Sistem Tetragonal

Bagian I : menerngkan nila sumbu c, mungkin bernilai 4 atau tidak bernilai dan ada
tidaknya bidang simetri yang tegak lurus sumbu c. Bagian ini di notasikan: 4, 4, 4
m
Bagian II: menerangkan ada tidaknya sumbu lateral dan ada tidaknya bidang
simetri yang tegak lurus y terhadap sumbu lateral tersebut. Bagian ini di notasikan:
2 ,2, m atau tidak ada.
Bagian III: menerangkan ada tidaknya sumbu simetri intermediet dan ada tidaknya
bidang simetri yang tegak lurus terhadap sumbu inetrmediet tersebut. Bagian ini di
notasikan: 2, 2, m atau tidak ada

CHAPTER 2. Symmetry and Groups, and Crystal

Structures
2.1. The Seven Crystal Systems

The unit cell. The unit cell of a mineral is the smallest divisible unit of a mineral that
possesses the symmetry and properties of the mineral. It is a small group of atoms,
from four to as many as 1000, that have a fixed geometry relative to one another. The
atoms are arranged in a "box" with parallel sides called the unit cell which is repeated
by simple translations to make up the crystal. The atoms may be at the corners, on the
edges, on the faces, or wholly enclosed in the box, and each cell in the crystal is
identical. This is what was meant by an "ordered internal arrangement" in our
definition of a mineral. It is the reason why crystals have such nice faces, cleavages,
and regular properties.
The box of the unit cell is, in general, a parallel-piped with no constraints on the
lengths of the axes or the angles between the axes. The box is defined by three axes
or cell edges, termed a, b, and c and three inter-axial angles alpha, beta, and gamma,
such that alpha is the angle between b and c, beta between a and c, and gamma
between a and b.

The presence of internal symmetry in the unit cell may place constraints on the
geometry of the unit cell. The different kinds of symmetry possible place different
constraints on the unit cell geome tries giving rise to characteristic cell geometries for
each of the seven Crystal Systems. These are outlined in Table 2.1.
Table 2.1 Unit Cell Axial Constraints, and Allowed Symmetry Operations of the
Seven Crystal Systems.
System

Constraints

Operations

Triclinic

None

1, -1

Monoclinic

alpha = gamma = 90

1, -1, 2, -2(m)

Orthorhombic

alpha = beta = gamma = 90

1, -1, 2, -2(m)

Trigonal

alpha = beta = 90 gamma = 120 1, -1, 2, -2(m), 3, -3

a = b

Hexagonal

alpha = beta = 90 gamma = 120 1, -1, 2, -2(m), 3, -3, 6, -6

a = b

Tetragonal

alpha = beta = gamma = 90

a = b

1. -1, 2, -2(m), 4, -4

Cubic

alpha = beta = gamma = 90

a = b = c

1. -1, 2, -2(m), 3, -3, 4, -4

2.2. Symmetry Operations

A symmetry operation is a transposition of an object These may be of three distinct

types: rotations, inversions (including roto-inversions i.e. improper rotations), or
translations, or combinations thereof. We will discuss symmetry groups made up of
rotation and inversion operations only which are called the point groups, each of
which is one of the 32 crystal classes. We will also discuss the groups made up from
all three types of opera tion which give rise to the 230 space groups.
2.2.2. Rotations

Permissible rotations - Proper

1-fold 360

Identity

2-fold 180

3-fold 120

4-fold

90

6-fold

60

Permissible rotations - Improper (result in enantiomorphs).

1-fold 360

+ i

2-fold 180

+ i

-2 = m

3-fold 120

+ i

-3

4-fold

90

+ i

-4

6-fold

60

+ i

-6

2.2.3. Translations

Permissible translations are unit cell translations or fractions thereof that are
consistent with the rotational symmetry (e.g. 1/2, 1/3, 1/4, and 1/6), plus
combinations.
2.3. Stereographic Projections.

There are three common methods to graphically display orientations of vectors in

three dimen sions. In order to describe faces of crystals we would like to plot the
vectors normal (perpendicular) to crystal faces.
2.3.1. Spherical. The simplest to visualize is the spherical projection. In this method,
the vector is merely projected vertically onto the equatorial plane of the sphere.
However, this method has the serious disadvantage of compressing the low-angle
vectors onto the outside of the plot.
2.3.2. Stereographic. This disadvantage can be avoided if, instead of projecting
vertically, one projects radially to the pole of the opposite hemisphere. This is the
standard stereographic or equal-area plot that we will use to plot poles
(perpendiculars) to faces of crystals. The plot is also sometimes called the "Wulff net".

If the angle made by a vector with the vertical is r, then the distance from the center of

the plot is R tan r/2, where R is the radius.

2.3.3. Gnomonic. There is also a third type of plot called the gnomonic projection in
which the vector is extended till it intersects a plane tangent to the sphere at the north
pole. This has the disadvantage of not being able to display horizontal vectors. It is,
however, what arises naturally from x-ray and electron diffraction experiments where
each node corresponds to a lattice plane in real space and results in areciprocal
lattice.
However, for our purposes of displaying the orientations of crystal faces we will use
the stereo graphic projection exclusively.
2.4. Allowable Rotations.

Illustrated below are stereographic projections of general crystal forms that have the
allowable rotation operations that are consistent with translation symmetry.

Proper
Rotations:

Improper
Rotations:

Each of these ten allowable rotations generates, by itself, a unique point group. In
addition, there are 22 possible combinations of rotation operations, giving a total of 32
possible 3-dimensional point groups. Each point group corresponds to
different crystal class. Each crystal class places constraints on the axial geometry
such that each of these 32 classes may be associated into one of the 7 crystal
systems, each having different constraints on the axial lengths and inter-axial angles.
In determining a point group, one must have diagnostic faces such as the general
form. For example, if you have a cube, it can occur in several point groups as
a special form. Thus there is no way to uniquely determine the point group. If (when)
you encounter this situation in the lab, assign the highest point group symmetry (i.e.
4/m -3 2/m for a cube).
2.5. GROUPS
A set of elements (operations) is a group if the following properties hold:
1. Closure: combining any two elements of the group gives a third element of the
group.
2. Association: For any three elements of the group (ab)c = a(bc).
Note: not necessarily commutative (ab = ba). If it is true for all members of the group,
the group is called Abelian.
3. Identity: There is an element of the group, I, such that aI = Ia = a for each element
of the group.
4. Inverses: For each element, a, there is another element, b, such that ab = I = ba.
The order of the group is the number of elements of the group. We will first consider
groups made up of all allowable combinations of rotation and inversion operations to
make up the point groups in two dimensions and in three dimensions. There are ten
possible 2-dimensional point groups and 32 possible 3-dimensional point groups.
Each of these 32 3-D point groups corresponds to one of the crystal classes. We will
then combine these with the possible translation operations to form the 17 2dimensional space groups and 230 3-D space groups.
2.6. Crystal Morphology
At this point it is useful to develop some of the formalism of crystal morphology
(shapes). The morphology of a perfect crystal (i.e., our wooden blocks), in general,
reflects the maximum symme try that a crystal can have. That is, there may be

portions of the crystal structure that violate some of the apparent symmetry, but if
high-symmetry forms (crystal faces) are present, the crystal is likely to have high
symmetry. (e. g., if the crystal is a cube, it is most probably isometric.)
A crystal form is a crystal face plus its symmetric equivalents. For example, a cube is
a crystal form made up of six symmetrically equivalent faces.
A special form is a crystal form that is repeated by the symmetry operations onto
itself so that there are fewer faces than the order of the point group. The projections of
special forms or special faces will lie on symmetry operations in our stereographic
projections.
A general form is one that is not repeated onto itself by the symmetry operations so
that it has the same number of faces as the order of the group.
Forms are either general or special. In our stereographic projections, we will plot only
the general form because this defines the point group. In addition to being special or
general, forms may also be open or closed.
A closed form is one that encloses a volume; (e.g., a cube, tetrahedron, octahedron,
etc). A closed form may then be the only form present on a perfect crystal.
An open form is one that does not enclose a volume; (e.g., prism, pinacoid, etc.). A
crystal that has an open form must have more than one form present.
2.7. Miller Indices

2.7.1. Planes A crystal face (or plane) cuts the crystallographic axes at , 2, and 1.
These intersections are called intercepts. Because symbols are cumbersome, these
intercepts are in verted and all fractions are cleared, as shown below. , 1/2, 1/1 = 0,
1/2, 1 = (0 1 2)

These operations give us the Miller indices of any plane. These planes may be a
cleavage plane, a crystal face, or any diffracting X-ray plane. Thus, a cube face is (0 0
1), the octahedron (1 1 1), and a dodecahedron (1 1 0). There may also be negative (0
0 -1) Miller indices. Miller indices are always in relation to the crystallographic axes,
not any orthogonal system of convenience. The general form for Miller indices is (h k
l).
For hexagonal axes the general form is (h k i l). However, you will note in the
example below that h + k + i = 0. This is always the case so the i index is superfluous.
Hence, we can merely use (2 1 0). -1/2, 1, 1, 0 = (-2 1 1 0) = (-2 1 0) In general,
crystal faces, diffracting X-ray planes,and cleavages will be denoted with simple
parentheses, e.g. (2 1 0). However, a crystal form (a face plus its symmetric
equivalents will be denoted with curly brackets, e.g. {2 1 0}. Hence the cube, {1 0 0}
is made up of faces (1 0 0), (0 1 0), (0 0 1), (-1 0 0), ( 0 -1 0), and (0 0 -1).
2.7.2. Directions
Directions in a crystal are merely the vector components with respect to the
crystallographic axes that have been reduced to the smallest whole numbers. These are
given in square brackets [1 3 0], [0 1 0], etc. In general, the [1 1 1] is not normal to the
(1 1 1), except for isometric (cubic) crystals.
2.8. The 32 Crystal Classes
Following the rules of groups, there is a limited number of ways in which the 10
proper and im proper rotations can be combined to form groups, that is, there are 32
possible combinations to form groups. These are the 32 3-dimensional point
groups which correspond to the 32 Crystal Classes. Each of the 32 crystal classes
can be ascribed to one of the 7 crystal systems. The various crystal classes are
outlined in the table below. Table 2.2. The 32 Crystal Classes.
System

Classes (Point Group)

Triclinic
Monoclinic
Orthorhombic
Trigonal
Hexagonal
Tetragonal
Cubic

1, -1
2, -2 (= m), 2/m
222, 2mm, 2/m2/m2/m
3, -3, 3m, 32, -32/m
6, -6(= 3/m), 6/m, 6mm, 622, -6m2, 6/m2/m2/m
4, -4, 4/m, 4mm, 422, -42/m, 4/m2/m2/m
23, 2/m-3, -43m, 432, 4/m-32/m

Each of the 10 allowed proper and improper rotations is, by itself, one of the 32 point
groups, and we have seen stereographic projections of each of these. The additional 22

point groups are gener ated by combinations of these 10 symmetry operations. These
are illustrated below.
_________________________________________________________________

Monoclinic
____________________________________________________________________
Orthorhombic

____________________________________________________________________
Tetragonal

____________________________________________________________________

Tetragonal

____________________________________________________________________
Trigonal

____________________________________________________________________
Hexagonal 6mm Hexagonal 6/m Hexagonal 622

____________________________________________________________________

Hexagonal

____________________________________________________________________
Cubic

____________________________________________________________________
Cubic

____________________________________________________________________
2.11. The 14 Three-Dimensional Bravais Lattices
1. Primitive Triclinic

C-centered are no constraints on axial lengths or on b. The standard choice of axes is that b is
unique. The centered cell is also unique and preserves the axis identities and has an additional
lattice point at 1/2+x, 1/2+y, z, so that there is an additional lattice point per cell for a total of
two, whereas the primitive cell have just one lattice point per cell (eight corners, each of which is
1/8th within the cell). Because there are several possible choices of the a and b axes, it is possible
to choose an A- centered or I-centered cell. It is possible to show that centering of any other face
reduces to one of these two.

4. &

5.
Primitive C-centered Primitive and C-centered orthorhombic. alpha = beta gamma = 90. There
are no constraints on axial lengths. Labeling of axes is arbitrary. Just as in the monoclinic case,
the centered cell preserves the axis orthogonality and has an additional lattice point at 1/2+x,
1/2+y, z. It would also be possible to choose equivalent A or B centered cell, but
conventionally c is the centered axis.

6&

7.
I-centered F-centered centered (body-centered) cell has an additional lattice point at 1/2+x,
1/2+y, 1/2+z, for a total of two points per cell. In the F-centered cell each of the faces contains
1/2 of an additional lattice point for a total of four per cell. In each, the labeling of axes is
arbitrary.

8&

9.
Primitive I-centered Primitive and I-centered Tetragonal alpha = beta = gamma = 90 degrees. a
= b; and c is unique axis with 4 or -4 symmetry. The I- centered (body-centered) cell has an
additional lattice point at 1/2+x, 1/2+y, 1/2+z, for a total of two points per cell. Note that there is
no C-centered tetragonal cell be cause it would be possible to choose a primitive tetragonal cell
with half the volume. Similarly an F-centered cell would reduce to an I-centered cell.
10 & 11. Primitive I-centered Primitive and I-centered Cubic (Isometric) alpha = beta = gamma
= 90 a = b = c. These are similar to the above except for the additional axial length constraint.

12. F-centered Face Centered Cubic (Isometric) alpha = beta = gamma = 90 a = b = c. Each of
the six faces contains a lattice point for a total of four per cell.
13. 120 120 Primitive R-centered Primitive Hexagonal
The R-centered cell contains lattice points at 1/3 and 2/3 along the body diagonal. This makes it
pos sible to choose an alternative primitive cell such that alpha = beta = gamma, but not 90 or
120 degrees.
2.12. The 230 Three-Dimensional Space Groups
2.12.1. Screw Axes. In addition to glide planes we have a new symmetry operation - the screw
axis. A screw axis involves both rotation and translation. The symbol Nm indicates a rotation of
360/N plus a translation m/N times the repeat (cell edge) in the direction of the rotation axis.
A. when they are parallel to c and as when they lie in the plane of the page.
B. axis or screw triad. 31 = 120 rotation + 1/3 cell translation 32 = 120 rotation + 2/3 cell
translation 31 and 32 are right and left handed enantiomorphs of each other and so can only occur
in acentric trigonal space groups.
C. 43 42 41, 42, and 43 - Screw tetrads occur in the tetragonal and cubic systems
41 = 90 rotation + 1/4 cell translation 42 = 90 rotation + 2/4 cell translation 43 = 90 rotation +
3/4 cell translation 41 and 43 are right and left handed enantiomorphs of each other and so can
only occur in acentric space groups.
D. 61 62 64 65 agonal system.
61
62
63
64
65

=
=
=
=
=

60
60
60
60
60

rotation
rotation
rotation
rotation
rotation

+
+
+
+
+

1/6
2/6
3/6
4/6
5/6

cell
cell
cell
cell
cell

translation
translation
translation
translation
translation

2.12.2. Glide Planes. Glide planes are reflections plus translations. In space groups, glide planes
can have several orientations and are noted according to their orientation.
A c-glide is a reflection plus a translation of 1/2 cell along the c-axis. They can be perpendicular
to a or b. In symmetry diagrams, in the standard orientation with a vertical, b horizontal
and c normal to the page, they are denoted as row of dots:
of 1/2 cell along the b-axis. It can be perpendicular to a or c.
An a-glide is a reflection plus a translation of 1/2 cell along the a-axis.

An n-glide is a reflection plus a translation of 1/2 cell along both the axes in the plane of
reflection.
There is also a d-glide (a diamond glide), but we will not encounter it in rigorous fashion. It
occurs in both the cu bic and the tetragonal systems with its glide plane in clined to a major axis.
Space group symbols are called Hermann-Mauguin symbols and are entirely consistent with our
point group and plane group notations. The first symbol refers to the type of lattice (space or
Bravais Lattice). In the case of protoenstatite, the P refers to primitive orthorhombic. The three
symbols which follow refer to symmetry operations which are normal (for plane operations, i.e
glide operations) to or parallel (rotation operations) to the major axes a, b, c, respectively.
For Pbcn we have a b-glide normal to the a-axis, a c -glide normal to the b-axis and an n-glide
normal to the c-axis. When we refer to a glide operation as a c-glide, the c denotes the translation
direction (e.g. 1/2 cell along c), and the position refers to its orientation, as perpendicular to a, b,
or c. .
2.13.3. Example: Pbcn
At right is asymmetry diagram for space group Pbcn showing the location and orientation of the
symmetry symbols. In these diagrams a is horizontal, b vertical, and c normal to the page, so that
the symmetry diagram is a c-axis projection of the symmetry operations of the unit cell.
The full Hermann-Mauguin symbol for the space group symbol Pbcn is P21/b 2/c 21/n.
Inversions are marked with a small circle. Mirrors are marked with a heavy solid line when
perpendicular to the page and an arrow (2 barbs) when in the plane of the page. Screw and
rotational axes have symbols as described above.
In space group Pbcn, it is important to understand how the symmetry elements affect the location
and point symmetry of the atoms that compose the structure. If we place an atom at a random
location in the unit cell de noted by x, y, z where x, y, and z are in fractions of the unit cell edges,
then the symmetry operations of the space group will generate exactly equivalent atoms at the
following coordinates.

(x,y,z);

(x,-y,1/2+z);

(-x,-y,-z);

(-x,y,1/2-z);

(1/2-x,1/2-y,1/2+z);

(1/2-x,1/2+y,z);

(1/2+x,1/2+y,1/2-z);

(1/2+x,1/2-y,-z)

These locations are shown in the diagram at right. Thus for any atom at a random location in the
cell (called the general position) there are eight equivalent positions (atoms) in the unit cell.
Because the general position does not lie on a symmetry operation, the point symmetry or
symmetry of the site is always 1, i.e. no symmetry. However, some atoms may lie directly on a
symmetry operation such as mirrors, two-folds, or inversions where the symmetry operation
repeats the atom onto itself giving a redundant position. These are special positions, and have
point symmetries greater than one, and will havefewer equivalents in the cell. If an atom
in Pbcn lies on the inversion at 0,0,0, it can be seen by substituting into the equivalence
equations above that there will only be four such positions: (0,0,0); (0, 0, 1/2);a (1/2, 1/2, 1/2);
and (1/2, 1/2, 0) rather than eight. This site will have point symmetry -1.
In the crystal structure of proto enstatite (MgSiO3), there are two different Mg atom sites, both
lying on the two-fold axis (point symmetry 2). Mg1 has fractional coordinates 0, 0.087, 3/4 and
Mg2 is at (0, 0.262, 1/4). There are thus four Mg1 and four Mg2 atoms in each unit cell. The Si
atom lies in a general position at (0.298, 0.098, 0.074). Substituting into the equivalence
equations there are thus eight Si atoms per cell. There are three different oxygen sites in the cell,
O1, O2, and O3, each of which is in a general position. O1 is at (0.123, 0.094, 0.084); O2 at
(0.376, 0.257, 0.072); and O3 at (0.361, 0.983, 0.302). There are thus eight O1 atoms, eight O2
atoms, and eight O3 atoms in each cell, for a total of 24 oxygens per cell. There are then 24
oxygens, eight silicons, and eight magnesiums per cell giving us eight formula units (MgSiO3)
per cell. The Z-number is thus 8. The group of unique atoms (Mg1, Mg2, Si, O1, O2, O3) is
called the asymmetric unit. In the laboratory, we will calculate the positions of all the atoms of
the unit cell, and plot their positions giving us a drawing of the crystal structure. As you can
imagine, this computation is somewhat tedious, so we have several computer programs for
drawing crystal structures.

The equivalent positions in each of the

230 space groups are given in
International Tables for Crystallography,
Vol I or Vol A (on reserve in the library, or
in the X-ray Lab). In order to draw the
structure, we will need the unit cell
parameters (a, b, c, alpha, beta, gamma),
the symmerty equations from the
International Tables, and the fractional
coordinates of the atoms in the
asymmetric unit. To find the cell
parameters and atom coordinates for your
mineral, you will need to find a study of
the structure in the mineralogical
literature. Most commonly, these are
published as research articles in scholarly
journals, such as American
Mineralogist, Mineralogical
Magazine, European Journal of
Mineralogy, Zeitschrift fuer
Kristallographie, Acta Crystallographica, or in summary publications such as Structure
Reports or Wyckoff's Crystal Structures. One very good place to start looking for structural data
for any given mineral is in Hoelzel's Systematics of Minerals which is usually in the X-ray Lab.
(The library has a copy.)
In drawing crystal structures, particularly of oxygen minerals, we typically think of a cation
(positively charged ion (metal) as being surrounded by a coordination polyhedron in which the
corners represent the oxygen atoms. This is because the crystals commonly have only one type of
anion (negative ion), oxygen, and several types of cation, Na+, Mg2+, Al3+, Si4+, etc., and the
coordination polyherda are commonly highly regular tetrahedra or octahedra. A tetrahedron is a
polyhedron with four faces. It also has four corners which represent our oxygen ions. An
octahedron is a polyhdron with eight faces, but only six corners reprsenting nearest-neighbor
oxygens.
Tetrahedron is a polyhedron with four faces and four corners. It represents coordination number
four. Octahedron is a polyhedron with eight faces and six corners. It represents cations in
coordination number six.
These polyhedra are then used to help visualize complex crystal structures such as those
illustrated below.
Polyhedral representation of the crystal structure of biotite mica. The structure is made up of a
layer of octahedrally coordinated Mg and Fe cations with a layer of tetrahedrally coordinated Al
and Si cations above and below. The circles indicate the positions of K atoms that hold the layers
together. The chemical bonds holding the K atoms in place are very weak giving rise to the
perfect cleavage of the micas.

Further Reading and References

Bloss, F.D. (1971) Crystallography and Crystal Chemistry, An Introduction. Holt Rinehart
Winston 545 pp.
McKie, D. and McKie, C (1986) Essentials of Crystallography. Blackwell 437 pp.
.