INTERNAL ORDER IN CRYSTALS

The internal or crystal structure of a mineral can be thought of as what is called a

“motif”

Motif can be likely to a group of atoms or ions repeated on a lattice (which is a periodic

array of points in space).

 A motif is the smallest representation unit of as structure in other words it is an atom or

group of atoms that when repeated by translation give rise to an infinite number of

identical regularly organized units.

 Lattice could probably be a periodic array of points in space, it is an imaginary three

dimensional frame work that can be linked to a network of regularly spaced of a motif.

 Unit cell: A unit cell is the smallest unit of a structure (or pattern) that can be

indefinitely repeated to generate the whole structure (or to generate the complete print

of a pattern). The 3-dimensional order of a crystal can be considered as a periodic

repetition of a motif (l.e. a unit of pattern) in such a way that the environment of and

around each repeated motif is identical.

The two dimensional order. The comma is the motive.

٫ ٫ ٫ ٫

٫ ٫ ٫ ٫

٫ ٫ ٫ ٫
A simple and ordered arrangement of a motif in 2-dimension is shown with comma as the motif

In crystals the motif may be molecules such as H2O, anionic group such as CO3 2-, SiO44, PO43-

, cations such as Ca2+ , Mg2+ Fe 2+ , atoms such as CU, or combinations of anionic groups, ions

and or atoms.

SYMMETRY ELEMENTS (without translation)

The previous diagram has no symmetry. However, many motif such as those used to create

two-dimensional printed patterns, do contain symmetry. The geometrical locus that aids in the

visualization of symmetry of an ordered arrangement is known as a SYMMETRY ELEMENT.

Rotation axes, mirror planes and centers of symmetry are example of symmetry elements.

The act rotation about an axes, the act of reflection by a mirror and the act of inversion about

a central paint are collectively referred to as symmetry operations.

Rotation alone, through an angle (ɑ) about an imaginary axis, generates another motif or several

other motifs. A rotation axis is a line about which a motif unit may be rotated and repeat itself

in appearance once or several time during a complete rotation.

ROTATIONAL SYMMETRY

This is generally expressed by any whole number (n) from 1 to infinity. The number “n”

expresses the number of times a motif unit is repeated during a complete rotation (3600)

rotation. A rotational symmetry of n = 1 means that after a complete rotation of 3600 about an

axis, all aspects of an object come into coincidence with themselves just once. The other

limiting case of rotational symmetry is with a rotation axis of infinite order (n = ∞). An object

possessing this kind of an axis may be made to coincide with itself by any angle of rotation,

because the amount of rotation necessary is definitely small. Figure 1 below shows how a
hollow cylinder is compatible with a rotational axis, parallel to the length of the cylinder, of n

= ∞. It also show that this same hollow cylinder with a single notch has rotational symmetry

of n = 1.

Fig. 1: The two extremes of rotational symmetry (n = 1 and n = ∞) as shown by independent

objects (a) a perfect hollow cylinder and (b) a hollow cylinder with a V-shaped notch at the

top.
The type of rotation found in internally ordered crystals and also expressed external shape

called morphology are 1-fold (ɑ = 3600), 2-fold (ɑ = 1800), 3-fold (ɑ = 1200), 4-fold (ɑ = 900),

6-fold (ɑ = 600). A 5-fold axis and 7- and higher fold axes are not possible. This will be proved

geometrically after lattice translation has been discussed. This becomes clearer when one tries

to completely cover a plane surface with a five-sided motif such as a pentagon (Figure 2),

without mismatches and gaps. While on the other hand, six-sided motif, hexagon, can

completely cover a surface.

Fig. 2: Arrangement of pentagons and hexagons which individually have 5-fold and 6-fold

symmetry axes perpendicular to the page respectively.

The possible rotation axes are portrayed in Figure 3 with the graphic symbols used to represent

them. The number of duplications of the motif during 3600 rotation gives the rotation axis its

name. For example, two equivalent units per 3600 rotation are related by a 2-fold rotation axis.

Rotation produces patterns in which the original motif and those generated from it are identical

in orientation with respect to each other. In other words, the original motif and the newly
generated one have same “handedness”. The original motif and those generated from it by

rotation are, therefore, said to be congruent.

The act of reflection of a mirror plane produce a mirror image across a mirror plane (m).

The motif generated are mirror reflections of the original motif and these make an

enantiomorphic pairs and this means that the motif (a generated motif and an original motif )

are related by a mirror and they cannot be super imposed on each other. This is exactly the

same relationship that exist between your right and your left hand.

An inversion (i) produces an inverted object through an inversion center. An inversion involves

drawing imaginary lines from every point on the object through the inversion center and out an

equal distance on the other side of the inversion center. The inverted object is then recreated

by connecting the points. Inversion, like reflection, produces an enantiomorphic pair.

ROTATION WITH INVERSION

In addition to the symmetry order generated by operation of rotation axes, there are 1-, 2-, 3-,

4- and 6-fold rotations that can be combined with inversion and they are known as roto-

inversion operations.

In combining rotation with inversion, it is best observed in the order of a pattern in 3-

dimensions.the combination of symmetry operation in one fold roto-inversion axes and it is

symbolized by 1. The original motif is rotated 3600, so that it returns to its original position and

it is then inverted through a center. This combination of operations produces the same result as

does the presence of a center of symmetry.

The ͞1 operation is there force also referred to as a center of symmetry or i for inversion.
The ͞2 operation is equivalent to the operation of a mirror plane coincident with the equatorial

plane of the globe.

The ͞3 operation is equivalent to the 3-fold rotation axes and inversion (i), which is the same as

the 3-fold rotation and a center symmetry.

The ͞4 operation is not re solvable into other operation and as such is unique.

The ͞6 operation is equivalent to the 3-fold axes of rotation with a mirror plane perpendicular

to the rotation axes.

Fig. 3: Illustration of rotations that allow the motif to coincide with an identical unit for 1-, 2-

, 3-, 4- or six fold rotation axes.

There are some possible combinations of ration symmetry elements and these are: 222, 23, 32,
4
432, 622 and 422. Combination rotation axis and the mirrors can be summarized as: 3 𝑚,

6 2 3 6 2 2 2 2 2
, , , 622, 𝑚 , 𝑚 , 𝑚 , 422, 𝑚 , 𝑚 , 𝑚.
𝑚 𝑚 𝑚

There are symmetry operation that are without translations e.g. the rotation axes (1, 2, 3, 4 and

6), center of symmetry (i) and mirror plane (m). The number of possible symmetry

combinations is not unlimited but the total number of the non-identical symmetry elements and

the combinations of the symmetry element is only 32 and these are called the 32 point group –

the 32 point group lead to the crystal system.

The word “point” indicates that symmetry operation leaves one particular point at least of a

pattern unmoved. The word “group” relates to the mathematical theory of groups which allows

for a systematic derivation of all the possible and non-identical symmetry combinations.

A crystal, under favourable conditions or circumstances of growth, will develop smooth planes

or faces that may assume regular geometric forms which are the expression of its internal,

regular, atomic arrangement. In crystals with well-developed faces, one can recognize the

elements of symmetry such as rotation axes, a center of symmetry and mirror planes. A

systematic study of the external forms of crystals leads to 32 possible symmetries or symmetry

combinations, which are the same 32 as the point groups noted above. Certain of the 32 crystal

classes have symmetry characteristics in common with others, permitting them to be grouped

together in one of the six crystal system. Table 1 shows the conventional arrangement of crystal

systems and classes. They are (i) monoclinic (ii) triclinic (iii) orthorhombic (iv) tetragonal (v)

hexagonal (vi) isometric.

Crystal System Symmetry of Crystal Classes

(1) Triclinic 1 and ͞1

(2) Monoclinic 2, m and 2/m

(3) Orthorhombic 222, 2mm, and 2/m2/m2/m

(4) Tetragonal 4, ͞4, 4/m,422, 4mm/ ͞4 2m and 4/m2/ m2/m

(5) Hexagonal 3, ͞3 32,3m and ͞3 2/m 6, ͞6, 6/m, 622,

6mm, ͞6m2 and 6/m2/m2/m

(6) Isometric 23, 2/m ͞3, 432, ͞43/m and 4/m ͞32/m

CRYSTAL MORPHOLOGY

As crystals are formed by the repetition in 3-dimensions of a unit structure, the limiting surfaces

which are known as the faces of a crystal depend on the path of the shape of the unit. They also

dependent on the condition of growth. These conditions include all the external influences such

as temperature, pressure, nature of solution, direction of flow of solution and availability of

open space for free growth. The angular relationship, sizes and shape to face on the crystal are

aspect of crystal morphology.

Within a given internal structure, a limited number of planes bound a crystal and only a

comparatively few are common. In determining the type of crystal faces that may develop in

a crystal, we must also consider the internal lattice. Faces that are most likely to form on

crystals parallel to lattice planes that have a high density of lattice point called “NODES”

The frequency with which a given face is observed is roughly proportional to the number of

nodes it intercept in the lattice. The larger the number of nodes (lattices face) the more common
the face. This rules is known as the “law of Bravais” and it is generally confirmed by

observation.

CRYSTAL SYMMETRY

The external shape of a well formed crystal reflects the presence/absence of translation free

symmetry element and these are: the rotation axes, roto-inversion axes, center of symmetry and

mirror planes.

The presence of these symmetry element can be detected in a well-formed crystal, by the

angular arrangement of the bounding faces and sometimes by their size and shape. In poorly

developed or distorted crystals, symmetry is generally not obvious, but can derived from

careful measurement of the angular relation of the bounding faces.

The aspect of symmetry element in relation to crystal morphology includes:

1. An axes of rotation: this is just an imaginary line through a crystal about which the

crystal can be rotated and repeats itself in appearance, 1, 2, 3, 4 or 6 times during a

complete rotation.

2. An axes of roto-inversion: it is an imaginary line that relates rotation about an axes with

inversion.

3. Center of symmetry: a center of symmetry is present in a crystal if an imaginary line

can be passed from any point on its surface through its center and similar point is found

on the line at any equal distance beyond the center.

4. Mirror plane: it is an imaginary plane that divide the crystal into halves, each of which

in a perfectly developed crystal, is the mirror image of the other.

Certain group of crystal classes have common symmetry characteristic these group

are known as CRYSTAL SYSTEM.

In the description of crystals, it is convenient to refer the external forms or internal symmetry

to a set of 3 or 4 reference axis. These imaginary reference lines are known as crystallographic

axes and are generally taken parallel to the intersection edges of major crystal faces. Such axes

are in most instances fixed by the symmetry and coincide with symmetry axes or with normals

to symmetry planes. For some crystals, there may be more than one choice of crystallographic

axes when selection is made by morphology alone. Ideally, the axes should be parallel to their

lengths proportional to the edges of the unit cell.

All crystals, with the exception of those belonging to the hexagonal system are referred to three

crystallographic axes designated as a, b and c. In general case (triclinic system), all the axes

are of different lengths and at oblique angles to each other. The ends of each axis are designated

plus or minus; the front end of a, the right-hand end of b, and the upper end of c are positive;

the opposite ends are negative. The angles between the positive ends of the axes are

conventionally designated by the Greek letter α, β and γ. The α angle is enclosed between axial

directions b and c, the β angle between a and c, and the γ angle between a and b. In summary,

the six crystal systems are referred to the following axial directions and axial angles (Figure

4).

1. Triclinic System: Three unequal axes all intersecting at oblique angles.

2. Monoclinic System: Three unequal axes, two of which are inclined to each other at an

oblique angle and the third perpendicular to the plane of the other two.

3. Orthorhombic System: Three mutually perpendicular axes all of different lengths.

4. Tetragonal System: Three mutually perpendicular axes, two of which (the horizontal

axes) are of equal length (a1 and a2), but the vertical axis is shorter or longer than the

other two.
5. Hexagonal System: Referred to four crystallographic axes; three equal horizontal axes

(a1, a2 and a3) intersect at angles of 1200, the fourth (vertical) is of different length and

perpendicular to the plane of the other three.

6. Isometric/Cubic System: Three mutually perpendicular axes of equal lengths (a1, a2 and

a3).
Fig. 4: Illustrations of the conventional system of crystallographic axes adopted for each of the

six crystal systems.