Voids (tetrahedral, octahedral) in hexagonal and cubic systems

Another important feature of close-packed structures is the interstitial sites or voids

Two different types of interstitial sites are present in c.p. structures
a. Octahedral holes
Six spheres surround each of these holes: three in layer A
and three in layer B.
For n spheres are in the c.p. array, there are n
octahedral holes.
b. Tetrahedral holes
Four spheres surround each of these holes with centres at
the corners of a tetrahedron
For n spheres are in the c.p. array, there are 2n tetrahedral
holes. 5
In a ccp or fcc structure there are 4 octahedral holes and 8
tetrahedral holes in the unitcell.

Octahedral voids are at edge Tetrahedral voids are at body

centers and body center
(shown with open small
circles)
(½ 0 0), (0 ½ 0), (0 0 ½), (½ ½ ½)
centers of eight small cubes.
(¾ ¼ ¼), (¼ ¾ ¼), (¼ ¼ ¾), (¾ ¾ ¾)
(¼ ¾ ¾), (¾ ¼ ¾), (¾ ¾ ¼), (¼ ¼ ¼)
NaCl structure
Each sodium ion is surrounded by six Cl ion.
Cl ions are arranged in ccp array. All the octahedral holes are filled.

Na at 4b (½, ½, ½)
Cl at 4a (0, 0, 0)
(Edge-Sharing Octahedra along c)

8
 HCP layers and the interstitial voids

A sites

B sites

A sites

Hexagonal close packed array may be represented by a tetragonal cells (three

such cell combine to form full hexagonal unit cell). Each of these tetragonal
cell contains two atoms per unit cell.
Tetrahedral sites: Octahedral sites:
(0 0 3/8), (1/3 2/3 7/8) (2/3 1/3 ¼), (2/3 1/3 ¾)
(1/3 2/3 1/8), (0 0 5/8)
 Structural Aspects
Sphere Packings: Description of some structures

ZnS (Wurzite) structure type (Ex: ZnO, ZnTe, CdS, CdSe, MnS, GaN, SiC)

Hexagonal variant of sphalerite structure is known as wurzite.

the sulfide ions are form hcp arrangement.

Zn ion occupies half of the tetrahedral voids

S
S

Zn
Zn
 Radius ratio rules
From the relative ionic size we can predict the coordination
number in ionic compounds.

X
Coordination Optimum Radius Coordination
Number Ratio (RM / RX) Polyhedron
X M X
4 0.225-0.414 Tetrahedron
X 6 0.414-732 Octahedron
8 0.732-0.902 Cube
9 0.732-0.902 Tricapped Trigonal Prism
12  0.902 Icosahedron

M = metal cation
X= anion
SMALL Atoms/Ions  LOW Coordination Numbers
LARGE Atoms/Ions  HIGH Coordination Numbers
12
NaCl structure
R+/r- = in the range of 0.414-53, so each sodium ion is surrounded by six Cl ion.
Cl ions are arranged in ccp array. All the octahedral holes are filled.

Na at 4b (½, ½, ½)
Cl at 4a (0, 0, 0)
(Edge-Sharing Octahedra along c)

NaCl (CCP; 3 )
 AcBaCbAcBaCb 

NaCl-type: 3 13