1)
0(1)
-1(1)
C(17)
24(2)
17(1)
20(1)
-3(1)
-2(1)
1(1)
C(18)
20(2)
23(1)
22(2)
1(1)
-3(1)
1(1)
C(19)
28(2)
21(1)
12(1)
-1(1)
0(1)
-2(1)
C(20)
30(2)
37(2)
18(2)
-4(1)
1(1)
-8(2)
C(21)
74(3)
51(2)
62(3)
-29(2)
-6(3)
10(2)
C(22)
78(4)
71(3)
69(3)
-24(3)
1(3)
-9(3)
C(23)
29(2)
36(2)
32(2)
-7(1)
2(2)
-3(2)
C(24)
49(2)
36(2)
28(2)
13(2)
0(2)
3(2)
251

x 103) for ethinylestradiol DMSO solvate.
Atom
U(eq)
H(2)
9280
1802
8979
31
H(1)
6717
2386
5378
37
H(2A)
6879
3730
5944
24
H(4A)
6044
4964
6583
25
H(4B)
8225
4801
6693
25
H(5A)
6823
5329
7327
25
H(5B)
5116
4414
7259
25
H(6)
8946
3632
7389
20
H(7)
6020
3505
8009
20
H(8A)
6938
5427
8150
26
H(8B)
9125
5147
8061
26
H(9A)
7219
4797
8829
27
H(9B)
9451
4690
8756
27
H(12A)
6495
1283
8125
24
H(12B)
8590
774
8177
24
H(13A)
9342
1325
7470
23
H(13B)
7511
492
7462
23
H(14)
5545
2213
7408
20
H(16)
6767
321
6806
24
H(17)
6667
93
6075
27
H(18A)
11331
2094
8262
29
H(18B)
11143
3518
8247
29
H(18C)
10992
2759
7823
29
H(20)
3246
2211
8969
37
H(21A)
11777
4502
9855
81
H(21B)
10448
3517
9644
81
H(21C)
10376
3732
10141
81
H(22A)
6769
3959
10167
94
H(22B)
6679
3655
9676
94
H(22C)
5563
4784
9857
94
252
H(23A)
7907
8542
8301
42
H(23B)
7059
7515
8594
42
H(23C)
9270
7782
8598
42
H(24A)
9377
7874
9400
49
H(24B)
7178
7578
9426
49
H(24C)
8033
8659
9694
49
253
17) 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzene.
Table 8.81 Crystal data and structure refinement for 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzene.

Identification code
phsulf_1
Empirical formula
C24 H20 O4 S2
Formula weight
436.52
Temperature
299.1 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 5.9436(3)
b = 14.0768(8), = 100.537(5)
c = 13.0684(8)
Volume
1074.95(11) 3
1.349 Mg/m3
0.276 mm-1
F(000)
456
254
Crystal size
0.50 x 0.40 x 0.20 mm
3.1647 to 29.0854
Index ranges
-7<=h<=6; -7<=k<=18; -17<=l<=12
5206
2704 [Rint = 0.0344]
2287
Data Completeness
0.999
1.00000 and 0.88884
Refinement method
2704 / 1 / 271
1.059
R1 = 0.0540 wR2 = 0.1286
R1 = 0.0666 wR2 = 0.1436
-0.02(12)
0.478 and -0.225 e.-3

parameters (2 x 103) for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-benzene. U (eq) is defined as one third of the trace of the orthogonalized Uij
tensor.
Atom
U(eq)
S(1)
-3021(2)
7800(1)
6061(1)
45(1)
S(2)
1747(2)
8008(1)
9515(1)
49(1)
O(3)
-641(5)
7965(3)
9588(2)
55(1)
O(1)
-5390(5)
7662(3)
6116(3)
57(1)
O(4)
3429(6)
7793(3)
10423(3)
67(1)
O(2)
-1990(6)
7248(3)
5350(3)
58(1)
C(1)
-2706(8)
9003(4)
5778(4)
41(1)
C(2)
-4245(9)
9660(5)
6011(5)
59(2)
C(3)
-3940(11)
10620(5)
5786(6)
75(2)
C(4)
-2116(11)
10890(5)
5323(6)
74(2)
C(5)
-617(11)
10231(5)
5104(6)
76(2)
255
C(6)
-867(9)
9279(4)
5331(5)
65(2)
C(7)
-1405(7)
7677(4)
7323(3)
40(1)
C(8)
652(7)
7300(3)
7509(4)
40(1)
C(9)
2223(7)
7261(4)
8500(4)
43(1)
C(10)
4154(8)
6714(4)
8692(4)
46(1)
C(11)
4858(7)
6010(4)
8055(4)
41(1)
C(12)
6847(8)
5551(4)
8365(4)
47(1)
C(13)
7807(8)
4768(4)
7873(4)
44(1)
C(14)
10038(9)
4464(5)
8297(4)
56(2)
C(15)
11011(10)
3712(5)
7873(5)
62(2)
C(16)
9837(11)
3261(6)
7055(5)
77(2)
C(17)
7628(12)
3524(6)
6599(6)
83(2)
C(18)
6665(9)
4275(5)
7013(4)
65(2)
C(19)
2327(8)
9169(4)
9096(4)
46(1)
C(20)
4567(9)
9495(4)
9299(5)
62(2)
C(21)
5014(11)
10398(5)
9002(6)
78(2)
C(22)
3276(12)
10969(5)
8498(6)
75(2)
C(23)
1091(13)
10628(5)
8311(6)
86(2)
C(24)
595(10)
9730(5)
8588(5)
68(2)
Table 8.83 Bond lengths [] and angles [] for 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzene.

Bond lengths []
S(1)-O(2)
1.432(4)
S(1)-O(1)
1.436(3)
S(1)-C(1)
1.751(5)
S(1)-C(7)
1.758(4)
S(2)-O(4)
1.438(3)
S(2)-O(3)
1.442(3)
S(2)-C(9)
1.756(5)
S(2)-C(19)
1.776(6)
C(1)-C(2)
1.374(7)
C(1)-C(6)
1.386(7)
C(2)-C(3)
1.402(9)
C(3)-C(4)
1.387(9)
C(4)-C(5)
1.353(10)
C(5)-C(6)
1.386(9)
C(7)-C(8)
1.315(6)
C(8)-C(9)
1.452(6)
C(9)-C(10)
1.367(6)
C(10)-C(11)
1.406(7)
C(11)-C(12)
1.344(6)
C(12)-C(13)
1.445(7)
256
C(13)-C(18)
1.388(8)
C(13)-C(14)
1.407(7)
C(14)-C(15)
1.371(8)
C(15)-C(16)
1.327(9)
C(16)-C(17)
1.389(9)
C(17)-C(18)
1.360(9)
C(19)-C(24)
1.370(7)
C(19)-C(20)
1.387(7)
C(20)-C(21)
1.369(10)
C(21)-C(22)
1.377(10)
C(22)-C(23)
1.364(9)
C(23)-C(24)
1.362(9)
Bond angles []
O(2)-S(1)-O(1)
119.9(2)
O(2)-S(1)-C(1)
108.2(3)
O(1)-S(1)-C(1)
106.6(2)
O(2)-S(1)-C(7)
109.3(2)
O(1)-S(1)-C(7)
108.2(2)
C(1)-S(1)-C(7)
103.4(2)
O(4)-S(2)-O(3)
118.7(2)
O(4)-S(2)-C(9)
108.3(2)
O(3)-S(2)-C(9)
108.8(2)
O(4)-S(2)-C(19)
107.7(3)
O(3)-S(2)-C(19)
107.9(2)
C(9)-S(2)-C(19)
104.6(2)
C(2)-C(1)-C(6)
120.9(5)
C(2)-C(1)-S(1)
120.2(4)
C(6)-C(1)-S(1)
118.9(4)
C(1)-C(2)-C(3)
119.1(6)
C(4)-C(3)-C(2)
119.8(6)
C(5)-C(4)-C(3)
120.1(6)
C(4)-C(5)-C(6)
121.2(6)
C(1)-C(6)-C(5)
119.0(6)
C(8)-C(7)-S(1)
123.0(4)
C(7)-C(8)-C(9)
127.3(4)
C(10)-C(9)-C(8)
124.5(5)
C(10)-C(9)-S(2)
116.4(4)
C(8)-C(9)-S(2)
119.0(3)
C(9)-C(10)-C(11)
128.2(5)
C(12)-C(11)-C(10)
120.1(5)
C(11)-C(12)-C(13)
129.1(5)
C(18)-C(13)-C(14)
117.0(5)
C(18)-C(13)-C(12)
124.6(5)
C(14)-C(13)-C(12)
118.5(5)
C(15)-C(14)-C(13)
120.8(6)
C(16)-C(15)-C(14)
119.8(6)
C(15)-C(16)-C(17)
122.3(7)
C(18)-C(17)-C(16)
118.1(7)
C(17)-C(18)-C(13)
122.1(5)
C(24)-C(19)-C(20)
120.8(6)
C(24)-C(19)-S(2)
120.6(4)
C(20)-C(19)-S(2)
118.6(4)
C(21)-C(20)-C(19)
118.8(5)
C(20)-C(21)-C(22)
120.7(6)
C(23)-C(22)-C(21)
119.1(7)
Table 8.84 Anisotropic displacement parameters (2 x 103) for 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-benzene. The anisotropic displacement
factor exponent takes the form: -2 2 [h2 a*2 U11 + ... + 2 h k a* b* U12].
257
Atom
U11
U22
U33
U23
U13
U12
S(1)
41(1)
35(1)
57(1)
-2(1)
7(1)
-3(1)
S(2)
46(1)
51(1)
48(1)
1(1)
9(1)
14(1)
O(3)
47(2)
64(3)
57(2)
-4(2)
19(1)
8(2)
O(1)
36(2)
57(3)
76(2)
5(2)
4(1)
-10(2)
O(4)
70(2)
79(3)
47(2)
1(2)
1(2)
30(2)
O(2)
73(2)
41(2)
60(2)
-14(2)
13(2)
0(2)
C(1)
40(3)
37(3)
45(3)
6(2)
5(2)
1(2)
C(2)
52(3)
47(4)
77(4)
11(3)
9(3)
4(3)
C(3)
78(4)
53(4)
94(5)
11(4)
12(4)
24(3)
C(4)
77(4)
49(4)
90(5)
24(4)
-2(4)
-7(3)
C(5)
68(4)
61(4)
103(5)
24(4)
28(4)
-11(4)
C(6)
63(4)
44(4)
95(5)
5(3)
30(3)
-4(3)
C(7)
35(2)
37(3)
48(2)
-3(2)
10(2)
-2(2)
C(8)
47(3)
26(2)
46(3)
-1(2)
11(2)
-1(2)
C(9)
47(2)
29(3)
56(3)
5(2)
17(2)
6(2)
C(10)
46(3)
44(3)
49(3)
-1(3)
10(2)
8(2)
C(11)
41(2)
36(3)
47(3)
7(2)
8(2)
5(2)
C(12)
49(3)
40(3)
53(3)
8(3)
14(2)
6(2)
C(13)
42(3)
42(3)
54(3)
10(3)
22(2)
9(2)
C(14)
51(3)
60(4)
58(3)
9(3)
12(2)
14(3)
C(15)
52(3)
67(4)
70(4)
15(4)
17(3)
25(3)
C(16)
88(4)
69(5)
76(4)
8(4)
25(3)
29(4)
C(17)
104(5)
75(5)
70(4)
-9(4)
17(4)
23(4)
C(18)
63(3)
68(5)
63(4)
-6(3)
9(3)
18(3)
C(19)
45(3)
43(3)
49(3)
-9(3)
5(2)
11(2)
C(20)
47(3)
60(4)
74(4)
-17(4)
3(3)
13(3)
C(21)
61(4)
61(5)
112(6)
-27(4)
22(4)
-4(3)
C(22)
94(5)
46(4)
83(5)
-11(4)
12(4)
-9(4)
C(23)
86(5)
43(4)
114(6)
2(4)
-20(4)
5(4)
C(24)
57(3)
51(4)
87(4)
4(4)
-12(3)
7(3)
258
Table 8.85 Hydrogen coordinates ( x 104) and isotropic displacement parameters

(2 x 103) for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4benzene.
Atom
U(eq)
H(2)
-5471
9471
6314
77
H(3)
-4957
11074
5946
98
H(4)
-1924
11525
5163
97
H(5)
602
10420
4797
99
H(6)
184
8832
5185
85
H(7)
-2035
7888
7883
52
H(8)
1158
7027
6944
52
H(10)
5125
6820
9325
60
H(11)
3945
5863
7418
54
H(12)
7731
5767
8982
61
H(14)
10862
4777
8873
73
H(15)
12490
3519
8157
81
H(16)
10516
2750
6777
99
H(17)
6832
3197
6027
108
H(18)
5194
4464
6710
84
H(20)
5744
9107
9632
80
H(21)
6505
10628
9141
101
H(22)
3589
11579
8289
98
H(23)
-89
11019
7986
112
H(24)
-897
9502
8435
88
259
18) 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4methoxybenzene.
Table 8.86 Crystal data and structure refinement for 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-methoxybenzene.

Identification code
phsulf_2
Empirical formula
C25 H22 O5 S2
Formula weight
466.55
Temperature
150.0 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21/c
a = 5.84331(18)
b = 25.5606(8), = 90.258(3)
c = 14.9540(5)
Volume
2233.49(12) 3
1.387 Mg/m3
0.274 mm-1
260
F(000)
976
Crystal size
0.50 x 0.25 x 0.20 mm
3.1502 to 29.1677
Index ranges
-7<=h<=7; -34<=k<=34; -20<=l<=20
32900
4078 [Rint = 0.0516]
3615
Data Completeness
0.999
1.00000 and 0.98856
Refinement method
4078 / 0 / 291
1.018
R1 = 0.0384 wR2 = 0.0838
R1 = 0.0463 wR2 = 0.0875
0.341 and -0.328 e.-3

parameters (2 x 103) for1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-methoxybenzene. U(eq) is defined as one third of the trace of the
orthogonalized Uij tensor.
Atom
U(eq)
S(1)
1960(1)
6051(1)
4947(1)
24(1)
S(2)
5195(1)
6598(1)
2097(1)
23(1)
O(2)
4415(3)
6043(1)
4976(1)
30(1)
O(4)
7592(3)
6482(1)
2030(1)
31(1)
O(3)
3711(3)
6487(1)
1352(1)
31(1)
O(5)
-9912(3)
4151(1)
665(1)
38(1)
O(1)
733(3)
5756(1)
5609(1)
36(1)
C(1)
-9532(6)
4200(1)
-275(2)
47(1)
C(2)
-8338(4)
4368(1)
1232(2)
28(1)
C(3)
-8856(4)
4346(1)
2135(2)
27(1)
C(4)
-7374(4)
4555(1)
2761(2)
26(1)
261
C(5)
-5346(4)
4802(1)
2506(2)
23(1)
C(6)
-4853(4)
4818(1)
1593(2)
31(1)
C(7)
-6311(5)
4600(1)
964(2)
32(1)
C(8)
-3885(4)
5028(1)
3193(2)
24(1)
C(9)
-2019(4)
5328(1)
3090(2)
23(1)
C(10)
-848(4)
5533(1)
3857(2)
23(1)
C(11)
1003(4)
5851(1)
3872(2)
21(1)
C(12)
2101(4)
6076(1)
3088(2)
21(1)
C(13)
4158(4)
6295(1)
3058(2)
21(1)
C(14)
4940(4)
7268(1)
2371(2)
22(1)
C(15)
2966(4)
7534(1)
2135(2)
27(1)
C(16)
2781(5)
8058(1)
2349(2)
34(1)
C(17)
4527(5)
8308(1)
2807(2)
36(1)
C(18)
6470(5)
8036(1)
3053(2)
36(1)
C(19)
6696(4)
7515(1)
2836(2)
28(1)
C(20)
1017(4)
6708(1)
5015(2)
25(1)
C(21)
-1131(4)
6805(1)
5366(2)
35(1)
C(22)
-1874(5)
7319(1)
5425(2)
48(1)
C(23)
-512(6)
7724(1)
5130(2)
48(1)
C(24)
1597(6)
7622(1)
4781(2)
42(1)
C(25)
2393(5)
7113(1)
4719(2)
30(1)
Table 8.88 Bond lengths [] and angles [] for 11-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-methoxybenzene.

Bond lengths []
S(1)-O(2)
1.4351(17)
S(1)-O(1)
1.4376(17)
S(1)-C(20)
1.769(2)
S(1)-C(11)
1.775(2)
S(2)-O(4)
1.4356(17)
S(2)-O(3)
1.4372(18)
S(2)-C(13)
1.745(2)
S(2)-C(14)
1.766(2)
O(5)-C(2)
1.367(3)
O(5)-C(1)
1.430(3)
C(2)-C(7)
1.385(3)
C(2)-C(3)
1.386(3)
C(3)-C(4)
1.381(3)
C(4)-C(5)
1.397(3)
C(5)-C(6)
1.396(3)
C(5)-C(8)
1.453(3)
262
C(6)-C(7)
1.383(4)
C(8)-C(9)
1.343(3)
C(9)-C(10)
1.432(3)
C(10)-C(11)
1.354(3)
C(11)-C(12)
1.456(3)
C(12)-C(13)
1.327(3)
C(14)-C(15)
1.384(3)
C(14)-C(19)
1.389(3)
C(15)-C(16)
1.383(4)
C(16)-C(17)
1.383(4)
C(17)-C(18)
1.380(4)
C(18)-C(19)
1.380(4)
C(20)-C(21)
1.385(3)
C(20)-C(25)
1.386(3)
C(21)-C(22)
1.386(4)
C(22)-C(23)
1.379(5)
C(23)-C(24)
1.366(4)
C(24)-C(25)
1.384(4)
Bond angles []
O(2)-S(1)-O(1)
118.27(11)
O(2)-S(1)-C(20)
108.81(11)
O(1)-S(1)-C(20)
107.51(12)
O(2)-S(1)-C(11)
109.55(11)
O(1)-S(1)-C(11)
108.46(11)
C(20)-S(1)-C(11)
103.18(11)
O(4)-S(2)-O(3)
119.36(11)
O(4)-S(2)-C(13)
107.96(11)
O(3)-S(2)-C(13)
109.84(11)
O(4)-S(2)-C(14)
107.44(11)
O(3)-S(2)-C(14)
108.73(11)
C(13)-S(2)-C(14)
102.11(10)
C(2)-O(5)-C(1)
117.8(2)
O(5)-C(2)-C(7)
124.6(2)
O(5)-C(2)-C(3)
116.0(2)
C(7)-C(2)-C(3)
119.4(2)
C(4)-C(3)-C(2)
120.3(2)
C(3)-C(4)-C(5)
121.3(2)
C(6)-C(5)-C(4)
117.4(2)
C(6)-C(5)-C(8)
123.8(2)
C(4)-C(5)-C(8)
118.8(2)
C(7)-C(6)-C(5)
121.6(2)
C(6)-C(7)-C(2)
120.0(2)
C(9)-C(8)-C(5)
128.4(2)
C(8)-C(9)-C(10)
120.2(2)
C(11)-C(10)-C(9)
127.8(2)
C(10)-C(11)-C(12)
125.4(2)
C(10)-C(11)-S(1)
115.87(18)
C(12)-C(11)-S(1)
118.47(17)
C(13)-C(12)-C(11)
126.6(2)
C(12)-C(13)-S(2)
122.30(19)
C(15)-C(14)-C(19)
121.2(2)
C(15)-C(14)-S(2)
119.23(18)
C(19)-C(14)-S(2)
119.57(19)
C(16)-C(15)-C(14)
118.9(2)
C(15)-C(16)-C(17)
120.3(2)
C(18)-C(17)-C(16)
120.2(2)
C(19)-C(18)-C(17)
120.3(3)
C(18)-C(19)-C(14)
119.1(2)
C(21)-C(20)-C(25)
120.9(2)
C(21)-C(20)-S(1)
118.4(2)
C(25)-C(20)-S(1)
120.68(19)
C(20)-C(21)-C(22)
118.7(3)
C(23)-C(22)-C(21)
120.6(3)
263
C(24)-C(23)-C(22)
120.1(3)
C(24)-C(25)-C(20)
119.1(3)
C(23)-C(24)-C(25)
120.6(3)
Table 8.89 Anisotropic displacement parameters (2 x 103) for1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-methoxybenzene. The anisotropic

displacement factor exponent takes the form: -2 2 [h2 a*2 U11 + ... + 2 h k a* b*
U12].
Atom
U11
U22
U33
U23
U13
U12
S(1)
24(1)
28(1)
20(1)
5(1)
-1(1)
-4(1)
S(2)
25(1)
23(1)
20(1)
0(1)
3(1)
0(1)
O(2)
25(1)
39(1)
27(1)
5(1)
-4(1)
-1(1)
O(4)
28(1)
31(1)
33(1)
4(1)
11(1)
4(1)
O(3)
40(1)
32(1)
22(1)
-2(1)
-1(1)
-4(1)
O(5)
37(1)
40(1)
37(1)
-9(1)
-3(1)
-11(1)
O(1)
36(1)
44(1)
26(1)
14(1)
-1(1)
-11(1)
C(1)
60(2)
47(2)
35(2)
-9(1)
-7(1)
-15(2)
C(2)
28(1)
19(1)
36(1)
-4(1)
-2(1)
0(1)
C(3)
23(1)
22(1)
36(1)
-2(1)
8(1)
-4(1)
C(4)
30(1)
19(1)
28(1)
-1(1)
7(1)
-1(1)
C(5)
24(1)
15(1)
29(1)
0(1)
1(1)
2(1)
C(6)
29(1)
30(1)
33(1)
4(1)
4(1)
-8(1)
C(7)
38(2)
34(1)
25(1)
2(1)
3(1)
-8(1)
C(8)
27(1)
17(1)
27(1)
2(1)
2(1)
3(1)
C(9)
26(1)
17(1)
27(1)
2(1)
1(1)
2(1)
C(10)
24(1)
20(1)
26(1)
4(1)
2(1)
2(1)
C(11)
23(1)
19(1)
22(1)
2(1)
-3(1)
1(1)
C(12)
24(1)
16(1)
22(1)
-1(1)
-1(1)
2(1)
C(13)
25(1)
18(1)
21(1)
0(1)
2(1)
4(1)
C(14)
24(1)
22(1)
18(1)
4(1)
3(1)
-2(1)
C(15)
26(1)
31(1)
24(1)
0(1)
-2(1)
1(1)
C(16)
39(2)
28(1)
36(2)
5(1)
-3(1)
10(1)
C(17)
49(2)
20(1)
41(2)
1(1)
2(1)
1(1)
C(18)
38(2)
27(1)
45(2)
1(1)
-5(1)
-10(1)
264
C(19)
24(1)
27(1)
34(1)
6(1)
-4(1)
-3(1)
C(20)
29(1)
30(1)
16(1)
-5(1)
-4(1)
-1(1)
C(21)
27(1)
49(2)
30(1)
-12(1)
-2(1)
-5(1)
C(22)
34(2)
68(2)
42(2)
-29(2)
-8(1)
14(2)
C(23)
61(2)
39(2)
44(2)
-20(1)
-16(2)
15(2)
C(24)
68(2)
29(2)
28(2)
-6(1)
-5(1)
-4(1)
C(25)
39(2)
32(1)
20(1)
-5(1)
4(1)
-4(1)

x 103) for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4methoxybenzene.
Atom
U(eq)
H(1A)
-9453
4564
-432
62
H(1B)
-10770
4038
-596
62
H(1C)
-8119
4032
-429
62
H(3)
-10209
4188
2320
35
H(4)
-7733
4532
3365
33
H(6)
-3512
4979
1404
40
H(7)
-5931
4610
361
42
H(8)
-4296
4955
3780
31
H(9)
-1486
5402
2519
30
H(10)
-1428
5435
4410
30
H(12)
1277
6065
2555
27
H(13)
5078
6286
3567
28
H(15)
1782
7363
1837
35
H(16)
1477
8244
2184
45
H(17)
4391
8661
2950
47
H(18)
7632
8206
3366
47
H(19)
8006
7331
3000
37
H(21)
-2055
6532
5558
46
H(22)
-3305
7391
5665
63
H(23)
-1031
8067
5170
62
H(24)
2507
7897
4583
54
H(25)
3830
7045
4482
40
265
19) 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4nitrobenzene.
Table 8.91 Crystal data and structure refinement for 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-nitrobenzene.

Identification code
phsulf_3
Empirical formula
C24 H19 N O6 S2
Formula weight
481.52
Temperature
149.9 K
Wavelength
0.7107
Crystal system
Triclinic
Space group
P1
a = 5.86394(16), = 87.204(3)
b = 8.2153(3), = 77.171(3)
c = 11.8849(4), = 86.386(2)
Volume
556.78(3) 3
1.436 Mg/m3
266
0.281 mm-1
F(000)
250
Crystal size
0.40 x 0.20 x 0.20 mm
2.99 to 28.9464
Index ranges
-7<=h<=7; -9<=k<=9; -14<=l<=7
4109
2552 [Rint = 0.0125]
2466
Data Completeness
0.999
1.00000 and 0.95971
Refinement method
2552 / 3 / 298
1.150
R1 = 0.0321 wR2 = 0.0961
R1 = 0.0335 wR2 = 0.0974
0.01(8)
0.398 and -0.197 e.-3

parameters (2 x 103) for1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1yl]-4-nitrobenzene. U(eq) is defined as one third of the trace of the orthogonalized
Uij tensor.
Atom
U(eq)
S(1)
4499(1)
2382(1)
650(1)
20(1)
S(2)
123(1)
7415(1)
2102(1)
23(1)
O(1)
2097(4)
2405(3)
546(2)
25(1)
O(3)
-2183(5)
7482(4)
1888(3)
38(1)
O(2)
6216(4)
1311(3)
-49(2)
27(1)
O(4)
1500(5)
8812(3)
1834(3)
33(1)
O(5)
18184(5)
11561(4)
-3167(3)
48(1)
N(1)
16099(6)
11763(4)
-2675(3)
32(1)
O(6)
15119(6)
13119(3)
-2469(3)
43(1)
267
C(1)
14745(7)
10316(5)
-2340(3)
24(1)
C(2)
15798(6)
8794(5)
-2599(4)
28(1)
C(3)
14500(6)
7432(5)
-2248(4)
27(1)
C(4)
12172(7)
7604(5)
-1644(4)
26(1)
C(5)
11170(7)
9173(5)
-1400(4)
31(1)
C(6)
12446(7)
10525(5)
-1748(4)
28(1)
C(7)
10852(7)
6141(5)
-1301(4)
29(1)
C(8)
8639(7)
6098(5)
-682(4)
30(1)
C(9)
7582(6)
4578(5)
-313(4)
28(1)
C(10)
5452(6)
4408(5)
368(3)
23(1)
C(11)
3950(6)
5757(5)
918(3)
24(1)
C(12)
1675(7)
5724(5)
1390(4)
27(1)
C(13)
-24(6)
6810(5)
3562(4)
27(1)
C(14)
-1808(8)
5810(5)
4118(4)
42(1)
C(15)
-1902(11)
5232(7)
5211(5)
57(2)
C(16)
-253(12)
5628(8)
5753(5)
66(2)
C(17)
1530(12)
6646(9)
5249(6)
73(2)
C(18)
1662(8)
7259(6)
4098(4)
42(1)
C(19)
4589(6)
1975(4)
2122(3)
21(1)
C(20)
6682(6)
1371(5)
2385(4)
26(1)
C(21)
6732(7)
1023(5)
3524(4)
33(1)
C(22)
4744(7)
1302(5)
4392(4)
34(1)
C(23)
2678(8)
1918(6)
4125(4)
36(1)
C(24)
2587(7)
2251(5)
2974(4)
28(1)
Table 8.93 Bond lengths [] and angles [] for1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-nitrobenzene.

Bond lengths []
S(1)-O(2)
1.437(3)
S(1)-O(1)
1.440(3)
S(1)-C(19)
1.776(4)
S(1)-C(10)
1.781(4)
S(2)-O(4)
1.427(3)
S(2)-O(3)
1.428(3)
S(2)-C(12)
1.757(4)
S(2)-C(13)
1.766(4)
O(5)-N(1)
1.237(4)
N(1)-O(6)
1.231(5)
268
N(1)-C(1)
1.461(5)
C(1)-C(2)
1.377(5)
C(1)-C(6)
1.379(5)
C(2)-C(3)
1.387(5)
C(3)-C(4)
1.396(5)
C(4)-C(5)
1.398(6)
C(4)-C(7)
1.463(5)
C(5)-C(6)
1.374(6)
C(7)-C(8)
1.344(5)
C(8)-C(9)
1.435(6)
C(9)-C(10)
1.340(5)
C(10)-C(11)
1.457(5)
C(11)-C(12)
1.329(5)
C(13)-C(18)
1.366(6)
C(13)-C(14)
1.398(6)
C(14)-C(15)
1.352(7)
C(15)-C(16)
1.339(9)
C(16)-C(17)
1.391(9)
C(17)-C(18)
1.422(8)
C(19)-C(24)
1.384(5)
C(19)-C(20)
1.389(5)
C(20)-C(21)
1.376(6)
C(21)-C(22)
1.389(6)
C(22)-C(23)
1.379(6)
C(23)-C(24)
1.394(6)
Bond angles []
O(2)-S(1)-O(1)
119.38(16)
O(2)-S(1)-C(19)
108.51(16)
O(1)-S(1)-C(19)
108.52(16)
O(2)-S(1)-C(10)
107.72(17)
O(1)-S(1)-C(10)
107.74(16)
C(19)-S(1)-C(10)
103.90(17)
O(4)-S(2)-O(3)
119.61(18)
O(4)-S(2)-C(12)
109.47(19)
O(3)-S(2)-C(12)
107.45(19)
O(4)-S(2)-C(13)
108.60(19)
O(3)-S(2)-C(13)
108.9(2)
C(12)-S(2)-C(13)
101.31(18)
O(6)-N(1)-O(5)
123.1(4)
O(6)-N(1)-C(1)
118.9(3)
O(5)-N(1)-C(1)
118.0(3)
C(2)-C(1)-C(6)
122.0(4)
C(2)-C(1)-N(1)
119.6(3)
C(6)-C(1)-N(1)
118.4(3)
C(1)-C(2)-C(3)
118.7(3)
C(2)-C(3)-C(4)
120.6(3)
C(3)-C(4)-C(5)
118.8(4)
C(3)-C(4)-C(7)
119.0(4)
C(5)-C(4)-C(7)
122.2(4)
C(6)-C(5)-C(4)
120.8(4)
C(5)-C(6)-C(1)
119.1(3)
C(8)-C(7)-C(4)
126.1(4)
C(7)-C(8)-C(9)
121.3(4)
C(10)-C(9)-C(8)
125.7(4)
C(9)-C(10)-C(11)
124.1(4)
C(9)-C(10)-S(1)
116.8(3)
C(11)-C(10)-S(1)
119.1(3)
C(12)-C(11)-C(10)
126.3(4)
C(11)-C(12)-S(2)
121.2(3)
C(18)-C(13)-C(14)
121.9(4)
C(18)-C(13)-S(2)
119.5(3)
C(14)-C(13)-S(2)
118.6(3)
269
C(15)-C(14)-C(13)
120.6(5)
C(16)-C(15)-C(14)
118.9(6)
C(15)-C(16)-C(17)
122.8(5)
C(16)-C(17)-C(18)
119.0(6)
C(13)-C(18)-C(17)
116.7(5)
C(24)-C(19)-C(20)
121.6(4)
C(24)-C(19)-S(1)
119.7(3)
C(20)-C(19)-S(1)
118.7(3)
C(21)-C(20)-C(19)
118.5(4)
C(20)-C(21)-C(22)
120.6(4)
C(23)-C(22)-C(21)
120.6(4)
C(22)-C(23)-C(24)
119.5(4)
C(19)-C(24)-C(23)
119.1(4)
Table 8.94 Anisotropic displacement parameters (2 x 103) for 1-[(1E,3E,5E)-4,6bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4-nitrobenzene. The anisotropic
displacement factor exponent takes the form: -2 2 [h2 a*2 U11 + ... + 2 h k a* b*
U12].
Atom
U11
U22
U33
U23
U13
U12
S(1)
19(1)
21(1)
21(1)
-3(1)
-6(1)
-1(1)
S(2)
23(1)
22(1)
26(1)
-3(1)
-7(1)
2(1)
O(1)
24(1)
25(1)
28(2)
-2(1)
-10(1)
-3(1)
O(3)
30(2)
41(2)
48(2)
-9(1)
-18(2)
10(1)
O(2)
27(1)
27(1)
25(2)
-5(1)
-4(1)
2(1)
O(4)
38(2)
21(1)
38(2)
1(1)
0(1)
-2(1)
O(5)
35(2)
36(2)
66(3)
6(2)
2(2)
-11(1)
N(1)
40(2)
32(2)
26(2)
2(2)
-7(2)
-10(2)
O(6)
60(2)
22(2)
42(2)
-2(1)
3(2)
-6(1)
C(1)
30(2)
26(2)
18(2)
2(2)
-8(2)
-4(2)
C(2)
24(2)
30(2)
26(2)
0(2)
1(2)
-3(2)
C(3)
26(2)
25(2)
28(2)
1(2)
-3(2)
2(2)
C(4)
24(2)
28(2)
23(2)
-1(2)
-2(2)
-5(2)
C(5)
24(2)
33(2)
32(2)
-8(2)
1(2)
-1(2)
C(6)
30(2)
26(2)
26(2)
-5(2)
-3(2)
1(2)
C(7)
29(2)
30(2)
31(2)
-3(2)
-10(2)
1(2)
C(8)
31(2)
33(2)
25(2)
0(2)
-6(2)
-2(2)
C(9)
23(2)
30(2)
31(2)
0(2)
-6(2)
-2(2)
C(10)
30(2)
25(2)
16(2)
1(2)
-8(2)
-2(2)
C(11)
23(2)
25(2)
25(2)
1(2)
-5(2)
-5(2)
270
C(12)
36(2)
24(2)
23(2)
-1(2)
-9(2)
2(2)
C(13)
29(2)
25(2)
25(2)
-5(2)
-2(2)
6(2)
C(14)
45(3)
38(2)
35(3)
-5(2)
8(2)
0(2)
C(15)
73(4)
55(3)
31(3)
1(2)
7(3)
10(3)
C(16)
84(4)
70(4)
28(3)
13(3)
10(3)
33(4)
C(17)
78(4)
95(5)
57(4)
-36(4)
-40(4)
38(4)
C(18)
40(2)
53(3)
36(3)
-10(2)
-18(2)
6(2)
C(19)
22(2)
19(2)
22(2)
0(2)
-8(2)
-1(1)
C(20)
20(2)
28(2)
28(2)
1(2)
-4(2)
1(2)
C(21)
34(2)
33(2)
37(3)
1(2)
-17(2)
0(2)
C(22)
45(2)
41(2)
19(2)
1(2)
-13(2)
-7(2)
C(23)
39(2)
40(3)
26(2)
1(2)
1(2)
2(2)
C(24)
25(2)
30(2)
27(2)
2(2)
-6(2)
1(2)

x 103) for 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5-trien-1-yl]-4nitrobenzene.
Atom
U(eq)
H(2)
17349
8680
-3001
36
H(3)
15188
6396
-2416
35
H(5)
9622
9302
-997
40
H(6)
11770
11566
-1588
36
H(7)
11616
5147
-1533
38
H(8)
7776
7073
-489
39
H(9)
8450
3628
-569
37
H(11)
4652
6735
942
32
H(12)
890
4790
1342
36
H(14)
-2941
5540
3732
54
H(15)
-3092
4570
5581
74
H(16)
-302
5205
6498
86
H(17)
2621
6921
5659
95
H(18)
2838
7932
3728
54
H(20)
8020
1205
1805
34
271
H(21)
8110
596
3715
43
H(22)
4807
1071
5158
44
H(23)
1355
2111
4710
48
H(24)
1200
2654
2781
36
272
20) 4-(phenylsulfonyl)biphenyl.
Table 8.96 Crystal data and structure refinement for 4-(phenylsulfonyl)biphenyl.

Identification code
phsulf_11
Empirical formula
C18 H14 O2 S
Formula weight
294.35
Temperature
297.0 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21/c
a = 16.5020(12)
b = 7.8520(5), = 101.480(8)
c = 11.3748(9)
Volume
1444.39(18) 3
1.354 Mg/m3
0.225 mm-1
F(000)
616
Crystal size
0.50 x 0.40 x 0.20 mm
273
2.8780 to 28.9560
Index ranges
-15<=h<=8; -10<=k<=8; -22<=l<=22
6662
2650 [Rint = 0.0331]
1648
Data Completeness
0.999
1.00000 and 0.88718
Refinement method
2650 / 0 / 190
1.066
R1 = 0.0519 wR2 = 0.1115
R1 = 0.0970 wR2 = 0.1506
0.251 and -0.353 e.-3

parameters (2 x 103) for 4-(phenylsulfonyl)biphenyl.U(eq) is defined as one third of
Atom
U(eq)
S(1)
1796(1)
3433(1)
1702(1)
55(1)
O(2)
1437(2)
1804(3)
1335(2)
77(1)
O(1)
1781(2)
4055(3)
2889(2)
77(1)
C(1)
5966(2)
4237(4)
1851(3)
65(1)
C(2)
1316(2)
6651(4)
1017(3)
56(1)
C(3)
7018(2)
3261(4)
849(3)
59(1)
C(4)
2835(2)
3397(3)
1524(3)
44(1)
C(5)
4224(2)
4363(4)
2102(3)
54(1)
C(6)
1332(2)
4974(4)
662(3)
44(1)
C(7)
6779(2)
4192(4)
1740(3)
74(1)
C(8)
1017(2)
4513(4)
-511(3)
56(1)
C(9)
974(2)
7864(4)
188(4)
72(1)
C(10)
3418(2)
4374(4)
2252(3)
55(1)
C(11)
681(2)
5737(5)
-1328(3)
70(1)
274
C(12)
5613(2)
2430(4)
187(3)
57(1)
C(13)
6429(2)
2392(4)
75(3)
65(1)
C(14)
3872(2)
2422(4)
500(3)
57(1)
C(15)
662(2)
7394(5)
-977(4)
74(1)
C(16)
3065(2)
2414(4)
637(3)
58(1)
C(17)
5356(2)
3354(3)
1079(2)
40(1)
C(18)
4482(2)
3379(3)
1229(2)
38(1)
Table 8.98 Bond lengths [] and angles [] for 4-(phenylsulfonyl)biphenyl.

Bond lengths []
S(1)-O(2)
1.436(2)
S(1)-O(1)
1.441(2)
S(1)-C(6)
1.758(3)
S(1)-C(4)
1.767(3)
C(1)-C(7)
1.372(4)
C(1)-C(17)
1.384(4)
C(2)-C(6)
1.379(4)
C(2)-C(9)
1.379(5)
C(3)-C(13)
1.358(4)
C(3)-C(7)
1.370(4)
C(4)-C(10)
1.372(4)
C(4)-C(16)
1.382(4)
C(5)-C(10)
1.375(4)
C(5)-C(18)
1.390(4)
C(6)-C(8)
1.381(4)
C(8)-C(11)
1.375(4)
C(9)-C(15)
1.373(5)
C(11)-C(15)
1.364(5)
C(12)-C(13)
1.377(4)
C(12)-C(17)
1.382(4)
C(14)-C(16)
1.372(4)
C(14)-C(18)
1.391(4)
C(17)-C(18)
1.484(4)
Bond angles []
O(2)-S(1)-O(1)
119.50(15)
O(2)-S(1)-C(6)
108.56(15)
O(1)-S(1)-C(6)
108.13(14)
O(2)-S(1)-C(4)
107.79(14)
O(1)-S(1)-C(4)
108.11(15)
C(6)-S(1)-C(4)
103.63(12)
C(7)-C(1)-C(17)
122.0(3)
C(6)-C(2)-C(9)
119.2(3)
C(13)-C(3)-C(7)
118.2(3)
C(10)-C(4)-C(16)
119.4(3)
C(10)-C(4)-S(1)
120.1(2)
C(16)-C(4)-S(1)
120.4(2)
C(10)-C(5)-C(18)
122.3(3)
C(2)-C(6)-C(8)
120.5(3)
C(2)-C(6)-S(1)
119.4(3)
C(8)-C(6)-S(1)
120.0(2)
C(3)-C(7)-C(1)
120.8(3)
C(11)-C(8)-C(6)
119.6(3)
275
C(15)-C(9)-C(2)
119.9(3)
C(4)-C(10)-C(5)
120.1(3)
C(15)-C(11)-C(8)
119.9(4)
C(13)-C(12)-C(17)
121.9(3)
C(3)-C(13)-C(12)
121.0(3)
C(16)-C(14)-C(18)
122.6(3)
C(11)-C(15)-C(9)
120.9(4)
C(14)-C(16)-C(4)
119.6(3)
C(12)-C(17)-C(1)
115.9(3)
C(12)-C(17)-C(18)
122.6(3)
C(1)-C(17)-C(18)
121.4(3)
C(5)-C(18)-C(14)
116.0(3)
C(5)-C(18)-C(17)
122.1(3)
C(14)-C(18)-C(17)
121.9(2)
Table 8.99 Anisotropic displacement parameters (2 x 103) for 4(phenylsulfonyl)biphenyl. The anisotropic displacement factor exponent takes the
form: -2 2 [h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
S(1)
52(1)
57(1)
62(1)
13(1)
22(1)
3(1)
O(2)
60(2)
51(1)
123(2)
16(1)
27(2)
-9(1)
O(1)
75(2)
110(2)
52(2)
15(1)
30(1)
14(1)
C(1)
51(2)
70(2)
74(2)
-28(2)
11(2)
-5(2)
C(2)
56(2)
52(2)
64(2)
-5(2)
20(2)
3(2)
C(3)
46(2)
62(2)
71(2)
12(2)
20(2)
-1(2)
C(4)
49(2)
41(2)
44(2)
8(1)
12(1)
5(1)
C(5)
52(2)
58(2)
52(2)
-16(2)
8(2)
-6(2)
C(6)
36(2)
45(2)
54(2)
3(1)
16(1)
0(1)
C(7)
54(2)
76(2)
90(3)
-18(2)
7(2)
-13(2)
C(8)
49(2)
58(2)
62(2)
-3(2)
13(2)
-10(2)
C(9)
69(3)
47(2)
105(3)
3(2)
31(2)
8(2)
C(10)
58(2)
58(2)
50(2)
-13(2)
14(2)
4(2)
C(11)
48(2)
93(3)
63(2)
10(2)
-1(2)
-10(2)
C(12)
52(2)
70(2)
51(2)
-14(2)
12(2)
-3(2)
C(13)
59(2)
80(2)
60(2)
-10(2)
22(2)
3(2)
C(14)
52(2)
67(2)
53(2)
-21(2)
13(2)
-1(2)
C(15)
49(2)
81(3)
92(3)
31(2)
18(2)
12(2)
C(16)
49(2)
63(2)
63(2)
-18(2)
9(2)
-7(2)
C(17)
47(2)
34(2)
38(2)
6(1)
6(1)
1(1)
C(18)
44(2)
35(1)
34(2)
4(1)
4(1)
4(1)
276

(2 x 103) for 4-(phenylsulfonyl)biphenyl.
Atom
U(eq)
H(1)
5821
4880
2464
84
H(2)
1533
6960
1806
73
H(3)
7569
3225
776
76
H(5)
4610
5037
2602
70
H(7)
7172
4801
2276
96
H(8)
1032
3381
-747
73
H(9)
956
8998
418
93
H(10)
3268
5044
2848
71
H(11)
466
5434
-2120
91
H(12)
5225
1816
-353
75
H(13)
6579
1762
-540
85
H(14)
4017
1760
-104
74
H(15)
435
8218
-1533
96
H(16)
2674
1750
136
76
277
21) 4-methoxybiphen-4-yl phenyl sulphone.
Table 8.101 Crystal data and structure refinement for 4-methoxybiphen-4-yl phenyl
sulphone.
Identification code
phsulf_22
Empirical formula
C19 H16 O3 S
Formula weight
324.38
Temperature
296.3 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21
a = 6.7378(3)
b = 7.9901(4), = 98.700(5)
c = 15.1328(7)
Volume
805.31(7) 3
1.338 Mg/m3
0.213 mm-1
F(000)
340
Crystal size
0.40 x 0.30 x 0.25 mm
3.0523 to 28.9594
Index ranges
-8<=h<=9; -7<=k<=10; -20<=l<=15
278
3681
2209 [Rint = 0.0255]
1914
Data Completeness
0.998
1.00000 and 0.88553
Refinement method
2209 / 1 / 209
1.055
R1 = 0.0384 wR2 = 0.0854
R1 = 0.0482 wR2 = 0.0909
0.09(10)
0.121 and -0.238 e.-3

parameters (2 x 103) for 4-methoxybiphen-4-yl phenyl sulphone.U(eq) is defined
as one third of the trace of the orthogonalized Uij tensor.
Atom
U(eq)
S(1)
3306(1)
6276(1)
8194(1)
51(1)
O(3)
-7038(3)
5910(3)
2516(1)
63(1)
O(1)
5232(3)
6173(5)
7916(1)
78(1)
O(2)
2783(4)
7717(3)
8680(2)
73(1)
C(1)
-8817(5)
6888(6)
2420(3)
92(2)
C(2)
-5735(3)
6031(4)
3287(2)
45(1)
C(3)
-3971(4)
5107(4)
3334(2)
57(1)
C(4)
-2576(4)
5127(4)
4082(2)
50(1)
C(5)
-2827(3)
6058(4)
4835(2)
39(1)
C(6)
-4575(4)
6991(4)
4769(2)
58(1)
C(7)
-6016(4)
6977(4)
4017(2)
58(1)
C(8)
-1323(3)
6067(4)
5663(2)
40(1)
C(9)
582(4)
5386(5)
5687(2)
57(1)
C(10)
1968(4)
5410(4)
6455(2)
59(1)
C(11)
1486(3)
6135(5)
7221(2)
46(1)
279
C(12)
-381(4)
6803(4)
7218(2)
54(1)
C(13)
-1765(4)
6759(4)
6453(2)
54(1)
C(14)
3001(4)
4485(4)
8839(2)
41(1)
C(15)
3875(5)
3007(4)
8648(2)
61(1)
C(16)
3683(6)
1625(5)
9156(3)
82(1)
C(17)
2663(6)
1718(6)
9851(3)
88(1)
C(18)
1789(6)
3191(7)
10055(3)
87(1)
C(19)
1956(4)
4602(5)
9549(2)
59(1)
Table 8.103 Bond lengths [] and angles [] for 4-methoxybiphen-4-yl phenyl

sulphone.
Bond lengths []
S(1)-O(1)
1.4256(19)
S(1)-O(2)
1.438(2)
S(1)-C(14)
1.761(3)
S(1)-C(11)
1.772(3)
O(3)-C(2)
1.353(3)
O(3)-C(1)
1.420(4)
C(2)-C(7)
1.375(4)
C(2)-C(3)
1.392(4)
C(3)-C(4)
1.358(4)
C(4)-C(5)
1.393(4)
C(5)-C(6)
1.384(4)
C(5)-C(8)
1.487(3)
C(6)-C(7)
1.380(4)
C(8)-C(9)
1.390(4)
C(8)-C(13)
1.391(4)
C(9)-C(10)
1.376(4)
C(10)-C(11)
1.378(4)
C(11)-C(12)
1.366(4)
C(12)-C(13)
1.372(4)
C(14)-C(15)
1.370(4)
C(14)-C(19)
1.374(4)
C(15)-C(16)
1.362(5)
C(16)-C(17)
1.344(6)
C(17)-C(18)
1.372(6)
C(18)-C(19)
1.377(5)
Bond angles []
O(1)-S(1)-O(2)
120.11(18)
O(1)-S(1)-C(14)
107.69(17)
O(2)-S(1)-C(14)
108.03(12)
O(1)-S(1)-C(11)
107.30(11)
O(2)-S(1)-C(11)
106.45(17)
C(14)-S(1)-C(11)
106.52(15)
C(2)-O(3)-C(1)
118.5(3)
O(3)-C(2)-C(7)
125.6(3)
O(3)-C(2)-C(3)
116.4(3)
C(7)-C(2)-C(3)
118.1(3)
C(4)-C(3)-C(2)
121.0(3)
C(3)-C(4)-C(5)
122.3(3)
280
C(6)-C(5)-C(4)
115.8(2)
C(6)-C(5)-C(8)
121.5(2)
C(4)-C(5)-C(8)
122.7(2)
C(7)-C(6)-C(5)
122.7(3)
C(2)-C(7)-C(6)
120.1(3)
C(9)-C(8)-C(13)
116.7(2)
C(9)-C(8)-C(5)
122.0(2)
C(13)-C(8)-C(5)
121.3(2)
C(10)-C(9)-C(8)
121.5(3)
C(9)-C(10)-C(11)
120.0(3)
C(12)-C(11)-C(10)
119.7(3)
C(12)-C(11)-S(1)
120.0(2)
C(10)-C(11)-S(1)
120.3(2)
C(11)-C(12)-C(13)
120.1(2)
C(12)-C(13)-C(8)
121.9(2)
C(15)-C(14)-C(19)
120.7(3)
C(15)-C(14)-S(1)
119.6(2)
C(19)-C(14)-S(1)
119.6(2)
C(16)-C(15)-C(14)
120.0(3)
C(17)-C(16)-C(15)
120.1(4)
C(16)-C(17)-C(18)
120.7(4)
C(17)-C(18)-C(19)
120.2(3)
C(14)-C(19)-C(18)
118.3(3)
Table 8.104 Anisotropic displacement parameters (2 x 103) for 4-methoxybiphen4-yl phenyl sulphone. The anisotropic displacement factor exponent takes the form: 2 2 [h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
S(1)
54(1)
53(1)
46(1)
4(1)
5(1)
-14(1)
O(3)
56(1)
72(2)
57(1)
1(1)
-5(1)
4(1)
O(1)
50(1)
121(2)
63(1)
17(2)
8(1)
-29(2)
O(2)
108(2)
39(1)
66(2)
-7(1)
-7(1)
-8(1)
C(1)
60(2)
123(4)
85(3)
1(3)
-8(2)
21(2)
C(2)
45(1)
42(2)
48(1)
8(2)
8(1)
-3(2)
C(3)
68(2)
54(2)
49(2)
-11(2)
10(2)
16(2)
C(4)
50(2)
49(2)
51(2)
-2(2)
7(1)
16(1)
C(5)
44(1)
33(2)
42(1)
4(1)
14(1)
2(1)
C(6)
55(2)
69(2)
51(2)
-8(2)
13(1)
17(2)
C(7)
43(2)
71(2)
62(2)
-2(2)
9(1)
18(2)
C(8)
41(1)
36(2)
45(1)
1(2)
12(1)
0(2)
C(9)
51(2)
75(2)
47(2)
-11(2)
13(1)
11(2)
C(10)
45(2)
80(2)
54(2)
-4(2)
8(1)
15(2)
C(11)
50(1)
46(2)
42(1)
5(2)
10(1)
-8(2)
C(12)
59(2)
63(2)
43(2)
-4(2)
17(1)
8(2)
281
C(13)
49(2)
68(3)
46(2)
-3(2)
16(1)
10(2)
C(14)
38(1)
42(2)
41(2)
-2(1)
1(1)
-3(1)
C(15)
59(2)
55(2)
67(2)
-10(2)
4(2)
1(2)
C(16)
76(2)
49(3)
110(3)
-3(3)
-23(2)
6(2)
C(17)
79(2)
74(4)
97(3)
43(3)
-30(2)
-23(2)
C(18)
91(3)
108(4)
66(2)
24(3)
25(2)
-20(3)
C(19)
63(2)
63(2)
56(2)
6(2)
22(2)
2(2)

(2 x 103) for 4-methoxybiphen-4-yl phenyl sulphone.
Atom
U(eq)
H(1A)
-9559
6631
2896
119
H(1B)
-9624
6640
1856
119
H(1C)
-8470
8054
2442
119
H(3)
-3745
4466
2846
74
H(4)
-1412
4496
4092
65
H(6)
-4786
7654
5251
75
H(7)
-7179
7610
4004
76
H(9)
929
4903
5173
74
H(10)
3230
4937
6457
77
H(12)
-714
7288
7734
70
H(13)
-3035
7206
6464
70
H(15)
4599
2946
8173
79
H(16)
4259
617
9021
107
H(17)
2548
773
10199
114
H(18)
1081
3237
10537
113
H(19)
1376
5608
9684
77
282
22) 4-nitrobiphen-4-yl phenyl sulphone.
Table 8.106 Crystal data and structure refinement for 4-nitrobiphen-4-yl phenyl
sulphone.
Identification code
phsulf_33
Empirical formula
C18 H13 N O4 S
Formula weight
339.35
Temperature
149.9 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21/c
a = 13.1110(9)
b = 7.6752(5), = 99.600(7)
c = 15.2536(13)
Volume
1513.47(19) 3
1.489 Mg/m3
0.237 mm-1
F(000)
704
283
Crystal size
0.30 x 0.30 x 0.25 mm
2.90 to 28.9327
Index ranges
-15<=h<=12; -9<=k<=6; -18<=l<=15
6953
2766 [Rint = 0.0445]
1772
Data Completeness
0.999
1.00000 and 0.89631
Refinement method
2766 / 0 / 217
0.998
R1 = 0.0541 wR2 = 0.0870
R1 = 0.1014 wR2 = 0.1021
0.237 and -0.375 e.-3

parameters (2 x 103) for 4-nitrobiphen-4-yl phenyl sulphone.U(eq) is defined as
Atom
U(eq)
S(1)
7046(1)
6567(1)
827(1)
30(1)
O(1)
7553(2)
5780(3)
152(1)
37(1)
O(2)
6629(2)
8302(2)
698(1)
36(1)
N(1)
12403(2)
7051(3)
6580(2)
34(1)
O(3)
12215(2)
8002(3)
7186(2)
41(1)
O(4)
13203(2)
6202(3)
6627(2)
50(1)
C(1)
11637(2)
6940(3)
5765(2)
24(1)
C(2)
10685(2)
7722(3)
5746(2)
28(1)
C(3)
9964(2)
7620(3)
4980(2)
27(1)
C(4)
10182(2)
6779(3)
4224(2)
23(1)
C(5)
11161(2)
6007(3)
4278(2)
27(1)
C(6)
11879(2)
6062(3)
5047(2)
28(1)
C(7)
9408(2)
6704(3)
3396(2)
22(1)
284
C(8)
8571(2)
7867(3)
3244(2)
28(1)
C(9)
7863(2)
7833(3)
2472(2)
28(1)
C(10)
7951(2)
6603(4)
1824(2)
25(1)
C(11)
8763(2)
5416(4)
1958(2)
29(1)
C(12)
9478(2)
5483(3)
2731(2)
28(1)
C(13)
6057(2)
5167(3)
1045(2)
24(1)
C(14)
5242(2)
5830(4)
1410(2)
30(1)
C(15)
4492(2)
4708(4)
1602(2)
38(1)
C(16)
4553(2)
2948(4)
1428(2)
35(1)
C(17)
5367(3)
2294(4)
1072(2)
38(1)
C(18)
6130(2)
3398(4)
880(2)
36(1)
Table 8.108 Bond lengths [] and angles [] for 4-nitrobiphen-4-yl phenyl sulphone.
Bond lengths []
S(1)-O(2)
1.4399(19)
S(1)-O(1)
1.447(2)
S(1)-C(13)
1.758(3)
S(1)-C(10)
1.766(3)
N(1)-O(4)
1.227(3)
N(1)-O(3)
1.234(3)
N(1)-C(1)
1.465(4)
C(1)-C(6)
1.368(4)
C(1)-C(2)
1.380(4)
C(2)-C(3)
1.378(4)
C(3)-C(4)
1.392(4)
C(4)-C(5)
1.404(4)
C(4)-C(7)
1.483(4)
C(5)-C(6)
1.377(4)
C(7)-C(12)
1.395(4)
C(7)-C(8)
1.403(4)
C(8)-C(9)
1.373(4)
C(9)-C(10)
1.386(4)
C(10)-C(11)
1.391(4)
C(11)-C(12)
1.380(4)
C(13)-C(14)
1.381(4)
C(13)-C(18)
1.387(4)
C(14)-C(15)
1.376(4)
C(15)-C(16)
1.381(4)
C(16)-C(17)
1.371(4)
C(17)-C(18)
1.379(4)
Bond angles []
O(2)-S(1)-O(1)
119.89(13)
O(2)-S(1)-C(13)
108.40(13)
O(1)-S(1)-C(13)
108.66(13)
O(2)-S(1)-C(10)
106.75(13)
O(1)-S(1)-C(10)
107.27(13)
C(13)-S(1)-C(10)
104.88(13)
O(4)-N(1)-O(3)
123.1(3)
O(4)-N(1)-C(1)
118.5(3)
285
O(3)-N(1)-C(1)
118.4(3)
C(6)-C(1)-C(2)
121.8(3)
C(6)-C(1)-N(1)
119.4(3)
C(2)-C(1)-N(1)
118.8(3)
C(3)-C(2)-C(1)
118.9(3)
C(2)-C(3)-C(4)
121.5(3)
C(3)-C(4)-C(5)
117.3(3)
C(3)-C(4)-C(7)
121.1(3)
C(5)-C(4)-C(7)
121.5(3)
C(6)-C(5)-C(4)
121.7(3)
C(1)-C(6)-C(5)
118.7(3)
C(12)-C(7)-C(8)
116.9(3)
C(12)-C(7)-C(4)
121.7(3)
C(8)-C(7)-C(4)
121.4(3)
C(9)-C(8)-C(7)
121.9(3)
C(8)-C(9)-C(10)
120.0(3)
C(9)-C(10)-C(11)
119.6(3)
C(9)-C(10)-S(1)
120.1(2)
C(11)-C(10)-S(1)
120.3(2)
C(12)-C(11)-C(10)
119.8(3)
C(11)-C(12)-C(7)
121.9(3)
C(14)-C(13)-C(18)
121.0(3)
C(14)-C(13)-S(1)
119.7(2)
C(18)-C(13)-S(1)
119.3(2)
C(15)-C(14)-C(13)
118.9(3)
C(14)-C(15)-C(16)
120.3(3)
C(17)-C(16)-C(15)
120.6(3)
C(16)-C(17)-C(18)
119.9(3)
C(17)-C(18)-C(13)
119.2(3)
Table 8.109 Anisotropic displacement parameters (2 x 103) for 4-nitrobiphen-4-yl

phenyl sulphone. The anisotropic displacement factor exponent takes the form: -2 2
[h2 a*2 U11 + ... + 2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
S(1)
26(1)
33(1)
33(1)
1(1)
11(1)
-5(1)
O(1)
29(1)
55(1)
31(1)
-5(1)
16(1)
-7(1)
O(2)
34(1)
30(1)
45(2)
9(1)
9(1)
-3(1)
N(1)
30(2)
27(2)
45(2)
0(1)
4(2)
-4(1)
O(3)
44(2)
36(1)
42(2)
-10(1)
4(1)
1(1)
O(4)
34(1)
48(2)
65(2)
-9(1)
-4(1)
15(1)
C(1)
26(2)
15(2)
33(2)
2(1)
5(2)
-6(1)
C(2)
31(2)
21(2)
37(2)
-2(2)
16(2)
-1(1)
C(3)
26(2)
22(2)
36(2)
2(2)
14(2)
2(1)
C(4)
24(2)
14(1)
32(2)
2(1)
11(2)
-2(1)
C(5)
32(2)
18(2)
36(2)
-1(1)
17(2)
-1(1)
C(6)
28(2)
19(2)
39(2)
2(2)
12(2)
0(1)
C(7)
26(2)
16(1)
30(2)
4(1)
17(1)
-3(1)
286
C(8)
26(2)
23(2)
36(2)
-4(1)
12(2)
-2(1)
C(9)
24(2)
22(2)
39(2)
0(2)
11(2)
2(1)
C(10)
22(2)
25(2)
31(2)
-1(2)
12(1)
-7(1)
C(11)
32(2)
23(2)
36(2)
-2(2)
16(2)
-1(1)
C(12)
27(2)
22(2)
37(2)
3(2)
12(2)
4(1)
C(13)
21(2)
25(2)
26(2)
3(1)
4(1)
-4(1)
C(14)
29(2)
25(2)
37(2)
1(2)
9(2)
1(1)
C(15)
30(2)
39(2)
49(2)
5(2)
20(2)
1(2)
C(16)
32(2)
33(2)
42(2)
7(2)
8(2)
-8(1)
C(17)
40(2)
24(2)
51(3)
-7(2)
10(2)
-4(1)
C(18)
30(2)
33(2)
48(2)
-4(2)
15(2)
3(2)

(2 x 103) for 4-nitrobiphen-4-yl phenyl sulphone.
Atom
U(eq)
H(2)
10534
8308
6242
37
H(3)
9317
8125
4967
35
H(5)
11328
5443
3781
36
H(6)
12517
5515
5077
36
H(8)
8495
8683
3679
36
H(9)
7324
8636
2384
37
H(11)
8824
4581
1528
38
H(12)
10023
4692
2811
36
H(14)
5202
7016
1523
39
H(15)
3941
5136
1850
49
H(16)
4038
2201
1554
46
H(17)
5405
1106
960
50
H(18)
6687
2961
643
47
287
23) 1,4-naphthaquinone.
Table 8.111 Crystal data and structure refinement for 1,4-naphthaquinone.

Identification code
14naph
Empirical formula
C10 H6 O2
Formula weight
158.15
Temperature
150.0 K
Wavelength
0.7107
Crystal system
Monoclinic
Space group
P21/c
a = 8.1933(3)
b = 7.7393(3), = 94.486(3)
c = 11.4405(4)
Volume
723.23(4) 3
1.452 Mg/m3
0.102 mm-1
F(000)
328
Crystal size
0.30 x 0.20 x 0.20 mm
3.1727 to 29.0378
Index ranges
-8<=h<=10; -7<=k<=10; -11<=l<=14
3141
1320 [Rint = 0.0120]

288
1184
Data Completeness
0.996
1.00000 and 0.97291
Refinement method
1320 / 0 / 109
1.054
R1 = 0.0306 wR2 = 0.0834
R1 = 0.0347 wR2 = 0.0859
0.192 and -0.164 e.-3

parameters (2 x 103) for 1,4-naphthaquinone.U(eq) is defined as one third of the
trace of the orthogonalized Uij tensor.
Atom
U(eq)
O(1)
371(1)
2190(1)
8840(1)
31(1)
O(2)
4346(1)
4615(1)
12387(1)
29(1)
C(1)
1275(1)
2785(1)
9640(1)
21(1)
C(2)
1782(1)
1727(1)
10677(1)
23(1)
C(3)
2821(1)
2314(2)
11539(1)
23(1)
C(4)
3464(1)
4092(1)
11550(1)
20(1)
C(5)
2990(1)
5211(1)
10523(1)
18(1)
C(6)
3605(1)
6885(2)
10470(1)
22(1)
C(7)
3190(1)
7904(2)
9498(1)
24(1)
C(8)
2130(1)
7285(2)
8587(1)
25(1)
C(9)
1493(1)
5635(1)
8638(1)
22(1)
C(10)
1930(1)
4578(1)
9598(1)
18(1)
Table 8.113 Bond lengths [] and angles [] for 1,4-naphthaquinone.

Bond lengths []
O(1)-C(1)
1.2217(13)
O(2)-C(4)
1.2226(13)
C(1)-C(2)
1.4742(16)
C(1)-C(10)
1.4900(15)
C(2)-C(3)
1.3320(16)
C(3)-C(4)
1.4732(16)
289
C(4)-C(5)
1.4863(15)
C(5)-C(6)
1.3928(16)
C(5)-C(10)
1.4041(15
C(6)-C(7)
1.3844(16)
C(7)-C(8)
1.3881(17)
C(8)-C(9)
1.3824(16)
C(9)-C(10)
1.3935(15)
Bond angles []
O(1)-C(1)-C(2)
120.63(10)
O(1)-C(1)-C(10)
121.71(10)
C(2)-C(1)-C(10)
117.65(9)
C(3)-C(2)-C(1)
121.99(10)
C(2)-C(3)-C(4)
122.17(10)
O(2)-C(4)-C(3)
120.30(10)
O(2)-C(4)-C(5)
121.86(10)
C(3)-C(4)-C(5)
117.83(9)
C(6)-C(5)-C(10)
119.77(10)
C(6)-C(5)-C(4)
120.21(10)
C(10)-C(5)-C(4)
120.02(10)
C(7)-C(6)-C(5)
119.86(10)
C(6)-C(7)-C(8)
120.41(10)
C(9)-C(8)-C(7)
120.24(10)
C(8)-C(9)-C(10)
120.05(10)
C(9)-C(10)-C(5)
119.65(10)
C(9)-C(10)-C(1)
120.09(10)
C(5)-C(10)-C(1)
120.26(10)
Table 8.114 Anisotropic displacement parameters (2 x 103) for 1,4-naphthaquinone.

The anisotropic displacement factor exponent takes the form: -2 2 [h2 a*2 U11 + ... +
2 h k a* b* U12].
Atom
U11
U22
U33
U23
U13
U12
O(1)
35(1)
30(1)
26(1)
-4(1)
-6(1)
-9(1)
O(2)
32(1)
28(1)
25(1)
-4(1)
-10(1)
2(1)
C(1)
18(1)
24(1)
20(1)
-4(1)
2(1)
-1(1)
C(2)
23(1)
18(1)
28(1)
0(1)
4(1)
-1(1)
C(3)
22(1)
22(1)
24(1)
4(1)
1(1)
4(1)
C(4)
17(1)
22(1)
20(1)
-3(1)
1(1)
4(1)
C(5)
16(1)
20(1)
19(1)
-2(1)
2(1)
3(1)
C(6)
19(1)
22(1)
24(1)
-6(1)
1(1)
0(1)
C(7)
24(1)
18(1)
31(1)
0(1)
7(1)
0(1)
C(8)
26(1)
26(1)
23(1)
5(1)
6(1)
5(1)
C(9)
20(1)
26(1)
18(1)
-2(1)
1(1)
2(1)
C(10)
16(1)
20(1)
19(1)
-3(1)
3(1)
2(1)
290

(2 x 103) for 1,4-naphthaquinone.
Atom
U(eq)
H(2)
1363
615
10730
30
H(3)
3151
1578
12155
30
H(6)
4294
7316
11086
29
H(7)
3623
9011
9454
32
H(8)
1848
7982
7941
32
H(9)
772
5230
8031
28
291
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Crystal Growth Using Low Temperature

Gradient Sublimation in Vacuo

Supervisors: Dr. Andrea Erxleben, Prof. Patrick McArdle

National University of Ireland, Galway

Thesis submitted to the School of Chemistry, National

Symbols and Terms Used in Crystallography

Nucleation and Crystal Growth:

Nucleation in polymorphic systems

Chapter 2: Experimental Section

Instrumentation and Techniques:

Low temperature gradient sublimation in vacuo,

Sublimation in a vacuum oven using an externally

Controlled heater, method B

X-Ray diffraction techniques

Chapter 3: Crystal Growth of Pure Form not Available From

Introduction: Crystalline forms of stanozolol

Crystallization of polymorphic forms stanozolol

Crystallization of solvated forms of stanozolol

Structural analysis of polymorphism in stanozolol

Structural diversity of stanozolol solvates

Molecular packing and hydrogen bonding of stanozolol

Tautomerism in stanozolol solvates

Thermal analysis of stanozolol solvates: strength of

Chapter 4: Crystal Growth of Pure Form not Available From

Crystallization of solvated forms of ethinylestradiol

Polymorphism in the crystal structures of ethinylestradiol 78

Structural diversity of ethinylestradiol solvates

Molecular packing and hydrogen bonding of

Unused Hydrogen Bonding Capacity in Steroid Crystal

Chapter 5: Detection of Bending Properties of Organic Crystals:

Introduction: Bending phenomena of molecular crystals

Crystal growth of naftazone and 1,3-dinitrobenzene

Detection of bending properties of naftazone

Detection of bending properties of 1,3-dinitrobenzene

Chapter 6: Combined Synthesis, by Thermal Transformation,

Synthesis and crystal growth of 4-(phenylsulfonyl)

Combined synthesis, by thermal transformation,

Analysis of intra-molecular interactions

Chapter 7: Using Driving Force to Control Crystal Morphology:

Application to metal-free phthalocyanine

Application to benzoic acid

Chapter 8: Crystallographic Data: Electronic Information

1) Stanozolol, polymorph 1 (stanozolol_1.cif):

2) Stanozolol, polymorph 2 (stanozolol_2.cif):

3) Stanozolol ethanol solvate (stanozolol_3.cif)

4) Stanozolol isopropanol solvate (stanozolol_4.cif)

5) Stanozolol butan-2-ol solvate (stanozolol_5.cif)

6) Stanozolol ethanol dihydrate solvate (stanozolol_6.cif)

7) Stanozolol isopropanol dihydrate solvate (stanozolol_7.cif)

8) Stanozolol monohydrate (stanozolol_8.cif)

9) Stanozolol acetic acid solvate (stanozolol_9.cif)

10) Stanozolol formamide solvate (stanozolol_10.cif)

11) Stanozolol pyridine solvate (stanozolol_11.cif)

12) Stanozolol dimethylformamide solvate (stanozolol_12.cif)

13) Ethinylestradiol: (EE_1.cif)

14) Ethinylestradiol acetone solvate (EE_2.cif)

15) Ethinylestradiol pentan-2-ol solvate (EE_3.cif)

16) Ethinylestradiol DMSO solvate (EE_4.cif)

17) 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5trien-1-yl]-4-benzene (phsulf_1.cif)

18) 1-[(1E,3E,5E)-4,6-bis(phenylsulfonyl)hexa-1,3,5trien-1-yl]-4-methoxybenzene (phsulf_2.cif)

19) 1-[(1E,3E,5E)-4,6-bis(phenylylsulfonyl)hexa-1,3,5trien-1-yl]-4-nitrobenzene (phsulf_3.cif)

20) 4-(phenylsulfonyl)biphenyl (phsulf_11.cif)

21) 4-methoxybiphen-4-yl phenyl sulphone (phsulf_22.cif)