S3 PG : Monsoon 2020 – 2021

CY7304 : SOLID STATE CHEMISTRY

Dr. Mini Mol Menamparambath

Laboratory for Advanced Materials and Applied Research
Department of Chemistry, NITC
 Types of close packing
 Close packing of hard spheres are also models of the crystal structures
 The packing of the underlying building blocks determines both the shapes of crystals and the angular

relationships between the faces

 ‘hard sphere’ model (Assumption): not as a representation of the structure of atoms, but as a representation
of the structures arising from the packing together of atoms
 Sphere packing problem: densest 3D packing
2D packing
1D packing

Kissing number 2
𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑙𝑒𝑛𝑔𝑔𝑡ℎ
Packing efficiency = = 1 = 100%
𝑡𝑜𝑡𝑎𝑙 𝑙𝑒𝑛𝑔𝑡ℎ

larger voids or gaps (properly called

interstices) between the atoms.
 Types of close packing
 The area belonging to each circle is a square whose are is 4R2,
Square packing Hexagonal packing  The area of the circle is πR2

Densest packing

Close packing directions 2 & 3

Coordination number 4 & 6
 Types of close packing

3D close packing

A A A A A A
C C C C C
B B B B B
A A A A A A
C C C C C
B B B B B
A A A A A A
C C C C C
B B B B B
A A A A A A

First layer A, 2nd layer could be B or C

If 2nd layer is B, 3rd layer could be A or C

Two important close packing

…ABABAB… Hexagonal Close Packing (HCP)

…ABCABC… Cubic Close Packing (CCP)

Courtesy : internet resources

 Types of close packing

Although the hcp and the ccp are the two most common stacking
sequences of close packed layers, some elements have crystal
structures which are ‘mixtures’ of the two!!
neodymium and samarium have the stacking sequence of ABACABAC
 Types of close packing
Unit cells of the hcp and ccp structures : A simple and economical method is now needed to represent
the hcp & ccp crystal structures
The models need to be ‘stripped down’ to the fewest numbers of atoms which show the essential structure and
symmetry. Such ‘stripped-down’ models are called the unit cells of the structures.
Construction of the cubic unit cell of the ccp structure

three close-packed layers separately—two triangular layers of

six atoms and a third layer stripped down to just one atom
• Simple hexagonal structure these are stacked
directly on top of each other, giving an a cube with the bottom corner atom missing
AAA…type of sequence
• hcp structure there is an interleaving layer
nestling in the interstices of the layers below and
above, giving an ABAB…type of sequence
 Types of close packing
ABAB stacking: HCP A A A A A A
C C C C C
B B B
A A A A A A
A A A A A A C C C C C
C C C C C B B B
B B B B B A A A A A A
A A A A A A C C C C C
C C C C C B B B
B B B B B A A A A A A
A A A A A A
C C C C C
B B B B B
A A A A A A

 Centers of all atoms are equivalent and form lattice

 Which unit cell?

Courtesy : internet resources

 Types of close packing
Do all these atoms are equivalent in lattice/ all of them form a lattice?

 Horizontal vector component from a center of A atom to the centroid of the triangle made of A atoms
 From the centroid we need to lift our self to find the B atom
 End up on C site for the same translational vector (for HCP, C is vacant !!)
 A & B have different neighborhoods, centers of A & B are not equivalent
 All A atoms or all B atoms are equivalents, therefore the we can not consider the centers of both
A & B together as a lattice point in HCP
2D unit cell for A layer of HCP: a = b, γ = 120°
3D unit cell of HCP crystal: a = b ≠ c, α = β = 90°, γ = 120°
Courtesy : internet resources
 Types of close packing
Unit cell for HCP crystal

2D unit cell for A layer of HCP: a = b, γ = 120°

3D unit cell of HCP crystal: a = b ≠ c, α = β = 90°, γ = 120°
The unit cell contains only 1 lattice points but two atoms
Courtesy : internet resources
 Types of close packing
3D close packing
A layer atoms

A A A A A A
C C C C C Unit cell has 2 atoms
B B B B B
A A A A A A
C C C C C Only 8 corner atoms forms the
B B B B B
A A A A A A
lattice and the centre of second
C C C C C atom is not a lattice point, unit
B B B B B
A A A A A A cell contains one lattice point

Projection of unit cell

Corners and inside atoms do not have the same neighbourhood

Courtesy : internet resources Lattice: simple hexagonal
 Types of close packing

Centre of all atoms forms a lattice

 Types of close packing

Cubic unit cell can be identified

whose body diagonal is
perpendicular to the staking planes
or 2D planes

Courtesy : internet resources

 Types of close packing

CCP crystal
Lattice FCC
 Voids in close packing
Metals usually take HCP or CCP structures: most of the properties are governed by voids
Metal oxides : smaller atoms in metal oxides
Foreign atoms in steels…etc

Classification of voids (interstices) : Tetrahedral & octahedral

A triangular void pointing up in one closest packed

layer is covered by a triangular void pointing down
4 spheres are arranged on the corners of a tetragon in an adjacent layer
 Voids in close packing
A A A A A A  A sphere in hexagonally close packed A layer, a sphere is
C C C C C surrounded by 6 triangular voids of B & C types
B B B B B
A A A A A A  When layer B is added, all the B sites becomes tetrahedral voids
C C C C C and C becomes octahedral voids
B B B B B
A A A A A A  If the 2nd layer is C, all the C sites becomes tetrahedral voids and B
C C C C C becomes octahedral voids
B B B B B
A A A A A A
 The #of tetrahedral voids belonging to one sphere is
given by ratio,
 A sphere in hexagonally close packed A layer is covering a
triangular void in above and below layer
 2 × 3 = 6 octahedral voids and 2 × 3 + 1 +1 = 8 tetrahedral
voids around each sphere
 Each octahedral void is covered by 6spheres and vice The #of octahedral voids in a closed packing is
versa equal to the # of spheres. Similarly, # of
 The #of octahedral voids belonging to one sphere is given tetrahedral voids in a closed packing is equal to
by ratio, twice the # of spheres.
 Voids in close packing
Coordination number of voids : The number of spheres surrounding the void is called coordination number
The collection of spheres coordinating the sphere representing the void : coordination polyhedron
Types of close packing

Consider a plane passing through

4 coordinating sphere and void

In addition to Td and Oh voids

: cubic voids

Cubical void: The cubical void is generally not found

in closed packed structures, but is generated as a
result of distortions arising from the occupancy of
voids by larger particles. Cubical voids found in simple
cubic unit cell and it is 3-dimensional and has
coordination number eight (8)

r = 0.732R

www.chemzipper.com
 Packing efficiency
…ABABAB… Hexagonal Close Packing (HCP)
…ABCABC… Cubic Close Packing (CCP)
Packing efficiency depends on
arrangements of atoms and type of
packing

Packing efficiency is defined as the percentage of space occupied by constituent particles packed inside the
lattice.

•HCP and CCP structures

•Body-Centred Cubic Structures
Following factors define packing efficiency of unit cell:
•Simple Cubic Lattice Structures
•Volume of Unit Cell
•Number of Atoms in a structure
•Volume of atoms
 Packing efficiency
CCP lattices Looking at the ABCD face of the cube, we see a triangle ABC. Let the radius of the each
sphere ball be ‘r’. Correlating radius and edge of the cube, we proceed as follows:
 Packing efficiency

4 16 3
4 × 3 𝜋𝑟 3 𝜋𝑟
= × 100% = 3 × 100% = 74%
(2 2𝑟) 3 16 2𝑟 3

Total # of atoms = (1/6*12) + (½*2) + (1*3) = 6

Similarly in HCP lattice !!

 Packing efficiency
Body-Centred Cubic Structures
In body-centred cubic structures, the three atoms are diagonally arranged. To find the packing
efficiency we consider a cube with edge length a, face diagonal length b and cube diagonal as c.
 Packing efficiency
Body-Centred Cubic Structures As there are two atoms in the bcc structure the volume of
constituent spheres will be, 2 × (4/3) π r3

Therefore packing efficiency of the body-centred unit cell is 68%

 Packing efficiency
Simple Cubic Lattice if radius of each atom is r and edge length of the cube is a, then
we can correlate them as, a = 2r
Since simple cubic unit cell contains only 1 atom, the volume of
the unit cell with occupied 1 atom will be, 4 / 3 π r3

And volume of unit cell will be ( a3) or ( 2r)3 that is, 8r3

Therefore the packing efficiency of simple unit cell is 52.4%

 Packing efficiency

Significance of Packing Efficiency : Packing efficiency holds importance in

following ways:

It defines structure of solid

It specifies different properties of solids such as density, consistency and

isotropy

Several attributes (electrical, optical and physical) of solids can be derived with
the help of packing efficiency
 The radius ratio rules
 In ideally ionic structures, the CNs of the ions are determined by electrostatic considerations.
 Cations surround themselves with as many anions as possible, and vice versa.
 This maximises the attractions between neighbouring ions of opposite charge and hence maximises the lattice
energy of the crystal

 The size of central atom is limited by the size and number of the coordinating atoms
 The ratio of the size of the central atom to the size of the coordinating atoms can be
expressed by the ratio of their respective radii: radius ratio
Effect of Radius Ratio:
 The coordination number of cations in actual structures are 3, 4, 6, 8 and 12
 4 and 6 are most common in structures having anions in closest packing and 4, 6 or 8 occurs
in almost all close packed structures
 3 occurs in planar complexes and 12 is the CN of like atoms in closest packing
 Rules governing the packing of atoms
 The three-fold coordination of an atom, It is possible to determine the limiting conditions
under which a given CN is possible

 If AB compound composed of equal amounts of A & B, whose radius are rA & rB

 The radius ratio must be at least 0.155 if A atom to touch B atom. Similarly RR
should be ≥ 0.155 if B atom to touch 3 A atoms
 Rules governing the packing of atoms
 If AB compound composed of equal amounts of A & B,  The coordinations 1:1 and 2:2 impose no limitations
whose radius are rA & rB since the atoms can take any size

 The radius ratio must be at least 0.155 if A atom to touch

B atom. Similarly RR should be ≥ 0.155 if B atom to touch
3 A atoms coordinating it

 The rules for ratios of coordination numbers for chemical

composition, AbBa
 Rules governing the packing of atoms
Pauling’s rules: rules that determine the nature of possible arrangements
(strictly to ionic compounds)

Concise statement of the

radius-ratio effect

In a stable structure local

charge neutrality must be
maintained
 Rules governing the packing of atoms
Pauling’s rules: Applications in to actual structures
 Rules governing the packing of atoms
Each Mg atom z = +2 and is tetrahedrally
MgAl2O4 coordinated by 4 O atoms

Each Al atom z = +3 octahedrally coordinated by

6 O atoms

Each O atom z = -2 , received 4 bonds like Mg or

Al
 Rules governing the packing of atoms
Pauling’s rules: rules that determine the nature of possible arrangements
(strictly to ionic compounds)

Concise statement of the

radius-ratio effect

In a stable structure local

charge neutrality must be
maintained

Considered jointly and

cations tend not to share
polyhedron elements
 Rules governing the packing of atoms
Cations tend not to share polyhedron elements
Two unit cubes sharing a corner, an edge and a face
 Higher the charge on the cation,
smaller the coordination number
 Tetrahedra shares corners, Oh shares
both corner and edges, cubes share
corners, edges and faces

√3 (1.73) √2 (1.4)
Separation between two +vly 1
charged cations
 Rules governing the packing of atoms
 If the edge is shared, the mutual repulsion of the two cations will shorten the edge
 Rutile, TiO2
 Opposite edges are shared (O bonding with Ti4+)
 The TiO6 octahedra in rutile share edges in
the c direction and corners in the ab planes.
 While anatase oxygen atoms (red balls) form
edge-sharing distorted octahedra, of which half
are occupied by Ti atoms, and the other half
are vacant providing potential intercalation
sites.
 The space between occupied octahedra, used
for Al intercalation, is larger in anatase than
that in rutile .

A polyhedral representation of the crystal structures of

a) rutile and b) anatase. Silver and red balls represent Ti
and O atoms, respectively.
Journal of Power Sources
Volume 384, 30 April 2018, Pages 249-255
 Rules governing the packing of atoms
 If the edge is shared, the mutual repulsion of the two cations will shorten the edge
 Rutile, TiO2
 Opposite edges are shared (O bonding with Ti4+)
 The TiO6 octahedra in rutile share edges in
the c direction and corners in the ab planes.
 While anatase oxygen atoms (red balls) form
edge-sharing distorted octahedra, of which half
are occupied by Ti atoms, and the other half
are vacant providing potential intercalation
sites.
 The space between occupied octahedra, used
for Al intercalation, is larger in anatase than
that in rutile .

A polyhedral representation of the crystal structures of

a) rutile and b) anatase. Silver and red balls represent Ti
and O atoms, respectively.
Journal of Power Sources
Volume 384, 30 April 2018, Pages 249-255