BASIC CONCEPTS OF CRYSTAL STRUCTURE

 DEFINITION
A crystal is a solid whose atoms are arranged in a "highly ordered" repeating pattern.
Crystals form in nature when molecules gather to stabilize when liquid starts to cool and harden.
This process is called crystallization

CRYSTAL STRUCTURE
A crystal structure is defined as the particular repeating arrangement of atoms (molecules or ions)
throughout a crystal. Structure refers to the internal arrangement of particles and not the external
appearance of the crystal.

Crystal Structure is obtained by attaching atoms, groups of atoms or molecules. This structure
occurs from the intrinsic nature of the constituent particles to produce symmetric patterns. A small
group of a repeating pattern of the atomic structure is known as the unit cell of the structure. A unit
cell is the building block of the crystal structure and it also explains in detail the entire crystal
structure and symmetry with the atom positions along with its principal axes. The length, edges of
principal axes and the angle between the unit cells are called lattice constants or lattice
parameters.
In a crystal, all of the atoms
(or ions) are arranged in a
regular grid pattern. For
example, in the case of table
salt (NaCl), the crystals are
made up of cubes of sodium
(Na) ions and chlorine (Cl)
ions. Each sodium ion is
surrounded by six chlorine
ions. Each chlorine ion is
surrounded by six sodium
ions. It's very repetitive,
which is exactly what makes
it a crystal.
  LATTICE STRUCTURE
 The crystal lattice refers to the three-dimensional, repeating pattern of points (lattice points) in
space that represents the positions of the fundamental building blocks (atoms, ions, or
molecules) in a crystal.
 It is an abstract geometric framework that defines the spatial arrangement of these points.
 The crystal lattice provides the foundation upon which the crystal structure is built.
 When we connect these straight lines we can get a three-dimensional view of the structure.
This 3D arrangement is called Crystal Lattice also known as Bravais Lattices.

Bravais Lattice refers to the 14 different 3-dimensional configurations into which atoms can be
arranged in crystals. The smallest group of symmetrically aligned atoms which can be repeated in
an array to make up the entire crystal is called a unit cell.
There are several ways to describe a lattice. The most fundamental description is known as the
Bravais lattice. In words, a Bravais lattice is an array of discrete points with an arrangement and
orientation that look exactly the same from any of the discrete points, that is the lattice points are
indistinguishable from one another.
Thus, a Bravais lattice can refer to one of the 14 different types of unit cells that a crystal structure
can be made up of. These lattices are named after the French physicist Auguste Bravais.
BASIC TYPES OF BRAVAIS LATTICES
These basic lattice types represent the fundamental ways in which atoms, ions, or molecules can
be arranged in a three-dimensional repeating pattern.
1. CUBIC LATTICE:
In a cubic lattice, the lattice points are arranged in a simple cube, with lattice parameters (lengths
of the edges) that are all equal and all angles between them are 90 degrees.
There are three subtypes of cubic lattices: simple cubic, body-centered cubic (BCC), and face-
centered cubic (FCC).

Examples: Polonium has a simple cubic structure,

iron has a body-centered cubic structure, and
copper has a face-centered cubic structure.
2. Tetragonal Lattice
A tetragonal lattice has lattice parameters where two of the edge lengths are equal, but the third
edge length is different. The angles between the edges are 90 degrees.
The lattice can be thought of as a stretched or compressed cubic lattice.

Examples of tetragonal Bravais

lattices are – stannic oxide
(simple tetragonal) and
titanium dioxide (body-
centered tetragonal)

3. ORTHORHOMBIC LATTICE
In an orthorhombic lattice, all three edge lengths are different, and all angles between the edges
are 90 degrees.
The orthorhombic lattice is more general than the tetragonal lattice, as it has no requirement for
two edge lengths to be equal.

Examples of Orthorhombic Systems:

 Rhombic Sulphur has a simple orthorhombic structure
 Magnesium sulfate heptahydrate (MgSO4.7H2O) is made up of a base centred
orthorhombic structure.
 Potassium Nitrate has a structure which is body-centered orthorhombic.
 An example of a substance with a face-centered orthorhombic structure is barium
sulfate.
4. RHOMBOHEDRAL (TRIGONAL) LATTICE
A rhombohedral lattice has three equal edge lengths, and all angles between the edges are equal
but not 90 degrees. The angles are typically larger than 90 degrees.
This lattice can be thought of as a distorted cubic lattice.

Calcite and sodium nitrate are made up of simple rhombohedral unit cells

5. HEXAGONAL LATTICE
In a hexagonal lattice, there are three equal edge lengths, with two angles between the edges
equal to 60 degrees and one angle equal to 120 degrees.
The hexagonal lattice can be thought of as a special case of the rhombohedral lattice.

Zinc oxide and beryllium oxide are made up of simple hexagonal unit cells.

6. MONOCLINIC LATTICE
A monoclinic lattice has all different edge lengths and two angles between the edges equal to 90
degrees, while the third angle is different.
It is asymmetric in its lattice parameters.
EXAMPLE:
Monoclinic sulphur (simple
monoclinic) and sodium sulfate
decahydrate (base centered
monoclinic)
7. TRICLINIC LATTICE
The triclinic lattice is the most general type, with all different edge lengths and angles between the
edges that are all different and not restricted to 90 degrees.
It is the least symmetric of all the basic lattice types.

Example of a Triclinic Lattice Crystal is the Potassium Dichromate

 TYPES OF UNIT CELLS

UNIT CELLS & ITS TYPES

Unit cell- smallest portion of a crystal lattice that shows the 3-dimensional pattern of the entire
crystal. It is also known as the building block of the crystal. Unit cell is the smallest group of atoms,
ions or molecules that, when repeated at regular intervals in three dimensions, will produce the
lattice of a crystal system.

Unit cells occur in different varieties called the crystal system.

Crystal System- refers to the classes of crystals, space groups and lattices. To identify the type of
crystal system, it depends on their lattice and atomic structure.
Types of Crystal Systems
1.Cubic Crystal System
2.Tetragonal Crystal System
3.Orthorhombic Crystal System
4.Monoclinic Crystal System
5.Triclinic Crystal System
6.Hexagonal Crystal System
7.Rhombohedron/ Rhombohedral Crystal System

Cubic Crystal System- otherwise known as the Isometric Crystal System. It is the most
symmetrical among the other systems. All the angles are equal to 90°, and all the sides are of the
same length (a = b = c).

3 Types of Cubic Crystal System

1.Primitive Cubic Unit Cell– also called simple cubic crystal system. When constituent particles
are present only on the corner positions of a unit cell.
There are 8 corners in a cube and it contains 1 atom each. A simple cubic crystal system contains
1 atom, and each corner atom is shared by eight unit cells. Hence, each corner atom contributes
⅛ atom to each unit cell.

2.Body-centered Cubic Unit Cell- the constituent particles are present not only on the corner, but
also at the center of the cube.
In a body-centered cell, there are 8 atoms at each corner positions and 1 atom at its body center.
As each corner atom contributed ⅛th to the unit cell, the contribution of those 8 corner atom to the
unit cell is 1 atom. The contribution of the center atom to the unit cell is also 1 as it is not shared
by other unit cell. Hence, the contribution of atoms in a body-centered cubic unit cell is 1+1= 2.

3.Face-centered Cubic Unit Cell- atoms are arranged at the corners and center of each cube
face of the cell.
Since we know that the 8 corner of each unit cell contributed ⅛ atom, it is equivalent to 1 atom.
Also, a cube has 6 faces. Each face on the unit cell consist of 1 atom on the center and is shared
by 6 unit cells. Thus, atom at the center on the face contributed 3 on the unit cell. Hence, the total
contribution of a face-centered cubic unit cell is 1+3=4.

Tetragonal Crystal System- Like the cubic system, the tetragonal system has three axes that all
meet at 90 degrees. It only differs from the isometric system in that the C axis is longer than the A
and B axis which are the same length. (a = b ≠c). The tetragonal crystal shape includes double
and 8-sided pyramids, 4-sided prism, pyrite, and trapezohedrons.
2 Types of Tetragonal Crystal System
1.Simple Tetragonal Unit Cell
2.Body-centered Tetragonal Unit Cell

Orthorhombic Crystal System- They are of different lengths and based on the rhombic structure,
the orthorhombic system contains several crystal shapes, like pyramids, double pyramids,
pinacoids, and rhombic pyramids. (a≠b≠c) and (α=β=y=90°)

4 Types of Orthorhombic Crystal System

1.Simple Orthorhombic Unit cell
2.Body-centered Orthorhombic Unit cell
3.Face-centered Orthorhombic Unit cell
4.Base-centered Orthorhombic Unit cell– also called end-centered orthorhombic unit cell. It is a
type of unit cell in which the points of the lattice are located on the corners of the cell, in addition to
one additional point located at the center of each face of one pair of parallel faces of the cell. As a
result, it possesses particles at each of the four corners and a single particle in the middle of each
of the opposing faces.

Monoclinic Crystal System– The monoclinic lattice has no sides of equal length, but two of the
angles are equal to 90°, with the other angle (usually defined as β) being something other than
90°. It is a tilted parallelogram prism with rectangular bases. (a≠b≠c) and (α=β= 90°, y≠90°)

2 Types of Monoclinic Crystal System

1.Simple Monoclinic Unit Cell
2.End-centered Monoclinic Unit cell

Triclinic Crystal System – it has either no symmetry at all, or that it has only a center of
symmetry. It is the most disordered of all the crystal systems. The term 'triclinic' literally translates
to 'three inclines'. The name is suggestive of the crystal system's unit cell that has three different
inclining axes. Three axes of different lengths define the unit cell, all having different angles, and
none of them is equal to 90 degrees. (a≠b≠c) and (α≠β≠y≠90°)

Hexagonal Crystal System – A hexagonal crystal structure has two angles equal to 90°, with the
other angle ( γsize 12{γ} {}) equal to 120°. For this to happen, the two sides surrounding the 120°
angle must be equal (a = b), while the third side c is at 90° to the other sides and can be of any
length.
Rhombohedral Crystal System– The rhombohedral lattice is also known as trigonal, and has no
angles equal to 90°, but all sides are of equal length (a = b = c), thus requiring only by one lattice
parameter, and all three angles are equal (α = β = γ).

 COORDINATION NUMBER
The coordination number in a crystal, also known as the coordination sphere, is a measure of the
number of neighboring atoms, ions, or molecules that are in direct contact with a central atom or
ion within a crystalline structure.
The coordination number is determined by the nature of chemical bonding and the arrangement of
atoms or ions in the crystal lattice. It can vary depending on the type of crystal and the specific
atom or ion of interest.

 ATOMIC PACKING FACTOR

atomic packing factor or packing fraction is the fraction of volume in a crystal structure that is occupied
by atoms. It is dimensionless and always less than unity. For practical purposes, the APF of a crystal
structure is determined by assuming that atoms are rigid spheres. It is represented mathematically by

The atomic packing factor (APF), also known as the packing fraction, is a dimensionless quantity
used to describe how efficiently atoms or ions are packed within a crystal lattice. It provides
information about the proportion of space within a crystal structure that is actually occupied by the
atoms or ions. The atomic packing factor is a critical parameter in solid-state physics and materials
science.
Different crystal structures, such as cubic, hexagonal, or others, have different atomic packing
factors due to their unique arrangements of atoms or ions. Understanding the APF is important for
predicting the physical and mechanical properties of materials, including their density and
mechanical stability, as well as for engineering and materials design purposes.

REFERENCES
https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/
Physical_Methods_in_Chemistry_and_Nano_Science_(Barron)/
07%3A_Molecular_and_Solid_State_Structure/7.01%3A_Crystal_Structure
https://byjus.com/chemistry/crystal-structure/
https://web.iit.edu/sites/web/files/departments/academic-affairs/academic-resource
center/pdfs/Crystal_Structures.pdf
https://is.muni.cz/el/sci/podzim2018/C7780/um/L2_Crystal_Structures.pdf
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/
Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Physical_Properties_of_Matter/
States_of_Matter/Properties_of_Solids/Crystal_Lattice/Closest_Pack_Structures?
fbclid=IwAR0cSK904fW1W6FwTe2sip4pw33ECoHhVEYZSx67jDb8NYBwPoLSbh7EQd8
https://byjus.com/chemistry/bravais-lattice/
https://www.chemeurope.com/en/encyclopedia/Atomic_packing_factor.html
https://flexbooks.ck12.org/cbook/ck-12-chemistry-flexbook-2.0/section/8.8/primary/les
son/coordination-number-chem/