Crystal structures

Structure plays an important role in

understanding properties

Need to be introduced to different ways of
describing structures

Models play an important role in
communicating structural ideas

Structures and properties

The three polymorphs of carbon, diamond,
graphite and C60 have markedly different
properties
– diamond is hard, insulating and insoluble in
common solvents
– graphite is a soft lubricant, semimetallic and
insoluble in common solvents
– C60 is soft and soluble in benzene

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The description of structures

There are two very useful ways of
describing solid structures
– the filling of holes in close packed arrays
– the linking of coordination polyhedra

Both may be applicable to a particular
structure, but one may be more revealing
than the other

Hexagonal close packing

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Unit cell for hcp material
 Note unit cell is not a hexagon shape

Cubic close packing

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Atomic positions in FCC structure

Can represent atoms on unit cell projection drawing
with heights marked

Can also give atomic coordinates
– 0,0,0 0,, ,,0 ,0,
– Only need to specify these four atoms as other a produced
by unit cell translational symmetry

Body centered packing

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Structures of the metallic elements

Many elements adopt close packed structures
– efficient space filling is generally favored
– both hcp and ccp give ~75% space filling
– not obvious why hcp/ccp should be prefered over ccp/hcp
– preference for bcc due to bonding

Cu3Au
 At high temperatures Cu3Au has a random
distribution Cu and Au atoms over the sites
available in a simple FCC structure
– on cooling the the atoms order
» Order-disorder phenomena of this type are quite
common in alloys and compounds

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Holes in cubic close packed structures

Tetrahedral holes

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Octahedral holes

Generalizations about holes in close

packed structures

 There is one octahedral hole per atom in a close

packed array

 There are two tetrahedral holes per atom in a close

packed array

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Structures based on hole filling in
close packed anion arrays

Holes in close packed arrays

Fo rmula ca tio n:a nio n ho le s e xa mple s e xa mple s
co o rdina tio n o ccupie d ccp hcp

MX 6:6 All octa he dra l Na Cl, Fe O,

MnS, TiC
NiAs , Fe S,
NiS

4:4 Ha lf ZnS , CuCl, ZnS, β-AgI

te tra he dra l γ-AgI

MX2 8:4 All

te tra he dra l
Ca F 2 , ThO 2 , No ne
ZrO 2 , Ce O 2

6:3 Ha lf
o ctahe dral
CdCl2 CdI2 , TiS 2

M2X3 6:4 Two-thirds

o ctahe dral
Al2O 3, Fe 2O 3,
V2O 3, Ti2O 3,
Cr2O 3

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Molecular structures
 Many molecular materials pack in a way
that can be described by using close
packing concepts
– Crystalline H2, CH4, and HCl can be described
as close packed as the molecules are
orientationally disordered in the solid state

Solid C60

Buckminster Fullerene (C60) is orientationally
disordered at room temperature a forms a FCC
structure

On cooling the orientational disorder is lost at 249K

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Fullerides
 SolidC60 can be doped with varying
amounts of alkali and other reactive metals
to make “fulleride” salts such as AC60,
A2C60, A3C60, A4C60, A6C60
– show interesting properties such as
superconductivity in Tl2RbC60 at 45K
– structures of simpler compositions can be
described in terms of filling holes in close
packed C60 anion array

Connected polyhedra
 Many structures can be represented as connected
polyhedra
– For example corner, edge or face sharing tetrahedra and
octahedra
» some connectivities are never found as they would bring the
cations at the center of the polyhedra to close together

Do not get face sharing tetrahedra
» Connectivities involving close approach of cations are only found
for compounds with low cation formal charge or high degree of
covalency

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Corner, edge and face sharing

 Going from corner, to edge

to face sharing decreases
the distance between
cations

NaCl, ZnS, Na2O and CaF2 structures

NaCl “Rock Salt”
– All O sites occupied: T+ and T- empty

ZnS “Zinc Blende”
– T+ (or T- ) sites occupied: O and T- (or T+ ) empty

Na2O “Antifluorite structure”
– close packed anions
– All T sites occupied: O empty

CaF2 “Fluorite structure”
– close packed cations – cations not in contact so Eutactic
– All T sites occupied: O empty

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 The NaCl (rock salt) structure

Compounds with the NaCl structure

Typically, do not have soft anion and soft cation

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The ZnS (Zinc Blende) structure

Compounds with the zinc blende structure

Bondingoften more covalent than in materials
with NaCl structure

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Fluorite and antifluorite

Compounds with a fluorite structure

There is no hcp analogue of the fluorite structure

as this would require filling face sharing
tetrahedra

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Wurtzite

Compounds with a Wurtzite structure

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NiAs

Made up from face sharing NiAs6 octahedra
– Short M-M distance favored by compounds that are not
strongly ionic

Compounds with a NiAs structure

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CsCl

CsCl does NOT have a body centered
lattice.

Compounds with a CsCl structure

 Adopted by salts with large cations and some
intermetallics including CsAu

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Other AX structures

Most AX compounds adopt either NaCl, NiAs,
CsCl or ZnS structures
– there are some exceptions
– PbO has Pb2+ in an irregular environment due to the
presence of a stereochemically active lone pair
– FeO at low T is distorted due to magnetic ordering
» Ferromagnetism is not compatible with cubic symmetry

Rutile (TiO2), CdCl2 and CdI2 structures

Formed by filling half of octahedral holes in close
packed array
– CdI2 and CdCl2 are formed by filling all the octahedral sites
between alternate close packed layers in hcp and ccp
lattices respectively
» They are layered structures
– Rutile structure is formed by filling octahedral sites to give
a 3D framework
» Adopted by smaller ions than those usually found in fluorite
structure

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Rutile (TiO2)
 Edge sharing chains bring metal centers close
together; possible metal-metal bonding

Compounds with a Rutile structure

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The CdI2 structure

Layers are held together by Van der Waals forces

Compounds with a CdI2 structure

Noteanions tend to be soft or capable of hydrogen
bonding

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The CdCl2 structure
 Long stacking repeat sequence

Compounds with a CdCl2 structure

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Polyhedral representation of ReO3

ReO3 is a redish colored metallic oxide
– Parent structure for perovskites and may tungsten bronzes
» e.g. NaxWO3 x < 1

Perovskite (CaTiO3)

There are many technologically important materials
with perovskite related structures

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Perovskites

Perovskite is debatably the most important
simple structure type.
– Ferroelectrics, pyroelectrics, piezoelectrics
– Superconductors, semiconductors, metals
– Ferromagnets, antiferromagnets
– Magnetoresistives
– Redox catalysts
– Deep earth mineral, MgSiO3
» octahedral silicon under pressure!!

Example Perovskites

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Distortions of the Perovskite structure

 Many “perovskites” do not have the ideal

cubic structure
– Often octahedra are rotated and/or cations
displaced from their ideal positions
– These displacements and rotations can be
responsible for important physical properties

Tolerance factor

In an ideal cubic perovskite we would predict that
a = 2
rA-O = 2rB-O but there are some deviations from this

A tolerance factor, t = (2
rA-O)/(2rB-O) can be defined

For 0.9< t < 1.0 cubic Perovskite typically forms

For t slightly > 1 a perovskite structure with cation displaced
from the octahedra centers may be formed (BaTiO3 t=1.06)
– This can lead to phenomena such as Ferroelectricity

For t φ 1 another structure with a lower B site coordination
number will be formed

For 0.8 < t < 0.9 a distorted Perovskite typically forms

For t < 0.8 a structure with lower A site coordination forms

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The GdFeO3 structure

Many different types of

octahedral rotations can occur
– These lead to larger unit cells
– Perovskites with 2
ap x 2
ap x 2ap
unit cells are common

Crystals with dipole moments

 Cation displacements in perovskites can lead to
macroscopic dipole
– e.g. BaTiO3
– Displacements lower symmetry in addition to any tilting

Ba
1.86Å

2.00Å
Ti O

2.17Å

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Glazer’s octahedral tilting scheme
 Mike Glazer considered all the possible simple
octahedral tilting schemes
– see Acta Cryst. B28, 3384 (1972)
– restricted discussion to structures with two layer
repeat (2ap x 2bp x2cp) unit cell
» covers most situations that are found in practice
» consider each octahedron to be tiltable by some amount
around each of cubic perovskite axes a, b and c.
» this places restrictions on tilts of neighboring octahedra

Effect of tilting on neighboring octahedra

Ifyou rotate an octahedron in a positive sense about
the c–axis, adjacent octahedra in the a-b plane must
rotate in a negative sense
– has no implications for rotation in next layer down c

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Possible tilt combinations

As rotation around an axis does not require the next
octahedron along the axis to do anything in particular
there are 10 possible tilt combinations compatible with
a two layer repeat
– ignoring special cases where rotation around two or more
axes is the same
no rotation about a-axis

a+b+c+ a+b+c- a+b-c- a-b-c- 3 tilts

Rotation of
2 tilts every second
a0b+c+ a0b+c- a0b-c- a0b+c- octahedron
a0a0c+ a0a0c- 1 tilt along the c-axis
Rotation of all with opposite
a0a0a0 No tilts octahedra along the sense
b-axis with the
same sense

Lattice centering of different tilts

Different tilts give rise to different lattice centering

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Derivation of space group symmetry

After considering possibility of equal magnitude tilts about
different directions 23 possible tilt systems can be derived
– Space group symmetry can be determined by identifying
symmetry elements from drawings

23 possible tilt systems

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Examples of tilted perovskites

Tilt system (10) and (14) are dominant in practice

Pyrochlores

Pyrchlores have the generic
formula A2B2X6X’
– Example La2Sn2O7
– The structure consists of a
framework of corner sharing BX6
octahedra
– Anions X’ may be completely
missing giving rise to defect
pyrochlores such as KTaO3
– Defect pyrochlores are often
readily ion exchangeable
– B ions may be mixed and
structure may be A deficient e.g.
KNbWO6

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Spinel (MgAl2O4)
 Spinelstructure can be viewed as ccp anions
with half of available octahedral holes filled
and 1/8 of tetrahedral holes filled
– Very important structure for magnetic materials

Inversion in Spinels

General formula is AB2O4 fraction of A cations

on octahedral sites determines degree of inversion
– all A cations on tetrahedral sites is a normal Spinel
– all A cations on octahedral sites is an inverse Spinel
– can have anything between normal and inverse in
practice

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Compounds with a Spinel Structure

Note occurrence of 2,3 2,4 1,3,4 and 1,2,5 spinels

Garnets (A3B’2B”3O12)

Ofinterest due to magnetism, optical properties and
abilitiy to function as Laser hosts

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 Al2O3, LiNbO3 and FeTiO3

 The corundum structure consists of a close

packed oxide array with 2/3 of the octahedral
holes filled by cations
 The LiNbO3 structure is closely related to that
of Al2O3 with the Li and Nb ordered in the
occupied octahedral holes
 FeTiO3 (Illmenite) has the same basic
structure as LiNbO3, but it has a different
cation ordering pattern.

Cation ordering in Al2O3, LiNbO3 and FeTiO3

Non-polar Polar

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