POINT GROUP

Symmetry elements can combine in a definite number of ways. For example consider BF 3
molecule. It has the C3 axis as the principal axis. Also, there are 3 C2 axes perpendicular to the C3 axis,
3 σv planes, and one σh plane. All these symmetry elements can combine. Take NH3. It also has C3 axis
as principal axis. There are 3σv planes, but no C2 perpendicular to C3 or a σh plane. For the N2F2
molecule there exist one C2 axis and a σh plane but no σv planes.

Thus in general we can say a Cn can combine with either nC2 or no C2 perpendicular to it; it can
combine with either one σh or no σh; or it can combine with n vertical planes or no vertical planes. These
are relevant only in the case of systems where we can identify a principal axis. Such systems are called
axial systems.

In the case of tetrahedral, octahedral, cubic, icosahedral and dodecahedral objects we cannot
identify the principal axis. Solids of these structures are called platonic solids. Crystals and molecules of
these shapes are highly symmetric and can be called multi higher order axial systems. They have several
higher order axes than C2 axis. The symmetry elements combine in definite ways in these systems also.

Point Groups

Point groups are possible combinations of symmetry elements. Since symmetry elements can combine
only in a definite pattern, there will be only a finite number of point groups possible. For crystals only
32 points groups exist. Crystals cannot have axes of symmetry order 5 or higher than 6. On the other
hand molecules can have proper axes of symmetry of order 5, 7 and ∞ also. Hence for molecules some
additional point groups are possible which are not possible for crystals.

Redundant symmetry elements: symmetry elements which combine to form a point group are known
as essential symmetry elements. There exist some symmetry elements which are present as a
consequence of the essential symmetry elements. Consider BF3 molecule. The essential symmetry
elements needed, for the point group under which this molecule comes, are E, C 3, 3σv, σh. The presence
of C3 and σh give rise to S3 (ie. σhC3). The following table provides the possible point groups for
molecules and crystals. The notation given is the Schoenflies notation which is applicable to molecules.
In the case of crystals the Hermann-Mauguin notation is used.
 Molecular point groups

Point group redundant

Values of n for Values of n for
(Schoenflies Essential symmetry elements symmetry
molecules crystals
notation) elements
Cn Only a proper axis Cn - 1,2,3,4,5,6 1,2,3,4,6
Cs Only a plane of symmetry -
Ci Only centre of symmetry -
Cnh A proper axis Cn and σh Sn 2,3,4,5,6,7,∞ 2,3,4,6
Cnv A proper axis Cn and nσv - 2,3,4,5,6,7, ∞ 2,3,4,6
A principal axis Cn and nC2
Dn - 2,3,4,5,6 2,3,4,6
perpendicular to that
Sn, nσv
A proper axis Cn, nC2
Dnh (i for even 2,3,4,5,6,7, ∞ 2,3,4,6
perpendicular to that and σh
values of n)
A proper axis Cn, nC2
Dnd S2n 2,3,4,5 2,3
perpendicular to that, and nσd
Sn Only an Sn - 2,4,6 2,4,6
T 4C3 and 3C2
Th 4C3 , 3C2 and σh or i
Td 4C3 , 3C2 and 6σd 3S4
O 3C4, 4C3 , and 6C2
3S4, 4S6,
Oh 3C4, 4C3 , 6C2 and 3σh
6σv and i

Cyclic point groups (Cn,Cnv, Cnh and Sn): A molecule which possesses only a C n axis come under the Cn
point group. Here C stands for cyclic and n stands for order of the axis. C n represents five groups,
namely, C1, C2, C3, C4, C5 and C6.C5 is a non-crystallographic point group. C1 is the point group with no
element of symmetry.

H O
O O
F P
Br H H H O H C5(CH3)5.
Cl O
O
H

Hydrogen peroxide Phosphoric acid pentamethyl

bromochlorofluoro methane
cyclopentadienyl
C1 point group C2 point group C3 point group C5 point group

S2
C6(CH3)6.

hexamethyl Br
N
cyclohexadienyl Quinoline
Cl Ci point group
C6 point group Cs point group i
Cl

Br
 Assigning Point Group

First of all we look for an axis of symmetry and find whether it is the principal axis or not. There
can be molecules without an axis of symmetry at all and corresponding point groups are C i, Cs, S4 and
C1only. If axes of symmetry are there and the principal axis cannot be identified, the point group can be
Td, Oh or Ih. If there is a Cn axis and nC2 axes perpendicular to it the point group will be dihedral, D n,
Dnh, Dnd. Otherwise, the point groups will be C n, Cnh, or Cnv. Thus the following steps are involved in
assigning the point group.
Identify,
1. The presence of an axis of symmetry
2. This axis as principal axis or not
3. The existence of subsidiary axes
4. The existence of σh
5. The presence of nσv’s
6. Whether belongs to Ci, Cs, S4 or C1, if principal axis is absent.
This procedure can be simplified by asking certain questions to ourselves and finding ‘yes’ or ‘no’
answers.
Is there an axis of symmetry?
(Find the highest order axis)

No Yes

Is there a plane of symmetry? Is it the principal axis?

No Yes No Yes

Is there an i? Cs Look for Td and Oh Are there nC2’s

point groups perpendicular Cn?
No Yes

No Yes
Is there anSn?
Ci
Is there a σh? Is there a σh?
No Yes
No Yes No Yes

C1 Sn Are there nσv?

Cnh Are there nσd? Dnh
No Yes No Yes

Cn Cnv Dn Dnd