Classification of Ionic Structures

Crystal structures refer to the specific arrangements of atoms, ions, or molecules within a
crystal lattice. In a crystal, these particles are arranged in a regular, repeating pattern, forming
a three-dimensional network. This arrangement gives crystals their characteristic shape and
properties.
The constituents of a solid can be arranged in two general ways: they can form a regular
repeating three-dimensional structure called a crystal lattice, thus producing a crystalline solid,
or they can aggregate with no particular order, in which case they form an amorphous solid
(from the Greek ámorphos, meaning “shapeless”).
Different types of crystal structures exist, such as cubic, tetragonal, orthorhombic,
monoclinic, triclinic, hexagonal, and rhombohedral, each with unique symmetries and
characteristics.
Crystal structures are like the blueprints that determine how atoms, ions, or molecules stack
together in a solid material, much like how bricks fit together to build a wall. These
arrangements repeat in all directions, forming the beautiful shapes we see in crystals. These
repeating units are called Unit Cell.
A unit cell is the smallest repeating structure in a crystal lattice. In other words, it's like a
building block that repeats over and over again to form the entire crystal structure. The
arrangement of atoms or molecules within the unit cell determines the properties of the
crystal.
Unit cells come in different shapes and sizes, depending on the crystal structure and system.
They help us understand how atoms or molecules are arranged within a crystal and provide
insights into the properties of the material.
Parameters of Unit Cell
Parameters of a unit cell describe its size and shape.
Lengths of Edges (a, b, c): These represent the lengths of the edges of the unit cell along the
three crystallographic axes. Each edge may have a different length, defining the size of the
unit cell in each direction.
Angles between Edges (α, β, γ): These parameters represent the angles between the edges
of the unit cell. They define the orientation of the edges with respect to each other. α is the
angle between edges b and c, β is the angle between edges a and c, and γ is the angle between
edges a and b. These angles are usually measured in degrees.
Types of Unit Cell
There are two types of unit cells
• Primitive Unit Cell
• Non-Primitive Unit Cell
Primitive Unit Cell
Primitive Unit Cell are those in which atoms are at corners of the unit cell. One such example
is simple cubic
Simple
• It has the simplest structure, with lattice points located at the corners of a cube.
• Atoms are only present at the corners.
Non-Primitive Unit Cell
In non-primitive unit cell, the atoms are present at corners as well as other parts of unit cell.
There are three types of non-primitive unit cell
➢ Body Centered
➢ Face Centered
➢ Edge Centered
➢ Body-Centered
• In addition to the lattice points at the corners there is one additional lattice point
at the body center
• This structure is denser than the simple and is commonly found in some metals,
such as iron and chromium.
➢ Face-Centered
➢ In addition to the lattice points at the corners of the unit cell, there is one lattice
point at the center of each face of the unit cell
➢ This structure is even denser than the body-centered and is found in many metallic
elements, including aluminum, copper, and gold.
➢ Edge Centered
• In addition to the lattice point at the corners of the unit cell, the lattice points are
present on the center of each edge

Crystal Systems
The different parameters of unit cell generate different types of crystal structures called
Crystal System. There are seven possible crystal with different configuration of unit cell
parameters. The seven crystal systems are:
• Cubic
• Tetragonal
• Orthorhombic
• Monoclinic
• Triclinic
• Rhombohedral
• Hexagonal
Cubic Crystal System
In cubic crystals, all three crystallographic axes are of equal length and intersect each other
at right angles (90 degrees). Examples include common substances like salt (sodium chloride)
and diamonds.
Close Packing In Solids
Close packing in solids is like arranging a bunch of marbles as tightly as possible in a box.
There are two common types of close packing: cubic close packing (CCP) and hexagonal
close packing (HCP). Both types involve stacking layers of spheres in a way that minimizes
empty space between them, resulting in a densely packed structure. Close packing is
important in materials science because it influences the physical and mechanical properties
of solid materials.
Cubic Close Packing (CCP): It's like arranging spheres in layers where the overall 3D
arrangement appears to be a cubic structure. Each sphere touches six other spheres. Then, the
layers are stacked so that the spheres in the first layer A fit into the spaces between the spheres
in the second layer B. The third layer could be positioned directly below the holes in the green
layer forming another uniquely positioned layer, Layer C. This arrangement is referred to as
ABC packing or cubic close packing (CCP)
Hexagonal Close Packing (HCP): It's similar to CCP, but the arrangement of spheres in
each layer forms a hexagon shape. The layers are stacked in a way that the spheres in the first
layer A fit into the spaces between the spheres in the second layer B. Alternatively, the third
layer C could be positioned directly below the second layer similar to that on the first layer -
essentially forming another Layer A as shown following a repeating ABAB... stacking pattern.
This creates a structure with a hexagonal shape.
Both types of close packing exhibit the largest theoretical packing efficiency — there is no
more efficient way to pack spheres. In both cases, 74% of the space is occupied by atoms and
26% of the space is from the holes between the atoms.

Structure of NaCl
➢ The crystal structure of sodium chloride (NaCl), also known as rock salt, is face-
centered cubic (fcc)
➢ The cubic unit cell of NaCl can be represented as a face-centered cubic array of anions
with an interpenetrating fcc cation lattice (or vice-versa).
 ➢ NaCl has a fcc lattice with a two-atom basis. This means that each unit cell contains
four atoms or ions.
➢ The structure can be represented as two separate fcc arrays for the positively charged
cations (Na+) and the negatively charged anions (Cl-). The ions are separated by half
of the body diagonal of the cubic unit cell.
➢ Each ion is surrounded by six ions of the opposite charge.
➢ Na¹⁺ is bonded to six equivalent Cl¹⁻ atoms, and Cl¹⁻ is bonded to six equivalent Na¹⁺
atoms. All Na-Cl bond lengths are 2.79 Å.
➢ NaCl has four cations and four anions in a face-centered cubic unit cell.
Since there are 4 atoms or ions present in each unit cell of a face centred cubic structure,
therefore, the number of NaCl units in a unit cell of NaCl is four.

Structure of ZnS
Zinc Sulphide is an ionic compound of AB type, i.e it has a ratio of 1:1 between cation and
anions. Zinc sulphide has two crystalline forms namely. Zinc Blende and Wurtzite. The more
stable cubic form is known as zinc blende. The hexagonal form is known as the mineral
Wurtzite, although it also can be produced synthetically. In both the structures, stoichiometry
is maintained i.e, 1:1 ratio between Zn and S atoms. The difference between these two
polymorphs arises due to the different arrangement of ions in their structure.

Arrangement of ions in zinc blende unit cell

➢ In the Zinc Blende structure, the ions are arranged in CCP (Cubic Close Packing)
manner. In the CCP arrangement, there are 8 tetrahedral voids and 4 octahedral voids
present.
➢ The S2- ions are present in FCC (Face Centered Cubic) arrangement. i.e The S 2- ions
are present at the corner of the cube and at the centre of each face.
➢ The Zn2+ ions are present in the alternative tetrahedral void.
➢ Each Zn2+ ion is surrounded tetrahedrally by four S2- ions and each S2- ion is surrounded
tetrahedrally by four Zn2+ ions. Thus the structure has 4:4 coordination.
➢ The radius ratio of ZnS is rZn2+ /rS2- = 74/184 = 0.4

Calculate the number of atoms present in the zinc blende unit cell
In the unit cell of Zinc blend (ZnS) structure, numbers of Zn2+ and S2- ions are calculated as:
(a) Number of Zn2+ ions present in alternative tetrahedral voids = 4 (present at the body
centres)
(b) Sulphide (S2-) present in fcc manner,
8 S2– ions present at the corners of the unit cell contribute ⅛ each = 8 × ⅛ = 1
6 S2- ions present at the centre of the face contribute ½ each = 6 × ½ = 3
So the total number of S2- ions present in the unit cell = 1+3 =4

Wurtzite structure of Zinc Sulphide

➢ This structure is different from the Zinc Blende Structure.
➢ In the Wurtzite structure, the sulphide ion is arranged in the hcp (hexagonal close-
packed) structure.
➢ The Zn2+ ions occupy half of the tetrahedral voids.
➢ This structure has a 4: 4 coordination number.
➢ No. of Zn+2 ions per unit cell
= {4 (within the unit cell) × 1} + {6 (at edge centres) × 1/3} = 6
➢ No. of S-2 ions per unit cell
= {12 (at corners) ×1/6} + {2 (at face centres) × ½ } + {3 (within the unit cell) ×1}
=6
➢ Thus, there are 6 formula units per unit cell.

Structure of Cesium chloride (CsCl)

➢ Cesium chloride (CsCl) is an ionic compound that crystallizes in a cubic structure.
➢ The unit cell of cesium chloride is a simple cubic lattice. In this structure, chloride ions
(Cl⁻) are located at the corners of the cube, while cesium ions (Cs⁺) are situated at the
body center of the cube.
 ➢ There are 8 corners in a cubic unit cell, and each corner contributes 1/8 of an ion to the
unit cell. Therefore, the total contribution of chloride ions from the corners is:
Total Cl- ion = 8 x ⅛ = 1
➢ The cesium ion at the body center contributes fully to the unit cell:
Total Cs+ ion = 8 x ⅛ = 1
➢ Thus, in one unit cell of cesium chloride, there is 1 cesium ion and 1 chloride ion. This
leads to the conclusion that the formula unit of cesium chloride is represented as CsCl.
➢ The coordination number refers to the number of nearest neighbors surrounding a given
ion. In the case of cesium chloride each Cs⁺ ion is surrounded by 8 Cl⁻ ions.
and each Cl⁻ ion is also surrounded by 8 Cs⁺ ions. Therefore, the coordination number
for both ions in cesium chloride is 8, which can be expressed as: Cs+ : Cl⁻ = 8 : 8

Fluorite Structure
➢ The fluorite structure is a type of crystal lattice that's common in compounds with the
formula MX2 (example CaF2).
➢ It's characterized by a face-centered cubic (FCC) arrangement of cations, with anions
occupying the tetrahedral sites.
➢ The cations have a coordination number of 8, while the anions have a coordination
number of 4.
➢ The fluorite structure has a large void in the center of the unit cell, which is made up of
cations.
➢ In the fluorite structure of calcium fluoride (CaF2), Ca2+ ions are at the center of a cube
of F − ions, and each F− ion is at the center of a tetrahedron of Ca2+ ions. This structure
is also known as the cubic motif.
➢ The Ca2+ ions are located at the face-centered cubic lattice points.
➢ The F − ions are located in the tetrahedral voids.
➢ The coordination number of Ca2+ ions is 8, and the coordination number of F − ions is
4.
➢ The ratio of F − ions to Ca2+ ions is 2:1, which is consistent with the stoichiometry of
the compound.
➢ The structure can be visualized as a cubic array of anions surrounding the calcium
cations.

Rutile Structure
➢ Rutile is a common crystal structure for AB2 compounds, where A is a metal and B is
oxygen.
➢ Example of Rutile is an oxide mineral composed of titanium dioxide (TiO2)
➢ Rutile has a tetragonal unit cell, with a = b ≠ c
 ➢ The titanium cations have a coordination number of 6, meaning they are surrounded by
an octahedron of 6 oxygen atoms. The oxygen anions have a coordination number of 3,
resulting in a trigonal planar coordination.
➢ The Ti⁴⁺ ions are bonded to six O²⁻ ions.
The layer structure of cadmium iodide (CdI2)
Cadmium iodide is made up of a hexagonal close-packed lattice of iodide anions and cadmium
cations occupying alternating layers of octahedral holes:
Cadmium iodide forms crystals with hexagonal symmetry.
The iodide anions form a hexagonal close packed arrangement while the cadmium cations fill
alternating layers of octahedral sites.
The resultant structure consists of a layered lattice.
Cadmium iodide is mostly ionically bonded but with partial covalent character.
In this structure Cd2+ ions are sandwiched between layers of I- ions

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Questions
Describe the structure of NaCl / CsCl / Zinc blende / Wurtzite / CdI2 / Fluorite / Rutile