Lecture 4

Crystal Geometry
and
Structure Determination

Recap
Crystal = Lattice + Motif/basis

Unit cell: Size and shape can be characterized by

defining the lattice parameters
Primitive and non-primitive unit cell
Symmetry in lattice: Rotational symmetry, translation
symmetry and mirror symmetry

UNIT CELLS OF A LATTICE

Nonprimitive cell

Primitive
cell

If the lattice
points are only
at the corners,
the unit cell is
primitive
otherwise nonprimitive
A unit cell of a
lattice is NOT
unique.

Primitive
cell

Unit cell shape

CANNOT be the
basis for
classification of
Lattices

UNIT CELLS OF A LATTICE

Can we select a
triangular unit
cell? Since it can
give a very small
repeat unit

Primitive
cell

Unit cell is a small volume

of the crystal which by
periodic repetition
generates the entire
crystal (without overlaps
or gaps)

Symmetry of lattices
Lattices have
Translational symmetry
Rotational symmetry
Reflection symmetry

What is the basis for

classification of lattices
into
7 crystal systems
and
14 Bravais lattices?

Based on the complete symmetry, i.e.,

rotational, reflection and translational
symmetry
14 types of lattices
14 Bravais lattices

7 crystal Systems
Defining
symmetry

Crystal system

Conventional
unit cell

Cubic

a=b=c, ===90

Tetragonal

a=bc, ===90

Orthorhombic abc, ===90

Hexagonal

Rhombohedral a=b=c, ==90

Monoclinic

none

Triclinic

a=bc, == 90, =120

abc, ==90

abc,

8/87

Lets consider one by one each lattice

and its corresponding defining symmetry

1. Cubic Crystals
a = b= c
= = = 90

Simple cubic
Primitive cubic
Cubic P

Body-centred cubic
Cubic I

Face-centred cubic
Cubic F

Why end centred cubic is missing?? Will address later

Common Symmetry in Cube

3-4 fold
4-3 fold
6-2 fold

Cubic symmetry

4 triads: 4 body diagonals

12

2. Tetragonal Crystals
a=bc
= = = 90
Possible lattices
Simple Tetragonal
Body Centred Tetragonal BCT

Primitive
Body centred

Common Symmetry in Tetragonal

1-4 fold
2-2 fold

Tetragonal symmetry

1 tetrad
15

3. Orthorhombic Crystals
abc
= = = 90
All lattices are possible
Simple Orthorhombic

Body Centred Orthorhombic

Face Centred Orthorhombic

End Centred Orthorhombic

Common Symmetry in Orthorhombic

3-2 fold

4. Hexagonal Crystals
a=bc
= = 90

= 120

Only possible lattice

Simple Hexagonal

Note that unit cell of hexagonal lattice is 120 degree

Rhombic prism
Actual hexagonal lattice is the composite of three such
Lattices

We draw this to visualise the hexagonal symmetry

Common Symmetry in Hexagonal

1-6 fold
3-2 fold symmetry

5. Trigonal/Rhombohedral Crystals
a=b=c
= = 90

Only possible lattice

Rhombohedral (simple)
Pull the cubic lattice along body diagonal the distortion will
be such that it will satisfy trigonal condition

Common Symmetry in Trigonal

1-3 fold (along the diagonal where we pulled)

6. Monoclinic Crystals
abc
= = 90

Two possible variants

Simple Monoclinic
End Centred (base centered) Monoclinic
(A/C)
Squashing of Orthorhombic lattice can lead to formation
of monoclinic lattice

Common Symmetry in Monoclinic

1-2 fold (along b)

7. Triclinic Crystals
abc

Simple Triclinic

No symmetry

Why we do not have 28 (7x4=28)

Bravais lattices?? We only have
half of this!
Why some of them are missing??

25

To answer this

Two arguments can be put forth

Symmetry based
Size based

26

Missing Bravais lattices

Why C-centred
Cubic is missing
Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

If you create end centred cubic then you

loose characteristic symmetry of cubic
system
You will also loose cubic 3-4 fold symmetry

The characteristic symmetry has been

destroyed so it can not be cubic lattice

28

End-centred cubic not in the Bravais list ?

Alternative
Choice of
Unit cell

Primitive cell
Smaller cell

End-centred cubic = Simple Tetragonal

14 Bravais lattices divided into seven crystal

systems
Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

Missing Bravais lattices

Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

Face centred tetragonal = Body centred

tetragonal
Smaller sized body centred tetragonal is
chosen

This choice of
unit cell is
smaller in size

32

14 Bravais lattices divided into seven crystal

systems
Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

Missing Bravais lattices

Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

?
C

Symmetry is not an issue here only the choice of unit

cell is important
End centred Tetragonal = Simple tetragonal

35

14 Bravais lattices divided into seven crystal

systems
Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

F
C
F

Missing Bravais lattices

Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

37

Why cant the FaceCentred Cubic lattice

(Cubic F) be considered
as a Body-Centred
Tetragonal lattice
(Tetragonal I) ?

14 Bravais lattices divided into seven crystal

systems
Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

Face-centred cubic in the Bravais list ?

Cubic F = Tetragonal I ?!!!

Tetragonal symmetry

Cubic C = Tetragonal P

Cubic symmetry

41/87

Cubic F Tetragonal I

Summary
Crystal and crystal systems are defined based on
Symmetry not on unit cell geometry
For instance
Cubic crystal does not mean a=b=c, = = = 90

It implies the existence of 4-3 fold axis in the structure

The choice of unit cell is based on size and symmetry

42