CRYSTAL STRUCTURES

Solids may be broadly classified as crystalline and noncrystalline depending upon the
arrangement of atoms or molecules.
Crystalline solids:
In crystalline solids atoms or molecules are arranged in regular or periodic fashion. Most
of the solids are crystalline in nature.
 Crystalline state may be subdivided into single crystals and polycrystals.
 In single crystals, the periodicity of atoms extends throughout the material.
For ex. Diamond, quartz etc.,
 A poly crystalline material is an aggregate of no. of small crystallites arranged
randomly, separated by well defined boundaries. The small crystallites are called “grains”
and the boundaries are called “grain boundaries”.
Non crystalline or amorphous solids: In Non crystalline solids, atoms or molecules are
arranged in random fashion. Ex.galss and rubber etc.,
SPACE LATTICE:
The arrangement of infinite number of imaginary points in three dimensional space such that
each point having identical surroundings is known as lattice points or space lattice.

In fig.a the environment about each point is same so it is space lattice.

In fig.b the environment about each point is not same and is not space lattice.

BASIS or PATTERN (Motif):

In order to obtain a crystal structure, an atom or group of atoms must be placed on each lattice
point in a regular fashion. Such an atom or group of atoms is called the “basis” and acts as a
building unit or structural unit for complete crystal structure.

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 CRYSTAL STRUCTURES

 Actual crystal structure = Lattice + basis.

The generation of crystal structure from two dimensional lattice and basis is shown in fig. the
basis consists of two atoms represented by ‘o’ and ’’.
UNIT CELL:
Unit cell is the smallest geometrical figure when it is repeated in three dimensional fashion, it
gives the actual crystal structure.

A part of two dimensional crystal structure is shown in

figuare. From fig. when a parallelogram such as ABCD is
repeated in three dimensions crystal structure is obtained.
The region ABCD is called unit cell and a, b are basis
vectors.

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 CRYSTAL STRUCTURES

Types of unit cells

There are two distinct types of unit cells: primitive and non-primitive.

a. Primitive cell or Simple cell: A primitive cell is defined as a unit

cell which contains only one lattice point at its corner only. i.e., one
lattice point is associated with each primitive cell.

Ex: Simple cubic (SC)

b. Non-primitive cell: If there are more than one lattice points in a unit cell, it is called a Non-
primitive cell.

Non-primitive unit cells contain additional lattice points, either on a face of the unit
cell or within the unit cell, and so have more than one lattice point per unit cell.
Ex: BCC and FCC contain more than one lattice point per unit cell

(a)BCC (b) FCC

LATTICE PARAMETERS:
The lattice is made up of repetition of unit cells and size
and shape of the unit cell can be completely described by
the three vectors a, b, c are called primitives and ,, are
interfacial angle. These primitives and interfacial angles are
called lattice parameters. By knowing the values of these
intercepts and interfacial angles we can easily determine the
shape and actual size of unit cell.

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 CRYSTAL STRUCTURES

CRYSTAL SYSTEMS:
On the basis of values of lattice parameters, crystal systems are classified into seven categories.
The primitives and interfacial angles for seven crystal are given in following table. The unit
cells of the crystal systems are shown in Figures.

Name Axial Interfacial angels No.of Bravais lattice

lengths Bravais
lattices
Cubic a=b=c α = β = γ = 90° 3 P, I ,F
Tetragonal a=b≠c α = β = γ = 90° 2 P, I
Orthorhombic a≠b≠c α = β = γ = 90° 4 P, I, F, C
Monoclinic a≠b≠c α = β = 90° ≠ γ 2 P, C
Triclinic a≠b≠c α ≠ β ≠ γ ≠ 90° 1 P
Rhombohedral a=b=c α = β = γ ≠ 90° 1 P
Hexagonal a=b≠c α = β = 90°, γ = 120° 1 P

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 CRYSTAL STRUCTURES

BRAVAIS LATTICES:
Bravais in 1880 showed that there are 14 possible types of space lattices in the 7 crystal
systems and are discussed briefly one by one as follows
1. Cubic Crystal System:
In cubic crystal the crystal axes are perpendicular to one another ( =  =  = 900). The
intercepts along three axes are same (a = b = c). Cubic lattice may be Simple cubic, body
centered, and face centered as shown in Figure.
Example: diamond, zinc sulphide, NaCl, etc,.

2. Tetragonal Crystal System:

The crystal axes are perpendicular to one another ( =  =  = 900 ). The intercepts along the
two axes are same and intercept on third axis is different (a = b ≠ c). Tetragonal crystal systems
may be simple or body centered as shown in figure.
Ex. Ordinary white tin and SnO2 and TiO2.

3. Orthorhombic Crystal System:

The crystal axes are perpendicular to one another ( =  =  = 900). But intercepts on three axes
are different (a ≠ b ≠ c). Orthorhombic may be simple, base centered, body centered or face
centered as shown in Figure.

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 CRYSTAL STRUCTURES

Ex. celestine, Olivinie, carnalite.

4. Monoclinic Crystal System:

Two crystal axes are perpendicular to each other but the third is obliquely inclined
( =  = 900 ≠ ). Intercepts along all the axes are different (a ≠ b ≠ c). Monoclinic system may
be simple and base centered as shown in Figure.

Ex. Borox and cryolite etc.

5. Triclinic Crystal System:

In this system none of the crystal axes are perpendicular to each other ( ≠ 
≠  ≠ 900) and intercepts on the crystal axes are also not same (a ≠ b ≠ c ).
This lattice may be simple ony as shown in Fig.

Ex. Potassium dichromate, blue vitriol etc.

6. Trigonal or Rhomohedral Crystal System:

Three axes are inclined equally to each other, other than 900 ( = 
=  ≠ 900). The lengths of three intercepts are equal (a = b = c). This
lattice may be simple ony as shown in Fig.
Ex. CaSo4.

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 CRYSTAL STRUCTURES

7. Hexagonal Crystal System:

Two axes are equal in length and angle between two axes is 1200 and
these two axes are perpendicular to third. i.e., a = b ≠ c, and  =  =
900,  = 1200.
This is simple primitive only as shown in figure.
Ex. SiO2, AgI etc.

PROPERTIES OF UNIT CELL:

i. Coordination Number: It is defined as the no. of equidistant neighbors that an atom has
in given structure. Greater the coordination number, the atoms are closely packed in a
given structure.
ii. Nearest neighboring distance: The distance between two nearest neighboring atoms in
a crystal lattice is known as the nearest neighboring distance.
iii. Atomic Packing Factor: It is defined as the ratio of the volume of the atoms occupying
the unit cell to the volume of unit cell.
volume of the atoms per unitcell (v)
Packing Factor =
volume of the unit cell (V )
Packing factor gives the available space occupied in the unit cell of atom.
iv. Atomic Radius: It is defined as the half the distance between two neighbouring atoms in
a crystal. Generally atomic radius (r) can be expressed interms of lattice constant (a).
v. Density of crystalline solid : The density of crystalline solid is defined as the ratio of
mass of the unit cell ans volume of the unit cell.
Let n be the number of atoms in a unit cell, M is the molecular weight, N A is the
avagadro number and a3 is the volume of unit cell. Then density of unit cell is given by
Mass of Unit cell
Density of Unit cell (ρ) =
Volume Unit cell
M
Mass of the each atom in the crystal =
NA

nM
Mass of the atoms in the unit cell =
NA

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 CRYSTAL STRUCTURES

nM
NA nM
 ρ= 3
=
a N A a3
1
 n M 3
a =  
 N A 

This is the expression for lattice constant (a) of the crystal.

PACKING FRACTION OF SIMPLE CUBIC CRYSTAL (SC):

The unit cell of cube having one atom or molecule at each
corner. So there are eight atoms or molecules at eight corners
of the cube. Since each corner atom is shared by eight
surrounding cubes. Hence share of each cube is one eighth of
an atom.
1
i. No. of atoms per unit cell (n) = 8 x = 1 atom.
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ii. Atomic radius (r): To calculate atomic radius, we
have to take the atoms which are in contact.
From the figure a = 2r or r = a/2
4
1  r 3
volume of the atoms per unitcell (v) 3 4 a3
iii. Packing Factor: = =
volume of the unit cell (V ) a3 3 a 3  8

= ≈ 0.52 or 52%
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This means 52% of the space is occupied by the atoms and 48% is free space in the unit
cell of the simple cubic structure. Polonium is the only element which possesses the
simple cubic structure.
iv. Coordination Number: In simple cubic structure each atom is surrounded by 6 nearest
neighbours. So coordination number is 6.
v. Nearest neighbor distance: 2r = a

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 CRYSTAL STRUCTURES

PACKING FRACTION OF BODY CENTERED CUBIC STRUCTURE (BCC):

The unit cell of body centered cubic structure is shown in figure. It has eight corner atoms and
one center atom. Hence it is called body centered cubic structure. This structure is more tightly
packed than simple cubic structure due the presence of additional atom at the center compared to
simple cubic structure. Each atom has only eight nearest neighbors.
Ex. Li, Na, K, Cr, α-iron etc.,
1
i. Total number of atoms in BCC cube (n) = 8 x + 1 = 2 atoms/unit cell.
8
ii. Atomic radius r: To calculate atomic radius we have to take atoms which are in contact
only. Here corner atom, body centered atom and opposite corner atoms are in contact as
shown in fig.
Therefore (4r)2 = ( 2 a)2 + a2

3a
= 3a2  r=
4
volume of atoms per unit cell
iii. Packing Factor:
volume of unit cell

4
2  r 3 2 4 3 3 a 3
3  3
= = = = 0.68 or 68%
a3 3 4  4  4  a 3
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This means 68% of the unit cell is filled with atoms and 32% is free space
iv. Coordination Number: Each atom in the structure is surrounded by 8 atoms that’s why
coordination number is 8.

3a
v. Nearest neighbor distance: 2r =
2
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 CRYSTAL STRUCTURES

FACE CENTERED CUBIC STRUCTURE (FCC):

The unit cell of face centered cube structure is shown in figure. It has 6 face centered atoms and
eight corner atoms. The six face centered atoms are shared by six adjacent cubes. So that on each
face only half of the atom is placed. Similarly each corner atom is shared by eight nearest cubes
so on each face 1/8 th part of the atom is located.
1 1
i. Total number of atoms per unit cell (n): 8 x + 6 x = 4 atoms per unit cell.
8 2
ii. Atomic radius (r): (4r)2 = a2 + a2

2a
r=
4
4
4 x  r3
Volume of atoms per Unit Cell 3 4 x 4 x 2 2 a 3
iii. Packing Factor: = =
Volume of unit cell a3 3 x 4 x 4 x 4 x a3
= 0.74 ≈ 74%
iv. Coordination Number: since each atom is surrounded by 12 atoms, coordination number is
12

2a
V. Nearest neighbor distance: 2r =
2
Examples: copper, gold, silver, aluminum etc.,

Packing Fraction
SC 52%
BCC 68%
FCC 74%

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 CRYSTAL STRUCTURES

Here FCC has high packing fraction, so it is closely packed structure. Where as SC structure has
low packing fraction. So it is called loosely packed structure.

PLANES IN CRYSTALS
A crystal is made up of a large number of parallel equidistant planes passing through the lattice
points called lattice planes. Different lattice planes shown in
the figure. The perpendicular distance between adjacent
planes is called Interplanar Spacing. The direction of these
planes are specified by miller indices h k l.

MILLER INDICES: These indices are defined as the reciprocals of the intercepts on the three
rectangular axes made by the plane. Miller indices are denoted by [h k l] or (h k l)
Procedure to obtain Miller indices:
1. Find the intercepts on the three crystallographic axes OX, OY and OZ.
2. Note their reciprocals.
3. Multiply the reciprocals by L.C.M of their denominator.
Hence the fraction is cleared.
For example: 2, 3, 6 are intercepts on OX, OY and OZ.
1 1 1
Reciprocals are , , their L.C.M is 6
2 3 6
Hence the Miller indices are (3 2 1)

Important Features of Miller Indices:

1. All the parallel planes have the same miller indices. For ex. (2 2 2) (4 4 4) are parallel to each
other
2. If any plane is parallel to any of three coordinate axes, its intercept on the axis is taken as
infinity. Hence miller index of the plane on that particular axis is zero.

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 CRYSTAL STRUCTURES

3. A bar on the Miller index indicates that the intercept of a plane of corresponding axis is
negative.
4. A plane passing through the origin is defined in terms of parallel plane having non zero
intercepts.
DISTANCE BETWEEN SUCCESSIVE (H K L) PLANES IN CUBIC CRYSTAL:
Let ‘a’ be the cube edge and h k l be the Miller indices of the plane ABC. This plane
belongs to a family of parallel planes. Let ON = d1 be the perpendicular distance of the plane
ABC from the origin. Let α β γ be the angles between normal and x axis, normal and y axis,
normal and z axis respectively.

Let the intercepts of the plane on the three axes are

a a a
OA = ; OB = ; OC =
h k l
d1 d d
From the figure cos α = , cos β= 1 , cos γ = 1
OA OB OC
We know that in directional cosines, cos2 α + cos2 β + cos2γ = 1
2 2 2
d   d   d 
Therefore  1  +  1  +  1  = 1
 OA   OB   OC 
2 2 2
 d 1 h   d 1 k   d 1l 
  +  +  =1
 a   a   a 

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 CRYSTAL STRUCTURES

d 12 2 a2
(h + K2 + l2) = 1  2
d = 2
h  k2  l2
2 1
a
a
 d1 = ------------- (1)
h 2
 k2  l2 
Let OM = d2 be the perpendicular distance of the next plane which is parallel to the first plane
ABC. The intercepts of this plane on three crystallographic axes are
2a 2a 2a
OA = ; OB = ; OC =
h k l
d2 d d
And cos α = , cos β= 2 , cos γ = 2
OA OB  OC 
We know that in directional cosines, cos2 α + cos2 β + cos2γ = 1
2 2 2
 d 2 h   d 2 k   d 2l 
  +  +  =1
 2a   2a   2a 

d 22 2 4a 2
(h + k2 + l2) = 1  d 22 =
4a 2 h2  k 2  l 2
2a
 d2 = --------------- (2)
h 2
 k2  l2 
Thus the interplanar spacing between two parallel planes of Miller indices (h k l) in a cubic
lattice is
d = d2 – d1
2a a
= -
h 2
 k2  l2  h 2
 k2  l2 
a
d = ----------- (3)
h 2
 k2  l2 

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