Coordination # and Ionic Radii

r cation
• Coordination # increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord ZnS
r anion # (zinc blende)
Adapted from Fig. 3.7,
< 0.155 2 linear Callister & Rethwisch 3e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 3.5,
Callister & Rethwisch 3e.

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic Adapted from Fig. 3.6,
Adapted from Table 3.3, Callister & Rethwisch 3e.
Callister & Rethwisch 3e.
1
 Computation of Minimum Cation-Anion
Radius Ratio
• Determine minimum rcation/ranion for an octahedral site (C.N. = 6)

2ranion  2rcation  2a

a  2ranion
2ranion  2rcation  2 2ranion

ranion  rcation  2ranion rcation  ( 2 1)ranion

rcation
 2  1  0.414
 ranion 
2
 AX Crystal Structures
NaCl (Rock Salt)

rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 Cations (Na+) prefer octahedral sites

Adapted from Fig. 3.5,
Callister & Rethwisch 3e.

3
 FeO
• On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077

Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069  0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is NaCl
Cl - 0.181
F-
Data from Table 3.4,
0.133 Callister & Rethwisch 3e.
4
 MgO
MgO also have the NaCl structure

O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

 cations prefer octahedral sites

Adapted from Fig. 3.5,

Callister & Rethwisch 3e.

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

5
 CsCl
Cesium Chloride structure:

rCs  0.170
  0.939
rCl 0.181

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred

Adapted from Fig. 3.6, So each Cs+ has 8 neighbor Cl-
Callister & Rethwisch 3e.

6
 AX2 Crystal Structures
Fluorite structure

• Calcium Fluorite (CaF2)

• Cations in cubic sites

• UO2, ThO2, ZrO2, CeO2

• Antifluorite structure –
positions of cations and
anions reversed
Adapted from Fig. 3.8,
Callister & Rethwisch 3e.

7
 ABX3 Crystal Structures
• Perovskite structure

Ex: complex oxide

BaTiO3

Adapted from Fig. 3.9,

Callister & Rethwisch 3e.

8
c03tf05