If you look at Table 6.

3 page120 of your text, you should see that this

belongs to crystal class 4/m2/m2/m. This class is the ditetragonal
dipyramidal class. We will discuss this notation and the various crystals
classes in the next lecture.

Symmetry in Crystallography

Introduction

In crystallography, symmetry is used to characterize crystals, identify repeating

parts of molecules, and simplify both data collection and nearly all calculations.
Also, the symmetry of physical properties of a crystal such as thermal conductivity
and optical activity must include the symmetry of the crystal. 1 Thus,
a thorough knowledge of symmetry is essential to a crystallographer. A clear, brief
description of crystallographic symmetry was prepared by Robert Von Dreele.

An object is described as symmetric with respect to a transformation if the object

appears to be in a state that is identical to its initial state, after the transformation.
In crystallography, most types of symmetry can be described in terms of an
apparent movement of the object such as some type of rotation or translation. The
apparent movement is called the symmetry operation. The locations where the
symmetry operations occur such as a rotation axis, a mirror plane, an inversion
center, or a translation vector are described as symmetry elements.
Symmetry in Crystals

Our discussion of symmetry in crystallography should begin with a description of

crystals. Crystals are defined as solids that have an atomic structure with long-
range, 3-dimensional order. Unfortunately, this long-range order cannot be
absolutely confirmed by any other method than some diffraction technique.
However, there are several observations that can be made that will strongly suggest
that a sample is crystalline before a diffraction experiment is undertaken.

Typically, crystals have flat faces and sharp edges. Also, many crystals will have
one or more directions that can be cleaved cleanly. Samples with a naturally round
shape, or samples that have a concoidal fracture pattern are nearly always
described as a glass having no significant, long-range, 3-D order. Similarly,
materials that can be gently poked with a probe, and retain the deformed shape are
gels or plastic materials and hence have not long-range, 3-D order.

When you look at several crystals from one material, you will soon notice that,
although the crystals may have different sizes, all crystals have the same shape
or habit. In particular, the angles between certain pairs of faces of the different
crystals will be the same. This observation was first made by Nicholas Steno in
1669.2 This observation became known as the law of constancy of interfacial
angles.

Figure 1. Models of crystals showing constant angles.3

Steno and others in the 17th century were interested in the specific make up of
crystals that would allow them to maintain the same angles between pairs of
faces.4 These scientists believed that crystals must be made of some regularly-
repeating components. Through these early studies, René-Just Haüy was able to
postulate that if crystals of calcite and cubic garnets were built from many small
blocks, then these blocks could easily be used to describe the faces of these crystals
in terms of rational indices.5 This law of rational indices forms the basis of optical
crystallography.
 Figure 2. Models from
Haüy's Traité de minéralogie (1801) - the crystal form have been redrawn in red.5

Unit Cells

These regularly-repeating blocks are now known as unit cells. The dimensions of a
unit cell are described by the lengths of the three axes, a, b, and c, and the three
interaxial angles, α, β, and γ. In most published papers the axial lengths are
expressed in terms of Å (Ångströms), and the interaxial angles are expressed in
terms of ° (degrees).

Figure 3. Unit cell showing cell parameters.

There are many choices of repeating blocks in any given lattice. The main
principles defining the lattice is that each lattice point must be in an identical
environment as any other lattice point, and that the individual blocks in the lattice
must have the smallest volume possible. Often there are many ways to select the
vectors between lattice points and even the locations of the lattice points
themselves. These unique lattice vectors are called basis vectors or basis set.

When researchers discuss a particular material, they need to work from one
standard or conventional description of the unit cell for that material. Thus
crystallographers have chosen the following criteria for selecting unit cells. By
convention the unit cell edges are chosen to be
right-handed (a × b is the direction of c), to have the highest symmetry, and to have
the smallest cell volume. If other symmetry considerations do not override, then the
cell is chosen so that a ≤ b ≤ c, and α, β, and γ all < 90 ° or all ≥ 90 °. This type of
cell is called the reduced cell. There are several other rules for obtaining the
conventional reduced cell for a given material.7

Crystalline materials are separated into 7 different crystal systems. These crystal
systems are most easily identified by the constraints on the cell parameters. Note,
however, that the cell parameter constraints are only necessary conditions. Thus a
particular sample could have cell parameters that appear to fall into one category
within experimental error, but are actually of lower symmetry.

The 7 crystal systems are listed in Table 1 below. In the lowest symmetry system,
triclinic, there are no restrictions on the values of the cell parameters. In the other
crystal systems, symmetry reduces the number of unique lattice parameters as
shown in the Table. Certain conventions have been followed in tabulating the
parameters. In the monoclinic system, one of the axes is unique in the sense that it
is perpendicular to the other two axes. This axis is selected by convention as either
the b or c axis so that either β or γ are ≥ 90°, respectively. Note that c-unique
monoclinic cells are common in French literature and b-unique cells are common
in most other languages. In the tetragonal, trigonal, and hexagonal systems, one
axis contains higher symmetry. By convention this axis is selected as the c axis.

Table 1. Crystal Systems

Crystal System # Cell Parameters Symmetry
Triclinic 6 a ≠ b ≠ c; α ≠ β ≠ γ 1
Monoclinic 4 a ≠ b ≠ c; α = γ = 90°, β ≥ 90° 2/m
Orthorhombic 3 a ≠ b ≠ c; α = β = γ = 90° mmm
Tetragonal 2 a = b ≠ c; α = β = γ = 90° 4/m, 4/mmm
Trigonal
Hexagonal 2 a = b ≠ c; α = β = 90°, γ = 120° 3, 3m
Rhombohedral 2 a = b = c; α = β = γ ≠ 90° 3, 3m
Hexagonal 2 a = b ≠ c; α = β = 90°, γ = 120° 6/m, 6/mmm
Cubic 1 a = b = c; α = β = γ = 90° 2/m3, m3m

The seven crystal systems each describe separate ways that simple 3-dimensional
lattices may be constructed. As with all lattice systems, crystalline lattices are
considered to have lattice pointson the corners of the unit cell. Lattice points are
selected so that the local environment around any particular lattice point is
identical to the environment around any other lattice point.
Some trigonal lattices can be expressed on the basis of either a hexagonal or
rhombohedral lattice. These lattices are shown in the drawings below. Note that
rhombohedral lattice vectors can be expressed in an obverse orientation a), or in a
reverse orientation b) below.

Figure 5.
Rhombohedral lattices in the obverse and reverse orientations.

Bravais Lattices

It is sometimes possible to generate a lattice with higher symmetry if the lattice

vectors are chosen so that one or more lattice points are also on the center of a face
of the lattice or inside of the unit cell. These lattices with additional lattice points
are described as centered lattices. Lattices with lattice points only on the corners
are called primitive and are designated with the symbol P. Note that reduced cells
described above are always primitive. In 1849, Auguste Bravais found that all
regular crystals could be described in terms of only 14 lattice types for the 7 crystal
systems.8 Remember that the environment around any one lattice point is exactly
the same as the environment around any other lattice point.