Basic Structural Chemistry

Crystalline state

Structure types
 Degree of Crystallinity

Crystalline – 3D long range order

Single-crystalline
Polycrystalline - many crystallites of different sizes and orientations
(random, oriented)
Paracrystalline - short and medium range order,
lacking long range order

Amorphous – no order, random

 Degree of Crystallinity

z Single Crystalline

z Polycrystalline

z Semicrystalline

z Amorphous

Grain boundaries
 Crystal Structure

•The building blocks of these two

are identical, but different crystal
faces are developed

• Cleaving a crystal of rocksalt

 Crystals
• Crystal consist of a periodic arrangement of structural motifs = building
blocks
• Building block is called a basis: an atom, a molecule, or a group of atoms
or molecules
• Such a periodic arrangement must have translational symmetry such
that if you move a building block by a distance:

T = n1a + n2b + n3c

where n1 , n2 , and n3 are integers, and a , b , c are vectors.
then it falls on another identical building block with the same
orientation.
• If we remove the building blocks and replace them with points, then we
have a point lattice or Bravais lattice.
Planar Lattice 2D
Five Planar Lattices
Unit Cell: An „imaginary“ parallel sided region of a structure from which the
entire crystal can be constructed by purely translational displacements
Contents of unit cell represents chemical composition

Space Lattice: A pattern that is formed by the lattice points that have identical
environment.

Coordination Number (CN): Number of direct neighbours of a given atom

(first coordination sphere)
 Crystal = Periodic Arrays of Atoms

Translation Vectors c
a, b , c b
Lattice point
(Atom, molecule, group of molecules,…) a

Primitive Cell:
• Smallest building block for
the crystal lattice.
• Repetition of the primitive cell
gives a crystal lattice
 Lattices and Space Groups

Bravais Lattice Crystal Structure

(Lattice point = Basis of (Structural motif = Basis of
Spherical Symmetry) Arbitrary Symmetry)
Number of 7 32
point groups: (7 crystal systems) (32 crystallographic point
groups)

Number of 14 230
space groups: (14 Bravais lattices) (230 space groups)
Seven Crystal Systems
Fourteen Bravais Lattices
 Simple Cubic (SC)
a =b = c Conventional Cell = Primitive Cell
a⊥b⊥c c

b
Add one atom at
Add one atom at the a the center of each
center of the cube face

Face-Centered Cubic (FCC)

Body-Centered Cubic (BCC)
Conventional Unit Cell ≠ Primitive Cell
 Primitive Cell
A primitive cell of the lattice = volume of space translated through all the
vectors in a lattice that just fills all of space without overlapping or leaving
voids.
A primitive cell contains just one Bravais lattice point.
The primitive cell is the smallest cell that can be translated throughout space to
completely recreate the entire lattice.
There is not one unique shape of a primitive cell, many possible shapes.
The primitive cell for the simple cubic lattice is equal to the simple cubic unit
cell (they are identical).

a
a
a
Body-Centered
Cubic (I)
(magenta)
Unit Cell Primitive Cell
 Primitive Cell of BCC
•Rhombohedron primitive cell

The primitive cell is smaller or

0.5√3a equal in size to the unit cell.

The unit cells possesses the

highest symmetry present in the
lattice (for example Cubic).

109o28’
 Primitive Cell of BCC

•Rhombohedron primitive cell

0.5√3a

109o28’•Primitive Translation Vectors:

 Nonprimitive Unit Cell vs. Primitive Cell

a
a Primitive Cell
Face-Centered
Cubic (F)

Unit Cell
a

Rotated 90º
The primitive cell is smaller or equal in size to the unit cell.
The unit cells possesses the highest symmetry present in the lattice (for
example Cubic).
Primitive Cell of FCC

•Angle between a1, a2, a3: 60o

 Index System for Crystal Planes (Miller Indices)
1) Find the intercepts on the axes in terms of the lattice constants a, b, c. The
axes may be those of a primitive or nonprimitive unit cell.

2) Take the reciprocals of these numbers and then reduce to three integers
having the same ratio, usually the smallest three integers. The result
enclosed in parenthesis (hkl), is called the index of the plane.
Miller Indices
Miller Indices
 Crystals and Crystal Bonding

• metallic (Cu, Fe, Au, Ba, alloys )

metallic bonding

• ionic (NaCl, CsCl, CaF2, ... )

Ionic bonds, cations and anions, electrostatic interactions

• covalent (diamond, graphite, SiO2, AlN,... )

atoms, covalent bonding

• molecular (Ar, C60, HF, H2O, organics, proteins )

molecules, van der Waals and hydrogen bonding
 Three Cubic Cells

SC or Primitive (P) BCC (I) FCC (F)

 Cube

a = edge

D d = face diagonl
(d2 = a2 + a2 = 2a2)
a
d
D = body diagonal
a (D2 = d2 + a2 = 2a2 + a2 = 3a2)
a

d = 2 ⋅a D = 3 ⋅a
SC = Polonium
CN 6

Z=1

Space filling 52%

 BCC = W, Tungsten

Z=2

Space filling 68%

D
CN 8 r

Fe, Cr, V, Li-Cs, Ba

BCC
FCC = Copper, Cu = CCP

r
d

Z=4

Space filling 74%

CN 12
Close Packing in Plane 2D
B and C holes cannot be occupied at the same time
Close Packing in Space 3D

Hexagonal Cubic
HCP CCP
hexagonal

cubic
hexagonal cubic
hexagonal cubic
Mg, Be, Zn, Ni, Li, Be, Os, He,
Sc, Ti, Co, Y, Ru

hexagonal

cubic

Cu, Ca, Sr, Ag, Au, Ni, Rh, solid

Ne-Xe, F2, C60, opal (300 nm)
Structures with Larger Motifs
Coordination Polyhedrons
Coordination Polyhedrons
 Space Filling
a = lattice Atom Radius, Number of Space filling
parameter
r Atoms (lattice
points), Z
SC a/2 1 52%

BCC √3a/4 2 68%

FCC √2a/4 4 74%

Diamond √3a/8 8 34%

 CCP = FCC

(ABC) CCP FCC

Close packed layers of CCP are oriented perpendicularly to the

body diagonal of the cubic cell of FCC
Two Types of Voids (Holes)
Tetrahedral Holes T+ Octahedral Holes Tetrahedral Holes T-

N cp atoms in lattice cell

N Octahedral Holes
2N Tetrahedral Holes
 Two Types of Voids (Holes)

Octahedral Holes Tetrahedral Holes

Tetrahedral Holes (2N)

Z=4
number of atoms in the
cell (N)

N=8
number of tetrahedral
holes (2N)
Octahedral Holes (N)

Z=4
number of atoms in
the cell (N)

N=4
number of octahedral
holes (N)
Different Types of Radii
Variation of the electron density
along the Li – F axis in LiF
P – Pauling radius
G – Goldschmidt radius
S – Shannon radius.
 Variation of ionic radii with coordination number

The radius of one ion was fixed to

a reasonable value
(r(O2-) = 140 pm) (Linus Pauling)
That value is then used to compile
a set of self consistent values for
all other ions.
Variation of atomic radii
through the Periodic table
 General trends for ionic radii
1. Ionic radii increase down a group.
(Lanthanide contraction restricts the increase of heavy ions)

2. Radii of equal charge ions decrease across a period

3. Ionic radii increase with increasing coordination number

the higher the CN the bigger the ion

4. The ionic radius of a given atom decreases with increasing charge

(r(Fe2+) > r(Fe3+))

5. Cations are usually the smaller ions in a cation/anion

combination (exceptions: r(Cs+) > r(F-))

6. Frequently used for rationalization of structures:

„radius ratio“ r(cation)/r(anion) (< 1)
 Cation/anion Radius Ratio

CN r/R
optimal radius
12 – hcp/ccp 1.00 (substitution) ratio for
8 – cubic 0.732 – 1.00 given CN
ions are in touch
6 – octahedral 0.414 – 0.732

4 – tetrahedral 0.225 – 0.414

 Structure Map
Dependence of the structure type (coordination number) on the
electronegativity difference and the average principal quantum number
(size and polarizability)
AB compounds
 Lattice Enthalpy
0
The lattice enthalpy change ΔH L is the standard molar enthalpy change for
the following process:

M+(gas) + X-(gas) → MX(solid) 0

ΔH L

Because the formation of a solid from a „gas of ions“ is always exothermic

lattice enthalpies (defined in this way) are usually negative.
If entropy considerations are neglected the most stable crystal structure of a
given compound is the one with the highest lattice enthalpy.
Lattice enthalpies can be determined by a
thermodynamic cycle → Born-Haber cycle

A Born-Haber cycle for KCl

(all enthalpies: kJ mol-1 for normal

conditions → standard enthalpies)

standard enthalpies of

- formation: 438
- sublimation: +89 (K)
- ionization: + 425 (K)
- atomization: +244 (Cl2)
- electron affinity: -355 (Cl)
- lattice enthalpy: x
 Born-Haber cycle
Na+(g) + Cl (g)
0=− ∆Hslučo + ∆Hsubl o+ 1/2 D + IE + EA + L
EA = - 354 kJ mol−1
IE = 502 kJ mol−1 Na+(g) + Cl- (g)

Na(g) + Cl (g)

Na(g) + 1/2 Cl2 (g) ½ D= 121 kJ mol−1

Na(s) + 1/2 Cl2 (g) ∆Hsublo = 108 kJ mol−1 L=?

∆Hslučo = - 411 kJ mol−1

NaCl (s)

0 = 411 + 108 +121 + 502 + (-354) + L

L = − 788 kJ mol−1
all enthalpies: kJ mol-1 for normal conditions → standard enthalpies
Lattice Enthalpy

L = Ecoul + Erep

One ion pair

Ecoul = (1/4πε0) zA zB / d

Erep = B / dn
n = Born exponent
(experimental measurement of
compressibilty)
 Lattice Enthalpy

1 mol of ions
Ecoul = NA (e2 / 4 π ε0) (zA zB / d) A

Erep = NA B / dn
2
Z AZ Be B
L = NAA + NA n
4πε 0 d d
L = Ecoul + Erep

Find minimum dL/d(d) = 0

 Calculation of lattice enthalpies

Coulombic contributions to lattice enthalpies

2
z+ z−e
V AB = −A N
4πε 0 rAB Coulomb potential
of an ion pair

VAB: Coulomb potential (electrostatic potential)

A: Madelung constant (depends on structure type)
N: Avogadro constant
z: charge number
e: elementary charge
εo: dielectric constant (vacuum permittivity)
rAB: shortest distance between cation and anion
 Madelung Constant
Count all interactions in the crystal lattice

Ecoul = (e2 / 4 π ε0)*(zA zB / d)*[+2(1/1) - 2(1/2) + 2(1/3) - 2(1/4) + ....]

Ecoul = (e2 / 4 π ε0)*(zA zB / d)*(2 ln 2)

Madelung constant A
(for linear chain of ions)
= sum of convergent series
 Calculation of the Madelung constant

Cl
3D ionic solids:
Coulomb attraction and
repulsion

Na

Madelung constants:
CsCl: 1.763
NaCl: 1.748
ZnS: 1.641 (wurtzite)
ZnS: 1.638 (sphalerite)
ion pair: 1.0000 (!)

12 8 6 24
A= 6− + − + ... = 1.748... (NaCl)
2 3 2 5 (infinite summation)
 Madelung constant for NaCl

Ecoul = (e2 / 4 π ε0) * (zA zB / d) * [6(1/1) - 12(1/√2) + 8(1/√3) - 6(1/√4) + 24(1/√5) ....]
convergent series
Ecoul = (e2 / 4 π ε0) * (zA zB / d) * A
Madelung Constants for other Structural Types

Structural Type A

NaCl 1.74756

CsCl 1.76267

CaF2 2.519

ZnS Sfalerite 1.63805

ZnS Wurtzite 1.64132

 Born repulsion VBorn

Repulsion arising from

overlap of electron clouds
Because the electron density of atoms decreases
r0 exponentially towards zero at large distances
from the nucleus the Born repulsion shows the
r same behavior

approximation:
B
V Born = n
r
B and n are constants for a given atom type; n can be
derived from compressibility measurements (~8)
 Total lattice enthalpy from Coulomb interaction
and Born repulsion

0
ΔΗ L = Min.(V AB + V Born)
(set first derivative of the sum to zero)

2
0 z+ z−e 1
ΔΗ = −A N (1 − )
L 4πε 0 r0 n
Measured (calculated) lattice enthalpies (kJ mol-1):
NaCl: –772 (-757); CsCl: -652 (-623)
(measured from Born Haber cycle)
 The Kapustinskii equation
Kapustinskii found that if the Madelung constant for a given structure is
divided by the number of ions in one formula unit (ν) the resulting values
are almost constant:

Structure Madel. const.(A) A/ν Coordination

CsCl 1.763 0.88 8:8

NaCl 1.748 0.87 6:6
CaF2 2.519 0.84 8:4
α-Al2O3 4.172 0.83 6:4

→ general lattice energy equation that can be applied to

any crystal regardless of the crystal structure
5
0 1 . 079 ⋅ 10 ν ⋅ z+ z−
ΔΗ = −
L r+ ⋅ r−
Most important advantage of the Kapustinski equation

→ it is possible to apply the equation for lattice

calculations of crystals with polyatomic ions (e.g. KNO3,
(NH4)2SO4 ...).

→ a set of „thermochemical radii“ was derived for further

calculations of lattice enthalpies
 Lattice Enthalpy

Born – Lande El. config. n

2
⎛ 1⎞
He 5
Z AZ Be
L = N AM ⎜1 + ⎟ Ne 7

4πε 0 d ⎝ n⎠ Ar
Kr
9
10
Xe 12

Born – Mayer
2
Z AZ Be ⎛ d ⎞
* d* = 0.345 Å
L = N AM ⎜⎜1 − ⎟⎟
4πε 0 d ⎝ d ⎠
 Lattice Enthalpy

Kapustinski

M/v je přibližně konstantní pro všechny typy struktur

v = počet iontů ve vzorcové jednotce

M je nahrazena 0.87 v, není nutno znát strukturu

Z A Z B ⎛ 0,345 ⎞
L = 1210v ⎜1 − ⎟
d ⎝ d ⎠
 Kapustinski
structure M CN stoichm M/v

CsCl 1.763 (8,8) AB 0.882

NaCl 1.748 (6,6) AB 0.874

ZnS sfalerite 1.638 (4,4) AB 0.819

ZnS wurtzite 1.641 (4,4) AB 0.821

CaF2 fluorite 2.519 (8,4) AB2 0.840

TiO2 rutile 2.408 (6,3) AB2 0.803

CdI2 2.355 (6,3) AB2 0.785

Al2O3 4.172 (6,4) A2B3 0.834

v = the number of ions in one formula unit

 Lattice Enthalpy of NaCl

Born – Lande calculation L = − 765 kJ mol−1

Only ionic contribution

Experimental Born – Haber cycle L = − 788 kJ mol−1

Lattice Enthalpy consists of ionic and covalent contribution

Applications of lattice enthalpy calculations:

→ thermal stabilities of ionic solids

→ stabilities of oxidation states of cations

→ Solubility of salts in water

→ calculations of electron affinity data

→ lattice enthalpies and stabilities of „non existent“
compounds
 Pauling’s Rules
Five principles which could be used to determine the
structures of complex ionic/covalent crystals

Pauling’s Rule no. 1 Coordination Polyhedra

A coordinated polyhedron of anions is formed about each cation.

Cation-Anion distance is determined by sums of ionic radii.

Cation coordination environment is determined by radius ratio.

Coordination Polyhedra
Cation/Anion Radius Ratio

CN r/R

12 – hcp/ccp 1.00 (substitution)

8 – cubic 0.732 – 1.00

6 – octahedral 0.414 – 0.732

4 – tetrahedral 0.225 – 0.414

 Ionic Radii
R.D. Shannon and C.T. Prewitt, Acta Cryst. B25, 925-945 (1969)
R.D. Shannon, Acta Cryst. A32, 751-767 (1976)

As the coordination number (CN) increases, the Ionic Radius increases

Sr 2+
CN Radius, Å
6 1.32
8 1.40 As the oxidation state increases, cations get smaller
9 1.45 (6-fold coordination, in Å)
10 1.50
12 1.58 Mn2+ 0.810
Mn3+ 0.785
Mn4+ 0.670

Ti2+ 1.000
Ti3+ 0.810
Ti4+ 0.745
 Ionic Radii
The radius increases down a group in the periodic table.
The exception - 4d/5d series in the transition metals - the lanthanide contraction

(6-fold coordination, in Å)
Al3+ 0.675
Ga3+ 0.760
In3+ 0.940
Tl3+ 1.025 Right to left across the periodic table the radius decreases

Ti4+ 0.745 (6 coordinate radii, in Å)

Zr4+ 0.86
Hf4+ 0.85 La3+ 1.172
Nd3+ 1.123
Gd3+ 1.078
Lu3+ 1.001
 Pauling’s Rules
Pauling’s Rule no. 2 Bond Strength

The bond valence sum of each ion equals its oxidation state.
The valence of an ion (Vi, equal to the oxidation state of the ion) is equal to a sum of
the valences of its bonds (sij).
In a stable ionic structure the charge on an ion is balanced by the sum of electrostatic
bond strengths (sij) to the ions in its coordination polyhedron.

TiO2 (Rutile) Ti - oxidation state of +4, coordinated to 6 oxygens.

VTi = 4 = 6 (sij) sij = 2/3

The bond valence of oxygen, coordinated by 3 Ti atoms

Vo = 3 (sij) = 3 (-2/3) = -2

Each bond has a valence of sij with respect to the cation and -sij with respect to the
anion.
 Bond Strength
Correlation of the valence of a bond sij with the bond distance dij.

Rij − d ij
sij = exp
b
b = 0.37, Rij is determined empirically from structures where bond distances and ideal
valences are accurately known.

Tables of Rij values for given bonding pairs (i.e. Nb-O, Cr-N, Mg-F, etc.) have been
calculated, just as tables of ionic radii are available.

Use of the bond valence concept

A) To check experimentally determined structures for correctness, or bonding
instabilities
B) To predict new structures
C) To locate light atoms such as hydrogen or Li ion, which are hard to find
experimentally
D) To determine ordering of ions which are hard to differentiate experimentally, such as
Al3+ and Si4+, or O2- and F-
 Pauling’s Rules
Pauling’s Rule no. 3 Polyhedral Linking

The presence of shared edges, and particularly shared faces decreases the
stability of a structure. This is particularly true for cations with large
valences and small coordination number.

Avoid shared polyhedral edges and/or faces.

Polyhedral Linking
The Coulombic interactions - maximize the cation-anion interactions
(attractive), and minimize the anion-anion and cation-cation interactions
(repulsive).
The cation-anion interactions are maximized by increasing the coordination
number and decreasing the cation-anion distance. If ions too close - electron-
electron repulsions.

The cation-cation distances as a function of the cation-anion distance (M-X)

Corner Edge Face

Polyhedron/Sharing
2 Tetrahedra 2 M-X 1.16 MX 0.67 MX
2 Octahedra 2 M-X 1.41 MX 1.16 MX

The cation-cation distance decreases, (the Coulomb repulsion increases) as

the

•degree of sharing increases (corner < edge < face)

•CN decreases (cubic < octahedral < tetrahedral)
•cation oxidation state increases (this leads to a stronger Coulomb repulsion)
 Pauling’s Rules
Pauling’s Rule no. 4 Cation Evasion
In a crystal containing different cations those with large valence and
small coord. number tend not to share anions.

Perovskite, CaTiO3

CaII 12-coordinate CaO12 cuboctahedra share FACES

TiIV 6-coordinate TiO6 octahedra share only VERTICES

 Pauling’s Rules
Pauling’s Rule no. 5 Environmental Homogeneity
the rule of parsimony

The number of chemically different coordination environments for a given

ion tends to be small.

Once the optimal chemical environment for an ion is found, if possible all
ions of that type should have the same environment.
 Characteristic Structures of Solids = Structure
Types

Rock salt NaCl LiCl, KBr, AgCl, MgO, TiO, FeO, SnAs, UC, TiN, ...

Fluorite CaF2 BaCl2, K2O, PbO2 ...

Lithium bismutide Li3Bi

Sphalerite (zinc blende) ZnS CuCl, HgS, GaAs ...

Nickel arsenide NiAs FeS, PtSn, CoS ...

Wurtzite ZnS ZnO, MnS, SiC

Rhenium diboride ReB2

Structure Types Derived from CCP = FCC
Structure Types Derived from CCP = FCC
 Structure Types Derived from CCP = FCC

Anions/cell (= 4) Oct. (Max 4) Tet. (Max 8) Stoichiometry Compound

4 100% = 4 0 M4X4 = MX NaCl
(6:6 coord.)
4 0 100% = 8 M8X4 = M2X Li2O
(4:8 coord.)
4 0 50% = 4 M4X4 = MX ZnS, sfalerite
(4:4 coord.)
4 50% = 2 0 M2X4 = MX2 CdCl2
4 100% = 4 100% = 8 M12X4 = M3X Li3Bi

4 50% = 2 12.5% = 1 M3X4 MgAl2O4,

spinel
 Comparison between structures
with filled octahedral and tetrahedral holes

o/t fcc(ccp) hcp

all oct. NaCl NiAs

all tetr. CaF2 ReB2

o/t (all) Li3Bi (Na3As) (!) problem

½t sphalerite (ZnS) wurtzite (ZnS)

½o CdCl2 CdI2
 Fluorite CaF2 and antifluorite Li2O

Fluorite structure = a face-centered cubic array (FCC)

of cations = cubic close packing (CCP) of cations with
all tetrahedral holes filled by anions = a simple cubic
(SC) array of anions.

Antifluorite structure = a face-centred cubic (FCC)

array of anions = cubic close packing (CCP) of anions,
with cations in all of the tetrahedral holes (the reverse
of the fluorite structure).
 Fluorite (CaF2, antifluorite Li2O)

F / Li

K2[PtCl6], Cs2[SiF6], [Fe(NH3)6][TaF6]2

 Fluorite structures (CaF2, antifluorite Li2O)

Oxides: Na2O, K2O, UO2,

ZrO2, ThO2
alkali metal sulfides,
selenides and tellurides
K2[PtCl6], (NH4)2[PtCl6],
Cs2[SiF6],
[Fe(NH3)6][TaF6]2.

CaF2, SrF2, SrCl2, BaF2, BaCl2, CdF2, HgF2, EuF2, β-PbF2, PbO2

Li2O, Li2S, Li2Se, Li2Te, Na2O, Na2S, Na2Se, Na2Te, K2O, K2S
Fluorite structures (CaF2, antifluorite Li2O)
Sphalerite (zincblende, ZnS)

Cubic close packing of anions

with 1/2 tetrahedral holes
filled by cations
Sphalerite (zincblende, ZnS)
 Sphalerite (zincblende, ZnS)

13-15 compounds: BP, BAs, AlP, AlAs, GaAs, GaP, GaSb, AlSb, InP, InAs, InSb

12-16 compounds: BeS, BeSe, BeTe, β-MnS (red), β-MnSe, β-CdS, CdSe, CdTe, HgS,
HgSe, HgTe, ZnSe, ZnTe

Halogenides: AgI, CuF, CuCl, CuBr, CuI, NH4F

Borides: PB, AsB

Carbides: β-SiC
Nitrides: BN
Diamond
 Diamond
cubic hexagonal
6,16 Å

4,10 Å
2,50 Å

SiO2 cristobalite SiO2 tridymite

ice
Cubic Diamond
 Diamond Structure

C, Si, Ge, α-Sn

• Add 4 atoms to a FCC

• Tetrahedral bond arrangement
• Each atom has 4 nearest neighbors and 12 next nearest neighbors
Elements of the 14th Group
Diamond Lattice (111) Hard Sphere Model
Diamond Lattice (111) Hard Sphere Model
Face Centered Cubic Lattice (111) Hard Sphere Model
Wurzite, ZnS

Hexagonal close packing of anions

with 1/2 tetrahedral holes filled by
cations
 Wurzite, ZnS

ZnO, ZnS, ZnSe, ZnTe, BeO, CdS, CdSe, MnS, AgI, AlN
Semiconductors of 13-15 and 12-16 type
Rock Salt, NaCl

Cubic close packing of anions with all

octahedral holes filled by cations
Rock Salt, NaCl
 Rock Salt, NaCl

Anion and cation sublattices

Rock salt structures (NaCl)
Hydrides: LiH, NaH, KH,
NH4BH4 – H2 storage material

Borides: ZrB, HfB

Carbides: TiC, ZrC, VC, UC

Nitrides: ScN, TiN, UN, CrN, VN, ZrN

Oxides: MgO, CaO, SrO, BaO, TiO, VO, MnO, FeO,

CoO, NiO
Chalcogenides: MgS, CaS, SrS, BaS, α-MnS, MgSe,
CaSe, SrSe, BaSe, CaTe

Halides: LiF, LiCl, LiBr, LiI, NaF, NaBr, NaI, KF,

KCl, KBr, KI, RbF, RbCl, RbBr, AgCl, AgF, AgBr

Intermetallics: SnAs
Other
FeS2 (pyrite), CaC2, NaO2
NiAs - type

Hexagonal close packing of

anions with all octahedral holes
filled by cations

NiS, NiAs, NiSb, NiSe, NiSn, NiTe, FeS,

FeSe, FeTe, FeSb, PtSn, CoS, CoSe,
CoTe, CoSb, CrSe, CrTe, CoSb,

PtB (anti-NiAs structure)

 NiAs - type
Hexagonal close packing of anions with all octahedral holes filled by cations
ReB2 - type

Hexagonal close packing of

anions with all tetrahedral holes
filled by cations
Li3Bi - type (anti BiF3)

[Cr(NH3)6]Cl3, K3[Fe(CN)6]
bcc
Li3Bi - type (anti BiF3)

Fe3Al
[Cr(NH3)6]Cl3
K3[Fe(CN)6]

Cubic close packing of anions

with all tetrahedral and
octahedral holes filled by
cations
CsCl Primitive cubic packing of
anions with all cubic holes
filled by cations

Primitive cubic packing of

CsCl8 cubes sharing all faces
 CsCl

CsCl is not BCC

CsBr, CsI, CsCN, NH4Cl, NH4Br, TlCl, TlBr, TlI, CuZn, CuPd, LiHg
 ReO3

SC of ReO6 octahedra

NaCl structure with 3/4 of cations removed and 1/4 of

anions removed

UO3, MoF3, NbF3, TaF3, Cu3N

 Perovskite, CaTiO3
Two equvivalent views of the unit cell of perovskite

Ti

Ca
Ti O O
Ca
Cubic "close packing" of Ca and O with 1/4 octahedral holes filled by Ti cations
Perovskite structure CaTiO3

TiO6 – octahedra

CaO12 – cuboctahedra

(Ca2+ and O2- form a cubic close packing)

preferred structure of piezoelectric,

ferroelectric and superconducting
materials

Goldschmidt’s tolerance factor

 Perovskite, CaTiO3
Cubic "close packing" of A and X with 1/4 octahedral holes filled by B cations

Similarity to CsCl
Perovskite, CaTiO3

MgSiO3, CaSiO3

KNbO3, KTaO3, KIO3,

NaNbO3, NaWO3, LaCoO3,
LaCrO3, LaFeO3, LaGaO3,
LaVO3, SrTiO3, SrZrO3,
SrFeO3

ThTaN3, BaTaO2N
 Rutile, TiO2

CN – stoichiometry Rule
Ax By
Distorted hexagonal close packing of anions with 1/2
octahedral holes filled by cations (giving a tetragonal
CN(A) / CN(B) = y / x lattice)
 Rutile, TiO2

GeO2, CrO2, IrO2, MoO2, NbO2, β-MnO2, OsO2, VO2

(>340K), RuO2, CoF2, FeF2, MgF2, MnF2
The rutile structure: TiO2

TiO6 – octahedra

OTi3 – trigonal planar

(alternative to CaF2 for highly

charged smaller cations)
The spinel structure: MgAl2O4

fcc array of O2- ions, A2+ occupies

1/8 of the tetrahedral and B3+ 1/2
of the octahedral holes

→ normal spinel:
AB2O4

→ inverse spinel:
B[AB]O4 (Fe3O4):
Fe3+[Fe2+Fe3+]O4

→ basis structure for several

magnetic materials
 Spinel

AB2X4 Spinel normal: Cubic close packing of anions with 1/2 octahedral
holes filled by B cations and 1/8 tetrahedral holes by A cations

MgAl2O4, CoAl2O4, MgTi2O4, Fe2GeO4, NiAl2O4, MnCr2O4

AB2X4 Spinel inverse: As for spinel but A cations and 1/2 of B cations
interchanged

MgFe2O4, NiFe2O4, MgIn2O4, MgIn2S4, Mg2TiO4, Zn2TiO4, Zn2SnO4,

FeCo2O4.
 Garnets
Naturally occuring garnets A3B2Si3O12 = A3B2(SiO4)3

A3 = divalent cation (Mg, Fe, Mn or Ca) dodecahedral

B2 = trivalent (Al, Fe3+, Ti, or Cr) octahedral
Si3 = tetravalent, tetrahedral
Since Ca is much larger in radius than the other divalent cations, there
are two series of garnets: one with calcium and one without:
pyralspite contain Al (pyrope, almandine, spessartine)
ugrandite contain Ca (uvarovite, grossular, andradite)

Synthetic garnets A3B5O12

A3 = trivalent cations, large size (Y, La,…)

B5 = trivalent (Al, Fe3+, Ti, or Cr) 2B octahedral, 3B tetrahedral
Y3Al5O12
Y3Fe5O12
 Garnets
Pyrope Mg3Al2(SiO4)3
Almandine Fe3Al2(SiO4)3
Spessartine Mn3Al2(SiO4)3
Uvarovite Ca3Cr2(SiO4)3
Grossular Ca3Al2(SiO4)3
Andradite Ca3Fe2(SiO4)3
 Garnets
Garnet Y3Al5O12

Y3 = red - dodecahedral
trivalent cations, large size

Al5 = blue
2 octahedral
3 tetrahedral
O12
 Layered Structures

CdI2 Hexagonal close packing of anions with 1/2 octahedral holes filled
by cations

CoI2, FeI2, MgI2, MnI2, PbI2, ThI2, TiI2, TmI2, VI2, YbI2, ZnI2, VBr2,
TiBr2, MnBr2, FeBr2, CoBr2, TiCl2, TiS2., TaS2.

CdCl2 Cubic close packing of anions with 1/2 octahedral holes filled by
cations

CdCl2, CdBr2, CoCl2, FeCl2, MgCl2, MnCl2, NiCl2, NiI2, ZnBr2, ZnI2,
Cs2O* (anti-CdCl2 structure)
CdI2 Hexagonal Close Packing
CdCl2 Cubic Close Packing
CdCl2 Cubic close packing
 High Pressure Transformations

•high pressure phases

•higher density
•higher coodination number
•higher symmetry
•transition to from nonmetal to metal
•band mixing
•longer bonds
Pressure/Coordination Number Rule: increasing pressure – higher CN
Pressure/Distance Paradox: increasing pressure – longer bonds
X-ray structure analysis with single crystals
Principle of a four circle X-ray diffractometer
for single crystal structure analysis
CAD4 (Kappa Axis Diffractometer)
IPDS (Imaging Plate Diffraction System)