CHAPTER 7

Basic Concepts of Crystal Structure

LEARNING OBJECTIVES
At the end of this lesson, the student should be able to:
1. understand various concepts related to crystalline solids;
2. illustrate the different lattice system;
3. compute for the atomic packing factor and density of the given crystal structure; and
4. appreciate the relevance of crystal structure in the study of engineering.

INTRODUCTION

Solids are substances that have a definite shape and volume. They are highly
incompressible and rigid and have high mechanical strength. The atoms, molecules, and ions
constituting the solid are closely packed and held together by strong intermolecular forces.
The constituent particles occupy fixed positions in the solid and cannot move about freely.
They can only oscillate about their mean positions. A true solid is characterized by a sharp
melting point, a characteristic heat of fusion, incompressibility, and a definite three-
dimensional arrangement.
In crystallography, crystal structure is a description of the ordered arrangement of
atoms, ions, or molecules in a crystalline material. Ordered structures occur from the intrinsic
nature of the constituent particles to form symmetric patterns that repeat along the principal
directions of three-dimensional space in matter (Moore & Smart, 2005).
The smallest group of particles in the material that constitutes the repeating pattern
is the unit cell of the structure. The unit cell completely defines the symmetry and structure
of the entire crystal lattice, which is built up by repetitive translation of the unit cell along its
principal axes. The repeating patterns are said to be located at the points of the Bravais lattice.
The lengths of the principal axes, or edges, of the unit cell and the angles between
them are the lattice constants, also called lattice parameters. The symmetry properties of the
crystal are described by the concept of space groups. All possible symmetric arrangements of
particles in three-dimensional space may be described by the 230 space groups.
The crystal structure and symmetry play a critical role in determining many physical
properties, such as cleavage, electronic band structure, and optical transparency.
Crystal structure is one of the most important aspects of materials science and
engineering as many properties of materials depend on their crystal structures. The basic
principles of many materials characterization techniques such as X-ray diffraction (XRD),
Transmission electron microscopy (TEM) is based on crystallography. Therefore,
understanding the basics of crystal structures is of paramount importance.
Matter exists usually in solid or fluid (liquid, gas) state. According to modern concept
matter classification is specified as condensed state and gaseous state. Solids and liquids come
under condensed state. Any material whose position of constituent particles is fixed can be
regarded as solids.
Solids are characterized by incompressibility, rigidity and mechanical strength. This
indicates that the molecules, atoms or ions that make up as solid is closely packed. Thus, in
solids we will have a well ordered molecular, atomic or ionic arrangement.
 In general, solids can be classified into:
a. Crystalline - particles are orderly arranged (long range order).
b. Amorphous - particles are randomly oriented.
If the atoms or molecules are uniquely arranged in crystalline solid or liquid, we call it
a crystal structure. A crystal possesses long range order and symmetry. The main property of
crystal structure is its periodicity. This periodicity is due to the arrangement of
atoms/molecules in the lattice points. The crystal structure as a whole can be considered as
the repetition of unit cell. For a given crystal structure the shape of unit cell is same but varies
from crystal to crystal (Schaffer et al, 1999).

General Classification of Solids

UNIT CELL

Crystal structure is described in terms of the geometry of arrangement of particles in

the unit cell. The unit cell is defined as the smallest repeating unit having the full symmetry
of the crystal structure. The geometry of the unit cell is defined as a parallelepiped, providing
six lattice parameters taken as the lengths of the cell edges (a, b, c) and the angles between
them (α, β, γ). The positions of particles inside the unit cell are described by the fractional
coordinates (xi, yi, zi) along the cell edges, measured from a reference point. It is only
necessary to report the coordinates of a smallest asymmetric subset of particles. This group
of particles may be chosen so that it occupies the smallest physical space, which means that
not all particles need to be physically located inside the boundaries given by the lattice
parameters. All other particles of the unit cell are generated by the symmetry operations that
characterize the symmetry of the unit cell. The collection of symmetry operations of the unit
cell is expressed formally as the space group of the crystal structure (Atkins & de Paula, 2006).

Unit Cell
 Unit cell can be of primitive as well as non-primitive type. A primitive cell is a minimum
volume unit cell and has only one lattice point in it and the latter contains more than one.

Primitive and non-primitive unit cell

In the given figure below, simple cube is a primitive cell. No. of atoms per unit cell is
one for it. The rest two is non primitive. No. of atoms per unit cell is 2 and 4 respectively.

BRAVAIS LATTICES

The number of lattices that can fill two- or three-dimensional space with periodically
repeating units without leaving gaps or causing overlaps is limited. Therefore, there is a finite
number of different crystal structures, and different crystalline solids may crystalline according
to the same pattern. The metrics of the lattice may be different, but the symmetry is the same
in such cases. Lattices which fill space without gaps are called Bravais lattices. There are five
of them in two dimensions and 14 in three dimensions (Hermann, 2017).

Bravais Lattices in Two Dimensions

The most general and least symmetric Bravais lattice in two dimensions is the oblique
lattice. If the angle between the two lattice vectors is 90°, the higher symmetry of the cell
gives rise to a distinct Bravais lattice, either rectangular or square depending on whether the
unit cell vectors have different length or not. In the case of a rectangular lattice, we can
distinguish between a primitive rectangular lattice and a centered rectangular lattice, which
has an extra lattice point (atom) at the center. The centered rectangular lattice could be set
up as a primitive lattice with lower symmetry (unit cell shown in green), but convention prefers
the more symmetric description. Finally, if the lattice vectors are the same length and the
angle is 120°, we have another special case with higher symmetry, the hexagonal lattice (Ellis
et al, 1995).

Bravais lattices in two dimensions

Bravais Lattices in Three Dimensions

Based on the lattice parameters a, b, c, α, β and γ and applying the restrictions as

above, only 14 types of lattices are possible in three dimensions. One general (triclinic) and
thirteen specials. Only seven different systems of axis are found to be sufficient to represent
all Bravais lattice. This fourteen-space lattice is divided into seven crystal systems (Callister,
2002).
They are triclinic, monoclinic, orthorhombic, tetragonal, trigonal, hexagonal and cubic.

Bravais lattices in three dimensions

ATOMIC COORDINATION

In chemistry, crystallography, and materials science the coordination number, also

called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or
ions bonded to it. The ion/molecule/atom surrounding the central ion/molecule/atom is
called a ligand. This number is determined somewhat differently for molecules than for
crystals.
By considering the arrangement of atoms relative to each other, their coordination
numbers (or number of nearest neighbors), interatomic distances, types of bonding, etc., it is
possible to form a general view of the structures and alternative ways of visualizing them.
Simple cubic, face-centered cubic (FCC) and body-centered cubic (BCC) have
coordination numbers of 6, 8, and 12 respectively (Atkins, 2006).

ATOMIC PACKING FACTOR

In crystallography, atomic packing factor (APF), packing efficiency, or packing fraction

mainly gives us an idea about the arrangement of atoms/ions in solids. It will give the
efficiency with which the available space is being filled by atoms (Callister, 2002).
Packing fraction is defined as the ratio of volume of atoms occupying the unit cell to
the volume of unit cell.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

𝐴𝑃𝐹 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

Following are the calculations of the packing efficiency and atomic radius of the
different types of unit cells:

1. Simple cubic unit cell

Consider a cube of side 'a'. Atoms of radius ‘r’ is placed at the corner. As the
𝑎
spheres are touching each other, a = 2r, or 𝑟 = 2

In a simple cubic structure, the atoms occupy at the eight corners. An atom at
the corner is equally shared by 8 unit cells. So, the contribution of one atom to a unit
cell is 1/8. Therefore the no. of atoms per unit cell is (1/8) * 8 (corner atoms) =1.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎3 = (2𝑟)3 = 8𝑟3

 4
(1 𝑎𝑡𝑜𝑚) (3 𝜋𝑟 3 ) 𝜋
𝐴𝑃𝐹 = = = 𝟓𝟐%
8𝑟 3 6

2. Body centered cubic (BCC) unit cell

Consider a cube of side ‘a’, and atoms of radius ‘r’ are placed at corners and
at the body center. As the sphere at the body center touches the spheres at the
4𝑟
corners, the length of the body diagonal 4r = 𝑎√3, or 𝑎 = 3
√

In a body centered cube, there will be one atom at the center along with 8
corner atoms. This corner atom is shared by 8 unit cells and the atom at the center is
not a shared one. Therefore no. of atoms per unit cell is (1/8) * 8 (corner atoms) + 1
(body center) = 2.

4𝑟 3 64𝑟 3
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎3 = ( 3) =
√ 3√3

4
(2 𝑎𝑡𝑜𝑚𝑠) (3 𝜋𝑟 3 ) 𝜋√3
𝐴𝑃𝐹 = = = 𝟔𝟖%
64𝑟 3 8
( )
3√3

3. Face centered cubic (FCC) unit cell

Consider a cube of length ‘a’ and atoms of radius ’r’ are placed at the corners
4𝑟
as well as at the face center. Length of face diagonal 4r = 𝑎√2, or 𝑎 =
√2

In a face centered cube, each face possesses one atom along with 8 corner
atoms. The atoms at the faces are equally shared by two unit cells. Corner atoms by 8
 unit cells. So, the no. of atoms per unit cell is (1/8) * 8 (corner atoms) + (1/2) * 6 (atoms
at face) = 4.

4𝑟 3 64𝑟 3
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = 𝑎3 = ( 2) =
√ 2√2

4
(4 𝑎𝑡𝑜𝑚𝑠) (3 𝜋𝑟 3 ) 𝜋
𝐴𝑃𝐹 = = = 𝟕𝟒%
64𝑟 3 3√2
( )
2√2

4. Hexagonal close packed unit cell

For the hexagonal close-packed structure, the unit cell (equivalent to 3
primitive unit cells) is a hexagonal prism containing six atoms (if the particles in the
crystal are atoms). Indeed, three are the atoms in the middle layer (inside the prism);
in addition, for the top and bottom layers (on the bases of the prism), the central atom
is shared with the adjacent cell, and each of the six atoms at the vertices is shared with
other five adjacent cells. So the total number of atoms in the cell is 3 + (1/2)×2 +
(1/6)×6×2 = 6. Each atom touches other twelve atoms.

Now let a be the side length of the base of the prism and c be its height. The
latter is twice the distance between adjacent layers, i.e., twice the height of the regular
tetrahedron whose vertices are occupied by (say) the central atom of the lower layer,
two adjacent non-central atoms of the same layer, and one atom of the middle layer
"resting" on the previous three. Obviously, the edge of this tetrahedron is a. If a=2r,
8 2
then its height can be easily calculated to be √3 𝑎, and, therefore, 𝑐 = 4√3 𝑟. So, the
3√3
volume of the hcp unit cell turns out to be 𝑎2 𝑐, that is 24√2𝑟 3 .
2

4
(6 𝑎𝑡𝑜𝑚𝑠) (3 𝜋𝑟 3 ) 𝜋
𝐴𝑃𝐹 = = = 𝟕𝟒%
24√2𝑟 3 3√2

DENSITY CALCULATION

The density of a solid is that of the unit cell, obtained by dividing the mass of the atoms
(n atoms x Matom) and dividing by Vc, the volume of the cell (a3 in the case of a cube). If the
mass of the atom is given in amu (A), then we have to divide it by the Avogadro number to get
Matom. Thus, the formula for the density is:

𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴
Where:
ρ = density
n = no. of atoms
A = atomic/formula weight
Vc = volume of unit cell
NA = Avogadro’s Number

Examples:

1. Polonium crystallizes in a simple cubic pattern with a unit cell length of 3.36 angstrom
(Å). Estimate the density of Po in g/cm3. (1 Å = 1 x 10-8 cm)

Basis: 1 unit cell

Given:
n = 1 atom a = 3.36 x 10-8 cm A = 209 g/mol
Solution:
𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴
𝑔
(1 𝑎𝑡𝑜𝑚) (209 ) 𝒈
𝜌= 𝑚𝑜𝑙 = 𝟗. 𝟏𝟓
𝑎𝑡𝑜𝑚𝑠 𝒄𝒎𝟑
(3.36 x 10 − 8 cm)3 (6.022 𝑥 1023 )
𝑚𝑜𝑙

2. Aluminum has a face-centered cubic unit cell, that is, an atom at each corner of the
unit cell and an atom at the center of each face. The Al-Al distance (2r) is 0.2863 nm.
Calculate the density of aluminum in g/mL. The mass of aluminum atom is 26.98 amu.

Basis: 1 unit cell

Given:
n = 4 atoms A = 26.98 g/mol
2r = 0.2863 nm = 0.2863 x 10-7 cm
Solution:
4r = 2(2r) = 2(0.2863 x 10-7 cm) = 5.726 x 10-8 cm

4𝑟 = 𝑎√2
4𝑟 5.726 x 10−8 cm
𝑎= = = 4.0489 𝑥 10−8 𝑐𝑚
√2 √2

𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴
𝑔
(4 𝑎𝑡𝑜𝑚𝑠) (26.98 ) 𝑔 𝒈
𝜌= 𝑚𝑜𝑙 = 2.70 = 𝟐. 𝟕𝟎
𝑎𝑡𝑜𝑚𝑠 𝑐𝑚3 𝒎𝑳
(4.0489 𝑥 10−8 𝑐𝑚)3 (6.022 𝑥 1023
𝑚𝑜𝑙 )
 3. Chromium has a monoatomic body centered cubic structure with an edge length of
300 pm. Calculate its density if the molar mass of Cr = 52 g/mol.

Basis: 1 unit cell

Given:
n = 2 atoms a = 300 pm = 300 x 10-10 cm A = 52 g/mol
Solution:
𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴
𝑔
(2 𝑎𝑡𝑜𝑚𝑠) (52 ) 𝒈
𝜌= 𝑚𝑜𝑙 = 𝟔. 𝟒𝟎
𝑎𝑡𝑜𝑚𝑠 𝒄𝒎𝟑
(300 x 10−10 cm)3 (6.022 𝑥 1023 )
𝑚𝑜𝑙

EXERCISES

A. Solve the following problems:

1. Molybdenum forms body-centered cubic crystals and at 20°C, the density is 10.3 g/mL.
Calculate the distance between the centers of the nearest molybdenum atoms.
2. An element crystallizes in a body-centered cubic lattice. The edge of the unit cell is
0.286 nm, and the density of the crystal is 7.92 g/cm 3. Calculate the atomic weight of
the element.
3. Austenite form of iron has FCC crystal lattice structure, whereas its alpha form has BCC
crystal lattice structure. Assuming closest packed arrangement of iron atoms, what will
be the ratio of density of Austenite to that of alpha iron?
4. Sodium crystallizes in the body-centered cubic structure with a=0.424 nm. Calculate
the theoretical density of Na in kg/m3.
5. Find the distance (in nm) between the body-centered atom and one corner atom in
Na, given a=0.424 nm.

B. Answer the given question.

1. Compare and contrast the 3 Bravais lattice of the cubic crystal system.
2. How is learning crystal structure relevant in the study of engineering?

KEYWORDS:

1. Amorphous is a non-crystalline solid that lacks the long-range order that is characteristic
of a crystal.
2. Atomic Packing Factor is the ratio of volume occupied by the atoms in a unit cell to the
total volume of the unit cell.
3. Body-centered cubic has lattice points at the eight corners of the unit cell plus an
additional point at the center of the cell.
4. Bravais lattice is the fourteen distinguishable ways of arranging the points independently
in three-dimensional space.
5. Coordination number is defined as the number of equidistant nearest neighbors that an
atom has in a given structure.
6. Crystal lattice is the symmetrical three-dimensional arrangement of atoms inside a crystal.
7. Crystalline is a solid material whose constituents are arranged in a highly ordered
microscopic structure, forming a crystal lattice that extends in all directions.
8. Crystallographic axes are 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.
9. Density is defined as mass per unit volume.
10. Face-centered cubic has lattice points at the eight corners of the unit cell plus additional
points at the centers of each face of the unit cell.
11. Hexagonal close-packed are layers of spheres that are packed so that spheres in
alternating layers overlie one another. As in cubic close packing, each sphere is surrounded
by 12 other spheres.
12. Interfacial angles are the angles between three crystallographic axes.
13. Lattice parameters is a collective term for primitives and interfacial angles.
14. Primitives are the dimensions of a unit cell.
15. Simple cubic is the simplest repeating unit in a simple cubic structure. Each corner of the
unit cell is defined by a lattice point at which an atom, ion, or molecule can be found in
the crystal.
16. 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.
17. Unit cell is the smallest group of atoms of a substance that has the overall symmetry of a
crystal of that substance, and from which the entire lattice can be built up by repetition in
three dimensions.
18. Void space is a vacant space left or unutilized space in unit cell, and more commonly
known as interstitial space.

REFERENCES

1. Agarwal, S. (2019). Engineering chemistry: Fundamentals and applications 2nd edition.

Cambridge University Press.
2. Atkins, P., & de Paula, J. (2006). Atkins’ Physical Chemistry 8th ed. Oxford University
Press. Chapter 20: Materials 2: The Solid State
3. Callister, W. (2002). Materials Science and Engineering (6th ed.). San Francisco, CA: John
Wiley and Sons.
4. Ellis, Arthur B.; et al. (1995). Teaching General Chemistry: A Materials Science
Companion (3rd ed.). Washington, DC: American Chemical Society.
5. Hermann, K. (2017). Crystallography and surface structure : An introduction for surface
scientists and nanoscientists. Retrieved from
https://search.proquest.com/docview/2131386643/9651CF2002EF494EPQ/4?
accountid=31259. Chapter 2 Bulk Crystals: Three-Dimensional Lattices pp 7- 90
6. Hermann, K. (2017). Crystallography and surface structure : An introduction for surface
scientists and nanoscientists. Retrieved from
https://search.proquest.com/docview/2131386643/9651CF2002EF494EPQ/4?
accountid=31259. Chapter 2 Bulk Crystals: Three-Dimensional Lattices pp 7- 90
7. Moore, Lesley E.; Smart, Elaine A. (2005). Solid State Chemistry: An Introduction (3rd
ed.). Boca Raton, Florida: Taylor & Francis, CRC.
8. Schaffer; Saxena; Antolovich; Sanders; Warner (1999). The Science and Design of
Engineering Materials (2nd ed.). New York, NY: WCB/McGraw-Hill.

Prepared by:

ENGR. ARNEL N. BEN

Assistant Professor
College of Engineering
Sultan Kudarat State University