CRYSTAL STRUCTURE, CRYSTAL CHEMISTRY AND CHEMICAL

COMPOSITION

The chemical composition of a mineral is of fundamental importance for many of its properties

are of great measure dependent on it. However, such properties depend not only on chemical

composition but also on the geometric arrangement of the constituent atoms or ions and the

nature of the electrical forces that bind them together. Thus, for understanding of minerals, one

must consider as well as their chemistry.

CHEMICAL COMPOSITION OF THE EARTH’S CRUST

Before discussing the chemistry and structure of minerals and mineral groups, it is instructive

to look briefly at some aspects of chemistry of the earth’s crust. Patterns of mineral distribution

and assessment of our mineral wealth are directly related to the abundance and distribution of

elements in the earth’s crust.

Geophysical investigations indicate a division of the earth into crust, mantle and core. The crust

is approximately 36 km thick under the continents and under the oceans, its thickness ranges

from 10 to 13 km. The boundary between the crust and the underlying mantle is referred to as

the Mohorovicic discontinuity. The upper part of the crust, which consists of materials

immediately underfoot is composed of a relatively large percentage of sedimentary rocks and

unconsolidated materials. However, this sedimentary cover forms but a thin veneer of an

underlying basemen of igneous and metamorphic rocks.

Eight elements make up approximately 99 wt% of the earth’s crust. Some interesting features

result when their weights values are recalculated in terms of atomic percent and finally in terms

of volume %. This shows that oxygen constitutes more than 90% of the total volume of the

crust. In other words, the earth’s crust on an atomic scale consist essentially of a packing of

oxygen anions with interstitial metal ions, chiefly Si-Oxygen, containing minerals such as
silicates, oxides, and carbonates, must be the most abundant types of minerals in the earth’s

crust. Thus, the minerals are referred to as “rock forming minerals”.

It is noteworthy that many elements important to our economy have very low values for their

average abundances in the crust. For example, Cu has an average abundances of 55ppm in the

crust. Clearly, in order to produce metals needed for our economy, one must locate areas of

high concentrations in order to make mining profitable. Cu is not extracted from rocks of

average composition, but from ore deposits in which copper has been concentrated and is

present in specific copper minerals. Some elements for example, Rb are dispersed throughout

common minerals and are never concentrated. Rb does not form specific compounds, but is

housed in K-rich minerals, and are therefore an example of what is called DISPERSED

ELEMENTS.

CRYSTAL CHEMISTRY

It was first recognized in the 18th century that a relation exist between chemical composition

and crystal morphology. Our understanding of this relationship has been enhanced by the

discovery of X-ray and their use in crystallographic investigations. As a result of common

interests among crystallographers and chemists, an interdisciplinary science, crystal chemistry,

came into being. The goal of this science is the elucidation of the relationship between chemical

composition, internal structure and physical properties of crystalline matter. In mineralogy it

serves as a unifying thread upon which often apparently unrelated facts of descriptive

mineralogy may be strung.

COORDINATION PRINCIPLES

When oppositely charged ions unite to form a crystal structure in which the binding forces are

dominantly electrostatic, each ion tend to gather to itself, or coordinate, as many ions of

opposite sign as size permits. When the atoms are linked by simple electrostatic bonds, they

may be regarded as spheres in contact, and the geometry is simple. The coordinated ions always

cluster about the central coordinating ion in such a way that their centers lie at the apices of a

polyhedron. Thus, in a stable crystal structure, each cation lies at the center of a coordination

polyhedron of anions. The number of anions in the polyhedron is the coordination number (C.

N.) of the cation with respect to a given anion, and is determined by their relative sizes.

Thus, in NaCl, each Na+ has six closest Cl- neighbours and is said to be in 6-coordination with

Cl (C. N. 6). In fluorite, CaF2, each calcium ion is at the center of a coordination polyhedron

consisting of eight fluorine ions and hence is in 8-coordination with respect to fluorine (C. N.

8).

Anions may also be regarded as occupying the centers of coordination polyhedral formed of

cations. In NaCl, each chloride ion has six sodium neighbours and hence is in 6 coordination

with respect to sodium. Because both sodium and chlorine are in 6 coordination, there must be

equal numbers of both in agreement with the formula, NaCl.

On the other hand, examination of the fluorine structure reveals that each fluorine ion has four

closest calcium neighbours and hence is in 4-coordination with respect to calcium (C. N. 4).

Because each calcium ion has eight fluorine neighbours, while each fluorine has four calcium

neighbours, it is obvious that there are twice as many fluorine as calcium ions in the structure.

This accord the formula CaF2, and with the valence for calcium and fluorine (Figure 1a &b).
 Fig. 1a & b: Halite and Fluorite Structure

It is easily seen that the relative sizes of calcium and fluorine ions would permit a structure

containing equal numbers of each with both ions in 8-coordinaton. The fact that in fluorite,

only half of the possible calcium sites are filled calls attention to an important restriction on

crystal structure; namely, the total number of ions of all kinds in any stable crystal structure

must be such that the crystal as a whole is electrically neutral. That is, the total number of

positive charges must be equal to the total number of negative charges; hence, in fluorite, there
may be only half as many divalent positive calcium ions as there are monovalent negative

fluorine ions.

RADIUS RATIO

Each ion in the crystal affects every other ion to some extent but the strongest force exist

between ions that are nearest neighbours. These are said to constitute the first coordination

shell. The geometry of arrangement of this shell and hence the coordination number are

dependent on the relative sizes of the coordinated ions. The relative sizes of ions is generally

expressed as a radius ratio; Rx : Rz, where Rx is the radius of the cation and Rz is the radius of

the anion in Ångstrom units. The radius ratio of sodium and chlorite in halite, NaCl, is therefore

RNa+ = 0.97Å RCl- = 1.81Å

RNa+ : RCl- = 0.97/1.81 = 0.54

The radius ratio of calcium and fluorine in fluorite, CaF2 is

RCa2+ = 0.99Å RF- = 1.33Å

RCa2+ : RF- = 0.99/1.33 = 0.74

When two or more cations are present in a structure, coordinated with the same anion, separate

radius ratios must be computed for each.

When the coordinating and coordinated ions are the same size, the radius ratio is one (1). Trial

with a tray of identical spheres such as Ping-Pong balls reveals that spherical units may be

arranged in three dimensions in either of two ways called hexagonal closest packing (HCP)

and cubic closest packing (CCP). In either arrangement, each sphere is in contact with its 12

closest neighbours (C.N.12) (Figure 2 a, b & c). Twelve-fold coordination is rare in minerals

with the exception of the native metals. They and many of the alloys have structures based on

HCP and CCP.

 Fig. 2a, b & c: Hexagonal closest packing (HCP) and Cubic closest packing (CCP)

When the coordinating cation is slightly smaller than the anions, 8 coordination results. This is

also called a cubic combination for the centers of anions lie at the eight corners of a cube

(Figure 3). If we consider a cubic coordination polyhedron in which the anions touch each other

as well as the central cation, we may compute the limiting value of radius ratio for C. N. = 8.0.

Allowing the radius of the anion to equal unity, the radius of the cation for this limiting

condition must be 0.732. Hence, cubic coordination has a maximum stability for radius ratios

between 0.732 and 1.000.

 Fig. 3: Cubic or 8-coordination

For values of radius ratio less than 0.732, 8 coordination is not as stable as 6 coordination in

which the centers of the coordinated ions lie at the apices of a regular octahedron. Six-fold

coordination is accordingly called octahedral coordination (Figure 4). We may as before

calculate the limiting value for radius ratio for the condition in which six coordinated anions

touch each other and the central cation. The lower limit of radius ratio for stable 6-cordination

is found to be 0.414. Hence, we may expect 6 to be the common coordination number when

the radius ratio lies between 0.732 and 0.414. Many cations in silicates are examples of 6-

coordination.
 Fig. 4: Octahedral or 6-coordination

For values of radius ratio less than 0.414, 6-coordination is not as stable as 4-coordination in

which centers of anions lie at the apices of a regular tetrahedron. The four-fold coordination is

therefore called tetrahedral coordination. Calculation of the limiting value of radius ratio for

the condition in which four coordinated anions touch each other and the central cation, we find

it to be 0.225 (Figure 5). Therefore, we may expect 4 to be the common coordination number

when the radius ratio lies between 0.414 and 0.225. Tetrahedral coordination is typified by the

SiO4 group in silicates.

 Fig. 5: Tetrahedral or 4-coordination

Triangular or 3-coordination is stable between limits of 0.225 and 0.155 and is common in

nature in CO3, NO3. And BO3 groups (Figure 6).

Fig. 6: Triangular or 3-coordination

Linear or 2-coordination is very rare in ionic bonded crystals. Examples are the uranyl group

(UO2)2+ and nitrite group (NO2)2- (Figure 7).

Fig. 7: Linear or 2-coordination

Although, rare examples of 5, 7, 9 and 10 coordination are known. Such coordination numbers

are possible only in complex structures and result from the filling of interstices between other

coordination polyhedral. Figure 8 illustrates the various regular coordination polyhedral as a

function of radius ratio and coordination number.

Fig. 8: Various regular coordination polyhedral as a function of radius ratio and
Coordination number
Radius ratio CN
< 0.155 = 2
0.155 – 0.225 = 3
0.225 – 0.414 = 4
0.414 – 0.732 = 6
0.732 – 1.00 = 8
1.00 = 12
The coordination polyhedral are frequently distorted. The smaller and more strongly polarizing

the coordinating cation, or larger and more polarizing the anion, the greater the distortion and
wider the departure from the theoretical radius ratio limits. Also, if the bonding mechanism is

not purely ionic, radius ratio considerations may not be safely used to determine the

coordination number.

Obviously, every ion in a crystal structure has some effects on every other ion – it is attractive

if the charges are opposite, repulsive if the charges are the same. Hence, ions tend to group

themselves in crystal structures in such a way that cations are as far apart as possible yet

consistent with the coordination of the anions that will result in electrical neutrality. Thus, when

cations share anions between them, they do so in such a way to place themselves as far apart

as possible. Hence, the coordination polyhedral formed around each are linked more commonly

through corners through edges or faces. Cations tend to share as small a number of anions as

possible, and sharing of as many as three or four anions is relatively rare.

CRYSTAL STRUCTURE

The knowledge of the structure of crystalline materials is basic to the understanding of

properties such as cleavage, hardness, density, melting point, refractive index, x-ray diffraction

pattern, solid solution and exsolution. Also, our knowledge of atomic and ionic sizes, and of

the nature of the chemical bonds in crystals, derives from the precise determinations of crystal

structures.

An X-ray crystallographer determines the structure of a crystalline material through the

interpretation of the relationship of various properties such as external symmetry, X-ray

diffraction effects, electron diffraction patterns, density, and chemical composition. The

resulting crystal structure provides us with a knowledge of the geometric arrangement of all

the atoms (or ions) in the unit cell, and the bonding and the co-ordination between them. The
symmetry of the internal, atomic arrangement of a crystal is expressed by its space group,

whereas the morphology of the crystal is reflected in the point group symmetry.

THE UNIT CELL

Every crystal consists of certain atoms or groups of atoms arranged in a 3-dimentional pattern

which is repeated throughout the crystal. The UNIT CELL is the smallest complete unit of

pattern and the whole crystal structure can be thought of as being built up of unit cells stacked

together. If the atoms or ions are represented by points, their arrangement in the crystal can be

shown by the geometrical pattern or framework of the space lattice or point system.

The crystal of sodium chloride (Halite – NaCl), afford a simple example of crystal structure

and were the first to be studied. The Na+ cations are bonded by ionic bonds to Cl- anions in the

formation of sodium chloride crystals. The Na and Cl ions are sited at the corners of a series of

cubes; eight such cubes are stacked in the manner usually shown in Figure 9. This group of

eight cubes is the smallest unit of structural pattern which by repetition can build up a crystal

of sodium chloride and it is therefore the unit cell of the mineral.

Fig. 9: Sodium chloride (Halite – NaCl) Stucture

Instead of points, ions of the unit cell can be represented by spheres whose radii are

proportional to the ionic radii of sodium and chlorine. The unit cell can be considered to be

packed with spheres of these two sizes in appropriate orderly arrangement. It should be noted

that each Cl- and Na+ ion is in 6-fold coordination with surrounding Na+ and Cl- ions. This

coordination can be described as octahedral in that the six nearest neighbours of a central ion

form a regular octahedron about it. Also, the three edges of the unit cell that meet at a point

can be used as axes of reference to denote the position of any plane in the crystal lattice as a

whole. These axes lettered a, b, c are also crystallographic axes that are of fundamental

importance in morphology of crystals.

ILLUSTRATION OF CRYSTAL STRUCTURES

We have already seen in our discussion on the crystal structure of halite that the atoms or ions

can either be represented as points or as spheres whose radii are proportional to the radii of

sodium and chlorine.

For some purposes, it may be useful to represent a crystal structure in terms of coordination

polyhedral instead of the location of atoms and ions. To aid the visualization of complex crystal

structures, crystal structure models reproduce the internal atomic arrangement on an

enormously magnified scale. Several types of models are currently in use:

A close-packed model is the most realistic in terms of the representation of the filling of space

on an atomic scale. It is difficult, however to visualize the interior of such models. A polyhedral

model represents the coordination polyhedral instead of specific atomic locations. The two

models have very difficult appearance. An open ball and stick model allows the viewing of the

coordination inside the model and portrays best the irregularly coordinated environment of ions

in complex structures.
STRUCTURE TYPES

Uraninite (UO2) and fluorite (CaF2) at first sight seem to have very little in common. However,

their X-ray powder patterns show analogous lines, although different in spacing and intensity.

Structure analysis reveals that the U4+ ions in uraninite are in 4-fold coordination with respect

to oxygen whereas eight O2- are grouped about each uranium. In fluorite, four Ca2+ are grouped

about each fluorine and eight F-1 are packed about each calcium. Uraninite and fluorite have

structures that are analogous in every respect, although the cell dimensions are different and

other properties are ofcourse, totally dissimilar. These two substances are said to be

ISOSTRUCTURAL or ISOTYPOUS, and belong to the same structure type. Occasionally,

the term ISOMORPHISM is used instead of isostructuralism. Crystals in which the centres of

the constituent atoms occupy geometrically similar positions, regardless of the size of the atoms

or the absolute dimensions of the structure are said to belong to the same structure type.

Of great importance in mineralogy is the concept of the isostructural group: a group of minerals

related to each other by analogous structures, generally having a common anion, and frequently

displaying extensive ionic substitutions. Many groups of minerals are isotructural of which the

barite group of sulphates, the calcite group of carbonates and aragonite group of carbonates are

perhaps the best examples.

POLYMORPHISM

The ability of a specific chemical substance to crystallize with more than one type of structure

is known as polymorphism. The various structures of such a chemical element or compound

are known as polymorphs. Examples of polymorphous minerals are numerous: Diamond and

graphite (C), pyrite and marcasite (FeS2), calcite and aragonite (CaCO3) etc.
Three major types of mechanism are recognized by which one polymorphic form of a substance

can change to another. These are displacive, reconstructive, and order-disorder polymorphic

transformation.

Displacive:

In this polymorphic reaction, the internal adjustment in going from one form to another is very

small and requires little energy. The structure is generally left completely intact and no bonds

between ions are broken. Only a slight displacement of atoms (or ions) and readjustment of

bond angles (kinking) between ions is needed. This type of transformation occurs

instantaneously and is reversible. An example of such displacive transformation occur when

the low quartz form of SiO2 is heated to above 573oC (atmospheric pressure) and rearranges its

structure to that of high quartz.

Reconstructive:

Here, the internal rearrangement in going from one form to another is extensive. It involves the

breaking of atomic bonds and a reassembly of the structural units in a different arrangement.

This kind of transformation requires a lot of energy, is nonreversible and very sluggish. An

example of such polymorphic transformation/reaction is the change from tridymite (or

cristobalite) to low quartz. Cristobalite and tridymite are formed at high temperatures and

relatively low pressures (Figure 10). A high activated energy is needed to change the

cristobalite (tridymite) SiO2 network into the arrangement of the low quartz structure.

Cristobalite and tridymite are metastable under atmospheric conditions. However, both

minerals are abundantly present in very old terrestial volcanic flows as well as in Precambrian

lunar lavas. Such persistence metastable minerals testifies to the fact that high energy is

required to activate a reconstructive polymorphic transformation. Figure 11 shows a diagram

to illustrate both the displacive and reconstructive polymorphic transformation.

 Fig. 10: Stability relationship of SiO2 polymorphs

Fig. 11: Diagram to illustrate both the displacive and reconstructive polymorphic
transformation
Order-disorder:

This is most frequently observed in alloys but also in minerals. TO appreciate this

transformation, it should be noted that perfect order occurs only at absolute zero (0 kelvin,

which is equivalent to -273.15oC). An alloy of composition AB with 50% of A and 50% of B

can exist in various states of disorder of which a totally disordered and perfectly ordered states

are two extreme conditions. In perfectly ordered state, atoms of A are arranged in perfect and

regular repeat with respect to B atoms. Atom A is always in structural site 1 and B atoms in

structural site 2. In a somewhat disordered state, the distribution is not perfectly ordered and

yet also not random. A state of total disorder implies equal probability of finding A or B atoms

in a specific site in the structure.

There is no definite transition point between perfect order and complete disorder. Perfect order

is possible only at 0o Kelvin (absolute zero) and with increasing temperature the degree of order

generally decreases. At high temperatures, close to but below melting point of a substance,

atoms (or ions) tend to become complexly disordered and are indeed ready to break away from

the structure.

An example of order-disorder polymorphism in a mineral is shown by potassium feldspar

(KAlSi3O8), in which Al occupies a structural position identical with and replacing Si in the

mineral. The high-temperature form, sanidine, shows a disordered distribution of Al in the SiO2

network. The low-temperature k-feldspar, microcline, however, shows an ordered distribution

of Al in SiO2 network. Intermediate order (or disorder) states are present between high

temperature sanidine and low-temperature microcline – e.g the mineral orthoclase. Figure 12

gives an illustration of the order-disorder polymorphism.

Fig.12: Schematic illustration of the order-disorder polymorphism

POLYTYPISM

This is a special type or special variety of polymorphism. It occurs when two polymorphs

differs only in the stacking of the identical two dimensional sheets or layers. As a consequence,

the unit cell dimensions parallel to the sheet will be identical in the two polytypes. However,

their unit cell length perpendicular to the stacking sheets or layers will be related to each other

as multiples or sub-multiples.

Polytypism is a well-known feature in silicon carbide (Sic), Zinc sulphide (Zns) and the micas.

Zinc sulphide (ZnS) forms two different minerals namely wurtzite and sphalerite. The only
difference between these two minerals is that the S2- ions in sphalerite are in cubic closest

packing where in wurtzite, they are in hexagonal closest packing.

PSEUDOMORPHISM

The existence of a mineral with the outward crystal form of another mineral species is known

as pseudomorphism. If a crystal of a mineral is altered so that the internal structure or chemical

composition is changed but the external form is preserved, this is called a pseudomorph or a

false form. The chemical composition and the structure of a pseudomorph belong to one

mineral specie, whereas the crystal form corresponds to another. For example, pyrite (FeS2)

may change to limonite (FeO.OH.nH2O), but preserve the external features of the pyrite. Such

crystal is described as a pseudomorph of limonite after pyrite. Pseudomorphs are further

defined according to the manner .in which they were formed. They can form by: Substitution,

Encrustation and Alteration

Substitution: In this type of pseudomorph, there is a gradual removal of the original material

and a corresponding and simultaneous replacement of it by another two with no chemical

reaction between the two. A common example of this is the substitution of silica for wood fiber

to form petrified wood. Another example is Quartz (SiO2) after fluorite (CaF2).

Encrustation: In the formation of this type of pseudomorph, a crust of one mineral is deposited

over crystal of another. A common example is quartz encrusting the cubes of fluorite. The

fluorite may later be entirely carried away by solution, but its former presence is indicated by

the cast left in the quartz.

Alteration: In the type of pseudomorph, there has been only a partial addition of new mineral

or partial removal of the original material. The change of Anhydrite (CaSO4) to gypsum

(CaSO4. 2H2O) and a change of galena (PbS) to anglesite (PbSO4) are examples of alteration

pseudomorphs.