Crystal Chem  Crystallography

• Chemistry behind minerals and how they are

assembled
– Bonding properties and ideas governing how
atoms go together
– Mineral assembly – precipitation/ crystallization
and defects from that
• Now we will start to look at how to look at,
and work with, the repeatable structures
which define minerals.
– This describes how the mineral is assembled on
a larger scale
Symmetry
 Symmetry Introduction
• Symmetry defines the order resulting from how
atoms are arranged and oriented in a crystal
• Study the 2-D and 3-D order of minerals
• Do this by defining symmetry operators (there are
13 total)  actions which result in no change to the
order of atoms in the crystal structure
• Combining different operators gives point groups –
which are geometrically unique units.
• Every crystal falls into some point group, which are
segregated into 6 major crystal systems
 2-D Symmetry Operators
• Mirror Planes (m) – reflection along a plane

A line denotes
mirror planes
 2-D Symmetry Operators
• Rotation Axes (1, 2, 3, 4, or 6) – rotation of 360,
180, 120, 90, or 60º around a rotation axis yields
no change in orientation/arrangement

2-fold

3-fold

4-fold

6-fold
 2-D Point groups
• All possible combinations of the 5 symmetry
operators: m, 2, 3, 4, 6, then combinations
of the rotational operators and a mirror yield
2mm, 3m, 4mm, 6mm
• Mathematical maximum of 10 combinations

4mm
 3-D Symmetry Operators
• Mirror Planes (m) – reflection along any
plane in 3-D space
 3-D Symmetry Operators
• Rotation Axes (1, 2, 3, 4, or 6 a.k.a. A1, A2, A3,
A4, A6) – rotation of 360, 180, 120, 90, or 60º
around a rotation axis through any angle yields
no change in orientation/arrangement
 3-D Symmetry Operators
• Inversion (i) – symmetry with respect to a
point, called an inversion center

1
1
 3-D Symmetry Operators
• Rotoinversion (1, 2, 3, 4, 6 a.k.a. A1, A2, A3,
A4, A6) – combination of rotation and
inversion. Called bar-1, bar-2, etc.
• 1,2,6 equivalent to other functions
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

1: Rotate 360/4
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

1: Rotate 360/4

2: Invert
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

1: Rotate 360/4

2: Invert
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

3: Rotate 360/4
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

3: Rotate 360/4

4: Invert
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

3: Rotate 360/4

4: Invert
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

5: Rotate 360/4
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

5: Rotate 360/4

6: Invert
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

This is also a unique operation

 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

d. 4-fold rotoinversion ( 4 )

A more fundamental
representative of the pattern
 3-D Symmetry

New Symmetry
Elements
4. Rotoinversion

c. 3-fold rotoinversion ( 3 ) 3
5 1
This is unique
4 2
6
 3-D Symmetry Operators
• Mirror planes ┴ rotation axes (x/m) – The
combination of mirror planes and rotation
axes that result in unique transformations
is represented as 2/m, 4/m, and 6/m
 3-D Symmetry
3-D symmetry element combinations
a. Rotation axis parallel to a mirror
Same as 2-D
2 || m = 2mm
3 || m = 3m, also 4mm, 6mm
b. Rotation axis  mirror
2  m = 2/m
3  m = 3/m, also 4/m, 6/m
c. Most other rotations + m are impossible
 Point Groups
• Combinations of operators are often
identical to other operators or combinations
– there are 13 standard, unique operators
• I, m, 1, 2, 3, 4, 6, 3, 4, 6, 2/m, 4/m, 6/m
• These combine to form 32 unique
combinations, called point groups
• Point groups are subdivided into 6 crystal
systems
 3-D Symmetry
The 32 3-D Point Groups
Regrouped by Crystal System
(more later when we consider translations)

Crystal System No Center Center

Triclinic 1 1
Monoclinic 2, 2 (= m) 2/m
Orthorhombic 222, 2mm 2/m 2/m 2/m
Tetragonal 4, 4, 422, 4mm, 42m 4/m, 4/m 2/m 2/m
Hexagonal 3, 32, 3m 3, 3 2/m
6, 6, 622, 6mm, 62m 6/m, 6/m 2/m 2/m
Isometric 23, 432, 43m 2/m 3, 4/m 3 2/m

Table 5.3 of Klein (2002) Manual of Mineral Science, John Wiley and Sons
 Hexagonal class

Rhombohedral
form Hexagonal
form
 Crystal Morphology (habit)
Nicholas Steno (1669): Law of Constancy of
Interfacial Angles

120o 120o 120o

Quartz
120o 120o

120o 120o
 Crystal Morphology
Diff planes have diff atomic environments
 Crystal
Morphology
Growth of crystal is affected
by the conditions and matrix
from which they grow. That
one face grows quicker than
another is generally
determined by differences in
atomic density along a
crystal face

Note that the internal order of

the atoms can be the same
but the crystal habit can be
different!
 Crystal Morphology
How do we keep track of the faces of a crystal?
Face sizes may vary, but angles can't
Thus it's the orientation & angles that are the best
source of our indexing

Miller Index is the accepted indexing method

It uses the relative intercepts of the face in question
with the crystal axes
Miller Indices