IONIC CRYSTALS

In general, a unit cell is defined by the lengths of three axes (a, b, and c) and the
angles (α, β, and γ) between them, as illustrated in Figure 10. The axes are defined as
being the lengths between points in the space lattice. Consequently, unit cell axes join
points with identical environments.

Figure 10. A unit cell is defined by the lengths of its three axes (a, b, and c) and the
angles (α, β, and γ) between the axes.

There are seven different lattice systems, some of which have more than one type of
lattice, for a total of fourteen different unit cells, which have the shapes shown
in Figure 11.
Figure 11. There are seven different lattice systems and 14 different unit cells.
The Structures of Ionic Crystals
Ionic crystals consist of two or more different kinds of ions that usually have different

sizes. The packing of these ions into a crystal structure is more complex than the

packing of metal atoms that are the same size.

Most monatomic ions behave as charged spheres, and their attraction for ions of

opposite charge is the same in every direction. Consequently, stable structures for ionic

compounds result (1) when ions of one charge are surrounded by as many ions as

possible of the opposite charge and (2) when the cations and anions are in contact with

each other. Structures are determined by two principal factors: the relative sizes of the

ions and the ratio of the numbers of positive and negative ions in the compound.

In simple ionic structures, we usually find the anions, which are normally larger than

the cations, arranged in a closest-packed array. (Additional electrons attracted to the

same nucleus make anions larger and fewer electrons attracted to the same nucleus

make cations smaller when compared to the atoms from which they are formed.) The

smaller cations commonly occupy one of two types of holes (or interstices) remaining

between the anions. The smaller of the holes is found between three anions in one plane

and one anion in an adjacent plane. The four anions surrounding this hole are arranged

at the corners of a tetrahedron, so the hole is called a tetrahedral hole. The larger type

of hole is found at the center of six anions (three in one layer and three in an adjacent

layer) located at the corners of an octahedron; this is called an octahedral hole. Figure

12 illustrates both of these types of holes.

Figure 12. Cations may occupy two types of holes between anions: octahedral holes
or tetrahedral holes.

Depending on the relative sizes of the cations and anions, the cations of an ionic

compound may occupy tetrahedral or octahedral holes, as illustrated in Figure 13.

Relatively small cations occupy tetrahedral holes, and larger cations occupy octahedral

holes. If the cations are too large to fit into the octahedral holes, the anions may adopt

a more open structure, such as a simple cubic array. The larger cations can then occupy

the larger cubic holes made possible by the more open spacing.
Figure 13. A cation’s size and the shape of the hole occupied by the compound are
directly related.

There are two tetrahedral holes for each anion in either an HCP or CCP array of anions.
A compound that crystallizes in a closest-packed array of anions with cations in the
tetrahedral holes can have a maximum cation:anion ratio of 2:1; all of the tetrahedral
holes are filled at this ratio. Examples include Li2O, Na2O, Li2S, and Na2S. Compounds
with a ratio of less than 2:1 may also crystallize in a closest-packed array of anions with
cations in the tetrahedral holes, if the ionic sizes fit. In these compounds, however, some
of the tetrahedral holes remain vacant.

Example 3

Occupancy of Tetrahedral Holes

Zinc sulfide is an important industrial source of zinc and is also used as a
white pigment in paint. Zinc sulfide crystallizes with zinc ions occupying one-
half of the tetrahedral holes in a closest-packed array of sulfide ions. What is
the formula of zinc sulfide?

Solution
Because there are two tetrahedral holes per anion (sulfide ion) and one-half of
these holes are occupied by zinc ions, there must be , or 1, zinc ion per
sulfide ion. Thus, the formula is ZnS.

The ratio of octahedral holes to anions in either an HCP or CCP structure is 1:1. Thus,
compounds with cations in octahedral holes in a closest-packed array of anions can
have a maximum cation:anion ratio of 1:1. In NiO, MnS, NaCl, and KH, for example,
all of the octahedral holes are filled. Ratios of less than 1:1 are observed when some
of the octahedral holes remain empty.
Example 4

Stoichiometry of Ionic Compounds

Sapphire is aluminum oxide. Aluminum oxide crystallizes with aluminum ions
in two-thirds of the octahedral holes in a closest-packed array of oxide ions.
What is the formula of aluminum oxide?

Solution
Because there is one octahedral hole per anion (oxide ion) and only two-thirds
of these holes are occupied, the ratio of aluminum to oxygen must be ,
which would give . The simplest whole number ratio is 2:3, so the
formula is Al2O3.
Homework
The white pigment titanium oxide crystallizes with titanium ions in one-half of
the octahedral holes in a closest-packed array of oxide ions. What is the
formula of titanium oxide?

Answer:

TiO2

In a simple cubic array of anions, there is one cubic hole that can be occupied by a
cation for each anion in the array. In CsCl, and in other compounds with the same
structure, all of the cubic holes are occupied. Half of the cubic holes are occupied in
SrH2, UO2, SrCl2, and CaF2.

Different types of ionic compounds often crystallize in the same structure when the
relative sizes of their ions and their stoichiometries (the two principal features that
determine structure) are similar.

Unit Cells of Ionic Compounds

Many ionic compounds crystallize with cubic unit cells, and we will use these
compounds to describe the general features of ionic structures.

When an ionic compound is composed of cations and anions of similar size in a 1:1
ratio, it typically forms a simple cubic structure. Cesium chloride, CsCl, (illustrated
in Figure 14) is an example of this, with Cs+ and Cl− having radii of 174 pm and 181
pm, respectively. We can think of this as chloride ions forming a simple cubic unit
cell, with a cesium ion in the center; or as cesium ions forming a unit cell with a
chloride ion in the center; or as simple cubic unit cells formed by Cs+ ions overlapping
unit cells formed by Cl− ions. Cesium ions and chloride ions touch along the body
diagonals of the unit cells. One cesium ion and one chloride ion are present per unit
cell, giving the l: l stoichiometry required by the formula for cesium chloride. Note
that there is no lattice point in the center of the cell, and CsCl is not a BCC structure
because a cesium ion is not identical to a chloride ion.
Figure 14. Ionic compounds with similar-sized cations and anions, such as CsCl,
usually form a simple cubic structure. They can be described by unit cells with either
cations at the corners or anions at the corners.

We have said that the location of lattice points is arbitrary. This is illustrated by an
alternate description of the CsCl structure in which the lattice points are located in the
centers of the cesium ions. In this description, the cesium ions are located on the
lattice points at the corners of the cell, and the chloride ion is located at the center of
the cell. The two unit cells are different, but they describe identical structures.

When an ionic compound is composed of a 1:1 ratio of cations and anions that differ
significantly in size, it typically crystallizes with an FCC unit cell, like that shown
in Figure 15. Sodium chloride, NaCl, is an example of this, with Na+ and Cl− having
radii of 102 pm and 181 pm, respectively. We can think of this as chloride ions
forming an FCC cell, with sodium ions located in the octahedral holes in the middle
of the cell edges and in the center of the cell. The sodium and chloride ions touch each
other along the cell edges. The unit cell contains four sodium ions and four chloride
ions, giving the 1:1 stoichiometry required by the formula, NaCl.

Figure 15. Ionic compounds with anions that are much larger than cations, such as
NaCl, usually form an FCC structure. They can be described by FCC unit cells with
cations in the octahedral holes.
The cubic form of zinc sulfide, zinc blende, also crystallizes in an FCC unit cell, as
illustrated in Figure 16. This structure contains sulfide ions on the lattice points of an
FCC lattice. (The arrangement of sulfide ions is identical to the arrangement of
chloride ions in sodium chloride.) The radius of a zinc ion is only about 40% of the
radius of a sulfide ion, so these small Zn2+ ions are located in alternating tetrahedral
holes, that is, in one half of the tetrahedral holes. There are four zinc ions and four
sulfide ions in the unit cell, giving the empirical formula ZnS.

Figure 16. ZnS, zinc sulfide (or zinc blende) forms an FCC unit cell with sulfide ions
at the lattice points and much smaller zinc ions occupying half of the tetrahedral holes
in the structure.

A calcium fluoride unit cell, like that shown in Figure 17, is also an FCC unit cell, but
in this case, the cations are located on the lattice points; equivalent calcium ions are
located on the lattice points of an FCC lattice. All of the tetrahedral sites in the FCC
array of calcium ions are occupied by fluoride ions. There are four calcium ions and
eight fluoride ions in a unit cell, giving a calcium: fluorine ratio of 1:2, as required by
the chemical formula, CaF2. Close examination of Figure 17 will reveal a simple cubic
array of fluoride ions with calcium ions in one half of the cubic holes. The structure
cannot be described in terms of a space lattice of points on the fluoride ions because
the fluoride ions do not all have identical environments. The orientation of the four
calcium ions about the fluoride ions differs.
Figure 17. Calcium fluoride, CaF2, forms an FCC unit cell with calcium ions (green)
at the lattice points and fluoride ions (red) occupying all of the tetrahedral sites
between them.

Three dimensional view of a cubic unit cell

In order to define positions in a lattice, it has become imperative to have a mathematical

language that describes the positions of atoms. We define the bottom left corner of the
unit cell as the origin (0,0,0). The coordinates (1,0,0) indicate the lattice point that is
one cell edge length away from the origin along “a” axis and the coordinates 0,1,0 and
0,0,1 represent lattice points that are displaced by ne cell-edge length from the origin
along the b and c axes. The “a” axis is the vertical axis, the b axis describes the
movement across the front of the unit cell while the “c” axis describes the movement
towards the back of the unit cell.
EXAMPLES
For a body centred cubic unit cell of say CsCl, we can describe the structure using four
pieces of information as follows: (i) CsCl crystallizes in a body centered cubic unit cell
(ii) The unit cell edge is 0.4123nm, (iii) There is a Cl ion at coordinates 0,0,0 (iv) there
is Cs+ ion at the coordinates ½, ½, ½ . By convention, the cell edge must connect
equivalent lattice points. Therefore, the presence of a Cl ion at coordinates 0,0,0
translates to presence of Cl ion at every corner of the cell. The coordinates ½, ½, ½
describes the lattice point at the center of the cell and this is the only Cs+ at the
coordinates ½, ½, ½ .
For easy understanding of different unit cell,
Lattices at corners are represented as 0,0,0 (origin); 1,0,0 (vertical); 0,1,0 (front);
0,0,1 (back)
Lattice at center of body is represented as ½, ½, ½
Lattices at faces are represented as 0, ½ ½ ; ½ 0, ½ ; ½ ½ 0; 1, ½ ½ ; , ½ 1, ½ ; ½ ½ 1
Calculation of Ionic Radii
If we know the edge length of a unit cell of an ionic compound and the position of the
ions in the cell, we can calculate ionic radii for the ions in the compound if we make
assumptions about individual ionic shapes and contacts.

Example 5

Calculation of Ionic Radii

The edge length of the unit cell of LiCl (NaCl-like structure, FCC) is 0.514 nm
or 5.14 Å. Assuming that the lithium ion is small enough so that the chloride
ions are in contact, as in Figure 15, calculate the ionic radius for the chloride
ion.

Note: The length unit angstrom, Å, is often used to represent atomic-scale

dimensions and is equivalent to 10−10 m.
Solution
On the face of a LiCl unit cell, chloride ions contact each other across the
diagonal of the face:

Drawing a right triangle on the face of the unit cell, we see that the length of
the diagonal is equal to four chloride radii (one radius from each corner
chloride and one diameter—which equals two radii—from the chloride ion in
the center of the face), so d = 4r. From the Pythagorean theorem, we have:

which yields:

Solving this gives:

.
Homewok
The edge length of the unit cell of KCl (NaCl-like structure, FCC) is 6.28 Å.
Assuming anion-cation contact along the cell edge, calculate the radius of the
potassium ion. The radius of the chloride ion is 1.82 Å.

Answer:

The radius of the potassium ion is 1.33 Å.

It is important to realize that values for ionic radii calculated from the edge lengths of
unit cells depend on numerous assumptions, such as a perfect spherical shape for ions,
which are approximations at best. Hence, such calculated values are themselves
approximate and comparisons cannot be pushed too far. Nevertheless, this method has
proved useful for calculating ionic radii from experimental measurements such as X-
ray crystallographic determinations.