EXTERNAL FORM, INTERNAL ORDER &

SYMMETRY

(page numbers from Klein and Hurlbut)

We begin our study of crystallography by examining the properties of symmetry operations that do not
involve translation. In two dimensions we will examine rotations and reflections and combinations of these
elements. We will see that there are only 10 possible outcomes - 10 possible symmetry contents for planar
patterns (motifs) which can become part of infinitely extensive, ordered 2-D patterns - in other words, 10
planar point groups.

Moving into three dimensions allows the introduction of inversion, rotoinversion, perpendicular mirrors
and multiple axes of rotation combined at some special angles. There are 32 unique combinations in three
dimensions and these are the 32 3-D point groups also called the 32 crystal classes. Every crystal has one of
these 32 point groups as its underlying structure - if the crystal is able to form unhindered, its outward
morphology (shape) should be identifiable as belonging to one of these 32 classes.

Because crystals have long-range, internal 3-D order, we need to identify the possible ways this internal
order can be developed. As above we will start with 2-D translationally periodic patterns and then move to
3-D. There are five 2-D ways to repeat lattice points in space and these can be combined with the 10 planar
point groups to generate 17 2-D space groups. There are 14 ways to translationally repeat points in 3-D and,
when combined with the 32 3-D point groups, 230 3-D space groups result.

Specifically then:

[1] Combinations of a single rotation axis perpendicular to the paper with or without parallel mirrors
(perpendicular to the paper) give us the ten 2-D point groups.

[2] Add center of inversion, rotoinversion axes, perpendicular mirrors, and additional axes of rotation to the
first 10 point groups gives the 32 3-D point groups or Crystal Classes.

[3] Add crystallographic axes to the point groups, discuss their axial ratios and angular relationships, Miller
Indices, and the ideas of forms.

[4] Examine the five 2-D plane lattices and explore the result of combining these lattices with the 10 2-D
point groups forming the 17 2-D plane or space groups.

[5] See how to form the 14 3-D (Bravais) lattices from the five 2-D lattices and touch on the result of
combining these with the 32 3-D point groups: the 230 3-D space groups. Here we will also add the glide
plane and the screw axis to our symmetry "building blocks".

External Form and Symmetry

Symmetry operations/elements (without translation) (p.21):
Rotation: Rotation of a unit of pattern (a motif) about an imaginary axis produces one or more motifs
which are said to be "symmetrically equivalent" to the initial motif. Rotational symmetry is
commonly expressed as a whole number from 1 to infinity where the number refers to the number of
motifs in the finished pattern. We can draw or make single objects with rotational symmetries
anywhere between the extremes of 1 and infinity. However if we add the constraint that the pattern of
motifs must also be translationally periodic (have an ordered pattern and completely fill 2- or 3-D
space, then the only rotational symmetries permissible are 1, 2, 3, 4, and 6. These are expressed as 1-
fold (360 degrees), 2-fold (180 degrees), 3-fold (120 degrees), 4-fold (90 degrees) and 6-fold (60
degrees) axes. Note that rotation does not change the motif's "handedness" (a pattern made by rotating
a left hand about an axis will be composed of all left hands). The motifs are then said to be congruent
as distinct from the pairs of motifs created by reflection. These are the first 5 planar point groups.

Reflection: A reflection across a mirror (in 3-D) or a mirror line (in 2-D) generates a new motif that
has the opposite handedness and the two are said to be "enantiomorphic". This is the 6th planar point
group.

Rotation axis combined with parallel mirror planes (or perpendicular mirror lines): The other
four planar point groups are generated by adding a perpendicular mirror line to each of the 5 rotational
groups and letting the combined symmetry generate a pattern. (The combination of a mirror parallel to
a 1-fold axis is the same as the mirror by itself and thus we don't count it again.) Note in the cases of
2mm, 4mm and 6mm, the addition of a single mirror (the first 'm' in the symbol), when coupled with
the rotation axis, generates another mirror or set of mirrors half way between the mirrors in the first
set. When we define coordinate axes to define these symmetries in we will find that the first 'm' refers
to the symmetry along the axes while the 2nd 'm' refers to the symmetry in the interaxial directions. In
the case of 3m, additional interaxial mirrors are not generated.

These are the ten 2-D point groups; now let us move into the third dimension .

Inversion: Inversion through the center of an object produces an inverted object that is "facing the
other way". Inversion thus produces an enantiomorphic pair of motifs. (#11)

Rotoinversion: The combination of rotation and inversion produces several new point groups in three
dimensions.

1-fold plus inversion: this combination is the same as simply inverting through the center of the object
and thus the 'bar 1' operation (see p.23) is also referred to as 'i' which is the abbreviation for 'center of
symmetry'.

The 'bar 2', 'bar 3', 'bar 4' and 'bar 6' operations are depicted in Fig. 2.12 in your text (p.25).
Remember that in any of these cases, the rotation is immediately followed by inversion before you
stop to generate a new face on the crystal (even if there happens to be a face present prior to
inversion). The 'bar 2' operation is equivalent to a perpendicular mirror plane (see below) and thus
doesn't add a new point group and this notation is not used. Also the 'bar 6' operation is equivalent to
a 3-fold axis perpendicular to a mirror (see below) and thus some authors use one notation while
others will use the other. The 'bar 2' produces 2 motifs, the 'bar 4' produces 4 motifs and 'bar 6'
produces 6 motifs. The 'bar 3' operation however also produces 6 motifs and is equivalent to a 3-fold
and a center of symmetry. (#12, 13, 14: 'bar 3', 'bar 4' and 'bar 6')
 Combinations of Rotations: Some combinations of symmetry axes are permissible - the angular
relationships have to chosen carefully so as not to generate an infinite set of axes. The combination of
a 4-fold axis with a perpendicular 2-fold generates a second 2-fold at 90 degrees to the first and then,
by inspection, a second set of two 2-folds is observed half way between the first set. All these 2-fold
axes lie in the equatorial plane perpendicular to the 4-fold. This construction is shown in Fig. 2.14 in
the book and is called 422 - do you see the similarities and differences with the planar group 4mm? In
addition to 422 we can derive 622, 222, 32, 432, and 23. See the book for details (p. 26-27). (#15-20).

Rotations plus perpendicular Mirrors: Mirrors can be added perpendicular to the 2, 3, 4, and 6-fold
axes and thus generate the 2/m, 3/m, 4/m and 6/m point groups (3/m is equivalent to the 'bar 6' we
already made). (#21-23). Similar mirrors can be added to several other of the point groups mentioned
in the paragraph above and again generate new point groups. For instance 422 plus mirrors gives
4/m2/m2/m (#24). Compare this to 4mm (which we deduced from analysis of 2-D plane patterns) -
the distribution of symmetrically related points in these 3 closely related point groups is different (Fig.
2.18). (2/m2/m2/m, 6/m2/m2/m: #25-26). Perpendicular mirrors added to collections of axes that
include a 3-fold axis (32, 432, 23) also generate new point groups but the results are not as straight
forward as the first 26. (#27-29).

32 point groups: At this point we have constructed 29 of the 32 point groups. The remaining 3 can be
constructed starting with 'bar 4' and 'bar 6' operators. The 32 point groups are subdivided in Table 2.1
(p.31) on the basis of increasing rotational symmetry. These 32 point groups are also known as the 32
crystal classes which have been grouped in Table 2.2 into 6 crystal systems based on the major or
special rotational rotation axis. Finally, Fig. 2.21 shows all 32 of these crystal classes and their
appropriate symmetries.

The 32 crystal classes can be grouped into crystal systems based on common
symmetry characteristics.
Isometric (Cubic): three 4-fold or three 'bar 4' axes (or four 3-fold or four 'bar 3' axes)
Hexagonal: one 6-fold or 'bar 6' axis [Trigonal: one 3-fold or 'bar 3' axis]
Tetragonal: one 4-fold or 'bar 4' axis
Orthorhombic: three orthogonal (mutually perpendicular) 2-fold axes or mirrors
Monoclinic: one 2-fold axis or mirror
Triclinic: one center of inversion or '1-fold' axis

Crystal Morphology
Well-formed crystals may exhibit, in the geometrical relationships among their faces, rotation axes,
rotoinversion axes, centers of symmetry and mirror planes. Recognizing these symmetry elements will help
identify minerals.

Crystallographic Axes

It is convenient to refer the external morphology to 3 or 4 reference axes.

a, b, c; positive and negative ends

alpha, beta, gamma; angles between axes
See Fig. 2.27 (p.40) for summary of relations between angles and lengths
 Revisit the symmetry of the crystal systems

Axial Ratios

Measure of lengths of unit cell, ratioed to one another.

The `b' axis is commonly set equal to `1'
Thus a:b:c may be expressed as 0.813:1:1.903 for sulfur.

Face Intercepts

Crystal faces are defined by indicating their intercepts on the crystallographic axes.
Ex: 1 unit on 'a': 1 unit on 'b': infinite (parallel) on 'c' or infinite a: 2b: 1c

IMPORTANT: these measures are RELATIVE and not absolute

Miller Indices

"A series of whole numbers that have been derived from the intercepts by their inversions and, if necessary,
clearing fractions."

Note difference between intercept of zero and infinity: definition of parallel

Reported in parentheses: (100)
Unknown distances reported using (hkl)
Commas only if needed to deal with double digit numbers (1,12,3)
Hexagonal system: needs 4 numbers: (10í0)
however the sum of the first 3 digits (hki) is always zero

Form

Outward appearance of a crystal is its `habit'; the word "form" has a special and restricted use.
Form: group of crystal faces, all of which have the same relation to the elements of symmetry.
Ex: difference between {111} in the triclinic and cubic systems.
The number of faces that belongs to a form is controlled by the symmetry.
The group of faces that comprise a form are designated by braces: {111}

General Form: depends on class

Triclinic, monoclinic and orthorhombic: {111}

Tetragonal, hexagonal: {121}
Isometric: {123}

Special Form: faces that are parallel or perpendicular to a symmetry element.

Open vs closed forms.

Names and descriptions of forms: see figures

Zones

A group of faces whose lines of intersection are parallel. [100]

Direct vector sum of directions, no inversion as was done with Miller Indices.
 Internal Order and Symmetry
A crystal has long range, three dimensional internal order. How are we going to
quantify and communicate this?

Translational Symmetry:
Must specify Distances and Directions
Replace the motif being repeated by a point and you have a lattice.
"An imaginary pattern of points (or nodes) in which every point (node) has an environment that is
identical to every other point (node) in the pattern. A lattice has no specific origin..." p. 110

One Dimensional Rows:

Specify direction and repeat distance

2-D Order - (Plane Lattices):

Can describe patterns by identifying the translation vectors (which have direction and magnitude).
(See figures from text.)
Many choices of translations, some are more logical or conventional.
Smallest repeatable unit is the unit cell.

Only 5 possible and distinct plane lattices (or nets). (Fig 3.5, p. 113)

Oblique net where a ≠ b and gamma ≠ 90°

Rectangular net where a ≠ b and gamma = 90°
Centered rectangular net where a ≠ b and cos gamma =a/2b (or diamond net) with a' = b' and
gamma ≠ 90, 60, 120°
Hexagonal net with a = b and gamma = 60°
Square net with a = b and gamma = 90°
Again, remember that multiple choices of the unit cell are possible.
Consider ownership of the various lattice points among adjacent unit cells.

Rotation Angle Restrictions:

See pgs. 115-116 for the proof that 1, 2, 3, 4, and 6-fold axes are the only possible ones consistent
with 2-D periodic repeats that fill space.

Symmetry Content of Planar Motifs: (Fig 3.10, p. 117)

10 possible combinations: 1, 2, 3, 4, 6, m, 2mm, 3m, 4mm, 6mm (Fig 3.10) (These are the 10 2-D
point groups we derived earlier.)
Symmetry Content of Plane Lattices: (Fig 3.11, p. 118)
Note the symmetry which is explicit and implicit in each of the 5 plane lattices.
EX. p4 or p2
Glide planes appear as combinations of translation and reflection.

2-D Plane Groups: (Fig 3.13, 3.14)

These are the 17 allowable combinations of the 5 plane lattices and the 10 translation free point
groups.

All wall-paper and other repeating, 2-D patterns must be one of these 17 plane
groups.

3-D Order - (Bravais Lattices)

So far we have derived and examined the five 2-D plane lattices and combined them with the 10 planar
point groups to generate the 17 2-D plane (space) groups. Now we will examine the 14 Bravais 3-D lattices
and combine them with the 32 3-D point groups to generate the 230 3-D space groups. To make this final
step we will also have to introduce a new symmetry operation - the screw axis. We also need to revisit glide
planes because in 3-D there is a little more to this subject than the obvious 2-D "left-right-left-right"
walking analogy.

Three-Dimensional Lattices
Start with the five 2-D plane lattices and add one additional translation out of the plane of the paper.
Depending on the lattice you start with and how special or general your choice of a 3rd translation (in both
direction (angle) and magnitude (distance)), you can generate the 14 3-D lattices that are known as the
Bravais lattices. Remember that every lattice point or node must have an identical environment.

Figure 3.17 on pages 125 and 126 provides simple explanations of the construction of each of the lattices.
Here is the summary - numbers refer to Fig. 3.17.

[1] Oblique net: Stacking an oblique net (unequal 'a' and 'b' translations in the x and y directions
respectively, at no special angle to one another) at an arbitrary angle and distance 'c' (in the z
direction) produces a primitive triclinic lattice.

[2] Rectangular net: Stacking a primitive rectangular net (unequal 'a' and 'b' translations at 90
degrees) in a vertical direction (z) at an angle (x^z) not equal to 90 degrees and a random distance 'c'
produces a primitive monoclinic lattice.

[4] If the angle (x^z) is equal to 90 degrees this produces a primitive orthorhombic lattice.

[6] Stacking this same primitive rectangular net along a direction (a special angle) that will coincide
with the body diagonal of the finished unit cell (front lower left corner toward back upper right
corner) and translating the planar net half this distance (a special distance) produces a body-centered
orthorhombic lattice.

[3] Centered rectangular net: Stacking a centered rectangular net (unequal 'a' and 'b' translations at
90 degrees) in a vertical direction (z) at an angle (x^z) not equal to 90 degrees and a random distance
'c' produces a centered monoclinic lattice. Conventionally this is referred to as being "c-centered"
because the faces that have the centered lattice point are related by the 'c' translation. Because the beta
angle (x^z) is not constrained by symmetry, it is also possible to choose a different beta angle and 'a'
translation length (along a different x direction) and convert this array of lattice points to a body-
centered monoclinic one.

[5] If the angle (x^z) is equal to 90 degrees this produces a centered orthorhombic lattice. Because
all the angles in the orthorhombic lattice are 90 degrees and all the translations are different there is no
compelling reason for a particular choice among calling this centered lattice "a-centered" or "b-
centered" or c-centered". You may also see this referred to as end-centered.

[7] Stacking this same centered rectangular net along a direction that will coincide with the front face
diagonal of the finished unit cell (front lower left corner toward front upper right corner) and
translating the planar net half this distance (a special distance) produces a face-centered
orthorhombic lattice. There is thus a lattice point in the centers of all the faces in the three
dimensional lattice.

[8] Square net: Stacking a square net along the (z) direction a random distance 'c' but constraining
the angle to be 90 degrees produces a primitive tetragonal lattice.

[9] Stacking this same square net along a direction that will coincide with the body diagonal of the
finished unit cell (front lower left corner toward back upper right corner) and translating the planar
lattice half this distance (a special distance) produces a body-centered tetragonal lattice.

[12] Stacking a square net along the (z) direction a distance 'a' equal to the translation defining the
square net ('a') and constraining the angle to be 90 degrees produces a primitive isometric lattice.

[13] Stacking this same square net along a direction that will coincide with the body diagonal of the
finished unit cell (front lower left corner toward back upper right corner) and translating the square
net half this distance (a special distance) produces a body-centered isometric lattice.

[14] It is also possible to stack square nets along a special direction (angle) and distance (translation)
which will produce a face-centered isometric lattice. The direction and angle are not obvious and at
this time you may simply accept that this is possible.

It is also possible to generate a face-centered tetragonal lattice analogous to the face-centered

isometric one. However unlike the isometric system where all three translations must be identical, in
the tetragonal system the c-axis is a different length and it is possible to choose other, shorter,
translations in the face-centered tetragonal lattice which define a body-centered tetragonal lattice.
Since shorter means smaller and this is a positive attribute for a unit cell, the body-centered tetragonal
cell is chosen.

[10] Hexagonal net: Stacking a hexagonal net along the (z) direction a random distance 'c' but
constraining the angle to be 90 degrees produces a primitive hexagonal lattice. If this lattice is
repeated 3 times by rotation about the c-axis a c-centered hexagonal lattice results.

[11] A hexagonal lattice can also be stacked along the edge directions of a rhombohedron resulting in
a rhombohedral lattice.
All 14 of these possibilities are summarized in Fig. 3.18 in your text along with the axial and angular
assignments and the conventional abbreviations for the primitive (P), the c-centered (C), the body-centered
(I) and the face-centered (F) lattices respectively.

Screw Axes
A screw axis is the result of combining a rotational operation with translation parallel to the axis of rotation.
This is analogous to combining a translation parallel to a mirror and making a glide plane. See pages 129-
132 in your text for details:

can have 2-, 3-, 4- and 6-fold screw axes

the motifs generated by the combined operation of rotation and translation define a helix
the translation distance is 1/2, 1/3, 1/4, or 1/6
screw axes can be either right-handed or left-handed
screw axis symbols consist of the rotation axis number followed by a subscript which defines the total
translation by placing the subscript over the main axis symbol as a fraction: i.e. 41 means that the
translation distance would be 1/4 of the total translation for a right-handed screw
several screw axes make up enantiomorphic pairs (right- and left-handed): 31 and 32 , 41 and 43 , 61
and 65 , and 62 and 64 .
screw axes are never expressed morphologically in crystals - all you can see is the presence of
the rotation axis

Glide Planes
The glide-line operations that you have become expert at observing in 2-D patterns in the lab have their 3-D
manifestation in glide planes. See pages 132-134 for details:

glide translations are named after the direction in which the translation occurs
i.e. a t/2 glide component in the 'b' direction is referred to as a 'b-glide'
diagonal glides are referred to as 'n glides' and have glide components such as a/2 + b/2
a diamond glide (d-glide) has a glide component with a translation that can be defined by a/4 + b/4 +
c/4
in the space group symbols to come these glides are represented by replacing the 'm' for the mirror
symmetry by either 'a', 'b', 'c', 'n', or 'd'
glide planes are never expressed morphologically in crystals - all you can see is the presence of
the mirror plane

Space Groups
The combination of the 14 3-D Bravais space lattices with the 32 translation-free 3-D point groups (or
crystal classes) and the two symmetry operations that involve translation (screw axes and glide planes) gives
us the 230 space groups.

These are all the ways that atoms can be arranged in space in an infinite repeating pattern.
Because the translation distances in the lattice and the glide planes and the screw axes are on the order
of a few angstroms they can not be seen by eye and so morphologically all 230 space groups appear
to us as one of the 32 crystal classes.
All the space groups are said to be 'isogonal' with one of the 32 point groups, "the point group is the
translation-free residue of a family of possible isogonal space groups."
The space group symbol is composed of a letter designating the lattice type (P, A, B, C, I, F, R)
followed by the symmetry such as I2/b2/a2/m
Need to be aware of the use and meaning of abbreviated symbology in the systematic mineralogy
chapters where the above I2/b2/a2/m would be reported as Ibam. The justification of this abbreviation
is that mirrors (or glides) intersecting at 90 degrees create 2-fold axes and thus they don't really have
to mentioned explicitly in the symbol.
You definitely need to be able to reduce complete space group designations to their isogonal point
group because, again, this is what the crystal should actually look like. For example you need to
recognize that P 21 /n 21 /m 21 /a is an orthorhombic crystal with 2/m 2/m 2/m symmetry. In the
systematic mineralogy section this would be designated Pnma.