CRYSTALLOGRAPHY

What is a crystal?
Crystal is a naturally occurring solid with regular polyhedral form bounded by smooth and
planar surfaces with orderly or regularly arranged atoms, ions or molecules and the outward
orderliness is only the manifestation of internal orderly arrangement of motifs or basis.
Crystalline solid/Crystals and Amorphous solid
A solid that possesses all the properties of a crystal is known as crystalline solid.
Amorphous solids are those solids in which the atoms, molecules or ions are not orderly
arranged and lacks the structure of a crystal but meets other properties of a crystal.

Crystalline state
The term Crystalline state is used to describe substances which apparently may not look like
crystals but possess an orderly internal arrangement of atoms or molecules.
Morphology of Crystals
1) Faces
The crystal is bounded by flat surfaces which are known as faces. A crystal may have only two faces
of the same geometrical shape or it may have up to forty-eight faces of a combination of
geometrical shapes. Faces are produced naturally during the process of crystal growth.

2) Edges
The line of intersection formed by any two adjacent faces in a crystal is call an edge.
 3) Vertex/ Solid angle
The point of intersection of three or more adjacent faces or edges. The angle between three
adjacent faces are called solid angles (In 3 Dimension).
4) Forms
A crystal form is a set of crystal faces that are related to each other by symmetry. To designate a
crystal form (which could imply many faces) we use the Miller Index (singular form)/Miller indices
(plural form).

5) Zones
A zone is a group of similar or dissimilar faces in which the line of intersection between the
said faces are parallel to each other. A zone is denoted using zone symbol. The zone symbol
looks like a Miller Index, but is enclosed in square brackets, i.e. [uvw].
A zone is parallel to the one of the crystallographic axes that passes through the center of
the crystal and that axis is known as Zone axis.
If the given zone is [010], zone axis will be the b crystallographic axis.

6) Interficial angle
In a crystal, the angle between normal of two adjacent faces is called ‘interfacial angle’.
Interfacial angles are measured either with a contact goniometer or a reflecting
goniometer.
7) Plane angle
The angle between two adjacent lines or edges in a 2 dimensional plane.

Contact goniometer and its uses

A contact goniometer consists of two metal rules pivoted together at the centre of a graduated
semicircle. The instrument is placed with its plane perpendicular to an edge between two faces
of the crystal to be measured, and the rules are brought into contact with the faces. The angle
between the rules, as read on the graduated semicircle, then gives the angle between the two
faces.

Law of crystallography
Crystallography is based on three fundamental laws.
(i) Law of constancy of interfacial angles (Steno's Law):
This law states that angle between adjacent corresponding faces, called the inter facial
angles of the crystal of a particular substance, is always constant and independent of shapes
and sizes and mode of growth of crystal. This law is also known as Steno's Law.

(ii) Law of rational indices (Hauy’s Law):

This law states that the intercepts of any face of a crystal along the crystallographic axes
are either equal to unit intercepts or some whole number multiples of them. This law was
given by Hauy.
 (iii) Law of constancy of symmetry:
According to this law, all crystals of a substance have the same elements of symmetry is
plane of symmetry, axis of symmetry and centre of symmetry.
WHAT IS A CRYSTAL STRUCTURE?
A crystal structure is a unique arrangement of atoms, molecules or ions in a crystal. It is
composed of a motif, which is a set of atoms arranged in a particular way, and a lattice. Motifs
are located upon the points of lattice, which is an array of points repeating periodically in three
dimensions. Unit cell is considered as the smallest building block of a crystal structure or simply
the crystal.
Lattice point- A point where the motifs are placed to get a crystal structutre.
Crystal Lattice/Lattice (System of points defining the geometric pattern of a crystal)- Lattice is
the geometrical basis of all the crystals. A lattice can be considered as a regular and infinite
arrangement of points/ atoms where in each point/ atom has the same surrounding
environment. This is equally applicable in one, two and three dimensional space. In 3-D the
lattice is known as Bravais Lattice (Space lattice).In 2-D it is called Plane lattice
Motifs or Basis- It is an atom or group of atoms that is/are located within a lattice to a 2
dimensional or 3 dimensional crystal structure.

Lattice + Motif = Crystal

Unit cell-A unit-cell is the smallest building block of a crystal and is representative unit of the
repetative motifs in the crystal structure.
CRYSTAL SYMMETRY
In well-formed crystals, the symmetrically arranged faces reflect the internal arrangement of
atoms. Symmetry is an operation by which a face of a crystal comes into its congruent (exactly
equal shape and size) position which is indistinguishable from the initial one.

SYMMETRICAL OPERATIONS
These are the set of arrangements to be done with motifs or unit cells within a lattice in order
to obtain the crystal symmetry. There are two types of symmetrical operations: -1) Simple and
2) Compound symmetrical operations
1) Simple Symmetrical Operations
 Translation- It is a symmetric operation which when applied to a lattice point
gives new lattice point that has identical surroundings like initial lattice point.
 Reflection/Mirror symmetry- A crystal lattice is said to have reflection symmetry
if there exist a plane or line in the lattice which divides it into two identical
halves which are mirror images of each other. The change of handedness in the
mirror image is called enantiomorphism.

 Rotation- A crystal is said to have rotation symmetry, its appearance must be

repeated more than once during complete rotation about an axis.

 Inversion- A crystal is said to have an inversion symmetry, if for every lattice

point at position r there exist a lattice point at position –r.

ELEMENTS OF SYMMETRY
In well-formed crystals, the symmetrically arranged faces reflect the internal
arrangement of atoms. The symmetry of individual crystals is determined by
reference to three elements.
a) Axis of Symmetry

The axis of symmetry is a line about which a crystal may be rotated through
360°/n until it assumes a congruent position; n may equal 2, 3, 4, or 6 (but not
1), depending on the number of times the congruent position is repeated. These
correspond respectively to 2-fold (diad), 3-fold (triad), 4-fold (tetrad), and 6-fold
(hexad) axes
if an object can be rotated about an axis and repeats itself every 90o of rotation
then it is said to have an axis of 4-fold rotational symmetry. The axis along which
the rotation is performed is an element of symmetry referred to as a rotation
axis. The following types of rotational symmetry axes are possible in crystals.
1-Fold Rotation Axis - An object that requires rotation of a full 360o in order to
restore it to its original appearance has no rotational symmetry. Since it repeats
itself 1 time every 360o it is said to have a 1-fold axis of rotational symmetry.
2-fold Rotation Axis - If an object appears identical after a rotation of 180o, that
is twice in a 360o rotation, then it is said to have a 2-fold rotation axis (360/180 =
2). Note that in these examples the axes we are referring to are imaginary lines
that extend toward you perpendicular to the page or blackboard. A filled oval
shape represents the point where the 2-fold rotation axis intersects the page.
3-Fold Rotation Axis- Objects that repeat themselves upon rotation of 120o are
said to have a 3-fold axis of rotational symmetry (360/120 =3), and they will
repeat 3 times in a 360o rotation. A filled triangle is used to symbolize the
location of 3-fold rotation axis.
4-Fold Rotation Axis - If an object repeats itself after 90o of rotation, it will
repeat 4 times in a 360o rotation, as illustrated previously. A filled square is used
to symbolize the location of 4-fold axis of rotational symmetry.
6-Fold Rotation Axis - If rotation of 60o about an axis causes the object to repeat
itself, then it has 6-fold axis of rotational symmetry (360/60=6). A filled hexagon
is used as the symbol for a 6-fold rotation axis.
b) Palne of Symmetry

The plane of symmetry (also called the ‘mirror plane’ or ‘symmetry plane’) is a
plane by which the crystal may be divided into two halves which are mirror
images of each other
c) Centre of Symmetry

The centre of symmetry is a central point which is present when all faces or
edges occur in parallel pairs on opposite sides of the crystal. Using these
elements of symmetry, crystallographers have recognized 32 crystal classes and
seven crystal systems. Symmetry is highest (high symmetry) in the cubic system,
where many elements are repeated, and lowest (low symmetry) in the triclinic
system, where only a centre of symmetry may be present (i.e. there may be no
plane or axis of symmetry).

CRYSTALLOGRAPHY AXES AND AXIAL RATIO

The crystallographic axes are imaginary lines that we can draw within the crystal
lattice. These will define a coordinate system within the crystal. For 3-
dimensional space lattices we need 3 or in some cases 4 crystallographic axes
(for hexagonal system) that define directions within the crystal lattices.
Axial ratios are defined as the relative lengths of the crystallographic axes. They
are normally taken as relative to the length of the b crystallographic axis. Thus,
an axial ratio is defined as follows: Axial Ratio = a/b: b/b: c/b where a is the actual
length of the ‘a’ crystallographic axis, b, is the actual length of the ‘b’ crystallographic
axis, and c is the actual length of the ‘c’ crystallographic axis

Intercepts
The actual length of a crystallographic axis from its origin to a plane where it
cuts.
Parameters
The relative intercepts made by a crystal face on the three (or four)
crystallographic axes are known as its parameters.
Classification of crystal systems
In a crystal system, a set of point groups and their corresponding space groups
are assigned to a lattice system. Of the 32 point groups that exist in three
dimensions, most are assigned to only one lattice system, in which case both the
crystal and lattice systems have the same name. However, five point groups are
assigned to two lattice systems, rhombohedral and hexagonal, because both
exhibit threefold rotational symmetry. These point groups are assigned to the
trigonal crystal system. In total there are seven crystal systems: triclinic,
monoclinic, orthorhombic, tetragonal, trigonal, hexagonal, and cubic.
Holohedral
It is that form in a crystal system, which shows development of all the possible
faces in its domain. For instance, octahedron is a holohedral form because it
shows all the eight faces developed on the crystal. Generally, holohedral forms
develop in the crystals of highest symmetry in a crystal system. Such class of
highest symmetry in a system is called its normal class
Hemihedral
It shows, as the name indicates, only half the number of possible faces of a
corresponding holohedral form of the normal class of the same system. As such,
all hemihedral forms may be assumed to have been derived from holohedral
forms.
Hemimorphic
It is also derived from a holohedral form and has only half the number of faces as
in hemihedral form. In this case, however, all the faces of the form are
developed only on one extremity of the crystal, being absent from the other
extremity. In other words, such a crystal will not be symmetrical with reference
to a center of symmetry.
Enantiomorphous
An enantiomorphous form is composed of faces placed on two crystals of the
same mineral in such a way that faces on one crystal become the mirror image of
the form of faces on the other crystal.