Government College University Faisalabad, Sahiwal Campus

Topic:

Dimensional Relationships

Subject:

X-Ray Crystallography

Instructor:

Madam Rubina

Submitted by:

Boys Group BS Chemistry 8th Semester

Inorganic Chemistry
Dimensional Relationships
CRYSTAL SYSTEMS AND BRAVAIS LATTICES
Crystal system is a method of classifying crystalline substances on the basis of
their unit cell. There are seven unique crystal systems. The simplest and most
symmetric, the cubic (or isometric) system, has the symmetry of a cube. The
other six systems, in order of decreasing symmetry, are hexagonal, tetragonal,
trigonal (also known as rhombohedral), orthorhombic, monoclinic and triclinic.
Bravais lattice is a set of points constructed by translating a single point in
discrete steps by a set of basis vectors.
In 1848, the French physicist and crystallographer Auguste Bravais (1811-1863)
established that in three-dimensional space only fourteen different lattices may
be constructed. All crystalline materials recognized till now fit in one of these
arrangements

Point Group and Symmetry Classes

In crystals more symmetry axes (both proper and improper) with or without
translational components may coexist. We will consider here only those
combinations of operators which do not imply translations. The combinations of
proper and improper axes intersecting in a point, called point groups. The total
number of crystallographic point groups (for three dimensional crystals) is 32, and
they were first listed by Hessel in 1830.

Point groups in one and two dimensions

The derivation of the crystallographic point groups in a two-dimensional space is
much easier than in three dimensions. In fact, the reflection with respect to a
plane is substituted by a reflection with respect to a line (the same letter m will
also indicate this operation); and 𝑛̅ axes are not used. The total number of point
groups in the plane is 10, and these are indicated by the symbols: “1, 2, 3, 4, 6, m,
2mm, 3m, 4mm, 6mm”.
The number of crystallographic point groups in one dimension is 2: they are 1 and
m=(𝟏 ̅ ). Here “m” is the improper axis and show the reflection of the plane.
 Dimension Point Group

1-D 1 ̅
𝟏

2-D 1 2 3 4 6 M 2mm 3m 4mm 6mm

Table: Point groups in 1-dimension and 2-dimension

Bravais Lattices in Two Dimension

The most general and least symmetric Bravais lattice in two dimensions is
the oblique lattice. If the angle between the two lattice vectors is 90°, the higher
symmetry of the cell gives rise to a distinct Bravais lattice, either rectangular
or square depending on whether the unit cell vectors have different length or not.
In the case of a rectangular lattice, we can distinguish between a primitive
rectangular lattice and a centered rectangular lattice, which has an extra lattice
point (atom) at the center. The centered rectangular lattice could be set up as a
primitive lattice with lower symmetry (unit cell shown in green), but convention
prefers the more symmetric description. Finally, if the lattice vectors are the same
length and the angle is 120°, we have another special case with higher symmetry,
the hexagonal lattice.
Point Group in 3-Dimension-The seven crystal systems
If the crystal periodicity is only compatible with rotation or inversion axes of order
1, 2, 3, 4, 6, the presence of one of these axes will impose some restrictions on
the geometry of the lattice. It is therefore convenient to group together the
symmetry classes with common features in such a way that crystals belonging to
these classes can be described by unit cells of the same type. In turn, the cells will
be chosen in the most suitable way to show the symmetry actually present.
Point groups 1 and 1̅ have no symmetry axes and therefore no constraint axes for
the unit cell; the ratios a:b:c and the angles α, β, γ can assume any value. Classes
1 and 1̅ are said to belong to the triclinic system.
Groups 2, m, and 2/m all present a 2 axis. If we assume that this axis coincides
with the b axis of the unit cell, a and c can be chosen on the lattice plane normal
to b. We will then have α = γ = 90" and β unrestricted and the ratios a:b:c also
unrestricted. Crystals with symmetry 2, m, and 2/m belong to the monoclinic
system.
Classes 222, mm2, mmm are characterized by the presence of three mutually
orthogonal two folds rotation or inversion axes. If we assume these as reference
axes, we will obtain a unit cell with angles α = β = γ = 90" and with unrestricted
a:b:c ratios. These classes belong to the orthorhombic system.
For the seven groups with only one fourfold axis [4, 4̅, 4/m, 422, 4mm, 4̅2m,
4/mmm] the c axis is chosen as the direction of the fourfold axis and the a and b
axes will be symmetry equivalent, on the lattice plane normal to c. The cell angles
will be α = β = γ = 90o and the ratios a:b:c = 1: 1 : c. These crystals belong to the
tetragonal system. For the crystals with only one threefold or six fold axis [3, 3̅,
32, 3m, 3̅m, 6, 6̅, 6/m, 622, 6mm, 6̅2m, 6/mm] the c axis is assumed along the
three or six fold axis, while a and b are symmetry equivalent on the plane
perpendicular to c. These point groups are collected together in the trigonal and
hexagonal systems, respectively, both characterized by a unit cell with angles α =
β = 90o and γ = 120°, and ratios a: b :c = 1: 1:c. Crystals with four threefold axes
[23, m3̅, 432, 4̅3m, m3m] distributed as the diagonals of a cube can be referred to
orthogonal unit axes coinciding with the cube edges. The presence of the
threefold axes ensures that these directions are symmetry equivalent. The chosen
unit cell will have α = β = γ = 90o and ratios “a :b : c = 1: 1: 1”. This is called the
cubic system.

Class Point Group

Cubic 23 m3 432 43m m3m

6
Hexagonal 6 6 ⁄m 622 6mm 6m2 6/mmm

Trigonal 3 3 32 3m 3m

4
Tetragonal 4 4 ⁄m 422 4mm 42m 4/mmm

Orthorhombic 222 mm2 mmm

2
Monoclinic 2 ⁄m M

Triclinic 1 1

Table: In 3-dimensional system point Groups in seven crystal system

1. Cubic System

Primitive Body-centered Face-centered

Bravais lattice
cubic cubic cubic

Pearson symbol cP cB cF
 Unit cell

2. Hexagonal Family
• Hexagonal
The unit cell parameters are:
a=b≠c
α = β = 90° γ = 120°
Unit Cell Hexagonal & Bravais Lattice:

Crystallographic axes Hexagonal Unit cell Bravais Lattice

Hexagonal Unit

• Trigonal
The trigonal crystal system is described by three primitive vectors of
equal length that make equal angles (≠90°) with one another. The
trigonal unit cell is like a cube that has been stretched along on body
diagonal.
a=b=c
α = β = γ ≠ 90°
Unit Cell of Trigonal & Bravais Lattice:
 Crystallographic Axes primitive
primitive
hexagonal
rhombohedral
lattice (hP)
lattice (hR)

An alternative cell is sometimes used to describe the rhombohedral lattice. The cell
is of the same shape as the conventional hexagonal unit cell with two interior points
equally spaced along a diagonal. In practice, the hexagonal description is more
commonly used because it is easier to deal with coordinate system with two 90°
angles.
a=b≠c
α = γ = 90° β = 120°

R-centred hexagonal
lattice (hR)

This figure shows the rhombohedrally-centred hexagonal cell and its relationship
to the primitive rhombohedral cell.
 3. Tetragonal Crystal System
Minerals of the tetragonal crystal system are referred to three mutually
perpendicular axes. The two horizontal axes are of equal length, while the
vertical axis is of different length and may be either shorter or longer than
the other two.
a=b≠c
α = β = γ = 90°
Unit Cell and Bravais Lattice:

Crystallographic Axes
Primitive (tP) Body-Centered (tl)

4. Orthorhombic Crystal System

Minerals of the orthorhombic (or rhombic) crystal system are referred to
three mutually perpendicular axes, each of which is of a different length than
the others.
a≠b≠c
α = β = γ = 90°
Unit Cell & Bravais Lattice

Crystallographic Axes
 primitive (oP) Base-centered (oC) Body-centered (oL) Face-centered (oF)

5. Monoclinic Crystal System

Minerals of the monoclinic crystal system are referred to three unequal axes.
Two of these axes (a and c) are inclined toward each other at an oblique
angle; these are usually depicted vertically. The third axis (b) is perpendicular
to the other two and is called the ortho axis. The two vertical axes therefore
do not intersect one another at right angles, although both are perpendicular
to the horizontal axis.
a≠b≠c
α = γ = 90° ≠ β
Unit Cell & Bravais Lattice

Crystallographic axes Primitive (mP) Base-centered (mC)

6. Triclinic Crystal System

Minerals of the triclinic crystal system are referred to three unequal axes, all
of which intersect at oblique angles. The triclinic system is sometimes called
the anorthic system because there are no angles that are orthogonal.
a≠b≠c
α ≠ β ≠ γ ≠ 90°
Unit Cell & Bravais Lattice

Crystallographic Axes Primitive (tP)