Introduction to Crystal symmetry

and diffraction

The seven Crystal

Systems
Dr. Nasir Abbas
Classification of Matter
 Questions ?

• What is a phase?
• Phase Diagram?
• Crystalline, amorphous and glass systems?
• How to get (solve) Crystal structure
• Diffraction pattern (crystal lattice)
• Seven crystal systems
• Crystallization process
• Application of crystallization in Pharmacy
 What is a phase
• Definition: phase, in thermodynamics, chemically and physically
uniform or homogeneous quantity of matter that can be separated
mechanically from a nonhomogeneous mixture and that may consist
of a single substance or of a mixture of substances.
• The three fundamental phases of matter are solid, liquid,
and gas(vapour), but others are considered to exist, including
crystalline, colloid, glassy, amorphous, and plasma phases. When a
phase in one form is altered to another form, a phase change is said
to have occurred.
 Phase Diagram
• A phase diagram is common way to represent the various phases of a substance and the conditions
under which each phase exists.
• A phase diagram is a plot of pressure (P or ln P) vs temperature (T). Lines on the diagram represent
conditions (T,P) under which a phase change is at equilibrium. That is, at a point on a line, it is possible
for two (or three) phases to coexist at equilibrium. In other regions of the plot, only one phase exists at
equilibrium.
 Solids

Solids are again classified in to two types

 Crystalline

 Non-Crystalline (Amorphous)
 What is a Crystalline solid?

A crystal or crystalline solid is a solid material, whose

constituent atoms, molecules, or ions are arranged in
an orderly repeating pattern extending in all three
spatial dimensions.

So a crystal is characterized by regular arrangement of

atoms or molecules
Example2: 1,3-dimethylurea

Form I Form II

Form III Form IV

 Examples !

• Non-Metallic crystals:
Ice, Carbon, Diamond, Nacl, Kcl etc…

• Metallic Crystals:
Copper, Silver, Aluminium, Tungsten, Magnesium
etc…
Crystalline Solid
 Single crystal

Single Crystal example

 Amorphous Solid

• Amorphous (Non-crystalline) Solid is composed of

randomly orientated atoms , ions, or molecules that do
not form defined patterns or lattice structures.

• Amorphous materials have order only within a few atomic

or molecular dimensions.
• Amorphous materials do not have any long-range
order, but they have varying degrees of short-
range order.

• Examples to amorphous materials include

amorphous silicon, plastics, and glasses.

• Amorphous silicon can be used in solar cells and

thin film transistors.
Non-crystalline
 What are the Crystal properties?

o Zero entropy i.e. Highly ordered structure, Molecules/ atoms/ Ions are
orderly arranged in three dimensions

o Crystals have sharp melting points

o They have long range positional order

o Crystals are anisotropic

(Properties change depending on the direction)
o It has symmetry, translation symmetry
o
The relationship between a crystal structure and its diffraction pattern

Crystal structure (what we want to know)

Atom positions and displacements;
electron density distribution

Fourier transform:
(Reverse) Fourier transform:
add up the contributions to
add up the scattered waves,
scattering by all the atoms
imitating an X-ray
microscope lens system Calculation from model
structure
Calculation only; physically
unachievable Diffraction experiment

Diffraction pattern (what we can measure, in part)

Amplitudes [and phases] of X-ray waves
Crystalline Solid
Example2: 1,3-dimethylurea

Form I Form II

Form III Form IV

 Examples of diffraction patterns:

An actual X-ray photograph A computer-generated reproduction

3 obvious properties:

1. Geometry: regular arrangement of

spots
corresponding to directions of diffracted
beams of X-rays

2. Symmetry: in positions and intensities of

spots

3. Intensities: wide variation with no

apparent pattern except symmetry
Crystal structure Diffraction pattern

Unit cell geometry Diffraction geometry

(lattice (directions, positions)
parameters)
Crystal symmetry Diffraction symmetry
(space group) (Laue class)

Unit cell contents Intensities

(atom positions etc.) (amplitudes and phases)
 1.2 Translation symmetry in crystalline solids
The characteristic property of the crystalline solid state is its high degree of
internal order: molecules (or atoms, or ions) are arranged in a regular way an
in effectively infinite 3D repeat pattern, like 3D wallpaper (theoretically,
zero entropy).
This repetition is translation symmetry.
It is always present in crystalline solids. Other kinds of symmetry
(rotation, reflection, inversion, improper rotation) may also be present.
A complete crystal structure can be specified by describing the contents of one
repeat unit, together with the way in which this unit is repeated by
translation symmetry.
Concepts: lattice
unit cell
 White fish and grey birds: a
sort of 2D ionic structure?
[M. C. Escher]
All white fish are identical.
All grey birds are identical.
Basic structural unit is one
bird plus one fish, repeated
in a regular way in 2D to
give the complete structure.
There is no other
symmetry. How do we
specify the
geometry of the repeat unit?
Choose any point, such as a
fish’s eye.
Then mark all the other equivalent points in the same way.
Now take away the original picture…
 We are left with a regular
pattern of dots, showing the
geometrical form of the
translation symmetry but not
the detailed contents of the
structure.
This is called the lattice of
the structure.
How do we measure its
geometry?
Join up four
neighbouring lattice
points to form a
parallelogram (like a
rectangle but with
angles not equal to
This is called the unit cell of the structure.
90°).
Many different unit cells
could be chosen, all equally
valid.
For convenience and by
convention, the sides are
made as short as possible,
and the angles close to 90°.
Here, the blue unit cell is
the best choice.
a

b
The unit cell geometry is fully described by
giving the lengths of two sides and the
angle between them (in 2 dimensions).
In three dimensions, a unit cell is a parallelepiped (like a brick, but with
the angles not necessarily 90°).
To describe the unit cell geometry, we need three lengths (a, b, c) and
three angles (, , );  is the angle between b and c,  between a and
c,  between a and b.
Alternatively, using vectors, the unit cell is specified by the three axis
vectors: a, b, c.
In the absence of any rotation or reflection symmetry, the unit cell lengths
are
usually different from each other, and the angles do not have special
values such as 90° or 120°.
In other words, pure translation symmetry imposes no restrictions on
the values of unit cell parameters (lengths and angles).

Translation symmetry is what gives rise to X-ray diffraction, the crystal

acting as a 3D diffraction grating. Unit cell dimensions are comparable
to the wavelengths of X-rays.
1.3 Symmetry of individual molecules,
with relevance to crystalline solids

Symmetry element

A physically identifiable point, line, or plane in a molecule about which

symmetry operations are applied.

Symmetry operation

Inversion through a point, rotation about a line, or reflection in a plane (or a

special combination of two of these together), that leaves the molecule afterwards
with an identical appearance; also included, for completeness, is the identity
operation (doing nothing).

Each symmetry element provides a number (one or more) of possible symmetry

operations.
For individual molecules, all symmetry operations can be classified as one of two
types:
proper rotation – rotation by 360/n about a rotation axis;
improper rotation – combination of a rotation about an axis and a simultaneous
reflection in a perpendicular plane through the centre of the molecule.
This is the definition used in spectroscopy and bonding applications (Schoenflies
convention).

Crystallography uses a different definition (Hermann-Maugin or international

convention, for good reasons!):
proper rotation – rotation by 360/n about a rotation axis;
improper rotation – combination of a rotation about an axis and a
simultaneous inversion through a point at the centre of the molecule.

Reflection and inversion symmetry are just special cases of improper rotations.
Improper operations involve a change of hand; proper operations retain the
same hand.
3-fold rotation symmetry

Choose lattice points and

outline a unit cell.

This has equal sides

(a = b) and the
angle is exactly
120° as a direct
consequence
of the rotation
symmetry.
6-fold rotation
symmetry generates
the same unit cell
restrictions as 3-
fold rotation
symmetry.
 4-fold rotation symmetry

Choose lattice points and

outline a unit cell.

This has equal sides

(a = b) and the angle
is exactly 90° as a
direct consequence
of the rotation
symmetry. The unit
cell is a perfect
square.

The point at the centre of the unit cell is not identical to the corners! It has
the
opposite direction of rotation (look carefully). So it is not an equivalent
lattice point. The unit cell drawn here is the smallest possible.
Reflection symmetry

Choose lattice points and outline

a unit cell.

This is a rectangle: the sides are

not equal, but the angle must be
90° because of the reflection
lines (2D equivalent of
reflection planes in 3D) that run
vertically through the centres of
all the beetles.
In 3 dimensions similar restrictions apply, in the presence of ANY rotation or
reflection symmetry.
As a result, there are just 7 different possible types of unit cell shapes for 3D
crystal structures, and these are called the seven crystal systems.
Each one has a characteristic minimum symmetry associated with it, and its
own particular geometrical restrictions.
 The seven crystal systems

Crystal system Essential symmetry Restrictions on unit cell

triclinic none none

monoclinic 2 and/or m for one axis  =  = 90°

orthorhombic 2 and/or m for three axes  =  =  = 90°
tetragonal 4 for one axis a = b;  =  =  = 90°
trigonal 3 for one axis a = b;  =  = 90°;  = 120°
hexagonal 6 for one axis a = b;  =  = 90°;  = 120°
cubic 3 for four directions a = b = c;  =  =  = 90°
For some crystal structures with rotation and/or reflection symmetry, it is
convenient to choose a unit cell that has lattice points not only at the corners
but also in the centres of some faces or at the body centre of the cell, because
this gives the conventional shape for the crystal system, revealing the type of
symmetry present. These are called centred unit cells, as opposed to primitive
unit cells with lattice points only at the corners.

If all beetles are considered the same

regardless of colour, the smallest unit
cell is the blue one, with lattice points
only at the corners. However, this
does not have the 90° angle
characteristic of reflection symmetry.
If we use the rectangular red unit cell,
then this is twice the size and has a
lattice point right in the middle. This is
a centred unit cell (and is
conventional), while
the blue one is a primitive cell.
Centred unit cells

2 dimensions:
primitive (p) for all 4 unit cell shapes (oblique, rectangular, square,
hexagonal)
centred (c) for the rectangular shape only (unnecessary for other shapes)
3 dimensions:
primitive (P) for all 7 crystal systems
centred on one pair of faces (A, (B), C) for monoclinic, orthorhombic
centred on all faces (F) for orthorhombic, cubic
centred at the unit cell centre (I) for orthorhombic, tetragonal, cubic
rhombohedral unit cell on hexagonal/trigonal axes has 3 lattice
points per unit
cell (R)
A centred unit cell is larger by a factor of 2 (A, C, I), 3 (R), or 4 (F) than the corresponding
P cell.
Therefore the related reciprocal unit cell is smaller by the same factor, and a
corresponding fraction of its corners do not lie on reflection positions.
 The seven crystal systems

Crystal system Essential symmetry Restrictions on unit cell “Lattice types”

triclinic none none P

monoclinic 2 and/or m for one axis  =  = 90° P, C (I)

orthorhombic 2 and/or m for three axes  =  =  = 90° P, C (A), I, F

tetragonal 4 for one axis a = b;  =  =  = 90° P, I

trigonal 3 for one axis a = b;  =  = 90°;  = 120° P (R)

hexagonal 6 for one axis a = b;  =  = 90°;  = 120° P

cubic 3 for four directions a = b = c;  =  =  = 90° P, I, F

 Crystallization
(The Process)
• Dissolution and re-crystallization
• changes in solubility conditions of the solute in the
solution.
• Rate of crystallization
• The crystal particle size can be improved by using
dilute solutions and adding the precipitating
reagent slowly while mixing.
• Since the impurities are usually present in much
smaller amounts than the compound that is being
crystallized, most of the impurities will remain
dissolved in the solvent
 Crystallization

• Crystallization is the (natural or artificial) process

by which a solid forms, where the atoms or
molecules are highly organized into a structure
known as a crystal. Some of the ways by which
crystals form are precipitating from a solution,
melting, or more rarely deposition directly from a
gas.
• Attributes of the resulting crystal depend largely on
factors such as temperature, air pressure, and in
the case of liquid crystals, time of fluid
evaporation.
• Crystallization occurs in two major steps.
• The first is nucleation, the appearance of a
crystalline phase from either a super cooled liquid
or a supersaturated solvent.
• The second step is known as crystal growth, which
is the increase in the size of particles and leads to a
crystal state.
 Process

• The crystallization process consists of two major

events, nucleation and crystal growth which are
driven by thermodynamic properties as well as
chemical properties
• In crystallization Nucleation is the step where the
solute molecules or atoms dispersed in the solvent
start to gather into clusters, on the microscopic
scale (elevating solute concentration in a small
region)
• The clusters need to reach a critical size in order to
become stable nuclei.
 Nucleation

• Critical size depends on factors such as

temperature
• It is at the stage of nucleation that the atoms or
molecules arrange in a defined and periodic
manner that defines the crystal structure and
saturation
• "crystal structure" is a special term that refers to
the relative arrangement of the atoms or
molecules, not the macroscopic properties of the
crystal (size and shape), although those are a result
of the internal crystal structure.
 Primary and secondary Nucleation

• Primary nucleation is the initial formation of a

crystal where there are no other crystals present or
where, if there are crystals present in the system,
they do not have any influence on the process. This
can occur in two conditions.
• The first is homogeneous nucleation, which is
nucleation that is not influenced in any way by
solids. These solids include the walls of the
crystallizer vessel and particles of any foreign
substance.
• The second category, then, is heterogeneous
nucleation. This occurs when solid particles of
foreign substances cause an increase in the rate of
nucleation that would otherwise not be seen
without the existence of these foreign particles.
Homogeneous nucleation rarely occurs in practice
due to the high energy necessary to begin
nucleation without a solid surface to catalyse the
nucleation.
 Crystal Growth

• Size increase of nuclei

• Dynamic process occurs in equilibrium
• Supersaturation is one of the driving forces of
crystallization
• Depending upon the conditions, either nucleation
or growth may be predominant over the other,
dictating crystal size (crystal morphology)
• Phenomenon of polymorphism
 crystallization

• Crystallization from melt

Melting point
Degradation temperature
Enthalpy changes
Heating and cooling rate
 Crystallization process

• Preparation of solution.
– Saturated and super saturated solution
• Filtration.
• Crystal formation (Cooling).
– Decrease in solubility
– Induced crystallization
• Drying of crystals.
 Preparation of Solution

• Solvent selection
– Solubility of solute
– Polarity
– Hydrophilic and lipophilic nature
– Toxicity (Inertness)
– Vapour pressure
– Cooling
• Co-Solvency (Co-Solvent)
 Main crystallization process

• Cooling crystallization
• Evaporative crystallization
• Crystallization variables
• Temperature
• Solvent selection
 Solidification

• The creation of crystalline nuclei.

• The growth of these nuclei into crystals.
• Spontaneously due to cooling an unseeded
solution in the Labile region.
• Deliberate seeding with minute crystals.
• Fortuitous seeding by crystals left from the
previous batch.
• Attrition of existing crystals gives rise to fragments
that act as seeds. Degree of stirring affects this
factor.
• More than 80% of the substances used in
pharmaceuticals, fine chemicals, agrochemicals,
food and cosmetics are isolated or formulated in
their solid form.
• Crystallization is also used as a chemical solid-
liquid separation technique.
• It is used as a process for removing impurities.