Answers to Problem Set 3
(a) The Unit Cell,
(b) The Crystal Lattice,
(c) The Origin in Reciprocal Space,
(d) The Origin in the Crystal,
(e) The Space-Group Symmetry of the Crystal.
(a) The Unit Cell. (ii) Chosen by the crystallographer - the most convenient one.
(b) The Crystal Lattice. A set of equally-spaced points -
(i) due to packing of atoms/molecules in crystal.
(c) The Origin in Reciprocal Space. (iii) Neither (i) or (ii),
this origin corresponds to the streight through X-ray beam.
[straight]
(d) The Origin in the Crystal. An arbitrary point, (ii) chosen by the crystallographer.
(e) The Space-Group Symmetry of the Crystal. (i) Due to packing of atoms/molecules in crystal.
Actually, the space-group symmetry is the minimal set of rules which describe their packing in crystal.
5 Marks
There are eleven classes of crystal groups, descernable from 2D Laue photographs
(giving, hence, only 2D crystallographic groups). The diffraction pattern unavoidably
"adds" a center of symmetry to the actual point group, so that the observed Laue class
can be regarded as a "hint" for that group.
Derivation of Laue class from a point group: one should remove translational
components from operators. Here are two examples, for groups C2/c and P21c,
respectively:
Symmetry
After removal of
Symbol
operator
translational components
x, y, z
=>
x, y, z
1
-x+1/2, -y, z
=>
-x, -y, z
2
-x, -y, -z
=>
-x, -y, -z
-1
x+1/2, y, -z
=>
x, y, -z
m
=> group C2/c correponds to Laue class 2/m.
Symmetry
After removal of
Symbol
operator
translational components
x, y, z
=>
x, y, z
1
-x+1/2, y+1/2, -z+1/2
=>
-x, y, -z
2
-x, -y, -z
=>
-x, -y, -z
-1
x+1/2, -y+1/2, z+1/2
=>
x, -y, z
m
=> group P21c correponds to Laue class 2/m either.
Corrected HTML file just here:
Added </DD></DL>
Comment: Full marks can only be achieved
when two different Laue classes are given, despite the fact that you clearly
understand how the Laue class relates to the real-space symmetry of
the crystal.
Minor comment: Safest to state explicitly
that the Laue class has the symmetry of the reciprocal lattice.
4 Marks
Which of these symmetry operations cannot be found in the crystal structure of an enantiomorphic molecule, e.g. a naturally-occurring sugar such as D-glucose? Give brief reasons for your answer.
All the symmetry operations which change handedness are out of question in the case of
an enantiomorphic molecule. Practically, this means: symmetry operations which
contain inversion. From given operations such are rotary-inversion, and
glide planes (mirroring is combination of rotation by 180 degrees, plus inversion).
Comment: Correct symmetry operators identified,
but no explanation of the property of an enantiomorphic molecule which makes
the rotary-inversion and planes forbidden symmetry operations. (It is
tautological to simply state that an enenatiomorphic molecule is one to
which these symmetry operations cannot be applied.) Answer is just too brief.
3 Marks
If the coordinates of the central metal atom, Co, in this compound are 0.271,0.250,0.458, determine the coordinates of any other Co atoms within the unit cell, showing your workings.
Is the Co atom sited on a special position in this space group? Give brief reasons for your answer.
This group has four symmetry operators, and their action upon coordinates of given Co atom
is shown in the following table:
| Symmetry operation | New x | New y | New z | Final x | Final y | Final z | ||
| x, y, z | : | 0.271 | 0.250 | 0.458 | ||||
| -x, 1/2+y, 1/2-z | : | -0.271 | 0.750 | 0.042 | => | 0.729 | 0.750 | 0.042 |
| -x, -y, -z | : | -0.271 | -0.250 | -0.458 | => | 0.729 | 0.750 | 0.542 |
| x, 1/2-y, 1/2+z | : | 0.271 | 0.250 | 0.958 |
[The second and the third operation have given atom positions outside the unit cell, and had to be corrected by an appropriate translation.]
Apparently, there are four different Co atoms in the unit cell. Not a one of them is on a special position, i.e. at a point of inversion, or on a two-one screw axis, or a glide plane.
![]() |
![]() |
![]() |
| View A |
View A, but then rotated »35° about Y |
View A, but then rotated 90° about Y |
|---|
Only one symmetry element is present: point of inversion, situated in the middle of the bond
between two central atoms.
Corresponding molecular point symmetry, therefore, would be -1.
Comment: See model answer
1 Mark
Minor comment: Correct deduction if previous
answer were correct
2 Marks