Chapter 9 Structural chemistry of ionic

compounds

9.1 The ionic radii ratio and the coordination

polyhedra of ions

Interstices
octahedral holes tetrahedral holes

hole size is 0.414R hole size is 0.225R

CN: 6 CN: 4
Interstice type C.N. rhole /R

Triangular 3 0.155
Tetrahedal 4 0.225
Octahedral 6 0.414
Cubic 8 0.732
Cuboctahedron 12 1.000

The rule of the packing of ions

 Table 1. The limiting ratio of some coorrdination

Coordination polyhedra C.N. minimum r+/r-

Triangular 3 0.155
Tetrahedal 4 0.225
Octahedral 6 0.414
Cubic 8 0.732
Cuboctahedron 12 1.000

9.2 The crystal structures of

Some typical ionic compounds
Answer the following questions:
• The packing style of anions ?
• The position of cations ?
• Crystal System (Bravais Lattice)?
• The C.N. of anion and cation ?
• Atom number in one unit cell?
• Structural formula ?
• Atomic coordinates
 ZnS (0.225-0.414) C.N.+:C.N.- 4:4
(Sphalerite)

• The packing of fcc

anions:
•Bravais Lattice : Cubic F

•The position of ½ Tetrahedral

cations: holes
Zn:S = 4:4 cubic The C.N. of cation 4:4
and anion:
A: 0,0,0; 1/2,1/2,0, 1/2,0,1/2;
0,1/2,1/2 • Atom number in 4:4
one unit cell:
B: 3/4,1/4,1/4; 1/4,3/4,1/4;
1/4,1/4,3/4; 3/4,3/4,3/4

ZnS (0.225-0.414)
(Wurtzite) • The packing of hcp
anions:
•Bravais Lattice : Hexagonal P

•The position of ½ Tetrahedral

cations: holes
The C.N. of cation 4:4
and anion:
Zn:S = 2:2 hexagonal • Atom number in 2:2
A: 0,0,0, 1/3,2/3,1/2 one unit cell:
B: 0,0,3/8; 1/3,2/3,7/8
CuF, CuCl, CuBr, CuI; AgI; ZnO, ZnS, ZnSe, ZnTe; CdO, CdS,
CdSe, CdTe; HgS, HgSe, HgTe
 NaCl (0.732-0.414) Cubic, C.N.+:C.N.- 6:6,

• The packing of fcc

anions:
•Bravais Lattice : Cubic F

•The position of Octahedral

cations: holes
The C.N. of 6:6
Na:Cl = 4:4 cation and anion:
A: 0,0,0; 1/2,1/2,0, 1/2,0,1/2; 0,1/2,1/2 • Atom number 4:4
in one unit cell:
B: 1/2,1/2,1/2; 1/2,0,0; 0,1/2,0, 0,0,1/2
(0.732-0.414) KCl, KBr, SrS, RbI, BaTe, SrSe, CaS, KI, SrTe, MgO,
LiF, CaSe, NaBr, CaTe, MgS, NaI, LiCl, (>0.732) KF, SrO, BaO,
RbF, RbCl, BaS, CuO, CsF, RbBr, BaSe, NaF, (<0.414) MgSe,
LiBr, LiF

NiAs (0.732-0.414) Hexagonal, C.N.+:C.N.- 6:6,

(0.732-0.414) FeS
TiO2 (Rutile) Tetragonal C.N.+:C.N.- =6:3

• The packing of Distorted hcp

anions:
•Bravais Lattice : Tetragonal P

•The position of ½ distorted

cations: octahedral
holes
The C.N. of 6:3
cation and anion:
• Atom number in Ti:O = 2:4
A: 0,0,0; 1/2,1/2,1/2 (Ti) one unit cell:
B: u,u,0, -u,-u,0; 1/2+u, 1/2-u, 1/2; 1/2-u, 1/2+u, 1/2
(0.732-0.414 ) TeO2, MnF2, PbO2, FeF2, CoF2, ZnF2, NiF2, MgF2, SnO2,
NbO2, MoO2, WO2, OsO2, IrO2, RuO2, TiO2, VO2, MnO2, GeO2

CsCl cubic, C.N.+:C.N.- 8:8

• The packing of Cubic

anions:
•Bravais Lattice : Cubic P

•The position of Cubic holes

cations:
The C.N. of 8:8
cation and anion:
• Atom number in 1:1
A: 0,0,0 one unit cell:
B: 1/2,1/2,1/2
CsBr, CsI (1-0.732)
 CaF2 (Fluorite) AB2 type C.N.+:C.N.- =8:4
• The packing of Cubic
anions:
•Bravais Lattice : Cubic F

•The position of ½ Cubic

cations: holes
The C.N. of 8:4
cation and anion:
• Atom number in Ca:F = 4:8
one unit cell:
A: 0,0,0; 1/2,1/2,0, 1/2,0,1/2; 0,1/2,1/2
B: 3/4,1/4,1/4; 1/4,3/4,1/4; 1/4,1/4,3/4; 3/4,3/4,3/4
3/4,3/4,1/4; 3/4,1/4,1/4; 1/4,3/4,3/4; 3/4,1/4,3/4
(>0.732) BaF2, PbF2, SrF2, HgF2, ThO2, CaF2, UO2, CeO2, PrO2, CdF2;
(0.67) ZrF2, HfF2

Rb2O, Li2O --- anti- Fluorite structure type

• The packing of anions?

• The position of cations?
• Bravais Lattice ?
• The C.N. of anion and
cation?
•Atom number in one unit cell?
 Typical Crystal Structures of Binary Component
Structure Structure Anion Cation Coordination
Name Type Packing position Numbers Examples
Cations Anions
Soldium AB FCC All octahedral 6 6 NaCl, MgO,
Chloride holes FeO,LiF, CaO,
NiO
Cesium AB Simple cubic All cubic 8 8 CsCl
chloride holes

Zinc blende AB FCC 1/2 tetrahedral 4 4 ZnS, SiC

holes
(sphalerite)
Wurtize AB HCP 1/2 tetrahedral 4 4 ZnS
holes
Fluorite AB2 Simple cubic 1/2 cubic 8 4 CaF2,ZrO2
holes

Rutile AB2 HCP 1/2 octahedral 6 3 TiO2, MnO2,

holes SnO2

CaTiO3 (perovskite) ABX3

Ca
O

Ti

CaTiO3

YBa2Cu3O7
MgAl2O4 (spinel) AB2X4
O anions form fcc lattice
Mg2+cations (A) in 1/8 tetrahedral holes Al3+ cations
(B) in half of octahedral holes

eg. FeAl2O4, ZnAl2O4, MgAl2O4

anti-spinel B[AB]O4
magnetite (Fe3O4) = spinel ( Fe3+(Fe3+,Fe2+)O4 = B(AB)O4
O anions form fcc lattice
Fe3+ (B) cations in 1/8
tetrahedral holes,
(Fe3+,Fe2+) (A) cations in half of
octahedral holes

Spinel [A]t[BB]oO4
Anti-spinel [B]t[AB]oO4

eg. FeFe2O4, FeMgFeO4

 Summary of Some Common Crystal Structures
Structure Structure Anion Cation Coordination
Name Type Packing position Numbers Examples
Cations Anions
Rock Salt AB FCC All octahedral 6 6 NaCl, MgO,
holes FeO,LiF, CaO,
NiO
Cesium AB Simple cubic All cubic 8 8 CsCl
chloride holes

Zinc blende AB FCC 1/2 tetrahedral 4 4 ZnS, SiC

holes
(sphalerite)
Wurtize AB HCP 1/2 tetrahedral 4 4 ZnS
holes
Fluorite AB2 Simple cubic 1/2 cubic 8 4 CaF2,ZrO2
holes

Rutile AB2 HCP 1/2 tetrahedral 6 3 TiO2, MnO2,

holes SnO2

Perovskite ABX3 FCC(A and X) All octahedral 12(A) 6 BaTiO3, SrTiO3

holes for B 6(B)

Spinel AB2X4 FCC 1/8 octahedral 4(A) 4 MgAl2O4

holes for A
6(B) FeAl2O4
1/2 tetrahedral
holes

9.3 Lattice energy

The calculation and determination of lattice energy

Na+(g) + Cl- (g) ---Æ NaCl (s) + U

Z + Z −e2 12 Z + 8 6 Z+
rr
ε ( Na ) =
+
[6 + + + + ...]
4πε 0 r 2 Z− 3 4 Z−
Z + Z −e2 12 8 6
= [6 − + − + ...]
4πε 0 r 2 3 4
Z + Z −e2
= A
4πε 0 r

A ≈ 1.7476, Madelung constant

 Z + Z −e2
ε ( Na + ) = A
4πε 0 r Z + Z −e2
U = Ec + ER = AN A + Br − m
4πε 0 r
A ≈ 1.7476, Madelung constant ∂U Z + Z −e2 mB
( ) r = re = − AN A − m +1
Similarly, ∂r 4πε 0 re2
re
Z + Z −e2 Z + Z − e 2 AN A m −1
ε (Cl ) =
−
A B=− re
4πε 0 r m4πε 0
N Z + Z − e 2 AN A 1
Ec = A [ε ( Na + ) + ε (Cl − )] U =u = (1 − )
2 4πε 0 re m
Z + Z −e2
= AN A Lattice energy
4πε 0 r
ER = Br − m NaCl: m=8, re=2.8197*10-10m
U = -753kJ/mol
The repulsion energy

ΔHf
The lattice energy calculated Na(s) + 1/2 Cl2(g) -----Æ NaCl
from the Born-Haber cycle | |D Y |U
|S Cl(g)----ÆCl (g)+Na+(g)
-

| I |
Na(g) ------------------------------

Na(s) -Æ Na(g) S=+108.4kJ.mol-1

Na(g) -ÆNa+(g)+e I=+495.0kJ.mol-1
1/2Cl2(g) -ÆCl(g) D=+119.6kJ.mol-1
Cl(g)+e-ÆCl-(g) Y=-348.3 kJ.mol-1
Na(s) + 1/2 Cl2(g) -ÆNaCl ΔHf=-410.9 kJ.mol-1

ΔHf = S+I+D+Y+U
U=ΔHf –(S+I+D+Y)=-785.6 kJ.mol-1
 9.4 Ionic radii
9.4.1 The determination of ionic radii

Lande: (1920) The cell parameters for MnS and MgS as

well as MgSe and MnSe (NaCl structure type) are nearly
identical. Lande suggested that the anions in the structure
were contact with one another. Then
rs2-=2.60/√2 =1.84 A
rse2-=2.73/√2 = 1.93 A

Pauling (1927): Pauling deduced many ionic radii from the

internuclear separations of five different crystal (NaF, KCl,
RbBr, CsI and Li2O) using a semi-empirical method.
The size of an atom are determined by the valence sell
electron distribution which is inversely proportional to the
effective nuclear charge.

r=cn/(Z-σ) = cn/Z*

cn is a constant which is dependent on the quantum number n.

for NaF:
by Slater rule σ=2x0.85 + 8x0.35=4.5
Pauling gave σ a value of 4.52 for Ne type ions;
rNa+ = cn/(11-4.52)
rF-=cn/(9-4.52)
From the experimental value of
rNa+ + rF- = 2.31
Hence: rNa+ =0.95A, rF- = 1.36A, cn=6.15

From the value of cn, one can calculate the radii of all univalent
Ne-like ions:
rO2- = 6.15/(8-4.52)= 1.76 (1.77)A
rMg2+= 0.82 A
rO2- + rMg2+ = 2.58 A >> 2.10 A( the experimental value)

∂U Z + Z −e2 mB
( ) r = re = − AN − =0
∂r 4πε 0 re2 rem +1
A

-m B= [(Z+)(Z-)e2 AN]/( 4πε0)[ rem-1]

Z2rzm-1=12r1m-1
rz=r1 (Z)-2/(m-1)
For Ne-like ions, m=7, Z=2 r2=0.794r1
rO2- = = 1.76*0.794A =1.40A
rMg2+= 0.82 *0.794A =0.65A
 9.4.2 Effective ionic radii

Shannon and Prewitt recompiled the cation-anion separation

data for over a thousand oxide and fluorides. “Effective”
here means that these data were deduced from
experimentally determined values and the sum of the ionic
radii is most consistent with the measured separation
between ions.

9.4.3. The trend of variation of ionic radii

1. In each of the groups IA, IIA, IIIA-ViiA in the periodic table, the
ionic radius of the elements in the same group increases with the
atomic number.
Li+ Na+ K+ Rb+ Cs+
0.76 1.02 1.38 1.52 1.67
2. Within the same period of the periodic table, the ionic radius of
the isoelectronic cations decreases as the positive charge increases.
Na+ 1.02 Mg2+ 0.72 Al3+ 0.535
Au+ 1.37 Hg2+ 1.02 Tl3+ 0.885 Pb4+ 0.775
3. The ionic radii of the various valence states of a particular ion
vary proportionally to the number of electrons present.
Cr2+ 0.80 Cr3+ 0.62 Cr4+ 0.55 Cr6+ 0.44
4. For an isoelectronic pair of anions, the radius increases
slightly as the negative charge increases.
F- 1.33 O2- 1.40
Cl- 1.81 S2- 1.84
Br- 1.96 Se2- 1.98
5. “lanthanide contraction” effect: The six-coordinate
trivalent ionic radii of the lanthanides decreases with increasing
atomic number from 1.032 A of La3+ to 0.861A of Lu3+.
6. For cations in diagonal position (top-left to bottom-right)
of the periodic table, the radii are similar. (Li+ 0.60, Mg2+ 0.65;
Na+ 0.95, Ca2+ 0.99; Sc3+ 0.81, Zr4+ 0.80)

9.5 The Pauling rule of ionic crystal structure

1. The nature of the coordination polyhedra

The coordination number of the cation is determined by the
radius ratio.
2. The electrostatic valence rule
The charge of each anion is exactly of nearly equal to the sum of
the strengths of the electrostatic bonds to it from the adjacent
cations.

Zi
Z − = ∑ si = ∑
i i νi

Si2O76- Z-=4/4+4/4=2 (stable), S2O72- Z-=6/4+6/4=3 (not stable)

Oxygen

3. The rule of vertex-, edge- and face-sharing

The presence of shared edges and especially of shared
faces in a coordinated structure decreases its stability.
9.6 Structural chemistry of silicates

1. Discrete silicates SiO4

2. Infinite chain
silicates
 3. Sheet silicates

3. Three-dimensional network silicates

A-type
Zeolite
Meso-porous compounds
Syntheses
M-MCM-41
Template-ion exchange method

120 C Mn+ calcination

+ Silicate
96 h
aqueous or ethanol
(C16TMA+) solution ion-exchange
M-MCM-41 (TIE)

Direct hydrothermal synthesis method

150 C calcination
+ Silicate + Mn+
48 h

M-MCM-41 (DHT)

M= V, Cr, Mn, Fe, Co, Ni, Cu, Zn

 9.7 Crystals of Functional Materials

• High-Temperature Super-conductive Materials

(YBa2Cu3O7, …)
• Non-linear Optical Crystals (KDP, BBO, …)
• Magnetic Materials
• Piezocrystals
• Optical-electric Materials