Chapter 3

Crystal Systems

3.1 Bravais lattice

Something (the figure surrounding each lattice point or the content of the unit cell) is lost
in the process of idealization. Only when the lost information (known as the decoration or
basis) is added to the lattice, can we fully recover the original crystal structure. A Bravais
lattice is one of the possible 2 or 3-dimensional configuration of points used to describe the
regular arrangement of points in a crystal. According to symmetry there are a possible five 2D
Bravais lattices, while in 3D there are a possible 14 Bravais lattices. These 14 Bravais lattices
are divided into seven distinct crystal systems:

1. Triclinic

2. Monoclinic

3. Orthorhombic

4. Tetragonal

5. Rhombohedral

6. Hexagonal

7. Cubic

3.1.1 Lattices in 2-Dimension

In 2D, the Bravais lattices are oblique, rectangular, rhombic, square, hexagonal. These spe-
cial lattices are arrived at by imposing restrictions on the lattice parameters (a,b,c), as well as
requiring invariance under rotation of 120°, 80° or 60°, or invariance under mirror reflection.
Thus in 2D we arrive at these five lattice types.

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 b α b 90°
a a

b 90°
a b
a
b 90°
a 60°

Figure 3.1: The 2D Bravais lattices: from top left: Oblique; rectangular; rhombic; square;
hexagonal.

3.1.2 Lattices in 3-dimension

In 3-dimensions there are fourteen different possibilities when it comes to arranging a set of
mathematical points so for each of the resulting points in the set of points has a completely
identical environment in its neighbourhood. These 14 arrangements of points are known as
Bravais Lattice. The volumes of these lattices is not always primitive. The reason for this is
convenience, using a larger volume known as the crystallographic unit cell makes it possible
to visualize the symmetry in a vivid way, and make it easier to use orthogonal coordinate axes.
Looking at the elemental solids, it is the case that many have crystal structure that can
be associated directly with the simpler Bravais lattices, this is the case more so for metals.
However that said, this does not mean we can only have 14 possible crystal structures, the
Bravais lattices are rather the allowable spatial symmetries of an array of points. It is possible
to associate more than one atom with a lattice point, and this will create a large number of
possibilities for the structures. If we have more than one atom at a lattice point, we can refer
to it relative to the lattice point,

r123j = n1 a + n2 b + n3 c + Rj , (3.1)

here R j being a relative position vector, specifying the position of the j�th atom relative to the
point (n1 n2 n3 ). A group of one or more atoms that are associated with every lattice point is
referred to as a basis. The basis then becomes a geometrical arrangement of atoms associated
with each lattice point, this gives us a new definition for a crystal structure: it is a lattice with
a basis.
The introduction of the basis has the consequence of introducing the possibility of new
symmetry elements like rotations and reflections related to the basis about axes and planes that
pass through the lattice point, and where each operation or set of operations always ending
with the arrangement invariant with its previous arrangement. When translational and point
symmetry operations are considered, about 230 possible symmetry patterns exist for 3-D
structures. Regardless of all the possible crystal structures, the relative positions of the atoms,

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 Figure 3.2: The 3-D Bravais lattices.

as well as the different possibilities the basis could take (very large number of possibilities),
it is, at least as regards to symmetry, possible to limit each structure to one of these 230 space
groups.

Figure 3.3:

3.2 Crystal Directions and Indices

3.2.1 Plane and Miller Indices
A (Bravais) lattice is a spatial 3-D ordered distribution of atoms, however, it can be thought
of being made up of two-dimensional planes. These crystal planes can be thought of as some
imaginary planes inside a crystal in which large concentration of atoms are present. There
is effectively an infinite number of unique planes associated with a Bravais lattice, with each

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family of planes characterized by an arrangement and density of points as well as a specific
inter-planar spacing.
Crystals are anisotropic in nature, where the anisotropy implies that the physical proper-
ties will be different when measured from different crystallographic directions, and this effect
is more pronounced in cases of lower symmetry crystals. As a matter of necessity, its re-
quired then to be able to specify directions in a crystal in a systematic fashion, which is done
using what are known as Miller indices. For the purposes of this discussion, let us make the
following conditions the starting points:
• All the points in a Bravais lattice are equivalent, and the choice of origin and coordinate
axes is by convention,

• All the points will lie on one of the selected family of planes,

• A select number of planes in the family of planes will intersect the coordinate axes at
lattice points,

• All the planes in a given family of planes will be parallel, and in a rational ratio to one
another.
Miller Indices follow from these stipulations, and will allow for a description of the
crystallographic planes to be described within the unit cell. The Miller indices are derived
via the following steps:

1. Determine the planes x, y and z intercepts on the coordinate axes.

2. Take the ratio of the intercepts and the base vectors of the unit cell.
x y z
, , , (3.2)
a b c

3. Take the reciprocal of the ratio,

a b c
, , , (3.3)
x y z
4. Express this reciprocal in smallest integral ratio (hkl).

The triplet (hkl) describes a plane lying within the unit cell, and closest to the origin, from
a family of similar planes.
The origin has been set to a lattice point by convention, and it logically must lie on one of
the planes of the same family as (hkl) the separation between the plane and the origin therefore
is the inter-planar spacing dhkl . Mathematically, for any plane indexable as hkl, the plane (hkl)
lying closest to the origin will have the intercepts ah , bk , cl on the unit cell’s coordinate axes.
Therefore its clear that all planes are describable within the unit cell.
Whenever the intercepts are negative on the coordinate axes, they are treated the same
save for the sign that appears above the Miller index, in this fashion: h̄ (‘bar h‘). As shown, a
particular plane will be indicated as (hkl) while a set of symmetrically equivalent planes will
be given as { hkl }.
The distances between successive planes in a family of planes denoted by (hkl) will be
determined via the Miller indices. As an example, for cubic lattices it can be shown that the
distance between successive planes is given by:
a
dhkl = � (3.4)
(h2 + k2 + l 2 )

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 In lattices with a center of symmetry, many of the planes sharing indices are equivalent.
For example, in a cubic system the planes (123),(213),(321), (132), (231), and (312) will have
the same inter-planar spacing d as well as the same packing. This will have consequences in
X-ray diffraction, where these planes will be equivalent. For the case of (111), there will have
8 equivalent planes in a cubic lattice when the sign is taken into account. The total number of
equivalent planes for a given numerical values of the indices is called the multiplicity p.

Figure 3.4: The (011), the (100), the (110) and the (111) planes.

Direction
Directions in a lattice are specified via the coordinates of the lattice point that sits closest to the
origin in the selected direction. The direction is indicated as [uvz], note the square brackets,
and a set of similar directions is written as � uvz � . As a special case, in a cubic lattice one
can define directions in terms of the normals to the lattice planes, with [hkl] indicating the
direction normal to the (hkl) plane.

Sphere Packing
The amount of space an ideal set of spheres sitting next to each other occupies is a measure of
the efficiency of these spheres in filling space. This measure is known as the packing density
fp , its defined as the ratio of the volume occupied by the spheres to the volume of space. In
an ideal primitive lattice, defined as having only one lattice point, we presume that the lattice
point is occupied by a sphere, fp becomes the ratio of the volume of this sphere to the volume
of the primitive unit cell.
In 2D the sphere will be replaced with identical circular disks, and the volume by the area.
As an example, assume an array of disks in 2D with a radius of a/2, sitting at lattice points
spaced at a distance a apart. The unit cell is defined to be the square obtained by joining the
nearest neighbour lattice points. The unit cell therefore has sides of length a (see Fig. 3.5).
The ratio of the area occupied by the disk to the area of the unit cell can now be calculated.

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 Structure Coordination number Packing Fraction
fcc 12 0.74048
hcp 12 0.74048
bcc 8 0.68017
diamond 4 0.3401
Table 3.1: Coordination number and Packing fraction in 3D lattices.

a/2

Figure 3.5: Packing fraction for a 2D square lattice with disks.

AU = a ∗ a (3.5)
= a2 (3.6)

for each 1/4 portion of the sphere, the area is

1 1 a2
AS/4 = πr2 = π (3.7)
4 4 2
there are 4 1/4 sections of a circle in each unit cell, therefore
1 a2
AS = 4 × π (3.8)
4 2
a2
AS = π (3.9)
4
and therefore,
2
AU πa
fp = = 24 (3.10)
AS a
π
f p = ≈ 0.78 (3.11)
4
In 3D, the packing fraction for the various structures is as shown in Tab 3.2.1
For any system of hard spheres, a high packing fraction is the requirement for lowest
energy. Some types of crystal structures may be understood in terms of sphere packing re-
quirements. In crystals, the structural units would be atoms or ions, held together by various
types of bonds. Van der Waals, metallic and ionic bonds will favour densely packed struc-
tures with a high packing fraction. All the inert elements will have an fcc structure will a high

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packing fraction, these are Ne, Ar, Kr, Xe..; the crystalline structure of a significant number
of metals will be fcc: Cu, Ag, Au, Al, Pd, others will have the hcp structure: Co, Rum Os,
Sc, Y, La...; and some have the bcc structure: Li, Na, K, Rb, Cs,Fr...; Some non-elemental
ionic crystals may be understood in terms of close-packing of unequal spheres, such as NaCl.
Close packed in the context of crystal structure, is a lattice that has the densest packing of
hard spheres.

Coordination Number
The points in a Bravais lattice closest to a selected point at known as the nearest neighbours.
Since all the points on a lattice have an identical environment, they will all have the same
number of nearest neighbours. This property is therefore a characteristic of a lattice, and is
given the name coordination number.

Symmetry Operations
Rotation, Cn : Rotation by an angle 2π/n about the specified axis.
Inversion, I: Transformation r→ -r, a fixed point is selected as the origin.
Reflection, σ : Reflection across a plane.
Improper Rotation, Sn : Rotation Cn , followed by a reflection in the plane normal to the
rotation axis.

3.3 Details of various Structure

3.3.1 Cubic Systems
There are 3 distinct lattices in the cubic category, these are the sc (simple cubic lattice), the bcc
(body centred cubic lattice) and fcc (face centred cubic lattice). The primitive cell can contain
only one lattice point by definition, but the conventional bcc contains two lattice points, while
the fcc contains four lattice points. The positions inside a unit cell is specified in terms of a
fraction of the axial length a, b and c in the direction of the axes. The origin is defined to be
at one corner of the cell. Therefore we will have the body center of the cell being 12 21 21 , while
the face centres will include 12 21 0, 0 12 12 , 12 0 12 .

Figure 3.6: The cubic space lattices showing the conventional cells.

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 Simple Body-centred Face-centred
Volume (conventional cell) a3 a3 a3
Lattice points per cell 1 2 4
3 1 3 1 3
Volume, primitive cell a 2a 4a
Number of nearest neighbours 6 8√ 12
3a √a
Nearest neighbour distance a 2√ 2√
1 1 1
Packing fraction 6 π 8 π 3 6 π 2
Table 3.2: Characteristics of cubic lattices.

3.3.1.1 Sodium Chloride Structure

The NaCl structure has an fcc lattice, with a basis consisting of one Na+ and one Cl− ion at the
(0,0,0) and ( 12 , 12 , 12 ) fractional coordinates. In each unit cell there are therefore 4 formula units
of NaCl. Looking at the individual atoms, each has six nearest neighbours. Other compounds
that have a similar structure include LiH, MgO, and MnO.

Figure 3.7: The Sodium Chloride structure.

3.3.1.2 Caesium Chloride Structure

In the case of caesium chloride, there is one molecule per primitive cell, with one atom at
the origin 000, and the body centred position 12 21 21 of the simple cubic lattice counterpart.
The number of nearest neighbours (coordination number) is 8. Compounds with a similar
structure include BeCu, AlNi, and CuZn.

3.3.1.3 Hexagonal Close Packed Structure

In HCP structures, we have a layer of spheres arranged in a single close-packed layer, call
it A, with each sphere having six neighbours in the plane, a second layer call it B, is added
by placing each sphere of B in contact with three spheres of the bottom later. This pattern
continues with the spheres in the third layer being placed directly above those of the first
layer A. This creates a repeating pattern that is of the form ABABAB.... The number of
nearest neighbours is 12 for the hcp structure, and the fraction of the total volume occupied
by the spheres is 0.74.

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Figure 3.8: Left: The Caesium Chloride structure. Right: the primitive unit cell for the body
centered lattice in dashed (–) lines

Figure 3.9: The hexagonal close packed structure (hcp).

3.3.1.4 Diamond Structure

This is a structure found in diamond, and the semiconductors silicon and germanium. The lat-
tice in a diamond structure is fcc, with the primitive basis of this structure being two identical
species of atoms at coordinates 000 and 14 41 41 . As already discussed the fcc lattice will have 4
lattice points, it follows that the conventional unit cell of the diamond structure will have 2×
4=8 atoms. Each atom will have 4 nearest neighbours, while its packing fraction will be 0.34.

Figure 3.10: The diamond structure.

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3.3.1.5 Cubic Zinc Sulphide Structure
The cubic zinc sulphide structure may be considered as being derived from the diamond struc-
ture, but with the diamond structure viewed as two fcc structures displaced from each other
by 14 of the body diagonal. When Zn atoms are placed on one of the fcc structures and S
atoms on the other, then we have the Zinc Sulphide structure. This structure has cubic con-
ventional cell, with coordinates for the Zn atoms at 000, 0 12 12 , 21 0 12 , 12 12 0 and the S atoms at
111 133 313 331
4 4 4 , 4 4 4 , 4 4 4 , 4 4 4 . There are four molecules of ZnS per conventional cell. Next to each
atom there will be for equidistant neighbouring atoms of the opposite kind arranged at the
corners of a regular tetrahedron. Some examples of compounds that have this structure in-
cludes SiC, ZnS, AlP, GaP.

Figure 3.11: The Zinc Blende/ Zinc Sulphide structure, emphasizing the different atomic
species .

ADDENDUM:
The diamond and the rocksalt structures are not Bravais lattices. In the case of diamond,
we can distinguish two sets of carbon sites, see Fig. 3.12, each set of atoms froms a Bravais
lattice, and when both carbon sites are put together, we have the conventional cell.

a2
a3

a1

Figure 3.12: Left: The diamond structure, showing the two different carbon sites (FCC sub-
lattices). Right: In dashed lines, the primitive cell of the FCC structure, the cubic conventional
cell is used to take advantage of the cubic symmetry. a1 , a2 , a3 are the primitive cell vectors.

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 A lattice with a basis is neccessary to to describe crystals with atoms or ion located at
the lattice points of a Bravais lattices, but the crystal structure lacks the full translational
symmetry of the Bravais lattice since more than one kind of atom or ion is present. This is
the case for the NaCl structure, with alaternating Na+ and Cl− ions alternating on the lattice
points of a cubic lattice, with eac ion having siz other kinds of ions as its nearest neighbours.
The structure can be said to be an FCC cubic Bravais lattice with a basis of sodium at the
origin (0,0,0) and chlorine ion at the body center of the conventional cubic cell, (a/2,a/2,a/2).
See Fig. 3.13.

Figure 3.13: The Sodium Chloride structure and a depiction of the primitive cell of the FCC.

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