in your element
A brighter beryllium
Although it is mainly known for its toxicity, beryllium possesses an array of properties that makes it
attractive for a variety of non-industrial purposes. Ralph Puchta discusses why it is not always best avoided.
S
ince ancient times, people have been
fascinated by the green or red of emeralds
and the light blue of aquamarines. These
gems are composed of the mineral beryl — a
transparent beryllium aluminium cyclosilicate
(Be3Al2(SiO3)6) — and bear traces of transition
metals that endow them with striking colours.
The mineral beryl is also at the origin of the
German word ‘brille’ for eyeglasses.
It was while analysing beryl that the
Frenchman Louis-Nicolas Vauquelin
separated beryllium salts from aluminium
salts in 1798. At the time he proposed the
name ‘glucinium’, in reference to its sweet
taste, but beryllium was finally adopted in
French in 1957, in agreement with the other
languages. Beryllium was prepared in its
elemental form in 1828 by Friedrich Wöhler
and Antoine Bussy who, independently,
reacted beryllium chloride with potassium.
In 1898, Paul Lebeau obtained elemental
beryllium by electrolysis of a mixture
of molten BeF2 and NaF. Today, most
beryllium is produced by the redox reaction
of magnesium with BeF2, itself obtained
from beryl.
Number four in the periodic table,
beryllium is the smallest metal atom. It
is typically protected by a thin layer of
beryllium oxide (BeO), which renders it
resistant against concentrated oxidizing
acids — diluted hydrochloric acid, however,
dissolves it, generating hydrogen in the
process. The combination of its high melting
point (1,287 °C), good elasticity, ability to
scatter high-energy neutrons and other
physical characteristics, has led to several
practical applications.
Beryllium has traditionally been used to
construct radiation windows for X-ray tubes,
for example, as it hardly absorbs X-rays.
This transparency to energetic particles also
led to its use as a component in detectors
of the Large Hadron Collider accelerator.
Furthermore, beryllium serves in all kinds
of nuclear applications, for example, as a
H He Li
Be B C
416 NATURE CHEMISTRY | VOL 3 | MAY 2011 | www.nature.com/naturechemistry
neutron reflector in current power plants
based on fission and in nuclear weapons.
Beryllium also takes part in natural
nuclear processes in space, such as the
fusion reactions that generate carbon. In
old stars, during the ‘triple alpha process’,
three 42He nuclei (also called alpha particles)
are transformed into one 126 C atom. At first,
two 42He nuclei fuse into the highly unstable
4Be, which tends to simply decay into two
8
2He nuclei again. However, under particular
4
conditions, these beryllium nuclei are
formed faster than they decay. Some can
then fuse with an additional 42He nucleus
to form the stable 126 C atom. Our Sun will
undergo this process in around six billion
years, when it is around ten billion years old.
Beryllium alloys offer mechanical, thermal
and electrical properties of interest to various
practical usages. For example beryllium–
copper alloys (which typically contain up to
2.5% of beryllium) become non-magnetic
and can serve in gyroscopes or magnetic
resonance imaging devices. Beryllium can
also withstand lower temperatures than glass,
a convenient characteristic for military and
space applications.
Beryllium is used to dope semiconductors
such as gallium arsenide by molecular
beam epitaxy. In contrast, its oxide BeO
is an electrical insulator, yet excellent heat
conductor. Perhaps the most interesting new
possible application for beryllium today is
that beryllium ions may serve as processors
for quantum computers. Such a computer
has already been successfully tested for 160
programs, and operated accurately around
N O F Ne Na Mg
© 2011 Macmillan Publishers Limited. All rights reserved
80% of the time. It seems likely that larger
systems can be realized with a beryllium-
© ISTOCKPHOTO.COM / KETTAPHOTO
based processing unit 1.
However, most practical applications
are spoilt at an early stage by the toxicity
of beryllium and its compounds, especially
in the form of dust. When inhaled, small
particles can cause berylliosis — a chronic
lung disease that can take any time between
a few months and several years to declare
itself in the body, and cannot be treated2.
This does not mean that beryllium and its
compounds should not be used at all, but
they must be handled with care.
Current research with this element
focuses on basic investigations, such as
structural and mechanistic properties,
and has recently been relying more on
computational rather than experimental
studies. Research carried out 2 on tetra-
coordinated complexes, for example,
has provided further knowledge of the
structural diversity of beryllium complexes.
The possible coordination numbers of
beryllium have also recently been clarified3,4
and mechanistic studies are underway to
elucidate solvent-exchange processes5,6.
As further insight into the structure and
reactivity of beryllium compounds is gained,
this element will no doubt play an increasing
role in daily life applications. In light of this,
one might be tempted to conclude — to Be,
or not to Be, that is not the question. ❐
RALPH PUCHTA is at the Department
of Chemistry and Pharmacy, University
of Erlangen-Nürnberg, Egerlandstr. 1,
91058 Erlangen, Germany.
e-mail: ralph.puchta@chemie.uni-erlangen.de
References
1. Hanneke, D. et al. Nature Phys. 6, 13–16 (2009).
2. Dehnicke, K. & Neumüller, B. Z. Anorg. Allg. Chem.
634, 2703–2728 (2008).
3. Azam, S. S. et al. J. Chem. Phys. Chem. B 113, 9289–9295 (2009).
4. Rudolph, W. W., Fischer, D., Irmer, G. & Pye, C. C. Dalton Trans.
38, 6513–6527 (2009).
5. Puchta, R., Pasgreta, E. & van Eldik, R. Adv. Inorg. Chem.
61, 523–571 (2009).
6. Budimir, A., Walther, M., Puchta, R. & van Eldik, R. Z. Anorg.
Allg. Chem. 637, doi:10.1002/zaac.201000418 (2011).
Al Si P S Cl Ar K Ca Sc
Phys Chem Minerals (2013) 40:439–446
DOI 10.1007/s00269-013-0581-9
ORIGINAL PAPER
Structure analysis on synthetic emerald crystals
Pei-Lun Lee • Jiann-Shing Lee • Eugene Huang
Ju-Hsiou Liao
Received: 22 November 2012 / Accepted: 21 February 2013 / Published online: 14 March 2013
Ó Springer-Verlag Berlin Heidelberg 2013
Abstract Single crystals of emerald synthesized by
means of the flux method were adopted for crystallographic
analyses. Emerald crystals with a wide range of Cr3?-
doping content up to 3.16 wt% Cr2O3 were examined by
X-ray single crystal diffraction refinement method. The
crystal structures of the emerald crystals were refined to
R1 (all data) of 0.019–0.024 and wR2 (all data) of
0.061–0.073. When Cr3? substitutes for Al3?, the main
adjustment takes place in the Al-octahedron and Be-tetra-
hedron. The effect of substitution of Cr3? for Al3? in the
beryl structure results in progressively lengthening of the
Al–O distance, while the length of the other bonds remains
nearly unchanged. The substitution of Cr3? for Al3? may
have caused the expansion of a axis, while keeping the
c axis unchanged in the emerald lattice. As a consequence,
the Al–O–Si and Al–O–Be bonding angles are found to
decrease, while the angle of Si–O–Be increases as the
Al–O distance increases during the Cr replacement.
P.-L. Lee (&)
General Education Center, National Chiayi University,
Chiayi, Taiwan, ROC
e-mail: peilun@mail.ncyu.edu.tw
J.-S. Lee
Department of Applied Physics, National Pingtung
University of Education, Pingtung, Taiwan, ROC
E. Huang
Center for International Exchange, Chung-Chou University
of Science and Technology, Yuanlin, Taiwan, ROC
J.-H. Liao
Department of Chemistry and Biochemistry, National Chung
Cheng University, Minxiong, Chiayi County, Taiwan, ROC
•
Keywords Crystallography
Substitution
Single crystal

Emerald
Introduction
Emerald, one of the most attractive green precious gem-
stones, is a variety of beryl, a beryllium aluminum silicate
with a stoichiometric composition of Be3Al2Si6O18 which
is white when pure. The green color is attributed to the
substitution of minor amounts of Cr?3 impurities for Al?3.
The structure of beryl has long been determined to possess
a space group of P6/mcc, with lattice parameters
a = 9.221 Å and c = 9.186 Å (Bragg and West 1926;
Wyckoff 1968). It consists of six-member rings of Si-tet-
rahedron lying in planes parallel to (0001) with sheets of
Be and Al ions lying between layers of rings. These rings
are linked together both laterally and vertically by Be-tet-
rahedron and Al-octahedron, forming a three-dimensional
framework (Klein and Hurlbut 1985).
The color of beryl varies, which depends on the species
and charge valence of the impurities, such as V, Cr, Mn or Fe.
Substituting Al3? with Cr3? which is the most commonly
used dopant in beryl, results in the greenish color of emerald.
The radius of Al in 6 coordination is 0.535 Å and that of Cr in
6 coordination is 0.615 Å (Shannon 1976). Since the radius
of Cr3? is much greater than that of Al3?, one would expect
that replacement of larger cations might have some effects on
the crystallography of the hosting crystals.
In our previous investigation (Lee et al. 2011), we
reported that the maximum Cr2O3-content allowed in the
crystal lattice of emerald was about 3.5 wt%. It is interesting
to note that Cr impurity maximum reported to date on natural
emeralds is 3.46 wt% for a sample from Ianapera, Mada-
gascar (Vapnik et al. 2005). Similar result was reported by
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440 Phys Chem Minerals (2013) 40:439–446

Table 1 Crystallographic and structural refinement data of samples

Sample #1 #2 #3 #4 #5

Cr2O3 wt% 0 0.71 1.64 2.28 3.16

Crystal system Hexagonal Hexagonal Hexagonal Hexagonal Hexagonal
Space group P6/mcc P6/mcc P6/mcc P6/mcc P6/mcc
Lattice parameters a = 9.217 (1) a = 9.229 (1) a = 9.232 (1) a = 9.238 (1) a = 9.241 (1)
c = 9.190 (1) c = 9.192 (2) c = 9.187 (1) c = 9.190 (1) c = 9.185 (1)
c = 120° c = 120° c = 120° c = 120° c = 120°
l (mm-1)/F (000) 0.86/532.0 2.76/652.0 1.24/556.0 1.24/556.0 1.24/556.0
Limiting indices -12 B h B 11 -12 B h B 12 -12 B h B 12 -12 B h B 9 -12 B h B 10
-9 B k B 10 -12 B k B 10 -12 B k B 12 -7 B k B 11 -8 B k B 12
-11 B l B 12 -12 B l B 10 -11 B l B 12 -12 B l B 11 -6 B l B 12
Number of reflections 3,957 5,000 6,310 4,110 4,189
Number of unique reflections 309 311 310 311 311
Number of data/restraints/parameters 308/0/27 310/0/28 309/0/28 309/0/28 310/0/28
R (int) 0.0213 0.0170 0.0191 0.0151 0.0174
Final R1 [I [ 2r (I)], wR2 0.0195, 0.0591 0.0232, 0.0651 0.0182, 0.0526 0.0166, 0.0503 0.0191, 0.0569
R1, wR2 (all data) 0.0202, 0.0665 0.0238, 0.0734 0.0190, 0.0613 0.0205. 0.0679 0.0200, 0.0652
Largest diff. peak and hole (e Å-3) 0.26, -0.46 0.28, -0.44 0.33, -0.25 0.26, -0.37 0.28, -0.46

Table 2 Final atomic coordinates for emerald samples

Atom Multiplicity and Wyckoff letter Coordinates Sample no.
#1 #2 #3 #4 #5

Si 12l x 0.38750 (6) 0.38717 (6) 0.38690 (4) 0.38675 (5) 0.38658 (6)
y 0.11601 (6) 0.11570 (6) 0.11541 (4) 0.11528 (5) 0.11507 (5)
z 0.0000 0.0000 0.0000 0.0000 0.0000
Be 6f x 1/2 1/2 1/2 1/2 1/2
y 0 0 0 0 0
z 1/4 1/4 1/4 1/4 1/4
Al 4c x 2/3 2/3 2/3 2/3 2/3
y 1/3 1/3 1/3 1/3 1/3
z 1/4 1/4 1/4 1/4 1/4
Cr 4c x – 2/3 2/3 2/3 2/3
y – 1/3 1/3 1/3 1/3
z – 1/4 1/4 1/4 1/4
O1 24m x 0.49897 (10) 0.49857 (11) 0.49826 (8) 0.49806 (9) 0.49780 (10)
y 0.14576 (11) 0.14538 (12) 0.14500 (9) 0.14495 (10) 0.14466 (11)
z 0.14524 (10) 0.14520 (10) 0.14520 (8) 0.14516 (9) 0.14521 (10)
O2 12l x 0.30990 (17) 0.30954 (15) 0.30963 (14) 0.30964 (2) 0.30954 (15)
y 0.23688 (15) 0.23650 (18) 0.23625 (12) 0.23623 (1) 0.23601 (15)
z 0.0000 0.0000 0.0000 0.0000 0.0000

Andrianjakavah et al. (2009) that most emeralds at Ianapera
(Southern Madagascar) are anomalously depleted in Al and
enriched in Cr, with a Cr-content ranges between 0 and
3.39 wt% in the emerald. We also found that when the
doping Cr2O3-content exceeds 3.5 wt%, a significant
anomaly in the lattice parameters starts to take place and the
lattice is no longer stable. And the substitution of Cr3? for
Al3? at the octahedral sites of beryl results in the expansion
of the a axis, while the c axis remains nearly unchanged (Lee
et al. 2011). In order to understand more about the function of
Cr3?-dopant acts on the lattice, we attempted structural
analyses on some single crystals of emerald with a variety of

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Phys Chem Minerals (2013) 40:439–446 441

Table 3 Anisotropic and equivalent-isotropic displacement parameters (Å2) for each emerald crystal
Sample no. #1 #2 #3 #4 #5

Cr2O3 wt% 0 0.71 1.64 2.28 3.16

Si
U11 0.0050 (3) 0.0055 (3) 0.0057 (2) 0.0057 (2) 0.0050 (3)
U22 0.0044 (3) 0.0051 (3) 0.0048 (2) 0.0051 (2) 0.0044 (3)
U33 0.0047 (3) 0.0050 (3) 0.0055 (2) 0.0052 (2) 0.0048 (3)
U23 0.0000 0.0000 0.0000 0.0000 0.0000
U13 0.0000 0.0000 0.0000 0.0000 0.0000
U12 0.0024 (2) 0.0029 (2) 0.0026 (2) 0.0027 (2) 0.0024 (2)
Ueq 0.0047 (2) 0.0051 (2) 0.0053 (2) 0.0053 (2) 0.0047 (2)
Be
U11 0.0056 (9) 0.0076 (9) 0.0074 (7) 0.0076 (8) 0.0067 (9)
U22 0.0043 (12) 0.0076 (9) 0.0065 (10) 0.0067 (11) 0.0052 (12)
U33 0.0057 (12) 0.0054 (12) 0.0068 (10) 0.0057 (11) 0.0059 (12)
U23 0.0000 0.0000 0.0000 0.0000 0.0000
U13 0.0000 0.0000 0.0000 0.0000 0.0000
U12 0.0022 (6) 0.0046 (10) 0.0033 (5) 0.0034 (6) 0.0026 (6)
Ueq 0.0053 (5) 0.0065 (6) 0.0070 (5) 0.0068 (5) 0.0061 (6)
Al
U11 0.0056 (3) 0.0044 (4) 0.0045 (3) 0.0045 (3) 0.0036 (3)
U22 0.0056 (3) 0.0044 (4) 0.0045 (3) 0.0045 (3) 0.0036 (3)
U33 0.0055 (4) 0.0036 (5) 0.0044 (3) 0.0040 (4) 0.0036 (4)
U23 0.0000 0.0000 0.0000 0.0000 0.0000
U13 0.0000 0.0000 0.0000 0.0000 0.0000
U12 0.0028 (1) 0.0022 (2) 0.0022 (1) 0.0023 (1) 0.0018 (2)
Ueq 0.0055 (2) 0.0041 (3) 0.0044 (2) 0.0043 (3) 0.0036 (3)
O1
U11 0.0080 (4) 0.0093 (4) 0.0095 (3) 0.0096 (4) 0.0091 (4)
U22 0.0056 (4) 0.0082 (4) 0.0071 (3) 0.0073 (4) 0.0068 (4)
U33 0.0068 (4) 0.0071 (4) 0.0072 (3) 0.0074 (4) 0.0069 (4)
U23 -0.0003 (3) -0.0021 (4) -0.0002 (3) -0.0004 (3) -0.0006 (3)
U13 -0.0019 (3) -0.0023 (3) -0.0020 (3) -0.0019 (3) -0.0020 (3)
U12 0.0030 (2) 0.0053 (3) 0.0041 (2) 0.0043 (1) 0.0041 (3)
Ueq 0.0070 (2) 0.0078 (2) 0.0080 (2) 0.0080 (2) 0.0075 (2)
O2
U11 0.0110 (6) 0.0095 (6) 0.0120 (5) 0.0116 (6) 0.0090 (6)
U22 0.0088 (6) 0.0119 (6) 0.0091 (5) 0.0096 (6) 0.0058 (6)
U33 0.0129 (6) 0.0134 (7) 0.0137 (5) 0.0134 (6) 0.0132 (6)
U23 0.0000 0.0000 0.0000 0.0000 0.0000
U13 0.0000 0.0000 0.0000 0.0000 0.0000
U12 0.0071 (5) 0.0077 (5) 0.0073 (4) 0.0074 (5) 0.0020 (5)
Ueq 0.0100 (3) 0.0106 (3) 0.0107 (3) 0.0106 (3) 0.0101 (3)

Cr3?-doping content. The result will help resolve questions
such as how and to what extend the Cr3?-dopant concen-
tration affects the crystal structure of beryl and, furthermore,
to reveal the mechanism that causes the change in lattice
dimension of beryl with the addition of Cr3?-dopant.
Experimental methods
The synthetic emerald crystals were the same as the ones
used in our previous investigation (Lee et al. 2011). In
this study, we selected 5 perfect crystals with different

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442 Phys Chem Minerals (2013) 40:439–446

Table 4 Relevant bond distances (Å) and angle (°) from X-ray refinement
Sample no. #1 #2 #3 #4 #5

Cr2O3 wt% 0 0.71 1.64 2.28 3.16

Bond distance (Å)
Si–O2 1.5943 (12) 1.5958 (12) 1.5956 (10) 1.5956 (11) 1.5959 (12)
Si–O2 1.5960 (12) 1.5969 (12) 1.5960 (10) 1.5967 (11) 1.5968 (12)
Si–O1 (2x) 1.6223 (9) 1.6230 (10) 1.6222 (8) 1.6222 (8) 1.6219 (9)
Mean 1.6087 1.6096 1.6090 1.6092 1.6092
Be–O1 (4x) 1.6565 (9) 1.6569 (9) 1.6553 (7) 1.6568 (8) 1.6555 (9)
Al–O1 (6x) 1.9056 (9) 1.9105 (9) 1.9138 (7) 1.9159 (8) 1.9183 (9)
Be–(Al, Cr) 2.6595 (0) 2.6630 (2) 2.6639 (0) 2.6656 (0) 2.6667 (1)
Angle (°)
O1–Si–O1 110.81 (7) 110.77 (7) 110.73 (5) 110.74 (6) 110.74 (7)
O1–Si–O2 (2x) 108.44 (4) 108.51 (5) 108.46 (4) 108.47 (4) 108.48 (4)
O1–Si–O2 (2x) 110.41 (4) 110.43 (5) 110.43 (4) 110.39 (4) 110.39 (4)
O2–Si–O2 108.26 (10) 108.25 (10) 108.25 (8) 108.31 (9) 108.29 (10)
O1–Be–O1 (2x) 90.82 (6) 90.97 (6) 91.14 (5) 91.21 (5) 91.30 (6)
O1–Be–O1 (2x) 108.89 (6) 108.88 (7) 108.82 (5) 108.84 (6) 108.86 (6)
O1–Be–O1 (2x) 131.46 (6) 131.27 (6) 131.10 (5) 131.00 (5) 130.85 (6)
O1–Al–O1 (3x) 76.49 (5) 76.39 (6) 76.29 (4) 76.31 (5) 76.21 (5)
O1–Al–O1 (3x) 90.80 (5) 90.69 (6) 90.63 (4) 90.55 (5) 90.46 (5)
O1–Al–O1 (6x) 96.70 (4) 96.80 (4) 96.89 (3) 96.91 (3) 97.00 (4)
O1–Al–O1 (3x) 170.45 (5) 170.48 (6) 170.48 (4) 170.52 (5) 170.53 (5)
Al–O1–Si 136.65 (6) 136.59 (6) 136.52 (5) 136.56 (5) 136.48 (6)
Al–O1–Be 96.34 (4) 96.32 (4) 96.27 (3) 96.22 (4) 96.23 (4)
Si–O1–Be 126.98 (6) 127.04 (6) 127.17 (5) 127.17 (5) 127.23 (6)
Si–O2–Si 168.30 (10) 168.25 (10) 168.25 (8) 168.30 (9) 168.30 (10)

Cr2O3-contents, that is, 0, 0.71, 1.64, 2.28 and 3.16 wt%,
for additional refinement analysis.
Single crystal growth
Emerald crystals were synthesized by adding various
amount of Cr2O3 dopant to stoichiometric proportion
(BeO:Al2O3:SiO2 = 3:1:6 in mole ratio) of beryl. Each
batch of mixture was used as a starting material for syn-
thesis. A mixture of PbO and V2O5 (PbO/V2O5, molar
ratio = 1) was used as flux. The starting material and the
flux were put into a 50 cm3 platinum crucible and then
heated at 1,200 °C for 24 h in an electric furnace. The
maximum solubility of the PbO-V2O5 flux was tentatively
determined to be 8.6 mol% at 1,200 °C (Lee et al. 1995).
The crucible was covered with a lid, and the crystals were
allowed to grow by gradually cooling down to 800 °C at a
rate of 5 °C/h. When the cooling process was completed,
the power was switched off and the furnace was allowed to
cool to room temperature. The crystal products were
recovered by dissolving away the flux in a hot solution of
dilute nitric acid.
Analytical procedure
The synthetic single crystals obtained were examined by
means of an optical microscope and Raman spectrometer
for their identity before the X-ray experiments.
The synthetic single crystals were cut to a size of about
0.4 9 0.4 9 0.4 mm3 and then mounted on a 4-circle single
crystal X-ray diffractometer. The X-ray diffraction signals
were collected, and lattice parameters of the synthetic crystals
were determined by the Bruker APEX DUO diffractometer
using Mo-Ka radiation (k = 0.71073 Å). All crystals exam-
ined were of good quality for diffraction experiments. The
structure was solved and refined with SHELX program
(Sheldrick 2008). The structure pattern was plotted and dis-
played with the Mercury 3.0 program (Macrae et al. 2008).
Results
Single crystal X-ray diffraction analyses indicate that all 5
emerald single crystals synthesized possess hexagonal
symmetry with a space group of P6/mcc. X-ray structure

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Phys Chem Minerals (2013) 40:439–446
Fig. 1 The crystal of structure
of beryl crystal. Projected onto
(0001). Unit cell is outlined by
dash lines
refinements of those emerald crystals with lattice parame-
ters a = 9.22–9.24 Å and c = 9.19 Å show that Cr atoms
occupy the 2/3, 1/3 and 1/4 sites where Al atoms are nor-
mally located. All the crystallographic data relevant to
emerald single crystals studied are given in Table 1. The
values of R1 and wR2 for all data were 0.019–0.024 and
0.061–0.073, respectively. Atomic coordinates are given in
Table 2. Be atoms occupy the 1/2, 0 and 1/4 sites. Si atoms
occupy 0.3866–0.3875, 0.1151–0.1160 and 0 sites. Table 3
shows the anisotropic and equivalent-isotropic displace-
ment parameters for each emerald crystal. Selected bond
lengths and bond angles are listed in Table 4.
From Fig. 1, it can be seen that the structure of beryl is
composed of six-member rings of Si tetrahedra lying in
planes parallel to (0001). Sheets of Be and Al atoms lie
between the layers of rings. When Al3? is substituted by
Cr3? in synthetic emerald, the expansion is seen to occur
mainly on the a–b plane, as was observed in our previous
investigation (Lee et al. 2011). To understand this phe-
nomenon, we calculated the bonding distance of all M–O
bonds (Fig. 2; Table 4) and found that the Si–O1, Si–O2
and Be–O1 distances remain nearly unchanged. In contrast,
the Al–O1 bond distance was found to increase with the
substitution of Cr3? for Al3? (Fig. 2a). It is worthy of
443
noting that the distance between Be and Al also increases
with the increase in Cr-content (Fig. 2c).
We also found that the O–Si–O angle remain nearly
unchanged. In other words, the SiO4 polyhedra in the beryl
structure did not show signs of deformation but kept their
original shape when Al3? was substituted by Cr3?. However,
the main distortion was observed on the Be-tetrahedron and
Al-octahedron. In Be–O tetrahedron, there are 3 sets of
O–Be–O angles, denoting as \Be-a(2x), \Be-b(2x) and
\Be-c(2x) with decreasing bonding angle. Figure 3 clearly
shows the change of all O–Be–O bending angles in the
emerald with the substitution of Cr3? for Al3?. With an
increase in Cr-content, the largest angle, \Be-a, decreases,
the smallest angle, \Be-c, increases, while the medium one
\Be-b remains nearly intact. In Al-octahedron, there are 4
sets O–Al–O bonding angles which are represented by set-
I(3x), set-II(3x), set-III(6x) and set-IV(3x) following the
sequence of decreasing in the magnitude of angle (Fig. 4).
The angles of all O–Al–O bonds show different trends: set-I
and set-II increase, while set-III and set-IV decrease with the
Cr-content. There are four different kinds of M–O–M bonds
among the polyhedrons in this structure, that is, Al–O–Si,
Al–O–Be, Si–O–Be and Si–O2–Si. Figure 5 shows that the
angle of Al–O–Si and Al–O–Be becomes smaller, but the
123
444
Fig. 2 The variation of bond distance versus Cr2O3 wt% concentra-
tion. a Al–O distance versus Cr2O3-content, b Be–O distance versus
Cr2O3-content, c the distance between Be and Al(Cr) versus
Cr2O3 wt% concentration
angle of Si–O–Be becomes bigger, while that of Si–O2–Si
remains nearly unchanged with the substitution of Cr3?.
Discussion
In the synthetic emerald, when Al3? was substituted by
Cr3?, the original Al-octahedron is forced to expand in
order to accommodate the bigger Cr3?. In contrast, since
the bonding distances of Si–O do not show any significant
change, we conclude that the SiO4 tetrahedra behave as
rigid bodies and do not deform. In addition, the Si–O2–Si
angle remains unchanged (Fig. 5), indicating that the six-
member rings of Si-tetrahedron remain almost unchanged
during the substitution of Cr3? for Ar3?.
Although the length of Be–O bond keeps nearly its
original value (Fig. 2b), the Be-tetrahedron was distorted
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Phys Chem Minerals (2013) 40:439–446
Fig. 3 Variation of angle of O–Be–O with respect to the concentra-
tion of Cr2O3 impurity, which are denoted as \Be-a(2x), \Be-b(2x),
and \Be-c(2x) with decreasing bonding angle
due to the changes among the angles of O–Be–O (Fig. 3).
It means that the deformation of Be-tetrahedron may be
caused by oxygen atoms that coordinating with Si in the
six-member rings along the plane where the a-axes lie.
During the substitution of Cr3? for Al3?, the most obvious
change is the Al–O bonding lengths (Fig. 2a). Though
changes do occur in every bonding angle (Fig. 4), the sum
of all angles does not change, indicating that the octahe-
dron still maintains its integrity. As a consequence, we
infer the main adjustment takes place in the Al-octahedron
and Be-tetrahedron as Cr3? substitutes for Al3?.
In Fig. 5, we noted that the bonding angles of Al–O–Si
and Al–O–Be decrease, while that of Si–O–Be increases
with more substitution of Cr3? for Al3?. Due to the fact
that the hexagonal ring of SiO4 does not show obvious
adjustment, the effect of Cr3? substituting for Al3? in beryl
structure results in the expansion of the Al-octahedron.
This expansion affects the shape of Be-tetrahedron and
results in a change in the bonding angles of O–Be–O. It is
important to note that those adjustments take place along
the plane where the a-axes lie. The increase in the bonding
Phys Chem Minerals (2013) 40:439–446
Fig. 4 Variation of angle of O–Al–O with respect to the concentra-
tion of Cr2O3 impurity, which are denoted as set-I(3x), set-II(3x), set-
III(6x) and set-IV(3x) with decreasing bonding angle
length of Al–O may cause minor adjustment in the bonding
angles of M–O–M among the polyhedrons. Meanwhile, the
bonding angle of Al–O–Be becomes smaller as the distance
between Al and Be gets bigger. Since channels of the
hexagonal ring exist parallel to the c axis, less effect would
be expected to occur along this direction in response to the
expansion of (Al, Cr)-octahedron. This is consistent with
our previous study that the expansion occurs along the
direction of a axis, while c axis remains nearly unchanged
(Lee et al. 2011).
Conclusion
3? 3?
During the substitution of Cr for Al , we observed the
following phenomenon among the polyhedrons in the
structure: (1) (Al, Cr)-octahedrons are forced to expand; (2)
SiO4 tetrahedrons behave as a rigid body, and six-member
rings of Si-tetrahedrons remain almost intact; and (3)
Be-tetrahedrons deform slightly, especially in the bonding
angles of O–Be–O. The net result in the modification of
lattice dimension is the expansion in the a-axes, while the
445
Fig. 5 Variation of angle of M–O–M (M = Si or Al or Be) with
respect to the concentration of Cr2O3 impurity
c axis remains invariant. The amount of Cr3? substituting
for Al3? in beryl to synthesize emerald is limited to the size
of the Al-octahedron. Adding Cr2O3 above 3.5 wt% can
cause breakdown of the octahedron that accommodate Cr
atoms and therefore lead to failure in the emerald synthesis.
Acknowledgments We wish to thank the staff at Instrumentation
Center at the National Tsing Hua University for their help during the
experiments on the operation of diffractometer. This project was
supported by the National Science Council (NSC 101-2116-M-415-
001).
References
Andrianjakavah PR, Salvi S, Béziat D, Rakotondrazafy M, Giuliani G
(2009) Proximal and distal styles of pegmatite-related metaso-
matic emerald mineralization at Ianapera, Southern Madagascar.
Miner Deposita 44:817–835
Bragg WL, West J (1926) The structure of beryl, Be3Al2Si6O18.
Proc R Soc Lond B Math Phys 111(759):691–714. doi:
10.1098/rspa.1926.0088
Klein C, Hurlbut CS Jr (1985) Manual of mineralogy, 20th edn.
Wiley, New York
123
446
Lee PL, Lee JS, Yu SC (1995), The study on growth of emerald crystal
from the flux of PbO-V2O5 system, 1995 Annual Meeting of the
Geological Society of China, Mar 22–23, Taipei, pp 284–288
Lee PL, Huang E, Lee JS, Yu SC (2011) Effects of Cr3? impurity
concentration on the crystallography of synthetic emerald
crystals. J Cryst Growth 324:263–267
Macrae CF, Bruno IJ, Chisholm JA, Edgington PR, McCabe P, Pidcock
E, Rodriguez-Monge L, Taylor R, van de Streek J, Wood PA
(2008) Mercury CSD 2.0-new features for the visualization and
investigation of crystal structures. J Appl Cryst 41:466–470
123
Phys Chem Minerals (2013) 40:439–446
Shannon RD (1976) Revised effective ionic radii and systematic
studies of interatomic distances in halides and chalcogenides.
Acta Cryst A32:751–767. doi:10.1107/S0567739476001551
Sheldrick GM (2008) A short history of SHELX. Acta Cryst A64:
112–122. doi:10.1107/S0108767307043930
Vapnik Ye, Sabot B, Moroz I (2005) Fluid inclusions in Ianapera
emerald, Southern Madagascar. Int Geol Rev 47:647–662. doi:
10.2747/0020-6814.47.6.647
Wyckoff RWG (1968) Crystal structures, vol 4. Wiley, New York