Arrangement of atoms in crystals

At the end of this lecture, the students should

be able to:

- Describe the structures of common ionic

solids

- Determine the coordination environments of

the different ions in solids
Common structure may arise from different type
of packing, i.e. CCP, HCP or nonclose-packed.

The lattices are generally consist of the larger

anion, giving available octahedral, tetrahedral,
cubic or possible interstitial sites for cation.

The coordination environment is greatly

influenced by the ionic radii or specifically by
the radius ratio rule.
Some important structures types:
Rock salt Anatase
Zinc blende/Sphalerite Cadmium iodide
Fluorite Cadmium chloride
Antifluorite Caesium oxide
Diamond Perovskite
Wurtzite Rhenium trioxide
Nickel arsenide Spinel
Caesium chloride
Rutile
Table: Common binary solids derived from CCP and HCP packing
Type and fraction of sites
Formula CCP HCP
occupied
NaCl NiAs
AB All octahedral
Rock Salt Nickel Arsenide

Half tetrahedral ZnS ZnS

(T+ or T-) Zinc Blende(Sphalerite) Wurtzite

Na2O Antifluorite
AB2 All tetrahedral not known
CaF2 Fluorite

All octahedral
AB3 Li3Bi not known
& tetrahedral

Half octahedral (Alternate layers CdCl2 CdI2

A2B
full/empty) Cadmium Chloride Cadmium Iodide

Half octahedral (Ordered TiO2 CaCl2

framework arrangement) Anatase TiO2 (Rutile)

Third octahedral
A3B YCl3 BiI3
Alternate layers 2/3 full/empty

adapted from http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/strucsol.html

 The simplest ionic compounds contain just
one type of cation (A) and one type of anion
(B) present in various ratios, covering
compositions such as AB and AB2.

Several different structures may exist for each

of these compositions, depending on:
a) the relative sizes of the cations and anions
b) which holes are filled and to what degree in
the cp array
Structures discussed Rock salt, Fluorite, Antifluorite,
Zinc Blend, Diamond, Cadmium Chloride, Anatase
 CCP array of Cl- with Na+ in all octahedral holes
No. of octahedral holes = no. of ions forming the
array, X (in this case X is Cl-), then filling them
all with A ions (A = Na+) yield the stoichiometry
AX (NaCl).
Coordination: (6, 6) octahedral each ion is
surrounded by 6 counter-ions
Lattice type: fcc
 6 nearest neighbours of the central ion of the
cell - lie at the centres of the faces of the cell
and form an octahedron around the central ion.

Cl-

Na+
 No. of Na+ in a unit cell
Z = (12 edges x 1/4) + (1center x 1)
Cl- = 4 Na+

No. of Cl in a unit cell

Na+ Z = (8 corners x 1/8) + (6 faces x )
= 4 Cl-

Hence, ZNaCI = 4 why not 8?

Hence, each unit cell contains 4 NaCl formula units. The

no. of formula units present in the unit cell is commonly
denoted as Z, so in this case, Z=4.
 CCP Cl- with Na+ in all octahedral holes
Lattice: fcc
Motif: Cl- at (0,0,0); Na+ at (1/2,0,0)
4 NaCl in unit cell
Coordination: 6:6 (octahedral)
Cation and anion sites are topologically identical
adapted from http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/strucsol.html
 Typical examples are CaF2 or CsF
In fluorite, the Ca2+ ions lie in an expanded ccp
array and the F- ions occupy all the tetrahedral
holes.
(8,4)-coordination, which is being consistent with
there being twice as many anions as cations.
Anions in the tetrahedral holes have 4 nearest
neighbours and the cation site is surrounded by a
cubic array of 8 anions.
 No. of F in a unit cell
Z = (8 centers x 1)
=8
No. of Ca2+ in a unit cell
Z = (8 corners x 1/8)
+ (6 faces x )
=4
Z CaF2 = 4
Why not 8 or
Fluorite structure 12?
Coordination number
Ca : F = 8 : 4 (F- in tetrahedral sites)

Useful information from the CN

Ca/ F = 8 /4
Hence, Ca4 F8 Empirical formula = CaF2
 The inverse of the fluorite structure in the sense of the
locations of cations and anions are reversed. e.g. Na2O
Shown by some alkali metal oxides, including Li2O.
The cations occupy all the tetrahedral holes of a ccp
array of anions.
C.N. = Na : O = 4 : 8 (Na+ in tetrahedral site)
This structure is conversely in contrast to the CaF2
fluorite structure. Anion, O2-

Cation, Na+
Z= ? Do it yourself!!
 CCP Ca2+ with F in all
tetrahedral holes
Lattice: fcc
Motif: Ca2+ at (0,0,0); 2F
at (1/4,1/4,1/4) & (3/4,3/4,3/4)

4 CaF2 in unit cell
Coordination: Ca2+ 8
(cubic) : F- 4 (tetrahedral)
In the related Anti-
Fluorite structure cation
and anion positions are
reversed

adapted from http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/strucsol.html

 The structure derived from CCP by S2- giving rise
to FCC for which half of the available tetrahedral
sites are occupied by smaller Zn2+
Only 4 out of 8 tetrahedral sites are occupied, i.e.
T+ or T-
Coordination number =
Zn : S = 4 : 4
Unit formula Z (Zn2+) = ( 4 centers x 1) = 4
Z (S2-) = (8 corners x 1/8) + (6 faces x )
=4
Unit formula for ZnS = 4 Why?
Octahedral 1 : ( 0 0) 2 : (0 0) 3 : (0 0 ) 4 : ( )

Tetrahedral, 5 : ( ) 6: ( ) 7 : ( ) 8 : ( )
T+
Tetrahedral, 9 : ( ) 10 : ( ) 11 : ( ) 12 : ( )
T-
Summary
CCP S2- with Zn2+ in half tetrahedral holes (only T+ {or T-} filled)
Lattice: fcc
4 ZnS in unit cell
Motif: S at (0,0,0); Zn at (1/4,1/4,1/4)
Coordination: 4:4 (tetrahedral)
Cation and anion sites are topologically identical
adapted from http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/strucsol.html
 Important to the semiconductor industry.
The structure can be explained in the form of
zinc blende or sphalerite structure when the
two element in the zinc blende are identical
that is carbon atoms.
ccp array of carbon atoms, with one set of
tetrahedral sites (either T+ and T-) occupied
also by carbon atoms
Note: no different between packing and
interstitial atoms
Carbon atoms are arranged
tetrahedrally (sp3 hybridisation of C)
Each C atom is linked to its neighbors
by four single covalent bonds

The carbon atoms adopt structure similar to that of

Zinc blende, ZnS. FCC array with half tetrahedral
sites occupied.
Image taken from http://chem-guide.blogspot.com/2010/04/allotropes-of-
carbon-including.html
http://www.sv.vt.edu/classes/ESM4714/Student_Proj/class94/a
damzeakes/lattice.html
 The structure can be viewed as CCP array of
chloride anions with alternative of cadmium
cations occupying octahedral sites.
Dark Green FCC array of CI- ion
Solid light Blue- Cd2+ occupying half
available octahedral sites.
Light blue- unoccupied octahedral sites
 The structure is closely related to that of CdI2 and
differs only in the nature of the anion packing: Cl
ions are CCP in CdCl2 and I is HCP in CdI2.
Half the octahedral sites between alternate anion
layers are occupied similar to CdI2
Coordination number Cd : CI = 6 : 3
 Cl- Cd2+
The layers in the picture
continue longways and
sideways, and the stack of
layers upwards and
downwards.
Each Cd2+ ion (green) is
surrounded by six Cl ions
(blue)
Each Cl ion has three
Cd2+ ions on one side, and
three Cl ions from the
next layer on the other
side.
 Coordination
Ti 6 (octahedra)
O 3 (trigonal planar)

Distorted ccp O with Ti in

half of octahedral holes

Polyhedra - Edge-
sharing TiO6 octahedra ,
1/2 vertex- and 1/2 edge-
sharing OTi3 trigonal
slices

Adapted from
http://www.chemtube3d.com/solidstate/_anatase(final).htm
 Grey (larger) sphere- Ti4+
Red (smaller) sphere O2-

http://cst-www.nrl.navy.mil/users/sullivan/TiO2/tio2.html

http://www.chemtube3d.com/solidstate/_anatase(final).htm
Summary
Unit Cell: ?????

2TiO2 per unit cell

Motif: 2Ti at ?????
Ti: 6 (octahedral coordination)
O: 3 (trigonal planar coordination)
TiO6 octahedra share edges in chains along
c-axis
Edge-sharing chains are linked by vertices
Nickel Arsenide, Wurtzite, Cadmium Iodide, Rutile
 HCP array of As with Ni occupying all Octahedral
holes
This structure is adopted by NiS, FeS and a number
of other sulfides.
2 NiAs in unit cell
Coordination number
Ni : As : 6: 6
(Ni should be 6 since it is in octahedral site)
HCP array of As giving rise to
hexagonal unit cell
Position sites (0, 0, 0); (2/3, 1/3, )
c
Ni in the octahedral sites position
sites (1/3, 2/3, 1/4); (1/3, 2/3, 3/4);
Courtesy of picture: Encyclopaedia Britannica, Inc, b
1996 a

 Summary
HCP As with Ni in all
Octahedral holes

Lattice: Hexagonal - P
a = b, c (8/3)a

Motif: 2Ni at (0,0,0) &

(0,0,1/2) 2As at (2/3,1/3,1/4)
& (1/3,2/3,3/4)

2NiAs in unit cell

Coordination: Ni 6
(octahedral) : As 6 (trigonal
prismatic
Taken from
http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/strucsol.html
 Another type of polymorph of ZnS- derived
from different type of closed packing- HCP
Hexagonal lattice type from HCP array of S2-
with Zn2+ in half tetrahedral holes (only T+ {or
T-} filled), just like sphalerite (but CCP) array
Coordination: 4:4 (tetrahedral)
The structure is adopted by ZnO, AgI and one
polymorph of SiC
 Plan view- hexagonal which could be
subdivided into 3 hexagonal unit cells
Plan view
S2 - HCP array of sulfur anions
giving rise to hexagonal unit cell
Position sites (0, 0, 0); (2/3, 1/3, )

Zn2+ in the tetrahedral sites

position sites (2/3, 1/3, 1/8);
(0, 0, 5/8)

(Zn2+)

Z Zn2+ = (4 edges x ) + ( 1 center x 1)

= 2
Z S2- = (8 corners x 1/8) + (1 center x 1)
=2 Hence, unit formula ZnS = 2
Image: http://en.wikipedia.org/wiki/File:Wurtzite_polyhedra.png
 S2- anion

Zn2+
cation

a b c; 90; 120
Summary
HCP S2- with Zn2+ in half Tetrahedral holes (only T+ {or T-} filled)
Lattice: Hexagonal - P
a = b, c (8/3)a
Motif: 2S at (0,0,0) & (2/3,1/3,1/2); 2Zn at (2/3,1/3,1/8) & (0,0,5/8)
2 ZnS in unit cell
Coordination: 4:4 (tetrahedral)
Images taken from
http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/strucsol.html
http://www.geocities.jp/ohba_lab_ob_page/Structure/ZnO_Wurtzite_bond.JPG
 The CdI2 structure is nominally very similar to
rutile because it also has an HCP anion array with
half of the octahedral sites occupied by M2+ ions.
The octahedral holes between every other pair of
hcp layers of I- ions (that is half of the total number
of the octahedral holes) are filled with Cd2+ ions.
CdI2 is therefore a layered structure as the
repeating layers of atoms perpendicular to the
close packed layers form the sequence
I-Cd-I----I-Cd-I----I-Cd-I
With weak van der Waals interactions between the
iodine atoms in the adjacent layers.
I-
Cd2+

Alternatively viewed as
HCP array of I with
alternate layers of
octahedral sites
occupied by Cd2+
 Structure of CdI2
Solid green Iodide anion
Small purple Cadmium
cation

- HCP array of I- giving rise to hexagonal unit cell

Position sites (0, 0, 0); (2/3, 1/3, )

-Cd2+ in the octahedral sites position sites (1/3, 2/3, 3/4);

CdI2 vs NiAs

HCP array of As giving rise to

hexagonal unit cell
Position sites (0, 0, 0); (2/3, 1/3, )

Ni in the octahedral sites position

sites (1/3, 2/3, 1/4); (1/3, 2/3, 3/4);
 Rutile is a mineral form of
titanium(IV) oxide, TiO2 , derived
from expanded hcp anion lattice.

Note: Ti = grey O=red

https://commons.wikimedia.org/wiki/File:Ru
tile-unit-cell-3D-balls.png
 The oxide ions have three nearest neighbour
Ti4+ ions, one at slightly greater distance than
the other two.
The unit cell has Ti4+ ions at the corners and
in the body center.
Two O2- in opposite quadrants of the bottom
face, the other two directly above the first
two in the top face, and two O2- in the plane
with the body-centered Ti4+.
 Coordination - Ti 6 (octahedra) :
O 3 (trigonal planar)

Distorted hcp O with Ti in half of

Oh holes

Polyhedra - Layers of edge-

sharing TiO6 octahedra and
edge-sharing OTi3 trigonal slices
, vertex-sharing between layers

Adapted from
http://www.chemtube3d.com/solidstate/_anatase(final).htm
Grey (larger)
sphere- Ti4+

Red (smaller)
sphere O2-

Image: http://cst-www.nrl.navy.mil/users/sullivan/TiO2/tio2.html
Summary
Unit Cell: Primitive Tetragonal
a b c ; 90
2TiO2 per unit cell
Motif: 2Ti at (0, 0, 0); (1/2, 1/2, 1/2) & 4O at
(0.3, 0.3, 0); (0.8, 0.2, 1 /2)
Ti: 6 (octahedral coordination)
O: 3 (trigonal planar coordination)
TiO6 octahedra share edges in chains along c
Edge-sharing Chains are linked by vertices
Taken from
http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/strucsol.html
 Much less common than the rock-salt structure for
compounds of stoichiometry AX
Has a cubic unit cell with each corner occupied by
an anion and a cation occupying the cubic hole at
the cell centre (or vice versa), as a result, Z=1
Coordination (8:8) (cubic)
Many 1:1 alloys such as AlFe and CuZn, have a
caesium chloride arrangement of the two metal
atom types.
 The primitive nature of the lattice can be seen
by examining just one atom of the motif at a
time (i.e. just Cl or just Cs)
 There are several less common AX structures
FeO at low temperatures, < 90K has a rock salt
structure with a slight rhombohedral distortion (the
angle is increased from 90 to 90.07 by a slight
compression along one threefold axis). This
rhombohedral distortion is associated with
magnetic ordering in FeO at low temperatures.
TlF has a rock salt related structure in which the fcc
cell is distorted into a face centered orthorhombic
cell by changing the lengths of all three cell axes by
different amounts.
 NH4CN has a distorted CsCl structure (as in NH4Cl)
in which the CN- ions do not assume spherical
symmetry but are oriented parallel to face
diagonals. This distorts the symmetry to tetragonal
and effectively increases a relative to c.
 The structure of Cs2O is most unusual as it is
anti-CdCl2.
Cs forms CCP layers and O occupies the
octahedral sites between alternate pairs of Cs
layers.
Coordination no. (6,3)
 O2-

Ca2+
Ti4+
Is the structural
prototype of many ABX3
solids.
Lattice type: Cubic with
each A cation is
surrounded by 12 X
anions and each B cation
is surrounded by 6 X
anions.
Ca2+ 12-coordinate by
O2- (cuboctahedral)
Ti4+ 6-coordinate by
O2- (octahedral) ,O2-
distorted octahedral
(4xCa2+ + 2xTi4+)
 Closely related to the materials that show
interesting electrical properties
piezoelectricity, ferroelectricity, and high
temperature superconductivity.

View 1 = view 2?
 Closely related to perovskite, but without the body centre
atom.
Its unit cell contains Re at corners with O at edge
centers.
Re: 6 (octahedral coordination)
O: 2 (linear coordination)
 Also known as garnet structure is named after the mineral spinel
(MgAl2O4)
Normal spinel structures are usually
CCP array of O2- oxides (one octahedral and two tetrahedral sites)
per oxide.
Unit formula, Z= 8 How many A,B and O ions per unit cell?
B3+ ions - octahedral holes because of a charge factor, only occupy
half of the octahedral holes.
A2+ ions occupy 1/8 of the tetrahedral holes.
in order to maximise the lattice energy if the ions are similar in size.

The general composition is AB2O4. It is essentially cubic, with the

O - ions forming a fcc lattice. (8 fcc by O2-)
 http://en.wikipedia.org/wiki/File:Spinel.GIF

Image: http://www.tf.uni-kiel.de/matwis/amat/def_en/kap_2/basics/b2_1_6.html
 There are a number of important structures
of ionic solids.
These structures differ from each other by
the relative sizes of the cations and anions in
which holes are filled in the structures.