[105]

4000
2.50

Incremental Residual
Intensity (counts)

3000 2.00

1.50
2000

1.00
1000

0.50

40 60 80 100 120 140

2theta (degree)

X-ray Diffraction Analysis for

Advance Research
// LECTURER & RESEARCHER
Course Materials
Session 1 - Theory Session 2 - Theory
❖ Crystallography ❖ Qualitative Analysis (Identification)
• Symmetry & crystal system • Data base
• Phase Identification
• Bravais lattices
• Point group & space group ❖ Quantitative Analysis (Rietveld Analysis)
• Miller indices • Intensity Equation
• Profile Function
❖ Diffraction • Instrumental function
• Diffraction by atom and plane of atoms • Sample physical function
• Miller indices and diffraction • R-indices (How good is good enough)
• Structure Factor
• Instrumentation
• X-ray generation Session 3 & 4 - Practices
• Beam path (optics) ❖ Qualitative Analysis
➢ X-ray monochromatizating
• Practices with QualX2 with COD database
• Instrument configuration ➢ Sample : mixture of Al2O3, CaF2, Zincite (Quantitative Analysis
➢ Optimum setup Round Robin (QARR) sample from International Union for
❖ Sample Preparation Crystallography (IUCr))

• Particle/Crystallite Size ❖ Quantitative Analysis

• Homogeneity • Practices with GSAS/Profex-BGMN
• Texture/Preferred Orientation ➢ Sample : mixture of Al2O3, CaF2, Zincite (QARR sample from IUCR)

❖ Data Acquisition ❖ Microstructure Analysis

• Practices with PM2K (Whole Powder Pattern Modelling)
• Angular Range
➢ Sample : CeO2 (Size Strain Round Robin (SSRR) sample from IUCR)
• Step Size
• Counting Time
Software & References
Software: References:

1. Altomare, A., Corriero, N., Cuocci, C., Falcicchio, A., Moliterni, A., Rizzi, R.,
QualX2 : http://www.ba.ic.cnr.it/softwareic/qualx/
QUALX2.0: a qualitative phase analysis software using the freely available database
PowCod : http://www.ba.ic.cnr.it/softwareic/qualx/powcod- POW_COD, J. Appl. Cryst. 48 (2015) 598-603.
download/ 2. Larson A.C. and Von Dreele R.B., General Structure Analysis System (GSAS), Los
GSAS : https://subversion.xray.aps.anl.gov/trac/EXPGUI Alamos National Laboratory Report LAUR 86-748 (2004).
Profex : https://www.profex-xrd.org/?page_id=279 3. Döbelin, N., Kleeberg, R., Profex: a graphical user interface for the Rietveld
PM2K : Matteo.Leoni@unitn.it refinement program BGMN, J. Appl. Cryst. 48 (2015) 1573-1580.
4. Leoni M., Confente T. & Scardi P., PM2K: a flexible program implementing Whole
Powder Pattern Modelling, Z. Kristallogr. Suppl. 23 (2006) 249-254.
5. Scardi P., Leoni M., Whole Powder Pattern Modelling, Acta Crystall. A 58 (2002) 190-
200.
6. Madsen, I. C., Scarlett, N. V. Y., Cranswick, L. M. D. & Lwin, T., Outcomes of the
International Union of Crystallography Commission on Powder Diffraction Round
Robin on Quantitative Phase Analysis: samples 1a to 1h, J. Appl. Cryst. 34 (2001) 409-
426.
7. Balzar, D., Audebrand, N., Daymond, M. R., Fitch, A., Hewat, A., Langford, J. I., Le Bail,
A., Louer, D., Masson, O., McCowan, C. N., Popa, N. C., Stephens, P. W. & Toby, B. H.,
Size–strain line-broadening analysis of the ceria round-robin sample, J. Appl. Cryst. 37
(2004) 911-924.
8. Toby, B., R factors in Rietveld analysis: How good is good enough?, Powder
Diffraction, 21 (2006) 67-70
9. Cullity, B. D., & Stock, S. R., Elements of X-ray Diffraction, Third Edition. Prentice-Hall
(2001).
The life of a Scientist
Trade-in for Atomic Land Scale
Planck constant speed of light Currents
Voltage time
energy

wavelength

*PSI Synchrotron 10 MW, ~ USD 200 million

Scattering Techniques
Phase Identification Common
Some
Phase Quantification Rare
Never find
Microstructure Not applicable

Residual Stress

Crystalline

Texture

Small Angle Scattering Reflectometry

Elastic
Reciprocal Space
Thin Film
Map
Scattering

In-Elastic
Single Crystal Grazing Incidence

Pair Distribution
Amorphous
Function
X-Ray Scattering Techniques
Small angle
• Small Angle X-Ray Scattering (SAXS)
• X-Ray Reflectivity (XRR)
• Gracing Incidence X-Ray Scattering (GI-SAXS)
Wide angle
• X-Ray Diffraction (XRD)
• Gracing Incidence X-Ray Diffraction (GI-XRD)
• In-Plane X-Ray Diffraction (IP-XRD)
• Pair Distribution Function (PDF)
• Single Crystal
Selection Angle
• Reciprocal Space Map (RSM)
• Texture (Pole Figure, ODF)
• Residual Stress
In-situ
• Non ambient (time, temperature, pressure, etc)
• Battery (charge – discharge)
Sample Types
• POWDER
• Common powder (PXRD, SAXS)
• Bulk/Chunk
• Single/multi phase homogen (XRD, PF, Psi)
• Multiphase non-homogen (micro-XRD, Psi)
• Small quantity
• Precious material (XRD)
• Nano material (XRD, SAXS, PDF)
• Thin Film
• Epitaxy (XRR, HRXRD, RC)
• Polycrystalline (XRR, XRPD, GI, Psi)
• Textured (PF, Psi, RC, HRXRD, XRPD, XRR, GIXRD, IP-GI)
• Amorphous (XRR)
• Non-Ambient
• Material formation / structure changes
• Heat treatment & annealing
• Calcination & Sintering
• (De)Hydration processes
• Material changes during operation
• Single Crystal (SCD)
• Amorphous / Short Range Order (PDF)
Crystallographer

Physics

Crystal
Engineering Chemistry
Structure

Biology
BATAN – Badan Tenaga Nuklir Nasional
30 MW reactor
BATAN – Badan Tenaga Nuklir Nasional
H

0 kOe 420 kOe 840 kOe 10,000 kOe

SANS
In-situ
magnetic

Small Angle Neutron Scattering (SANS) Neutron Diffraction

SLRI – Synchrotron Light Research Institute
SLRI – Synchrotron Light Research Institute

Lysosome crystal Viruses 2020, 12, 254 Nature Medicine 2004, 10

ANSTO – Australian Nuclear Science & Technology Organisation
ANSTO – Australian Nuclear Science & Technology Organisation
1. Have the right (tuneable) wavelength

Human hair Red blood cells Deposited nanostructures

~100,000 nm ~7,000 nm ~500 nm

Influenza virus DNA Silicon atoms

~100 nm ~2 nm ~0.2 nm
JPARC – Japan Proton Accelerator Complex

Nano Structure Group

Spectroscopy Group
1 SANS Machine, 2 Refrectmeters and 1 total sca ering diffractometer 　Crystal Structure Group
6 Inelastic Scattering Instruments covering a wide energy and momentum
transfer range for Nano structure and surface/interface structure Pulsed Neutron Application Group 7 Diffrac on Instruments at MLF
1
BL15 TAIKAN 10
Glassy Carbon
BL21 Versa le Total SHRPD
Sca ering Diff.　（NOVA)
(SANS)
10
0 Absolute intensity Diffractometer in the World
data of Glassy Carbon
-1
intensity / cm

calibrated by Dr.
BL12 (H C) Ilavsky (APS)
(KEK) Spin Echo 10
-1
Pulsed Neutron Application Group
BL06( IN_ O E) small - angle bank ・Neutron Source Diagnostic & Test Port
(KEK, Kyoto niv.) 10
-2 (Semi Macro strct) BL10: NOBORU
backward
Middle
(intermid strct) Neutron Source Diagnostic & Test Port Neutron-Nucleus Reaction Meas. Inst. ・Neutron-Nucleus Reaction Meas. Inst.
High (atomic strct) BL04: ANNRI
10
-3
BL10: NOBORU BL04: ANNRI
-2 -1 0 1
BL02 (DNA) 10 10 10 10
・Fundamental Physics
BL14 (AMA E A ) q/Å
-1
(JAEA)
(JAEA) BL05: NOP
Ibaraki Powder Diff.
BL16 SOFIA ・Neutron Imaging Versa le Total Sca ering Diff.
(horizontal NR) BL22: RADEN

BL17
Figure 2 Covered E-Q space of inelastic neutron scattering instruments in MLF. (Ver cal NR)
BL23 (POLANO)  
Polarized Neutron Fundamental Physics Neutron Imaging
( ohoku niv., KEK) BL01(4 EA ON )
1
3 BL05: NOP BL22: RADEN 2
(JAEA)

Developments and highlight are explained by K. Nakajima 4

JPARC – Japan Proton Accelerator Complex
New Generation Super Ionic Conductor
Material Family discovered in 2016
Single crystal β-alumina
(NaAl11O17) Li9.54Si1.74P1.44S11.7Cl0.3 Super Ionic Conductor
discovered in 2011 3D diffusion path
β-alumina
(NaAl11O17) LGPS-family
Organic solvent electrolyte 1D diffusion path
Log [Ion conductivity (S/cm)]

Li9.6P3S12

Second Generation
Material Family
Li7La3Zr 2O12

First Generation
Material Family
Li2MCl4

Polymer Conductor
LI3.3PO3.9N0.17

2020
Li10GeP2S12 Li9.54Si1.74P1.44S11.7Cl0.3
Nature Materials (2011) Nature Energy (2016)
Newspaper (Tokyo Newspaper (7/25), Chunichi News Paper (7/28)) Neutron diffraction have revealed the diffusion path of ions,
TOYOTA will load all-solid buttery into Electric Vehicle in 2022 which is a key for development of new battery materials.
ORNL – Oak Ridge National Laboratory

Opportunities
• Multimodal analysis
• Applied Math. concepts
• Advanced Materials Modeling
ORNL – Oak Ridge National Laboratory
❖Traditional crystallographic approach to
structure determination is insufficient or fails
for

❖Non crystalline materials

❖Disordered materials: The interesting
properties are often governed by the
defects or local structure !
❖Nanostructures: Well defined local
structure, but long-range order limited to
few nanometers (-> poorly defined Bragg
peaks)

❖Total scattering approach allows to determine

S.J.L. Billinge and I. Levin, The Problem with Determining Atomic
local and nano-scale structures. Structure at the Nanoscale, Science 316, 561 (2007).
Energy and Packing
❖ Dense, ordered packing Crystalline materials...
Energy • atoms pack in periodic, 3D arrays
• typical of: ➢ metals
typical neighbor ➢ many ceramics
bond length
➢ some polymers
r
typical neighbor
bond energy

❖ Non dense, random packing Non-crystalline materials...

Energy • atoms have no periodic packing
typical neighbor
• occurs for: ➢ complex structures
bond length ➢ rapid cooling
typical neighbor r
bond energy
Metallic Crystal Structure
How can we stack metal atoms to minimize empty space?

2-dimensions 3-dimensions
Unit Cell and Packing Factor
❖ No. of atom in unit cell

➢ Cubic:

➢ Hexagonal:

4 3 16 3
𝑉𝑠 = 𝑁 × 𝑉𝑏𝑎𝑙𝑙 = 4 𝜋𝑅 = 𝜋𝑅
3 3
❖ Atomic Packing Factor 𝑉𝑐 = 𝑎3 = (2𝑅 2)3 = 16𝑅 3 2

𝑉𝑠 16/3 𝜋𝑅3
𝐴𝑃𝐹 = = = 0.74
𝑉𝑐 3
16𝑅 2
 Density and Material Selection
rmetals > rceramics > rpolymers Materials Selection in Mechanic
Metals/
Graphite/
Ceramics/ Polymers
Composites/ Ashby - Chart
Alloys fibers
Semicond
30
Based on data in Table B1, Callister
20 Platinum *GFRE, CFRE, & AFRE are Glass,
Gold, W
Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
Cu,Ni
Steels
Tin, Zinc
Zirconia
r (g/cm3 )

5
Titanium
4 Al oxide
Diamond
3 Si nitride
Aluminum Glass -soda Glass fibers
Concrete
Silicon PTFE GFRE*
2 Carbon fibers
Magnesium Graphite
Silicone CFRE*
PVC Aramid fibers
PET AFRE*
1 PC
HDPE, PS
PP, LDPE

0.5
Wood
0.4
0.3
Data from Table B.1, Callister & Rethwisch, 8e.
What is a Crystal ?
Imagine…
❖ having to describe an infinite crystal with an infinite number of atoms
❖ or even a finite crystal, with some 1020 atoms

Sounds horrible?... Well, there’s symmetry to help you out! Instead of an infinite number of atoms, you only
need to describe the contents of one-unit cell, the structural repeating motif…
❖ and life could be even easier, if there are symmetry elements present inside the unit cell!
❖ you only need to describe the asymmetric unit if this is the case
Systematization of Crystal Structures

1. Step: Crystal Systems

metric + symmetry of the UC
7
The Concept of the Unit Cell
Task
Divide a space/volume into identical building blocks
use only blocks that are geometrically regular
use only a single sort of blocks

a
a
a
( =  =  = 90°)

cube cube
The Concept of the Unit Cell
Task
Divide a space/volume into identical building blocks
use only blocks that are geometrically regular
use only a single sort of blocks

a
a

c
( =  =  = 90°)
cube square plate
The Concept of the Unit Cell
Task
Divide a space/volume into identical building blocks
use only blocks that are geometrically regular
use only a single sort of blocks

c
b

( =  =  = 90°)
cube rectangular prism
The Concept of the Unit Cell
Task
6 faces
Divide a space/volume into identical building blocks hexahedra
use only blocks that are geometrically regular
use only a single sort of blocks

8 faces
The Concept of the Unit Cell
Task
Divide a space/volume into identical building blocks
use only blocks that are geometrically regular
use only a single sort of blocks

1.

 = 120°

2. c
a
a  = 120°
a a
The Concept of the Unit Cell

voids completely space-filling

not completely space-filling but two orientations

no voids
completely space-filling
The Concept of the Unit Cell
▪ Which geometrical regular bodies fill the space completely (without gaps) by
joining them together only by translation along all three spatial directions?

a
b
parallelepipeds!

▪ A parallelepiped (epipedo = Greek for face)

is a geometric body, which is confined by six c
parallelograms, of which two of each are
congruent (superimposable) and lie in
parallel planes.

 ≠  ≠  ≠ 90°
The Unit Cell Definition
▪ The unit cell is the unit, which builds up the whole crystal structure by
repeated translations along all three spatial directions.
z

y y

x
Unit Cell Attributes
z
Metric
▪ it is defined by six cell/lattice parameters
▪ the three cell/lattice constants, the lengths of the edges (a, b, and c)
c ▪ and three angles between these edges (α, β, and γ)
β α b y
a γ Symmetry
▪ it contains all present symmetry elements
x ▪ defines the minimum size of the unit cell

Chemical Composition (Stoichiometry)

▪ the chemical content of an unit cell corresponds to the
chemical composition of the considered compound (!)

H2O HO HO HO H2O H2O H2O H2O H2O H2O

2H:1O HO HO HO H2O H2O H2O H2O H2O H2O
7 – Crystal System
z Classification of unit cells
Every imaginable crystal of the world belongs to one
of altogether 7 possible crystal systems
c
β α b
y
a γ

maximum
restrictions for symmetry
cell constants angles
x
triclinic a≠b≠c  ≠  ≠  ≠ 90° 1
monoclinic a≠b≠c  =  = 90°,  ≠ 90° 2/m
orthorhombic a≠b≠c  =  =  = 90° mmm
tetragonal a=b≠c  =  =  = 90° 4/mmm
trigonal a=b≠c  =  = 90°;  = 120° 3m
hexagonal a=b≠c  =  = 90°;  = 120° 6/mmm
cubic a=b=c  =  =  = 90° m3m
symmetry
hexagonal crystal family
7 – Crystal System
Crystal Structure = Lattice + Motif/Base

crystals have a
crystal structure

crystal structure = lattice + motif

Lattice
▪ Lattice = infinite arrangement of points in space (3D) / in the plane (2D) / on a line (1D),
in which all points have the same surroundings
Lattice - Surroundings
▪ Lattice = infinite arrangement of points in space (3D) / in the plane (2D) / on a line (1D),
in which all points have the same surrounding
Lattice - Surroundings
▪ Lattice = infinite arrangement of points in space (3D) / in the plane (2D) / on a line (1D),
in which all points have the same surrounding
Lattice Points
▪ the lattice points are the connection points between the unit cells

x
Crystal Structure = Lattice + Base/Motif
▪ every corner of all unit cells builds a lattice point
▪ a lattice is characterized by its lattice vectors (translation vectors) = they span the unit cell
▪ the lattice points can be transferred into each other by these vectors

c
y
b
Crystal Structure = Lattice + Base/Motif
▪ the motif consists of the arrangement of the building blocks (atoms, molecules) of a unit cell
▪ the motif is represented by a lattice point

c
y
b
Crystal Structure = Lattice + Base/Motif
▪ the motif consists of the arrangement of the building blocks (atoms, molecules) of a unit cell
▪ the motif is represented by a lattice point

three atomic molecule

c
y
b
Crystal Structure = Lattice + Base/Motif
▪ the motif consists of the arrangement of the building blocks (atoms, molecules) of a unit cell
▪ the motif is represented by a lattice point

three atomic molecule

c
y
b

All building blocks of a crystal structure are subject to the same translation principle!
Crystal Structure = Lattice + Base/Motif
▪ the motif consists of the arrangement of the building blocks (atoms, molecules) of a unit cell
▪ the motif is represented by a lattice point

three atomic molecule

c
y
b

All building blocks of a crystal structure are subject to the same translation principle!
Crystal Structure = Lattice + Base/Motif
▪ the motif consists of the arrangement of the building blocks (atoms, molecules) of a unit cell
▪ the motif is represented by a lattice point

three atomic molecule

c
y
b

All building blocks of a crystal structure are subject to the same translation principle!
All atoms of a crystal build congruent crystal lattices!
Morphology of Crystals

7 crystal systems
? countless forms
of appearance

triclinic

monoclinic
orthorhombic

tetragonal

trigonal

hexagonal

cubic

Rock Crystal (Quartz, SiO2)

Morphology of Pyrite
▪ FeS2
▪ cubic crystal system
▪ space group Pa3
▪ a = 5.14 Å
▪ FeS6 octahedra
▪ S-SFe3 tetrahedra

cube rhombic pentagon

octahedron
dodecahedron dodecahedron
Stacking Cubes – Face Development
Facet and Habitus
▪ the total set of faces developed on a crystal
is called Facet (‘costume’)

number and composition of faces of

the outer limiting planes of a crystal
same tracht – different habitus
▪ the relative face development, i.e. their
relative sizes gives rise to the habitus

▪ two crystals can have the same facet but

rhombic pyramid icositetra- hexakis-
cube octahedron
dodecahedron cube
trisoctahedron
hedron octahedron
different habitus, and they can have the same
habitus but different trachts
same habitus (isometric) – different tracht

▪ habitus: isometric, needle-like, plate-like,

cubically, column…
Miller Indices

Miller indices are used to name the crystal

faces in a systematic manner, and are also
(100) used to denominate lattice planes.

(110)

combination of a hexahedron (cube)

and a rhombic dodecahedron
Miller Indices
William Hallowes Miller

(1801 – 1880)

René Just Haüy

(1743 – 1822)
Hauyenite
hauyne / hauynite
tecto(alumo)silicate
Na3Ca(Si3Al3)O12(SO4)

René Just Haüy

(1743 – 1822)
Lattice Planes
unit cell

▪ lattice planes are a family of parallel planes

which intersects the Bravais lattice and are
periodic

▪ these crystallographic planes are

fictitious planes linking nodes, i.e. lattice points

a
Lattice Planes

▪ lattice planes are a family of parallel planes

which intersects the Bravais lattice and are
periodic

▪ these crystallographic planes are

fictitious planes linking nodes, i.e. lattice points

▪ in principle there is an infinite number of

plane families (all parallel planes of a
particular type)

▪ Miller indices form a notation system for

such planes and are expressed by three
integers: (h k l)
b

a
Determining Miller Indices
(010)
▪ In how many fractions do the planes
intersect the respective lattice constants
a, b, (and c)?

If one of the indices is zero, it

means that the planes do not
intersect that axis (the intercept is
"at infinity")

(120)
b

a
d - Spacings
d010
(010)
the lower the indices the higher
the density of lattice points onto
this plane
d120
the lower the indices the larger
the distance d between two
adjacent planes of a plane family

(120)
Negative Miller Indices
(120)
▪ if the intercepts are on the negative side
of the coordinate system the indices get
a bar above the number (= minus)

(120)
b

a
Exercise - Miller Indices

A: ?

B: ?

C: ?

D: ?

E: ?

a
Miller Indices in 3D
(1 0 0)

b
a
d
Miller Indices in 3D
(0 1 0)

b
a

d
Miller Indices in 3D
(1 1 1)

b
a
Miller Indices of Faces

(100)

(110)
combination of a hexahedron (cube) and
a rhombic dodecahedron

the outermost planes of a crystal

build the faces!
Miller Indices of Faces
+a
100
1-10 110

(100)
-b 0-10 010 +b
(110)
combination of a hexahedron (cube) and
a rhombic dodecahedron

-1-10 -110
-100 the outermost planes of a crystal
build the faces!
-a
Systematization of Crystal Structures

2. Step: Bravais lattices

primitive + centered
14
1. Step: Crystal Systems
metric + symmetry of the UC
7
7 Primitive Lattices

ortho- trigonal/
triclinic monoclinic tetragonal trigonal cubic
rhombic hexagonal

primitive = simple

there are lattice points only at every corner of the unit cell,
but not inside the cell or at the faces or edges

a primitive unit cell comprises exactly 1 motif (1/8 * 8 = 1)

the primitive unit cell is the smallest possible unit cell

it is always possible to find such a primitive unit cell

Choice of the Unit Cell

Is the smallest possible unit cell always the best cell?

? ? ?

centering of cells / 14 Bravais lattices

Choice of the Unit Cell
Choice of the Unit Cell
▪ The unit cell should be as small as
possible; short lattice vectors!

▪ At the same time it should represent the

symmetry of the crystal; this means that
m the lattice vectors should run parallel to
90° symmetry axes or perpendicular to
symmetry planes.

▪ The axes should be, if possible, orthogonal

(or hexagonal)!
m
5 possible primitive unit cells,
all with the same ‘volume’
Choice
The choice ofof
thethe Unit Cell
unit cell…

▪ Due to symmetry reasons it is sometimes

primitive unit cells advantageous to choose not the smallest
possible unit cell!

▪ Centered cells contain additional lattice points.

▪ The purpose is to describe the crystal in a higher

m symmetric system of coordinates!

▪ But note: The crystal system does not change!

90° ▪ The centered unit cell possess the same

symmetry as the primitive one, but the
symmetry becomes more evident!
m

centered unit cell (UC)

Centered Cells
▪ If lattice points are only at the corners of the unit cell, it is a primitive lattice; there are 7 different
primitive lattices.
▪ Addition of further lattice points – under retention of the symmetry – give rise to 7 more lattices,
7 centered lattices. This leads to the 14 Bravais lattices.

primitive single-side face-centered body-centered all-side face-centered

unit cell unit cell unit cell unit cell

P C(AB) I F
Centered Cells – Formula Units

8 corners x 1/8 = 1 lattice point/unit cell

Centered Cells – Formula Units

C(AB)

(8 corners x 1/8) + (2 faces x 1/2) = 2 lattice points/unit cell

Centered Cellsunits/lattice
Centered Cells – formula – Formula points Units

(8 corners x 1/8) + (1 inside) = 2 lattice points/unit cell

Centered Cellsunits/lattice
Centered Cells – formula – Formula points Units

(8 corners x 1/8) + (6 faces x 1/2) = 4 lattice points/unit cell

Centered
Centered Cells Cells

▪ If lattice points are only at the corners of the unit cell, it is a primitive lattice; there are 7 different
primitive lattices.
▪ Addition of further lattice points – under retention of the symmetry – give rise to 7 more lattices,
7 centered lattices. This leads to the 14 Bravais lattices.

primitive single-side face-centered body-centered all-side face-centered

unit cell unit cell unit cell unit cell

P C(AB) I F
14 Bravais
The 14 Lattices
Bravais lattices

Bravais lattices

crystal systems
7  4 = 14 (?)

kind of centerings
14 Bravais Lattices
triclinic monoclinic orthorhombic tetragonal hexagonal/trigonal cubic

C(AB)

R
I

F
14 Bravais Lattices
* 23th August 1811 in Annonay, Frankreich
† 30th March 1863 in Le Chesnay
French physicist, crystallographer, universal scholar

Auguste Bravais
in 1848 he could show that there are only
14 unique different lattice types in 3D space

some of the 28 conceivable lattice types are redundant

some of them are not possible due to symmetry reasons

14 Bravais Lattices - Redundancy

? !
monoclinic

P I
monoclinic C
14 Bravais Lattices – Incompatible Symmetry

? !
cubic
a

F C
a?
tetragonal P
14 Bravais Lattices

C(AB) ! ! ! !

R ?
I ! !

F ! ! ! !
14 – Bravais Lattice
Crystal Family Bravais Lattice
c

 
b

a
Higher Symmetry
Fractional Coordinates
▪ Atom sites: Where are the atoms a = 5 Å, b = 20 Å, c = 15 Å  =  =  = 90°
located inside of the unit cell?
Atom 1: x = 2.5 Å, y = 10 Å, z = 7.5 Å absolute coordinates
▪ usage of the crystallographic Atom 1: 0.5, 0.5, 0.5 relative or fractional coordinates
system of coordinates

▪ the lattice constants are used

as units
c
▪ the atomic site parameters
are given as a coordination
triple (x, y, z) and are
fractional amounts of the
lattice constants (a, b, c)

b
a
Fractional Coordinates
▪ Atom sites: Where are the atoms a = 5 Å, b = 20 Å, c = 15 Å  =  =  = 90°
located inside of the unit cell?
Atom 2: x = 5 Å, y = 10 Å, z = 0 Å absolute coordinates
▪ usage of the crystallographic Atom 2: 1, 0.5, 0 relative or fractional coordinates
system of coordinates

▪ the lattice constants are used

as units
c
▪ the atomic site parameters
are given as a coordination
triple (x, y, z) and are
fractional amounts of the
lattice constants (a, b, c)

b
a
Fractional Coordinates
▪ Atom sites: Where are the atoms a = 5 Å, b = 20 Å, c = 15 Å  =  =  = 90°
located inside of the unit cell?
Atom 3: x = 2.5 Å, y = 20 Å, z = 7.5 Å absolute coordinates
▪ usage of the crystallographic Atom 3: 0.5, 1, 0.5 relative or fractional coordinates
system of coordinates

▪ the lattice constants are used

as units
c
▪ the atomic site parameters
are given as a coordination
triple (x, y, z) and are
fractional amounts of the
lattice constants (a, b, c)

b
a
Fractional Coordinates
▪ Atom sites: Where are the atoms
located inside of the unit cell?
(½,1,1)
▪ usage of the crystallographic
system of coordinates (1,1,1)
(x,y,z)
▪ the lattice constants are used
as units (0,1,½)
(½,0,½)

▪ the atomic site parameters c (½,½,½)

are given as a coordination
triple (x, y, z) and are
fractional amounts of the b (0,0,0) = (1,0,0) = (0,1,0) =…
a
lattice constants (a, b, c)
(1,y,0)
Fractional Coordinates - CuSO4.5H2O
Atomic parameters (x/a y/b z/c)

Cu1 1/2 1/2 1/2

Cu2 1/2 0 0 Cu2 S1
S1 0.12527 -0.01315 0.28634 O5
O1 0.64893 -0.28899 0.11748 O9
O2 0.65182 0.18247 0.07346 O7
O3 1.12844 -0.43479 0.12435 Cu1
O4 0.20280 0.46556 0.59358 O4 O3
O5 -0.11557 -0.04315 0.30159
O6 0.13680 0.13959 0.37259 O7 O1
O7 0.29749 -0.24436 0.31756 O2
Chalcanthite O8 0.17223 0.09305 0.15153
O9 0.48076 0.75491 0.58387 S1 Cu2 O8

O6
Space-group P 1
triclinic
a = 5.9553 Å
b = 6.1084 Å Atomic parameters (x/a
y/b z/c)
CIF
c = 10.7048 Å Cu1 1/2 1/2 1/2
Cu2 1/2 0 0
S1 0.12527 -0.01315 0.28634
O1 0.64893 -0.28899 0.11748
O2 0.65182 0.18247 0.07346
O3 1.12844 -0.43479 0.12435
O4 0.20280 0.46556 0.59358

α = 77.4090°
O5 -0.11557 -0.04315 0.30159
O6 0.13680 0.13959 0.37259
O7 0.29749 -0.24436 0.31756
O8 0.17223 0.09305 0.15153

β = 82.3720° O9 0.48076 0.75491 0.58387

γ = 72.6740°
Crystallographic Information File
Systematization of Crystal Structures

3. Step: Crystal classes

crystallographic PG
32
2. Step: Bravais lattices
primitive + centered
14
1. Step: Crystal Systems
metric + symmetry of the UC
7
Symmetry Operation and Symmetry Element
Symmetry operation (SO)

▪ is a (geometrical) reorganization/transformation, which maps an object onto itself

▪ by this operation a congruent image of the motif is generated, i.e. an image which is
indistinguishable of the starting point

90°

indistinguishable

a=b=c a=b=c
 =  =  = 90°  =  =  = 90°
Symmetry Operation and Symmetry Element
Symmetry element (SE)

▪ is the geometrical object (point, line, plane) on which the SO is carried out

90° axis of rotation 360 °/ 90 ° = 4 4-fold axis of rotation

indistinguishable

a=b=c a=b=c
 =  =  = 90°  =  =  = 90°
Symmetry Operation and Symmetry Element
Symmetry element (SE)

▪ is the geometrical object (point, line, plane) on which the SO is carried out

▪ it comprises at least all invariant spatial points (fixed points) of the operation

90° axis of rotation 360 °/ 90 ° = 4 4-fold axis of rotation

indistinguishable

a=b=c a=b=c
 =  =  = 90°  =  =  = 90°
Symmetry Operation and Symmetry Element
Symmetry element (SE)

▪ is the geometrical object (point, line, plane) on which the SO is carried out

▪ it comprises at least all invariant spatial points (fixed points) of the operation

▪ usually on one SE several different SO can be carried out

180° axis of rotation 360 °/ 180 ° = 2 2-fold axis of rotation

indistinguishable

a=b=c a=b=c
 =  =  = 90°  =  =  = 90°
Symmetry concerning macroscopic object
Symmetry elements of macroscopic objects
even the most asymmetric
objects have at least one SE
1. Identity

2. Mirror plane

3. Axis of rotation

4. Center of inversion identity

1-fold axis of rotation
(rotation by 360°)
5. Rotoinversion axis
symbol E
Mirror Symmetry
▪ also called ‘line symmetry’ or ‘reflection symmetry’ or ‘bilateral symmetry’
▪ an object which does not change upon undergoing a reflection has mirror symmetry, it is mirror symmetric
▪ In 2D there is a line of symmetry or mirror line, in 3D a plane of symmetry or mirror plane

mm
mirror plane

symbol m
Rotational Symmetry
▪ single objects can have rotational symmetry of any order

▪ rotational symmetry may or may not be combined with mirror symmetry

120 ° 72 °
120 ° 120 °

120 °

3-fold axis of rotation 3-fold axis of rotation 5-fold axis of rotation -fold axis of rotation

3 3 5

SO = Rotation by 360° / n SE = n-fold axis of rotation symbol n (1, 2, 3…)

Axis of Rotation
Axis of Rotation… … in crystallography


▪ rotation around a axis (= fixed points of 2-fold
180°
the rotation) with an angle of rotation 

▪ after n rotations by  the starting 120° 3-fold

position is reached
90° 4-fold
▪ n = order of the axis

60° 6-fold

▪ the number of crystal classes is limited to 32

because of the restrictions of rotational
symmetry in crystals n = 2, 3, 4, 6
Mirror + Rotational Symmetry
▪ single objects can have rotational symmetry of any order

▪ rotational symmetry may or may not be combined with mirror symmetry

5-fold axis of rotation 6-fold axis of rotation

1 unique mirror plane 2 unique mirror planes
mm
5m 6mm
Inversion symmetry
▪ also called ‘origin symmetry’ or ‘center of symmetry’
▪ there is always a matching part, which has the same distance from a central
point but in the opposite direction
▪ in the plane it is identical with rotational symmetry of order 2
(2-fold axis of rotation)

180 °

symbol i or 1 (“one-bar”) x, y, z -x, -y, -z

Rotation + Inversions Symmetry
▪ a rotoinversion is a combined SO, where two transformations have to be carried out
(1) rotation around 360°/n
(2) immediately followed by an inversion at a center of symmetry, which lies on the rotoinversion
axis

Tetrahedron

90°
i

4-fold rotoinversion axis symbol 4 = 4 +1

Roto-inversion axes of order 1, 2, and 3
▪ odd rotoinversions possess automatically a center of inversion

1 1
1
5

2
2 2 4

1 =i 2 =m 3 = 3 +1
Roto-inversion
Rotoinversion axes of order axes
4 and 6 of order 4 and 6

▪ even rotoinversions contain automatically an axis of rotation of the half order (4-bar contains a 2-fold,
and 6-bar contains a 3-fold axis of rotation)

▪ if the order n is even, but not divisible by 4, then there is automatically a mirror plane perpendicular to
the rotoinversion axis (holds for 2-bar and 6-bar)

1 3 3

2
2

6
4 4

4 = 4 +1 6 = 6 +1 = 3 ⊥ m
32 Point Group
▪ A combined of Rotation, mirror and invrsion symmetry
Crystal Classes
▪ everyday objects can have any symmetry, and
symmetry elements can be combined, in principle,
arbitrarily
‘infinite’ number of symmetry classes
▪ the symmetry of crystals – i.e. the symmetry of the external
shape of crystals – is limited
▪ they can be classified into 32 classes only
▪ the symmetry has to be compatible with the repeating
pattern of the crystal lattice
32 symmetry classes (point groups)
see later
Classify Crystal into Classes
Recipe

1. What kind of symmetry elements (not operations) does the outer shape crystal sample possess?

2. Write down only those SE, which are ‘unique’ (i.e. a SE that exists by
itself and is not created by other SE)!

3. Crystals that have the same SE belong to the same crystal class!

4. You will see that the crystal classes can be categorized according to
the crystal systems (or crystal families, see below).
Classify Crystal into Classes
1st Example
no m
no n crystal class 1

c
i

pinacoidal
b
a
plagioclase
microcline (potassium feldspar),
turquoise, and wollastonite
Classify Crystal
Classify Crystals into Classes into Classes

2nd Example
Classify Crystal into Classes
2nd Example “perpendicular to”
one m 2
one 2 perpendicular to m m speak: ‘2 over m’

crystal class 2/m

m m

2 2

http://webmineral.com/data/Gypsum.shtml
Classify Crystal into Classes
2nd Example “perpendicular to”
one m 2
one 2 perpendicular to m m speak: ‘2 over m’

crystal class 2/m

i
there is also a center of inversion,
however this is not a ‘unique’ SE

it is automatically generated by 2/m!

http://webmineral.com/data/Gypsum.shtml
Classify Crystal into Classes
2nd Example “perpendicular to”
one m 2
one 2 perpendicular to m m speak: ‘2 over m’

crystal class 2/m

prismatic

CaSO4 · 2 H2O
Gypsum
azurite, chlorite, clinopyroxene,
epidote, malachite, kaolinite,
http://webmineral.com/data/Gypsum.shtml orthoclase, and talc
Classify Crystal into Classes
2nd Example “perpendicular to”
one m 2
one 2 perpendicular to m m speak: ‘2 over m’

crystal class 2/m

prismatic

Fe3(PO4)2 · 8 H2O
Vivianite
azurite, chlorite, clinopyroxene,
epidote, malachite, kaolinite,
http://webmineral.com/data/Gypsum.shtml orthoclase, and talc
Classify Crystal into Classes
3rd Example

b
a
Classify Crystal into Classes
3rd Example
Introducing viewing directions, here abc

b
a
Classify Crystal into Classes
3rd Example

b
a
Classify Crystal into Classes
3rd Example
symmetry elements 2 mm
2 m crystal class m m2 by convention
a bc
m

(ortho)rhombic-pyramidal

MgNH4PO4 · 6 H2O
c
Struvite

b http://webmineral.com/data/Struvite.shtml

a
Classify Crystal into Classes
3rd Example

2 m crystal class mm2

(ortho)rhombic-pyramidal

c
Zn4Si2O7(OH)2 · H2O
Hemimorphite
b
a
Classify Crystal into Classes
4th Example viewing directions
(hexagonal crystal system)

c a [210]

b
a 120°
Lattice Directions
[110]
[120]

-1,-2
-1,1

b (=a) [010]

<210> = [210],
2,1
[110],
[120]
a [210]
[100]
Classify Crystal into Classes
4th Example 6 viewing directions
(hexagonal crystal system)

c a [210]

b
a 120°
Classify Crystal into Classes
4th Example 6 viewing directions
m (hexagonal crystal system)

c a [210]

6
m m
m

b
a 120°
Classify Crystal into Classes
4th Example 6 viewing directions
(hexagonal crystal system)
m
c a [210]

6
m m m
m

b
a 120°
Classify Crystal into Classes
4th Example

crystal class 6/mmm

dihexagonal-dipyramidal

CuS
c
Covellite

b
a 120° (Mg, Graphite, Nickeline)
Systematization of Crystal Structures

4. Step: Space groups

complete symmetry
230
3. Step: Crystal classes
crystallographic PG
32
2. Step: Bravais lattices
primitive + centered
14
1. Step: Crystal systems
metric + symmetry of the UC
7
Translation – Glide – Screw axis

a/2

1/2 lattice (glide)

a/2

21 ( Screw )
Translational Symmetry
▪ There are three symmetry elements, which have a translational component

1. Translation (in units of whole unit cells along the lattice vectors)

translation

repeating unit (unit cell)

translation mirror plane repeating unit (unit cell)

Glide Planes/Lines

glide line

(a) reflection at a plane / line

glide reflection
(b) translation (usually by 1/2 of the unit cell)
Glide Planes/Lines

translation
reflection

(a) reflection at a plane / line

glide reflection
(b) translation (usually by 1/2 of the unit cell)
Glide Planes/Lines
▪ There are three symmetry elements, which have a translational component

1. Translations (in units of whole unit cells along the lattice vectors)
2. Glide planes / glide axes
3. Screw axes

translation
reflection
Kaiser's spotted newt
(a) reflection at a plane / line
glide reflection
(b) translation (usually by 1/2 of the unit cell)
Notation of Plane Groups
▪ Notation of Wallpaper groups symmetry elements
▪ in full notation always 4 symbols
p2mg
▪ begins with p or c according to the Bravais lattice type

▪ followed by the digit n indicating the rotational

glide plane
symmetry order
mirror plane
▪ plus two symbols indicating mirrors (m), glides (g)
2-fold axis of rotation
perpendicular to a) the x-axis and b) the y-axis
Bravais type
▪ if there are no such operators a (1)
is denoted
Notation of Plane Groups
▪ Full and Short Notation of Wallpaper groups

the short notation drops digits n or a m

that can be deduced, so long as that leaves
p2mg
no confusion with another plane group

Optional assignment: Overlay this pattern

with the unit cell and the respective
graphical symbols of the symmetry elements
at their correct positions within this pattern!

Full p111 p1m1 p1g1 c1m1 p211 p2mm p2mg p2gg c2mm p311 p3m1 p31m p411 p4mm p4gm p611 p6mm

Short p1 pm pg cm p2 pmm pmg pgg cmm p3 p3m1 p31m p4 p4m p4g p6 p6m
Glade Plane in Crystals

Symmetry operation (SO) Symmetry element (SE)

glide reflection glide plane

(a) reflection at a plane

(b) translation by 1/2 or 1/4 of the unit cell a, b, c, n, d, e
characters indicate
the translation direction
Glade Plane - a
▪ glide plane a translation direction = a x+½

▪ mirror plane runs parallel to the

+z
a drawing layer
▪ additional symbol that indicates the
direction of the transition
Glade Plane - a
▪ glide plane a translation direction = a x+½

▪ mirror plane runs parallel to the

-z
a drawing layer
▪ additional symbol that indicates the
direction of the transition
Glade Plane - a
▪ glide plane a translation direction = a x+½

▪ mirror plane runs parallel to the

a drawing layer
▪ additional symbol that indicates the
direction of the transition
-z
Glade Plane - b
▪ glide plane b translation direction = b y+½

▪ mirror plane perpendicular to the

+z
a drawing layer
Glade Plane - b
▪ glide plane b translation direction = b y+½

▪ mirror plane perpendicular to the

a drawing layer

+z
Glade Plane - b
▪ glide plane b translation direction = b y+½

▪ mirror plane perpendicular to the

a drawing layer

+z
Glade Plane - c
▪ glide plane c translation direction = c z+½

▪ mirror plane perpendicular to the

z
a drawing layer
Glade Plane - c
▪ glide plane c translation direction = c z+½

▪ mirror plane perpendicular to the

a drawing layer

z
Glade Plane - c
▪ glide plane c translation direction = c z+½

▪ mirror plane perpendicular to the

a drawing layer

z +½
Glade Plane
Glide Planes in Crystals
in Crystals

Symmetry operation (SO) Symmetry element (SE)

glide reflection glide plane

(a) reflection at a plane

(b) translation by 1/2 or 1/4 of the unit cell a, b, c, n, d, e
diagonal Glade Plane - n
▪ glide plane n translation direction = diagonal
y+½
i.e. in the (b,c) plane
b z+½

a z

▪ mirror plane perpendicular to the

drawing layer
diagonal Glade Plane - n
▪ glide plane n translation direction = diagonal
y+½
i.e. in the (b,c) plane
b z+½

a z

z+½

▪ mirror plane perpendicular to the

drawing layer
diagonal Glade Plane - n
▪ glide plane n translation direction = diagonal
y+½ x+½
i.e. in the (b,c) plane i.e. in the (a,b) plane
b z+½ y+½

a z z

z+½

▪ mirror plane perpendicular to the ▪ mirror plane runs parallel to the

drawing layer drawing layer
diagonal Glade Plane - n
▪ glide plane n translation direction = diagonal
y+½ x+½
i.e. in the (b,c) plane i.e. in the (a,b) plane
b z+½ y+½

a z -z

z+½

▪ mirror plane perpendicular to the ▪ mirror plane runs parallel to the

drawing layer drawing layer
diagonal Glade Plane - n
▪ glide plane n translation direction = diagonal
y+½ x+½
i.e. in the (b,c) plane i.e. in the (a,b) plane
b z+½ y+½

a z

-z

z+½

▪ mirror plane perpendicular to the ▪ mirror plane runs parallel to the

drawing layer drawing layer
diamond like Glade Plane - d
▪ glide plane d translation direction = diagonal as in diamond
y + ¼ (!)
i.e. in the (b,c) plane
z + ¼ (!)
b

▪ mirror plane perpendicular to the

z drawing layer
a
diamond like Glade Plane - d
▪ glide plane d translation direction = diagonal as in diamond
y + ¼ (!)
i.e. in the (b,c) plane
z + ¼ (!)
b

▪ mirror plane perpendicular to the

z drawing layer
a

z
diamond like Glade Plane - d
▪ glide plane d translation direction = diagonal as in diamond
y + ¼ (!)
i.e. in the (b,c) plane
z + ¼ (!)
b

▪ mirror plane perpendicular to the

z drawing layer
a

z + 1/4
diamond like Glade Plane - d
▪ glide plane d translation direction = diagonal as in diamond
y + ¼ (!)
i.e. in the (b,c) plane
z + ¼ (!)
b

▪ mirror plane perpendicular to the

z z+ 1/
2 drawing layer
a

z + 1/4
diamond like Glade Plane - d
▪ glide plane d translation direction = diagonal as in diamond
y + ¼ (!)
i.e. in the (b,c) plane
z + ¼ (!)
b

▪ mirror plane perpendicular to the

z z+ 1/
2 drawing layer
a

z + 1/4 z + 3/4
Double Glide Plane - e
▪ glide plane e translation direction = b and c
y+½
i.e. in the (b,c) plane
z+½
b

▪ mirror plane perpendicular to the

z drawing layer
a
▪ there are two glide planes at once
b with two glide directions
perpendicular to each other

these are two glide planes,

both equally oriented!
Double Glide Plane - e
▪ glide plane e translation direction = b and c
y+½
i.e. in the (b,c) plane
z+½
b

▪ mirror plane perpendicular to the

z drawing layer
a
▪ there are two glide planes at once
b with two glide directions
perpendicular to each other

these are two glide planes,

both equally oriented!
Double Glide Plane - e
▪ glide plane e translation direction = b and c
y+½
i.e. in the (b,c) plane
z+½
b

▪ mirror plane perpendicular to the

z drawing layer
a
▪ there are two glide planes at once
c with two glide directions
perpendicular to each other

z + 1/2 z

these are two glide planes,

both equally oriented!
Double Glide Plane - e
▪ glide plane e translation direction = b and c
y+½
i.e. in the (b,c) plane
z+½
b

▪ mirror plane perpendicular to the

z z + 1/
2 drawing layer
a
▪ there are two glide planes at once
c with two glide directions
perpendicular to each other

z + 1/ 2 z

these are two glide planes,

both equally oriented!
Double Glide Plane - e
▪ glide plane e translation direction = b and c
y+½
i.e. in the (b,c) plane
z+½
b

▪ mirror plane perpendicular to the

z z+ 1/
2 drawing layer
a
▪ there are two glide planes at once
b with two glide directions
c c perpendicular to each other

z + 1/2 z

these are two glide planes,

both equally oriented!
Double Helices

B-DNA double spiral staircase climber plant screw

double helix http://www.olafureliasson.net/
Characteristics of Helices
screw/helix axis

pitch
distance of a
whole turn
Characteristics of Helices

with the viewing direction along axis

handedness
of the helix…

…if a clockwise screwing motion moves

the helix away from the observer, then it is
called a right- handed helix

…if a counter-clockwise screwing motion

moves the helix away from the observer,
then it is called a left-handed helix

image mirror image

chiral objects
Screw Axes
Symmetry operation (SO) Symmetry element (SE)

screw rotation screw axis

(a) rotation around the axis

(b) translation parallel to the axis
Characteristics of Helices

screw axis screw axis

discrete atoms
continuous

rotational part limited

rotational order = ∞ rotational order is restricted to 1 to 4 and 6!
Screw Axes in Crystal Structure

translation along
the lattice vectors

a
Screw Axes in Crystal Structure
screw axis

(a) rotation by 360°/6 = 60°

(b) translation by 1/6 of the unit cell

6-fold screw axis 61 translational component = 1/6

Screw Axes in Crystal Structure
▪ Screw Axis nm ; where m < n
right-handed
coordinate system
rotation by an angle  of 360°/n

n = order of the axis = 360° / n t

translation of m/n of the whole unit cell


parallel to the screw axis

t = translation element = m / n
 = rotation angle
Screw Axes in Crystal Structure
▪ Screw Axis nm ; where m < n
right-handed
coordinate system
a 32 screw axis (n=3, m=2) means
t
rotation by 360°/3 = 120°
translation of m/n, i.e. 2/3 of the whole unit
cell parallel to the screw axis 

t = translation element = m / n
 = rotation angle

the possible screw axes are 21, 31, 41, 42, 61, 62, and 63, and the enantiomorphous 32, 43, 64, and 65.
Screw Axes in Tellurium
31 screw axis

trigonal crystal system

space group P3121
2-fold Screw Axes
order n m t symbol
nm
2 0 0 2
1 1/2 21
2 1 2

20 21
3-fold Screw Axes
order n m t symbol
nm
3 0 0 3
1 1/3 31
2 2/3 32
3 1 3

image mirror
image

30 31 32
4-fold Screw Axes

40 41 42 43
6-fold Screw Axes
m m

60 61 65 62 64 63
Systematization of Crystal Structures

4. Step: Space groups

complete symmetry
230
3. Step: Crystal classes
crystallographic PG
32
2. Step: Bravais lattices
primitive + centered
14
1. Step: Crystal systems
metric + symmetry of the UC
7
Space Groups
Combination of

14
with
32
Bravais lattices and

Point groups gives

screw and glide
symmetry
230

Space groups

dimensions 1 2 3 4 5 6

no. of ‘space’ groups 2 17 230 4894 ~220 k ~29 mill

International Tables for Crystallography
International Tables for Crystallography
Volume A: Space-group symmetry
Definition and Nomenclature of Space Groups
Space group

Set of symmetry elements (and respective operations), which completely describes

the spatial arrangement of a 3D periodic pattern.

‘Generators’

Nomenclature symmetry elements with respect to 3 given viewing directions

P c a 21 (orthorhombic)

21 screw axis || c

glide plane a ⊥ b

glide plane c ⊥ a

Bravais type
Crystallographic Viewing Directions
▪ monoclinic: determined by convention

▪ tetragonal, trigonal, hexagonal: rotational axis of highest order is by definition || to the c-axis and the first viewing direction

▪ rule of thumb: look for something new!

crystal system viewing directions

triclinic

monoclinic b (c)
orthorhombic a b c
a =b tetragonal c a [110]
a =b trigonal c a [210]
a =b hexagonal c a [210]
cubic a [111] [110]
Space groups to Point groups (Crystal class)
▪ Derivation of the crystal class from the space group

1) Leave out the Bravais type

2) Convert all SEs with translational components into their respective SEs without translation symmetry

Glide planes are converted into simple mirror planes

Screw Axes are converted into simple axes of rotation

3) Axes of rotation, rotoinversion axes and mirror planes remain unchanged

space group P 21/n crystal class 2/m

Crystal system – Crystal class – Space group
tetragonal c a [110]
a=b

 =  =  = 90°

b
a
Crystal system – Crystal class – Space group
tetragonal c a [110]
a=b

 =  =  = 90°

b
a
Crystal system – Crystal class – Space group
tetragonal c a [110]
a=b

 =  =  = 90°

b
a
Crystal system – Crystal class – Space group
tetragonal c a [110]
a=b

 =  =  = 90°

c
4/mmm
P4/mmm
a
b c a [110]
Crystal system – Crystal class – Space group
tetragonal c a [110]
a=b

 =  =  = 90°

c
4mm
I4mm
a
b c a [110]
Crystal system – Crystal class – Space group
tetragonal c a [110]
a=b

 =  =  = 90°

c
4mm
P4mm
a
b c a [110]
International Table for Crystallography
International Tables for Crystallography
Volume A: Space-group symmetry

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International Table for Crystallography

▪ Systematic listing of the 17 plane groups and 230 space groups

▪ Space group symbol in short and full notation as well as an unique #
▪ Indication of the crystal system and the crystal class in both systems of
nomenclature (H.-M. and Schoenflies)
▪ Diagrams of the position of the SEs
▪ General position diagram
▪ Listing of all SOs as coordination transformations
▪ Multiplicity, Wyckoff letters, Site symmetry
▪ …and some more (“incomprehensible”) things ☺

group theory / X-ray diffraction

Space group Pmm2
Header
Space group Pmm2 - Header
Schoenflies H.-M.
1
Short symbol Pmm2 Crystal class C2v mm 2 Crystal system Orthorhombic
Number No. 25 Full symbol Pmm 2 Patterson Symmetry P m m m
Space group Pmm2
Space group Pmm2 - Diagram of the Symmetry elements

horizontal mirror planes

b
Space group Pmm2 - Diagram of the Symmetry elements

vertical mirror planes

a

b
Space group Pmm2 - Diagram of the Symmetry elements

2-fold axes of rotation

b
Space group Pmm2
Space group Pmm2 – General Position Diagram

+ ,+ + ,+
+ , + + , +

+ , + + ,+
+ , + + , +
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram

an atom on a general position

(does not sit on a SE)
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram
Space group Pmm2 – General Position Diagram

+ ,+ + ,+
+ , + + , +

+
position along the c-direction
above the projection plane

+ , + + ,+
+ , + + , +

, image and mirror image

of chiral objects
Space group Pmm2 – General Position Diagram

+ ,+ + ,+
+ , + + , +

+
position along the c-direction
above the projection plane

+ , + + ,+
+ , + + , +

, image and mirror image

Space group Pmm2 – General Position Diagram

+ ,+ + ,+
+ , + + , +

+
position along the c-direction
above the projection plane

+ , + + ,+
+ , + + , +

, image and mirror image

230 Space Group

❖ When talking about crystal structures, people will usually

report the space group of a crystal
❖ Space groups are made up from
▪ point symmetry (not translational)
▪ lattice symmetry (translational)
▪ glide and/or screw axes (some translational component)

7 crystal 14 Bravais 32 point 230 space

systems lattices groups groups
Summary
Schoenflies vs. Hermann-Mauguin
Rotoinversions vs. Rotary reflections
Roto-inversions vs. Rotary reflections
International Tables for Crystallography – Space group P2 1 /c
Space group P2 1 /c – Header
5
Short symbol P2 1 /c Crystal class C2h 2/ m Crystal system Monoclinic
Number No. 14 Full symbol P12 1 /c1 Patterson Symmetry P12/ m 1

UNIQUE AXIS b, CELL CHOICE 1

settings

P21/c – standard space group

P21/a
P21/b non-standard space group variants of P21/c
P21/n
Space group P2 1 /c – Header
viewing direction a b c

Full symbol P12 1 /c1

primitive lattice
no symmetry element
in the c direction

a 21 screw axis parallel to the

b direction and a glide plane c
perpendicular to the b
no symmetry element
direction
in the a direction
International Tables for Crystallography – Space group P2 1 /c
Diagram of the Symmetry elements – Space group P2 1 /c
Diagram of the Symmetry elements – Space group P2 1 /c

glide plane perpendicular

to the b direction with
translation direction c a
1 0
4
height along
the b direction

21 screw axes
Diagram of the Symmetry elements – Space group P2 1 /c

0 a
1
4

centres of inversion
International Tables for Crystallography – Space group P2 1 /c
General Position Diagram – Space group P2 1 /c

, image and mirror image

+ – above / below
the projection plane
General Position Diagram – Space group P2 1 /c

, image and mirror image

– , + – above / below
the projection plane

+
General Position Diagram – Space group P2 1 /c

, image and mirror image

– , + – above / below
the projection plane

½
,½

½+=½+y= y+½
½ – = ½ – y = -y + ½
General Position Diagram – Space group P2 1 /c

, image and mirror image

– , + – above / below
the projection plane

½ ½
,½ ,½
–

,+
General Position Diagram – Space group P2 1 /c

, image and mirror image

– , – , + – above / below
the projection plane

+ +

½ ½
,½ ,½
– , – ,
+ +

general multiplicity (here: 4)

General Position Diagram – Space group P2 1 /c

, image and mirror image

1
4
– , – , + – above / below
the projection plane
+ +

½ ½
,½ ,½
– , – ,
+ +
Asymmetric Unit – Space group P2 1 /c

▪ by pure translations of the unit cell in all 3

1
4 spatial directions the whole crystal is build

+ ▪ however, the SEs of the space group act also on

atoms inside the unit cell, they will be multiplied
½
asymmetric unit: is the set of objects/atoms,
,½ which is sufficient to describe all other
positions, the complete content of one unit cell,
– , when we apply the SOs of the space group

asymmetric unit: must not have any

internal symmetry