Handout 2: Symmetry in

Crystallography
Chem 4850/6850/8850
X-ray Crystallography
The University of Toledo

[email protected]
 Symmetry and crystals
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
 Lattice symmetry

 Lattice symmetry
refers to the unit cell
size and shape
 Without rules, there
would be an infinite
number of different
unit cells to describe
any given lattice
“Crystal Structure Analysis for Chemists and
Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
 Unit cell choice

 By convention, a unit cell is chosen as

- the smallest possible repeat unit
- which has the highest symmetry

 This can result in primitive unit cells or centered unit cells

- not all crystal systems can be centered by this definition
- the seven crystal systems in combination with the centering operations
give rise to the 14 Bravais lattices
 An example of unit cell choice

 According to our definitions, the centered cell would be preferred

“Crystal Structure Analysis for Chemists and Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
 The 14 Bravais lattices

“Elements of X-ray Diffraction”, Cullity and Stock, Prentice Hall College Div., 3rd edition, 2001.
Why can only some lattices be centered?

. .a a
 A tetragonal base
centered cell can
always be transformed
into a tetragonal
primitive cell
a’ .
.
a’
Why can only some lattices be centered? (2)
 90

c
c b . a’
. a’
a

 An orthorhombic base centered cell cannot be

transformed into a primitive cell without losing the
orthorhombic symmetry
 Symmetry elements

 When talking about symmetry operations, we must distinguish

- point symmetry elements
- translational symmetry

 Point symmetry elements will always leave at least one point

unchanged
- rotation axes
- mirror planes
- rotation-inversion axes
 Rotation axes

 Example: A two-fold
rotation axis
- no change in handedness
- referred to as “proper
symmetry operation”

 An n-fold rotation axis

will rotate the object by
360/n°
 Symbol: n (e.g., 2, 3, 4, 6)
“Crystal Structure Analysis for Chemists and Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
Mirror planes

 A mirror plane changes

the handedness of the
object it is operating on
- cannot exist in crystals of
an enantiomerically pure
substance
- referred to as “improper
symmetry operation”

 Symbol: m
“Crystal Structure Analysis for Chemists and
Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
Inversion centers
 “Turning an object inside
out”
 Equivalent to a “point
reflection” through the
inversion center
- similar to focal point of a
lense
- changes handedness

 Symbol: i
“Crystal Structure Analysis for Chemists and
Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
Rotation-inversion centers

 Rotation followed by
inversion
 An inversion center can
be regarded as a “one-fold
rotation” followed by an
inversion
 Symbol: -n or n

“Crystal Structure Analysis for Chemists and

Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
 Watch out…
 Crystallographers work with rotation-inversion axes

 If you take a class in Group Theory or another subject

involving symmetry operations, your teacher may not
consider rotation-inversion axes a symmetry operation
- they use rotation-reflection axes (symbol: Sn)

- rotation-inversion and rotation-reflection axes are NOT the same!

- an inversion center corresponds to a “–1 axis”, but to an S2 axis!

- however, any compound that has a –4 axis will also possess an S4 axis
S4 versus -4
 Combining symmetry operations
 An object can possess several symmetry elements
 Not all symmetry elements can be combined arbitrarily
- for example, two perpendicular two-fold axes imply the existence of a
third perpendicular two-fold
 Translational symmetry in 3D imposes limitations
- only 2, 3, 4 and 6-fold rotation axes allow for space filling
translational symmetry
 The allowed combinations of symmetry elements are called
point groups
- there are 32 point groups that give rise to periodicity in 3D
Space filling repeat patterns

Only 2, 3, 4 and 6-fold rotations

can produce space filling patterns
“Structure Determination by X-ray Crystallography”,
Ladd and Palmer, Plenum, 1994.
 Point groups

 Show 3D repeat
pattern
 Contain symmetry
elements
 32 point groups exist

“Structure Determination by X-ray Crystallography”,

Ladd and Palmer, Plenum, 1994.
 Space groups
 When talking about crystal structures, people will usually
report the space group of a crystal
 Space groups are made up from
- lattice symmetry (translational)
- point symmetry (not translational)
- glide and/or screw axes (some translational component)
 There are 230 space groups

7 crystal 14 Bravais 32 point 230 space

systems lattices groups groups
 Screw axes

 A 21 screw axis translates an object by half a unit cell in the

direction of the screw axis, followed by a 180° rotation
“Crystal Structure Analysis for Chemists and Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
 Higher order screws
“Structure Determination by X-ray Crystallography”,
Ladd and Palmer, Plenum, 1994.

 A Cn screw axis translates an object by the unit cell dimension

multiplied by n/C along the direction of the screw axis, followed by
a C-fold rotation
 Glide planes
 A glide plane corresponds to a reflection-translation operation
- reflection through the glide plane
- translation within/parallel to the glide plane
- exact translation depends on type of glide
 There are a, b, c, n and d glide planes
- a, b and c glides correspond to translations of ½ a, ½ b and ½ c
respectively
- called “axial glide planes”
- n glide corresponds to a translation of ½ a + ½ b, ½ a + ½ c, or ½ b + ½ c
- called “diagonal glide plane”
- d glide corresponds to a translation of ¼ a + ¼ b, ¼ a + ¼ c, or ¼ b + ¼ c
- called “diamond glide plane”
 Example of an a glide plane

“Crystal Structure Analysis for Chemists and

Biologists”, Glusker, Lewis and Rossi, VCH, 1994.
Limitations on combination of symmetry elements
 As for point groups, not all symmetry elements can be combined
arbitrarily
 For three dimensional lattices
- 14 Bravais lattices
- 32 point groups
- but only 230 space groups

 For two dimensional lattices

- 5 lattices
- 10 point groups
- but only 17 plane groups
Graphical symbols used for symmetry operations
“International Tables for Crystallography, Vol. A”, Kluwer, 1993.
 Graphical symbols (2)
“International Tables for Crystallography, Vol. A”, Kluwer, 1993.
Symmetry elements parallel to the plane of projection
“International Tables for Crystallography, Vol. A”, Kluwer, 1993.
Symmetry elements inclined to the plane of projection
“International Tables for Crystallography, Vol. A”, Kluwer, 1993.