UMT202: Structure of Materials

WEEK 3
Crystal Structures 3: Paulings rules and structure of ionic crystals
Objectives:
1. To use Crystalmaker to understand build some simple ionic structures and understand its connection to
Paulings rules
2. To use ball and stick model to build crystal specific crystal structures
Materials and Methods:
3. Crystalmaker software package, styrofoam balls, sticks
Theoretical background:
Structures of many ionic solids follow some simple geometrical and chemical rules. These were summarized by
Linus Pauling in 1929. His set of rules give the shape of the polyhedron of anions that is formed about each
cation. The structure itself is considered to be an optimized (on the basis of chemistry and other rules) collection
of these polyhedra. The cation-anion distance determined by the sum of ionic radii. The following are Paulings
rules:
Rule 1. A coordination polyhedron of anions is formed around every cation (and vice-versa) - it will only be
stable if the cation is in contact with each of its neighbours.

Ionic crystals may thus be considered as sets of linked polyhedra.

The cation-anion distance is regarded as the sum of the ionic radii.
The coordination of the smaller atom and the polyhedron formed around it will depend on the ratio of the
radius of the smaller ion (typically the cation) to that of the larger ion (typically the anion). Examples of
radius ratios and the expected polyhedron are shown in Table 1. Images of some of these polyhedral can be
seen in Figure 1.

Thus the first rule tells you about the expected coordination for the smaller ion (typically the cation) and the
possible polyhedron whose centre is occupied by the smaller ion.
Table 1: Examples of radius ratios and related polyhedra

Radius ratio (cation/anion)

0.225 0.414
0.414 0.592
0.592 0.645
0.645 0.732
0.732 1
0.732 1
1.00
1.00

Coordination Number
4
6
7
8
8
9
12
12

Polyhedron
tetrahedron
octahedron
capped octahedron
square antiprism (anticube)
cube
triaugmented triangular prism
cuboctahedron
anti-cuboctahedrom

Figure 1. Common coordination polyhedra around the central pink atom are (the coordination is indicated in bold)

Rule 2. In a stable ionic structure the charge on an ion is balanced by the sum of electrostatic bond strengths
to the ions in its coordination polyhedron
i.e. A stable ionic structure must be arranged to preserve local electroneutrality (ions in a crystal are surrounded
by appropriate number of ions of opposite charge so as not to produce large volumes of similar charge in the
crystal)
For each anion (or cation) the sum of the electrostatic bond strengths of the surrounding cations (or anions)
must balance the negative (or positive) charge on the anion (or cation)
For a binary compound AxBy the coordination numbers of A and B are in the ratio y:x e.g. Fluorite, CaF2 Ca2+ (8coordinated, based on rule 1), F- (4-coordinated, based on rule 2)
The second rule thus tells you what the coordination of the larger atoms should be, given the coordination of
the smaller atom (as determined by rule 1)
Rule 3. Once you know what the polyhedron and coordination is for the smaller atom, then you can build the
entire structure by linking polyhedral such that two polyhedral either share a vertex or an edge or a face. See
Figure 2, to see how this linking appears. The stability of the structure formed is determined by the nature of
the sharing. The stability of structures with different types of polyhedral linking is vertex-sharing > edgesharing > face-sharing.

Figure 2. Linking of polyhedral by vertex sharing (left), edge sharing (middle) and face sharing (right)

This effect is largest for cations with high charge and low coordination number (such as Si4+ in SiO2)
Sharing edges/faces brings ions at the centre of each polyhedron closer together, hence increasing electrostatic
repulsions and thus makes the structure unstable
There are two other Paulings rules which are briefly summarized here. These wont be required for this lab.
Rule 4. In a crystal containing different cations those of high valency and small coordination number tend not
to share polyhedron elements with each other
Rule 5. The number of essentially different kinds of constituent in a crystal tend to be small
In this lab, we will be exploring the validity of these rules for some simple ionic structures. For each structure
you will have to speculate on the possible coordination of the two ions based on Paulings rules (the radius ratio
and formula are given). Then you compare this to the actual structure to see if Paulings rules are obeyed or not.
Procedures:
1. Validity of Paulings riles and creation of the following ionic structures using Crystalmaker
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NaCl: Space group = Fm-3m; a=5.64 A; rNa+ = 1.16A, rCl- = 1.67A

Based on radius ratio and the valence of the species, what coordination number is expected
for the anion and cation?
Now build the actual structure using Crystalmaker. If Cl- atoms sit at (0,0,0), Na+ ions sit at the
octahedral void sites. How many atomic positions do you have to enter to build the crystal
and why?
What is the actual coordination for the anions and cations? Are first three of Paulings rules
followed for this structure?
What is the lattice and motif for this structure?

CsCl: Space group = Pm-3m; a=4.123 A; rCs+ = 1.81A, rCl- = 1.67A

Based on radius ratio and the valence of the species, what coordination number is expected
for the anion and cation?
Now build the actual structure using Crystalmaker. If Cl- atoms sit at (0,0,0), Cs+ ions sit at the
body center.
What is the actual coordination for the anions and cations? Are first three of Paulings rules
followed for this structure?
What is the lattice and motif for this structure?

CaF2: Space group = Fm-3m; a=5.46 A; rCa2+ = 1.14A, rF- = 1.19A

Based on radius ratio and the valence of the species, what coordination number is expected
for the anion and cation? Is the coordination of anion different from that of the cation and
why?
Now build the actual structure using Crystalmaker. If Ca2+ atoms sit at (0,0,0), F- ions sit at the
tetrahedral void sites
What is the actual coordination for the anions and cations? Are first three of Paulings rules
followed for this structure?
What is the lattice and motif for this structure?

ZnS: (as Zinc blende) Space group = F-43m; a=5.41 A; rZn2+ = 0.88A, rS2- = 1.7A
Based on radius ratio and the valence of the species, what coordination number is expected
for the anion and cation? Is the coordination of anion different from that of the cation and
why?
Now build the actual structure using Crystalmaker. If S2- atoms sit at (0,0,0), Zn2+ ions sit at
some of the tetrahedral sites.
What is the actual coordination for the anions and cations? Are first three of Paulings rules
followed for this structure?
What is the lattice and motif for this structure?

NaCl and ZnS have different space groups. But what about their lattices? Can you even generate a ZnS
structure with an Fm-3m spacegroup and by filling tetrahedral sites? What do you end up getting if you
did so? What do these exercises tell you about the space group concept?
2. You will be given stryrofoam balls of specific sizes (Collect from Lab A114, Materials Eng. on Friday). Determine
what the structure should be for the compound of interest based on Paulings rules and build your ball and stick
model of the structure accordingly.
a. Think simple. Think first of the appropriate polyhedron for A (see point (c) below. Build several of these
A-centred polyhedrons. Then consider the coordination for B and then how you will put the structure
together (using the A-centred polyhedra) based on vertex-, edge- and face- sharing principles.
b. In your report, explain the reasons for why you picked that specific structure.
c. Remember that the radius ratio and the consequent coordination, as shown in Table 1 are only
guidelines and not exact. Dont be scared of violating Paulings rules if you have to, but dont stray too
far! If you need to violate some of the Paulings rules to build the structure, do that as the last resort
and explicitly mention which Paulings rule you have violated and why?
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Group 1 (W1-W5): A=1 and B=2, Formula = AB

Group 2(W6-W10): A=1 and B=2, Formula = AB2
Group 3 (W11-W14): A=2 and B=3, Formula = AB
Group 4 (T1-1-T1-5): A=2 and B=3, Formula = AB2
Group 5 (T1-6-T1-10): A=2 and B=2, Formula = AB
Group 6 (T1-11-T1-14): A=2 and B=2, Formula = AB2
Group 7 (T2-1-T2-5): A=1 and B=3, Formula = AB
Group 8 (T2-6-T2-10): A=1 and B=3, Formula = AB2
Group 9 (T2-11-T2-14): A=1 and B=3, Formula = AB3