1

AUTONOMOUS
CRYSTALLOGRAPHY
&
CRYSTAL STRUCTURES
2
CRYSTALLINE NATURE OF MATTER:
Elements and their chemical compounds are found in
three states, i.e. Solids, liquids and Gases.
Some solids are brittle, some are ductile, some are strong,
some are weak, some are good conductors of heat and
electricity.
Solids can be broadly classified as Crystalline or Non-
Crystalline solids
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If the atoms or molecules in a solid are arranged
in some regular fashion then it is known as
Crystalline solids .
If the atoms or molecules in a solid are arranged
in irregular fashion ,then it is known as Non-
Crystalline solids.
Non- Crystalline is also called as Amorphous
solids
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Mono crystals Poly crystals
Amorphous
5
Distinction between Crystalline
solids and Amorphous solids:
Crystalline solids have a regular arrangement of
particles whereas the Amorphous solids have a
completely random arrangement.
Crystalline solids have different physical
properties in different direction i.e, they are
anisotropic while amorphous solids are isotropic
i.e., they have their physical properties same in
all direction
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All the bond in Crystalline solids are equally
strong due to their symmetry .When a crystalline
solids is heated all the bonds are ruptured at a
unique temperature but amorphous solids are not
equally strong .When it is heated, the weakest
bonds are ruptured first while stronger ones later
at high temperature .
Crystalline solids have a very sharp melting point
but in amorphous solids does not have the sharp
melting point
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Space lattice
A crystal is a 3-Dimensional body.
Crystals are made up of a regular and periodic
3-D patterns of atoms in space is called the
Crystal Structure
The Crystal Structure may be described in terms
of an idealized geometrical concept called a
Space lattice.
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Definition of Space lattice
A space lattice is defined as an infinite
array of points in three dimensions in
which every point has surroundings
identical to that of every other point in
the array.
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An array of points such that every point has identical
surroundings
In Euclidean space infinite array
We can have 1D, 2D or 3D arrays (lattices)
Space Lattice
Translationally periodic arrangement of points in space is
called a lattice
or
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- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -


- - - - - - - - - - - - - - - - -
a

2D Lattices
Two basis vectors generate the lattice
There are three lattice parameters which describe this lattice
One angle: o
Two distances: a, b
= 90 in the current example
o
b
a
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Lattice lines
Lattice points
Three dimensional lattice
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Basis and Unit Cell:
Basis : A set of one or more atoms about
the lattice point is called Basis .or A group
of atoms or molecule identical in
composition is called the basis
basis
Lattice point
The crystal structure is formation when a basis of atoms is attached identically to
each lattice point .
Lattice+basis = crystal structure
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Basis and Unit Cell:
Space Lattice + Basis = Crystal Structure
=



14
UNIT CELL
UNIT CELL:A unit cell is the smallest geometric figure
the repetition which gives actual crystal structure
Or
The unit cell may also be defined as the fundamental
elementary pattern of minimum number of atoms,
molecules or group of molecules which represent fully
all the characteristics of crystal.
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Square Lattice
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X X X X X X
X X X X X X
X X X X X X
X X X X X X
X X X X X X
X X X X X X
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Lattice Parameters of an unit cell
Z
X
Y
a
b
c
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Lattice Parameters of an unit cell
CRYSTALLOGRAPHIC AXES:
The lines drawn parallel to the lines of
intersection of any three faces of the unit
cell which do not lie in the same plane are
called crystallographic axes.
PRIMITIVES:
a, b and c are the dimensions of an unit cell and are
known as Primitives.
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Lattice Parameters of an unit cell
INTERFACIAL ANGLES:-
The angles between three crystallographic axes
are known as Interfacial angles , and .
The primitives a,b and c and Interfacial angles
, and .are the basic lattice parameters .
The unit cell formed by the primitives a,b and c is
called primitive cell
A primitive cell will have only one lattice point
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Crystal Systems:
on the basis of the lengths and direction of the
axis of the symmetry may be classified as Seven
Crystal Systems.
Cubic system:
* Lattice parameters
* All three sides are equal,
* All three angles ,
a b c = =
e.g :Nacl, diamond etc..
90 o | = = =
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Crystal Systems
Tetragonal System:
Lattice Parameters
* two sides equal
* all three right angles equal
a b c = =
90 o | = = =
e.g: NiSo4 etc..
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Crystal Systems
Orthorhombic system:
Lattice parameters
* All three sides different
* All three right angles equal
a b c = =
90 o | = = =
Eg; KNO3
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Monoclinic System :
Lattice parameters
* All three sides
different
Two right angles ,
third arbitrary,
a b c = =
90 o | = = =
E.g; FeSo4
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Crystal Systems
Triclinic System:
Lattice parameters
* All three sides
different
* All three angles
different
a b c = =
o | = =
Eg. CuSO
4
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Crystal Systems
Trigonal
(rhombohedral):
Lattice parameters
* All three sides equal
All three angles ,
of arbitrary value ,
a b c = =
90 o | = = =
E.g CaSO4,Quartz,etc.
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Some times an alternate hexagonal cell
is used instead of the Trigonal Cell
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Crystal Systems
Hexagonal System:
Lattice parameters
* Two sides equal,
third arbitrary
* Two right angles ,
third angle
a b c = =
90 , 120 o | = = =
a b c = =
E.g SiO2 ,etc..
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Crystal Systems
* Cubic a = b=c = = =90

* Tetragonal a = b c = = =90
* Orthorhombic a b c = = =90
* Monoclinic a b c = = 90
* Triclinic a b c 90
* Trigonal a = b = c = = 90
* Hexagonal a=b=c ==90,=120
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BRAVAIS LATTICES
BRAVAIS LATTICES:-
In 1848 Bravais showed that there are only fourteen ways
arranging points in 3-dimensional space.These fourteen
space lattices are known as Bravaias lattices.
They belong to Seven crystal systems.
In case of a cubic system, there are three Bravais lattice
each with collection symmetry elements and the Lattice.
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Simple Cubic or (Primitive) Or Cubic P
type Lattice:
There is one lattice point at each of eight
corners of the unit cell. There is no lattice
point inside the unit cell.
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32
Lattice Point per Unit cell:
Simple Cubic lattice :one lattice point at each
of the eight corners of the unit cell. Each lattice
point forming the simple cubic lattice is a
member of 8 surrounding cell.
the share of each lattice point to the cubic
lattice=1/8.
Number of lattice points in unit cell=(8*1/8)=1
Hence it is Primitive.
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Body Centred Cubic (bcc) I Lattice:
* There is one lattice point at each of the
eight corners and one lattice point at centre
of each cell. So there is a lattice point at
the centre of each unit cell
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35
lattice Points Per Unit Cell:
There are eight lattice points at the eight corners and each
of them is a member of 8 surrounding cells.
Also there in one lattice point at the centre of the body.
** total number of body centre of lattice point per unit
cell =1
** total number of corner lattice point attached to unit
cell=(8*1/8)=1
** total number of lattice point in unit cell 1+1=2
*** hence its not primitive.
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Face Centred Cubic or Cubic F Lattice:
* There is one lattice Point at each of the
eight corners and one lattice point at the
centres of each of the six faces of the unit
cell.
* Thus there is an extra point point in at the
centre of each face.
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38
LatticePoints Per Unit Cell:
unit cell consists of 8 corner lattice point ,each
being a member of 8 surrounding cells.
*** Six face lattice points,each being a member
of two cells.
** total no. of corner lattice point concerned with
unit cell=8*1/8=1.
** total no.of face centred lattice atoms
concerned with unit cell=6*1/2=3
*** total no.of lattice points concerned with unit
cell=1+3=4
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Position of lattice
points
Effective number of Lattice points /
cell
1 P 8 Corners = [8 (1/8)] = 1
2 I
8 Corners
+
1 body centre
= [1 (for corners)] + [1 (BC)] = 2
3 F
8 Corners
+
6 face centres
= [1 (for corners)] + [6 (1/2)] = 4
4
A/
B/
C
8 corners
+
2 centres of opposite
faces
= [1 (for corners)] + [2 (1/2)] = 2
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1 Cubic Cube
P I F C
P
I
F
90 o | = = = a b c = =
BRAVAIS LATTICES
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P I F C
2 Tetragonal Square Prism (general height)
I
P
a b c = = 90 o | = = =
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P I F C
3
Orthorhomb
ic
Rectangular Prism (general height)
P
I
F
C
a b c = = 90 o | = = =
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6 Monoclinic Parallogramic Prism
I F
P I F C
a b c = =
P C
90 o | = = =
a b c = =
44
P I F C
7 Triclinic Parallelepiped (general)
a b c = =
o | = =
45
P I F C
5 Trigonal
Parallelepiped (Equilateral,
Equiangular)

90 o | = = =
a b c = =
Rhombohedral
46
P I F C
4 Hexagonal 120 Rhombic Prism
Note: there is only one type of hexagonal
lattice (the primitive one)
a b c = = 90 , 120 o | = = =
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BRAVAIS LATTICES
**Cubic Simple p
Body centred I
Face centred F
**Tetragonal simple p
Body centered I
**Orthorhombic simple p
Base centred C
Body centred I
Face centred F
**Monoclinic sim ple p
Base centred c
**Triclinic simple p
**Trigonal simple p
**Hexagonal simple p
`
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The distance between the centers of two nearest
neighboring atoms is called nearest neighbor
distance.
Atomis radius (r). Half the distnce between the NND
i.e 2r/2=r
NEAREST NEIGHBOUUR DISTANCE
(2r):
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CO-ORDINATION NUMBER:
Co-ordination number is defined as the
number of equidistance nearest neighbors
that an atom has in a given structure.
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ATOMIC PACKING FACTOR:
Atomic packing factor is the ratio of volume
occupied by the atoms in an unit cell to the total
volume of the unit cell. It is also called packing
fraction.
V
v
A.P.F =
51
Void space:
Void space in the unit cell is the vacant
space left or unutilized space in unit cell ,
and more commonly known as interstitial
space.
Void space = ( 1-APF ) X 100
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SIMPLE CUBIC STRUCTURE-
Effective number of atoms per unit cell
(8 x 1/8) =1
Nearest neighbour distance
2r = a
. Atomic radius r = a / 2
co-ordination number = 6
a
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SIMPLE CUBIC STRUCTURE
54
SIMPLE CUBIC STRUCTURE
5. Atomic packingfactor
Vol. of all atoms in the unit cell
Vol.of the unit cell
6.Void space = (1-APF) X 100
= (1-0.52)X 100
=48%
Ex: polonium.
3
3
3
3
4
1
3
2
4
1
3
(2 )
0.52
(52%)
r
a
wherea r
r
r
t
t

=
=

=
=
=
55
BCC STRUCTURE
Close packed directions are cube diagonals.
56
BCC STRUCTURE
Effective number of atoms per unit cell (8 x 1/8) + 1 =2
Atomic radius r = 3a /4
Nearest neighbour distance
2r =3a/2
Co-ordination number = 8
C
A
a
a
B
a 2
a 3
D
D
C
a
57
BCC STRUCTURE
5.Atomic packing factor
6.Void space = (1-APF) x 100
= (1-0.68) x 100
= 32%
Ex: Na, lithium and
Chromium.
3
3
3
3
4
2
3
3
4
4 3
2 ( )
3 4
( )
0.68
(68%)
r
a
wherer a
a
a
t
t

=
=

=
=
=
58
FCC Crystal Structure
Effective number of atoms per unit cell (8 x 1/8) + 1/2 X 6 = 4
2.Atomic radius r = a / 22
3.Nearest neighbour distance
2r = a /2
4.Co-ordination number = 12
A B
C
4r

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FCC Crystal Structure
Close packed directions are face diagonals.
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FCC Crystal Structure
How the co-ordination number is 12 in FCC
Structure ?
Ans. Centre of each face as one atom. this centre
atom touches four corner atoms in its plane, four
body centered atoms in each of the two planes on
either side of its plane. thus the co-ordination
number is 12.
61
FCC coordination number
4
C
1
2
3
5
6
7
8
9
10
11
12
a
a /2
a /2
a
62
5.Atomic packing factor
6.Void space = (1-APF) X 100
= (1-0.74) X 100
= 26%
Ex: Copper , Aluminum, silver and Led
3
3
3
3
4
4
3
2 2
4
4 ( )
3
2 2
( )
0.74
(74%)
r
a
a
r
a
a
t
t

=
=

=
=
=
63
Hexagonal (Unit cell)
64
Hexagonal close packed
structure:
Effective number of atoms per unit cell
2 x (6x 1/6) + 2 x 1/2 + 3 = 6.
2.Atomic radius r = a / 2.
3.Nearest neighbor distance
2r = a
4.Co-ordination number = 12.
C
C/2
a
65
HCP Co ordination Number
66
Calculation of c/a ratio
Let c be the hight of the unit cell and a
be its edge, the three body atoms lie in a
horizontal plane at height c/2 from the
bottom layer
a
a
c
c
B
A
O
B
O
x
A
30
0
C
X
A
/
O
/
a
2
c
CX =
67
A
/
AB=30
0
From the figure, Triangle ABA
/
Cos
=A
30
0
A
/
AB
A
=
A
/
But AX=2/3 A=A
/
2
3
a
3
a
=
68
3
8
3
2
4
2
3
2
3
2
2
2
2
2
2 2 2
2 2 2
=
=
=
=
=
+ =
a
c
a
c
therefore
c
butCX
a
a
a
AX AC CX
CX AX AC
In Triangle AXC,
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Atomic packing factor
Area of the base=6* Area of the triangle ABO
6*1/2*AB*
OO
/
2 / 3 3
2
a
2 / 3 3
2
a
*
C
a a
2
3
* * 3
VOL. OF UNIT CELL IS=Area of the base * hight
70
0
0
2
3
2
3
74
2 3
8
3
3 3
2
2
.
3 3
16
2
3 3
3
4
* 6
=
=
=
=
=
=
t
t
t
t
c
a
Since
c
a
a
r Sub
c a
r
c a
r
A.P.F=
Eg; Mg,Zn,Cd
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Diamond structure:
Diamond structure:
Diamond is a combination of two
interpenetrating FCC - sub lattices along
the body diagonal by 1/4
th
Cube edge.
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73
1
2
3
4
5
6
74
x p
y
z
a/4
a/4
a/2
a
a
75
Diamond - APF
Effective number of atoms per
unit cell (8 x 1/8) + 1/2 X 6
+ 4 = 8.
2.Atomic radius r = 3a / 8.
3.Nearest neighbor distance

2r = 3a / 4.
4.Co-ordination number = 4.
a/4
a/4
a/4
x p
z
y
2r
8
a
76
Diamond Structure
77
Diamond Structure
* The fraction such as 1/4,1/2,3/4 denote
the height above the base in units of cube
edge.
1/2
1/2
0
1/2
0
0
0
1/4
0
3/4
1/2
1/4
3/4
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5. Atomic packing
factor
3
3
3
3
4
8
3
3
8
4 3
8 ( )
3 8
( )
0.34
(34%)
r
a
r a
a
a
t
t

=
=

=
=
=
6. Void space = (1-APF) x 100
= (1-0.34) x 100
= 66%
Ge, Si and Carbon atoms are
possess this structure
79
Structure of a zinc sulphide:
ZnS structure is interpenetration of two fcc
lattices where One of zinc and other is of
sulpher atoms. This structure is similar to
Diamond crystal structure
80
Zn
S
81
1
2
3
4
5
6
Zn
S
82
Sodium chloride structure:
Nacl crystal is an ionic crystal.
In Nacl structure Na+ and Cl- are situated side by side
NaCl Structure is consists of two fcc sub lattices.
One of the chlorine ion having its origin at the
(o, o, o) point. and other of the sodium ions having its
origin at (a/2,0,0).
Each ion in a Nacl lattice has six nearest neighbor ions at
a distance a/2.i,e its co-ordination number is 6.
83
2
a
2
a
84
2
a
a
a
2
a
2
a
85
Structure of cesium chloride
CsCl is an ionic compound. It
has simple cubic structure.
The Unit cell of CsCl as shown
In Fig.
From the figure Cs+ ions are
situated at the corners of the
cubic cell and Cl- ions at the
body centre or vice versa
So the crystal may be considered
to be a combination of two
simple cubic Sublattice one is
cs+ ions and other of Cl- ion.
The co-ordination number is 8
Cs
+
Cl
86