IONIC CRYSTAL STRUCTURES

Types of cation sites

Rocksalt Structure
Simple Cubic Anions
Metallic Solids
Conduction properties

This page:
Radius Ratio rules
ZnS Structure
Cesium Chloride Structure
Link to:
Ionic Solids
Chem 101 Homepage

Ccp Anions
Hcp anions
Fluorite Structure
Covalent Solids
Solid State Chemistry page

General Bonding considerations.

For compound (A)n(B)m we can expect ionic bonding to predominate when atom A has low electronegativity and atom B has a high
electronegativity. In this case electron transfer from one atom to another leads to the formation of A+B-. For the main group elements the
electron transfer continues until the ions have closed shell configurations.
For ionic compounds the bonding forces are electrostatic and therefore omni-directional. The bonding forces should be maximized by
packing as many cations around each anion, and as many cations around each anion as is possible. The number of nearest neighbor ions of
opposite charge is called the coordination number. We must realize however that the coordination numbers are constrained by the
stoichiometry of the compound and by the sizes of the atoms.
e.g. For sodium chloride, Na+Cl-, there are 6 anions around each cation (coordination number Na = 6); because of the 1:1 stoichiometry
there must also be 6 Na cations around each Cl anion. For Zr4+O2-2 there are 8 anions around each cation, therefore there must be only 4
cations around each anion.
Simple ionic crystal structures can be approached in terms of the close packing procedures developed for metallic structures. In most (but
by no means all) ionic compounds the anions are larger than the cations. In these cases it is possible to visualize the structures in terms of a
close packed arrangement of the larger anions, with the cations occupying the vacant interstices between the close packed layers. Recall
that although ccp & hcp are the most efficient ways of packing spheres, only 74% of the available space is filled, the 26% "free space" is in
the form of different types of holes or sites which can be occupied by the smaller cations in the ionic structures .
First let us consider the types of holes available in a close packed anion arrangement.

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Types of cations sites available in close packed anion arrays.

As shown below, the stacking of two close packed anion layers produces 2 types of voids or holes. One set of holes are octahedrally
coordinated by 6 anions, the second set are tetrahedrally coordinated by 4 anions. One octahedral site and two tetrahedral sites are created
by each anion in the close packed layer.

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"Stuffing" of the holes by the cations.

Having determined what types of holes are available we must now decide:
(a) Which sites are occupied by a given cation. This determined by the radius ratio (= rcation/ranion)
(b) How many sites are occupied. This is determined by the stoichiometry.
Which sites ?: Radius Ratio rules.
The relative sizes of the anions and cations required for a perfect fit of the cation into the octahedral sites in a close packed anion array can
be determined by simple geometry:

Similarly for a perfect fit of a cation into the tetrahedral sites it can be shown that rcation/ranion = 0.225.
For these two "ideal fit" radius ratios the anions remain close-packed.
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Stable Bonding Configurations in Ionic solids.
In reality an ideal fit of a cation into the close packed anion arrangement almost never occurs . Now consider what would be the
consequence of placing a cation that is (a) larger than the ideal, (b) smaller than the ideal, into the cation sites.

For a stable coordination the bonded cation and anion must be in contact with each other.
If the cation is larger than the ideal radius ratio value the cation and anion remain in contact, however the cation forces the anions apart.
This is not a problem as there is no need for the anions to remain in contact.
If the cation is too small for the site then the cation would "rattle" and would not be in contact with the surrounding anions. This is an
unstable bonding configuration.
Note however in a few rare cases solids do contain cations that are too small for their sites, in these cases the cation moves off the center of
the site and adopt a distorted octahedral coordination. These solids typically exhibit novel properties, such as, for example, ferroelectricity
and piezoelectricity.
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Summary, Radius ratio rules for close packed anion structures.

Ccp Anion Packing: Examples.

Now we know how to determine which sites will be filled, we place the appropriate number of cations into the structure, making sure that
we observe the correct stoichiometry. The figure below shows a view of the octahedral and tetrahedral interstices that are available in the
fcc cell of a ccp anion arrangement . By filling these to differing degrees a number of very common types of crystal structures can be
produced.

Circles labeled O represent centers of the octahedral interstices in the Circles labeled T represent the centers of the tetrahedral interstices
ccp arrangement of anions (fcc unit cell). The cell "owns" 4 octahedral in the ccp arrangement of anions. The cell "owns" 8 tetrahedral
sites.
sites.
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Cubic Close Packed (FCC) Anion Arrangement:

Summary of Possible Cation Occupancies & Structure Types
The table below shows several structure types that result from different site filling schemes. We will focus on two of them: the rocksalt
structure and the ZnS structure.
# Anions/cell
(always = 4)

Oct. sites filled

(Maxm. = 4)

Tet. sites filled

(Maxm. = 8)

Stoichiometry

Examples

100% = 4

M4X4 = MX

100% = 8

M8X4 = M2X

50% = 4

M4X4 = MX

50% = 2

M2X4 = MX2

NaCl, rocksalt
(6:6 coordination)
K2O
(4:8 coordination)
ZnS, zincblende
(4:4 coordination)
CdCl2

100% = 4

100% = 8

M12X4 = M3X

no examples known

50% = 2

12.5% = 1

M3X4

MgAl2O4, spinel

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Rocksalt (Sodium chloride, NaCl) Structure.

Anions ccp (fcc). Radius Na+ = 1.02, radius Cl- = 1.81; radius ratio = 0.563.
Therefore Na octahedral.
1 octahedral / anion therefore 100% octahedral sites are filled.
Coordination # Na = 6; coordination # Cl = 6.
The figure below shows the filling of the octahedral sites by Na (green) within the
ccp (ABCABC) anion (red) array.

This figure shows the face centered cubic unit cell of

the NaCl structure.

Note that there is an fcc arrangement of the Na cations and Cl anions.

We can make sense of the cell contents using our knowledge of lattices. For an fcc lattice there are 4 lattice points per cell, the motif in this
case is a Na cation and a Cl anion. Therefore the cell contents are 4 Na cations + 4 Cl anions.

Lattice parameter and Density calculations.

The cation and its nearest neighbor anions are, by definition in contact.
Therefore the cell edge = 2r(Na+) + 2r(Cl-) = 2(1.02) + 2(1.81) = 5.66
Knowing the size of the cell and its contents, the density of solid NaCl can be calculated using the same procedures used earlier for the
metallic structures.
Other examples of solids with the rocksalt structure:
Many halides and oxides have this structure. Examples include: LiF, LiCl,LiBr,LiI,NaBr,NaI, NaF, KF,
KCl,KBr,KI,RbF,RbCl,MgO,CaO,SrO,BaO,TiO,VO,MnO,FeO,CoO, NiO,CdO, etc.
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Zincblende (Zinc sulfide, ZnS) structure.

Anions ccp (fcc). Radius Zn2+ = 0.6, radius S2- = 1.84; radius ratio = 0.33 Zn tetrahedral.
Have 2 tetrahedral sites/ anion, therefore from formula of ZnS only 50% of the tetrahedral sites can be filled.
Coordination # Zn = 4; coordination # S = 4.
Which sites are filled ?: see picture below.
Note the filling of diagonally opposite sites to maximize the cation-cation separations .

Again the lattice is fcc, the motif consists of 1 S and 1 Zn.

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HCP ANION PACKING

It is also possible to follow the simple methods used above to fill the octahedral and tetrahedral sites in an hcp (ABAB) array of anions.
Again many common structure types can be generated. These will not be considered in this class.
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CUBIC ANION PACKING

In these structures the anions are not close packed, but occupy just the corners of a cube. In this case the center of the cube (surrounded by
8 anions) can be occupied by a suitably sized cation. This site is larger than the tetrahedral or octahedral positions in the close packed
structures. The radius ratio for a perfect fit of a cation in a cubic site can again be calculated using simple geometry and is 0.73. This
structure should therefore be adopted when the rcation/ranion is equal to or greater than 0.73.
By including the possibility of cubic coordination we can now complete our table for predicting cation coordinations from the radius ratio
rules:

Cesium Chloride Structure.

CsCl: radius Cs+ = 1.74, radius Cl- = 1.81: radius ratio = 0.96 predict cubic coordination.
All cubic sites are filled by Cs cations.
Coordination numbers: Cs = 8; Cl = 8.
Note Cs and Cl are in contact along the body diagonal.

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FLUORITE STRUCTURE (CaF2).

Simple cubic arrangement of anions - 50% cubic sites filled. e.g.CaF2
ionic radius Ca2+ = 1.12; radius F- = 1.31; radius ratio = 0.85 Ca2+ cubic coordination.
One cubic site per F anion; from stoichiometry only 50% cubic sites filled by Ca cations.
Arrangement of the filled cubic sites is such that the Ca-Ca distances are as large as possible (compare the Ca distribution to that of Zn in
ZnS)
Coordination numbers: Ca2+ surrounded by 8 F- 's; F- surrounded by 4 Ca2+'s.

Other examples: ZrO2,

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