Dept.

of Chemistry , CH-402, Solid State Chemistry

Lecture no: 10

Chapter: Symmetry elements and operations

Contents:
➢ Crystal systems
➢ Symmetry elements
➢ Symmetry Operations
➢ Point groups
1. High order point groups
2. Low order point groups
➢ Assigning point groups

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Crystal Systems

Crystal system is a method of classifying crystalline substances on the basis of their

unit cell. There are seven unique crystal systems. A Crystal System refers to one of
the many classes of crystals, point groups, space groups, and lattices.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Symmetry elements: Discussed before in previous lecture.

Symmetry Operations: A symmetry operation is an action that leaves an object looking the
same after it has been carried out.

1. Reflection is a symmetry operation which causes a set of points to be mirrored across a

plane. We call this plane the “mirror plane.” Any point (X,Y,Z) becomes (-X,Y,Z) if there is
a mirror axis perpendicular to the X direction.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

2. Rotation is a symmetry operation which causes a set of points to be rotated around

a point. We call this point an “axis of rotation.” In polar coordinates, any point (R, θ,
φ) becomes (R, θ + 360º/n, φ) for an n- fold rotation axis perpendicular to θ.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

N-Fold Axis of Rotation Symmetry

➢ This is an axis passing through the crystal such that if the crystal is rotated around it through
some angle, the crystal remains unvaried.
➢ The axis is called `n-fold, axis’ if the angle of rotation is 360o/n
➢ If equivalent configuration occurs after rotation of 180º, 120º , 90º and 60º the axes of
rotation are known as two-fold, three-fold, four-fold and six-fold axes of symmetry,
respectively.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

➢ If n=1, the crystal has to be rotated through an angle = 360º, about an axis to achieve
self coincidence. Such an axis is called an `identity axis’. Each crystal possesses an
infinite number of such axes.
➢ If n=2, the crystal has to be rotated through an angle = 180º about an axis to achieve
self coincidence. Such an axis is called a `diad axis’. Since there are 12 such edges
in a cube, the number of diad axes is six.

➢ If n=3, the crystal has to be rotated through an angle = 120º about an axis to achieve
self coincidence. Such an axis is called is `triad axis’. In a cube, the axis passing
through a solid diagonal acts as a triad axis. Since there are 4 solid diagonals in a
cube, the number of triad axis is four.
➢ If n=4, for every 90º rotation, coincidence is achieved and the axis is termed `tetrad
axis.
➢ If n=6, the corresponding angle of rotation is 60º and the axis of rotation is called a
hexad axis. A cubic crystal does not possess any hexad axis.
➢ Crystalline solids do not show 5-fold axis of symmetry or any other symmetry axis
higher than `six’, Identical repetition of a unit can take place only when we consider
1,2-,3-,4- and 6-fold axes.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Let us consider a lattice P Q R S as shown in figure

Why not 5-fold

symmetry?

➢ Let this lattice has n-fold axis of symmetry and the lattice parameter be equal to ‘t’.
➢ Let us rotate the vectors Q P and R S through an angle ɷ = 360°/n in the clockwise and anti
clockwise directions, respectively.
➢ After rotation, the ends of the vectors be at A and D.
➢ Since the lattice PQRS has n-fold axis of symmetry, the points A and D should be the lattice
points.
➢ Further the line AD should be parallel to the line PQRS. Therefore, the distance AD must
equal to some integral multiple of the lattice parameter ‘t’ say, mt
➢ Where, m = 0, ±1, ± 2, ± 3, ….

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Again, AB = CD, Thus, AD = t+ 2AB
mt = t+2t cos ɷ ………… (1)
From equation (1), 2t cos ɷ = m t – t
2cos ɷ = (m-1)
N= (m-1), where N is again 0, ± 1, ± 2, {since (m-1) is also an integer say, N}
cos ɷ = N/2 ………………..(2)

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

3. Inversion is a symmetry operation which pulls every point through an “inversion center” to
the other side. Any point (X, Y, Z) becomes (-X, -Y, -Z) if there is an inversion center at the
origin. You can combine rotation with inversion to produce the roto-inversion symmetry
operation

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

4. Translation is a symmetry operation that moves a set of points through space. Point groups
DO NOT involve translation. Any point (X,Y,Z) becomes (X+a, Y, Z) for translation of length
a in the X-direction.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Molecular Point Groups

It is only possible for certain combinations of symmetry elements to be present in a molecule
(or any other object). As a result, we may group together molecules that possess the same
symmetry elements and classify molecules according to their symmetry. These groups of
symmetry elements are called point groups (due to the fact that there is at least one point in
space that remains unchanged no matter which symmetry operation from the group is applied).
There are two systems of notation for labeling symmetry groups, called the Schoenflies and
Hermann-Mauguin (or International) systems. The symmetry of individual molecules is
usually described using the Schoenflies notation, which is used below.

Low Symmetry Point Groups

Group Description Example

C1 only the identity operation (E) CHFClBr
Cs only the identity operation (E) and one mirror plane C2H2ClBr
Ci only the identity operation (E) and a center of inversion (i) C2H2Cl2Br

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

High Symmetry Point Groups

High symmetry point groups include the Td, Oh, Ih, C∞v, and D∞h groups. The table below
describes their characteristic symmetry operations. The full set of symmetry operations
included in the point group is described in the corresponding character table.

Group Description Example

linear molecule with an infinite number of rotation axes and vertical
C∞v HBr
mirror planes (σv)
linear molecule with an infinite number of rotation axes, vertical mirror
D∞h planes (σv), perpendicular C2 axes, a horizontal mirror plane (σh), and an CO2
inversion center (i)
typically have tetrahedral geometry, with 4 C4 axes, 3 C2 axes, 3
Td CH4
S4 axes, and 6 dihedral mirror planes (σd)
typically have octahedral geometry, with 3 C4 axes, 4 C3 axes, and an
Oh SF6
inversion center (i) as characteristic symmetry operations
typically have an icosahedral structure, with 6 C5 axes as characteristic
Ih B12H122-
symmetry operations

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Table : Common Point Groups for Molecules

Nonaxial
C1 Cs Ci - - - - - -
groups
Cn groups C2 C3 C4 C5 C6 C7 C8 - -
Dn groups D2 D3 D4 D5 D6 D7 D8 - -
Cnv groups C2v C3v C4v C5v C6v C7v C8v - -
Cnh groups C2h C3h C4h C5h C6h - - - -
Dnh groups D2h D3h D4h D5h D6h D7h D8h - -
Dnd groups D2d D3d D4d D5d D6d D7d D8d - -
Sn groups S2 - S4 - S6 S8 S10 S12
Cubic
T Th Td O Oh I Ih - -
groups
Linear
C∞v D∞h - - - - - - -
groups

*** Some of the point groups share their names with symmetry operations and or
elements, so be careful you do not mix up the two. It is usually clear from the context
which one is being referred to.
Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal
 Dept. of Chemistry , CH-402, Solid State Chemistry

1. C1 - contains only the identity (a C1 rotation is a rotation by 360° and

is the same as the identity operation) e.g. CHDFCl.

2. Ci - contains the identity E and a center of inversion i .

3. Cs - contains the identity E and a plane of reflection σ .

4. Cn - contains the identity and an n -fold axis of rotation.

5. Cnv - contains the identity, an n -fold axis of rotation, and n vertical

mirror planes σv .

Point groups – Symmetry operations

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

6. Cnh - contains the identity, an n-fold axis of rotation, and a horizontal

reflection plane σh (note that in C2h this combination of symmetry
elements automatically implies a center of inversion).

7. Dn - contains the identity, an n-fold axis of rotation, and n 2-fold

rotations about axes perpendicular to the principal axis.

8. Dnh - contains the same symmetry elements as Dn with the addition of a

horizontal mirror plane.

9. Dnd - contains the same symmetry elements as Dn with the addition of n

dihedral mirror planes.

10. Sn - contains the identity and one Sn axis. Note that molecules only belong to Sn if they
have not already been classified in terms of one of the preceding point groups (e.g. S2 is the
same as Ci, and a molecule with this symmetry would already have been classified).

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

11. Td - contains all the symmetry elements of a regular tetrahedron,

including the identity, 4 C3 axes, 3 C2 axes, 6 dihedral mirror planes, and
3 S4 axes e.g. CH4.

12. T - as for Td but no planes of reflection.

13. Th - as for T but contains a center of inversion.
14. Oh - the group of the regular octahedron e.g. SF6.

15. O - as for Oh, but with no planes of reflection

Once you become more familiar with the symmetry elements and point groups described
above, you will find it quite straightforward to classify a molecule in terms of its point
group. In the meantime, the flowchart shown below provides a step-by-step approach to
the problem.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Flowchart to identify molecular point groups using Schoenflies notation system.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Identifying Symmetry Elements and Point group:

Practice session

(a) HCN (b) H2O

Symmetry elements:
E, C2, 2σv
Symmetry elements: E, C∞, σv
Point group = C∞v Point group: C2v

C2v Cnv
Yes, 2σv

Linear ? Linear ? nσv ?

Yes No No

Centre of inversion, i ? 2 or more Cn where n>2 ? σh ?

No No No

C∞v Cn ? n C2 ┴ to principle Cn ?
Yes, C2
Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal
 Dept. of Chemistry , CH-402, Solid State Chemistry

(c) (d) Ethane (Eclipsed)

Symmetry elements: E
Point group: C1 Symmetry
Elements:

E, Principle C3 axis
of rotation, 3
perpendicular C2
Linear ? axes. 3 σv , σh
No
2 or more Cn where n>2 ? σh σv
σv
N
o
Cn ? σv
No
σh ?
No
No 3D representation of horizontal and vertical mirror plane
Centre of inversion, i ? C1
Problem: Prepare the flow chart to find the point
groups of Ethane (eclipsed and staggered).

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

(e) Benzene
Symmetry Elements:
E, principle axis C6 , 6C2, 3σv , σh , 3σd

Prepare the flow chart to

determine the point group of
benzene.

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

(f) SF6
Symmetry Elements:
E, 3 C4, 4 C3, 9 C2, 4 S6, 3 S4, 3 σh, 6 σd
and a centre of inversion i .

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Determine symmetry elements and assign point

groups of the following compounds

• HCl • C4H4
• CO2 • CH3Cl
• H3C-CH3 • CO
• NH3 • SF6
• CH4 • H2O2
• CHFClBr
• H2C=CClBr

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal

 Dept. of Chemistry , CH-402, Solid State Chemistry

Nahida Akter, Assistant Professor, Dept. of Chemistry, University of Barisal