1

_________________________________________________________________________________________

Subject Chemistry

Paper No and Title 13 Applications of molecular symmetry and group theory

Module No and Title 7: Classification of molecules into point group part-II

Module Tag CHE_P13_M7

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 2
_________________________________________________________________________________________

TABLE OF CONTENTS

1. Learning outcomes
2. Introduction
3. Some more types of point groups
3.1 Examples of type-III dihedral point groups i.e. D-groups
(i)Dn (ii) Dnh (iii) Dnd
3.2 Examples of type-IV Cubic group or special point groups
4. Special point groups
5. Classification of molecules in point groups
5.1 Different ways of classification
5.2 Flow chart scheme and flow chart
5.3 Examples of molecules
6. Summary

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 3
_________________________________________________________________________________________

1. Learning Outcomes

After studying this module, you shall be able to

o Learn more examples of molecules belonging to different point groups

o Learn more examples of type III dihedral point groups i.e. D-groups ie
o Dn, Dnh, Dnd
o Learn more examples of type IV cubic point group or special point groups ie
o T d, O h, I h
o Examples of some more special point group, C∞v , D∞h , kh
o Recognize the symmetry elements present in the molecules
o Have the knowledge that presence of certain symmetry elements require the existence of
other symmetry elements
o Know the scheme of classifications of molecules into point groups
o Have the practice of finding the point group

2. Introduction
In earlier modules classification of molecules into point group we have discussed type-I and type –II
Point groups and various examples have been discussed. In this module we will continue with other types
of point group and their examples. Only few examples will be taken and discussed.
In earlier module on classification of molecules you have come across the various types of point groups,
Number of examples of each point group were given and explained in detail. In this module you will see
how to classify the molecules into point group.

3. Some more types of point groups:

In this module we will continue with more point groups and their examples

3.1 Examples of type-III dihedral point groups (D - groups):

In the molecule of type III dihedral point groups there are Cn axis and nC2 axes perpendicular to
Cn axis. Point groups belonging to this category are Dn , Dnh , Dnd . Let us discuss each of
these separately.

(i) Dn point groups:

Molecules belonging to this type only have Cn axis and nC2 axes perpendicular to Cn axis and no
other symmetry elements are present in them .Few examples of this type are shown in fig.1.
These are (i) Cation [Co(en)3]3+ (ii) Twisted biphenyl (D2) (iii)Twisted ethylene (D2) (iv)
perchloro triphenylamine(D3) (v) Twistane (D2) (vi)Gauche form of ethane(D3).

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 4
_________________________________________________________________________________________

5
en
1
C2 en 5
C3
5 1
4 en
3 4 4
C2 '
en 2 1
en 6 en
2 en 2
3 3
en en
C 2"
6 6 (ii)
(i) Cl D2
Cl Cl
D3
Cl Cl H
H H
H H
C C N
Cl Cl H
H
H Cl Cl H
H (iii) Cl Cl
Cl Cl Cl Cl (v) (vi)
D2 (iv) D3
D3 D2

Fig.1 Examples of molecules belonging to Dn point group

(ii) Dnh point groups:

Molecules belonging to Dnh point group must have Cn axis, nC2 axes perpendicular to Cn axis
and σh.These symmetry elements generate all symmetry operations which belong to Dnh point
group. Presence of these symmetry elements automatically requires the existence of nσv. If the
Cn axis is of even order its combination with σh generates ‘i’. Hence the elements of the Dnh
group are: E,C2, nC2, σh, i, Sn. If Cn axis is of odd order, then the elements of the group are; E,
C2, nC2,σh, S2n , nσv. The order of the group is 4n. Some examples of Dnh point group are shown
in fig.2 These are: (i)Ethylene,(ii)Naphthalene,(iii)[PtCl4]2-,(iv)Trans –[PtCl2Br2]2-
,(v)Cyclopentadienyl

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 5
_________________________________________________________________________________________

C2 C C2 C2 C4
2
H H Cl Cl 2-
C C C2 σh
Pt
σh
C2
H H Cl Cl
i
( ) D2h
(iii) D4h,C4 axis is ⊥ to plane of
C2 axis is ⊥ to
(ii) D2h plane of molecule the molecule ie σh and 4C2 axes are lying
in σh

C2 C
2
Cl Br 2-
Pt
Br Cl
C2
(v) D5h C5 axis is ⊥ to ring and
(iv) D2h oneC2 axis is⊥ to plane of
the molecule ie σh and 2C2 axes are lying 5C2 axes are lying in σh
in σh the plane of the molecule

Fig.2 Examples of molecules belonging to Dnh point group

(iii) Dnd point groups:

Molecules belonging to Dnd point group must have Cn axis, nC2 axes perpendicular to Cn axis and
σd. The dihedral planes lie in Cn axis but bisect the angle made by perpendicular axes. The order
of the group is 4n. But order changes with the order of the principal axis of rotation. For n=odd,
symmetry elements are; Cn, nC2, nσd , S2n and for n =even the elements are; S2n, nC2,
nσd,(symmetry operations of Cn are included in that of S2n ). Examples of molecules belonging to
the Dnd point group are given in fig.3. These are: (i)Quashed Td Cs2[CuCl4] (ii) allene,(iii)
staggered ethane(iv) S8 molecule.
C2 C2
C2 C2
H
Cl
Cl H
Cu C C C C2
C2
Cl H
Cl
(i) D2d, 3C2 passing through opposite H
faces two of these are shown here
σd throughClCuCl bonds and bisecting (ii) D2d ,allene molecule σd,s are
opposite ∠ClCuCl through longer edges top face and
that of lower opposite face and C2 axes are
as shown

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 6
_________________________________________________________________________________________

C3

H H C2 axis 1 2
S S
S
H H S3 4 S
S S
S
H H
(iv)D4d S1,S2,S3S4 are in one plane
(iii) D3d C2 and C3 axes as and C4 axis is ⊥to this plane, it has 4C2
shown and σd's lies between C2 axes axes and σd, use model for this
Fig.3 Examples of molecules belonging to Dnd point group

3.2 Examples of type-IV Cubic group or special point groups:

The point group discussed so far contained only one high order axis Cn.≥2. Now we will deal
with the molecules which have more than one Cn axis of higher order (n>2). The set of symmetry
elements that are obtained from combination of several higher order axes correspond to the
symmetry of regular polyhedra. All the faces of regular polyhedra have same regular polygon
shapes. The angle and edges have same dimensions. There are five types regular polyhedra .The
five polyhedra together with their characteristics are given in fig.4

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 7
_________________________________________________________________________________________

Fig.4 Characteristic of five Platonic solids

Point groups belonging to this category are, T, Th Td , O ,Oh, I, Ih, and so on. Of these point
groups only common point groups Td, Oh and Ih will be discussed.

(i)Td point group:

In this point group molecules have four C3 axes along the body of diagonals of a cube if
tetrahedron is inscribed into the cube. The centre of the cube is the origin of coordinate system in
which the coordinate axes are parallel to the sides of the cubes as shown below in fig .5

Fig.5 Tetrahedron inscribed in a cube

The symmetry operations of Td point group are [ E,8C3 3C2,6S4,6σds’]. Three S4 coinciding with
three Cartesian coordinates are taken as principal axes. The six 6σds’ bisect the angles between
CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory
MODULE No.9 : Classification of molecules into point group part- II
 8
_________________________________________________________________________________________

each pair of C3 axes. The order of the group is 24.Example of molecules belonging to Td point
group is given in fig.6. These examples are

CH3

H3C CH CH3
3
(i) Td point group (ii)Td point group (iii) Td point group
Fig.6 Examples of molecules belonging to Td point group

(ii) Oh point group:

These point group’s molecules possess three mutually perpendicular C4 axis which coincide with
cartesian coordinates x,y,z axes and point of their intersection is the origin.. Its symmetry
operations are [ E,8C3,6C4,3C2,6C2, 6σv’s,3σh’s ,i,,6S4 and 8S6]. The order of the group is 48. The
octahedron inscribed in cube and some symmetry elements/symmetry operations are shown in
figure.7
C4

σh

C2

Fig.7 Octahedron inscribed in a cube

Examples of molecules belonging to Oh point group are given in fig.8 and these are;(i)
Mn(CO))6,(ii) [PtCl6]2-,(iii)PF6 ( iv) SF6,(v) [AlF6]3-.

CO CO
Cl Cl 2-
F F -

OC Mn CO Cl Pt Cl F P F
CO
CO Cl Cl F
(i) (iii)
F
(ii

F F F 3-
F
F S F F Al F
F F
(iv) F F
(V)

Fig.8 Examples of molecules belonging to Oh point group

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 9
_________________________________________________________________________________________

(iii) Ih point group:

Molecules belonging to this point group are rare. Molecules with icosahedral (20 triangular
faces) and dodecahedral (12 pentgonal faces) belong to Ih point group. The [B12H12]2- anion is
an example of regular icosahedral (fig.9). The symmetry operations in Ih point group
are;[E,6C51,6C52,6C53, 6C54,10C31,10C32, 15 C2 ,i ,6S10,6S103,6S107, 6S109, 10S6,10S65,15 σ]
and order of the group is 120, Some more examples for Ih are; dodecahedron, and
fullerene(C60) .
BH 2-

BH
BH

BH
BH
HB BH

BH BH
BH

BH

Fig.9 Structure of [B12H12]2- belongs to Ih point group

4. Special point groups

(i) Linear molecules: All linear molecules belong to C∞v or D∞h point groups. Linear molecules
with centre of inversion i.e. symmetric linear molecules such as H2, CO2, C2H2, N2 belong to D∞h
point group . These have 2C ∞ axes and ∞ C2 axes ┴ to C∞ axes,i ∞ σv and 2S ∞ and non
Φ Φ

symmetric linear molecules i.e. which lack centre of symmetry such as hetero nuclear diatomic
molecules; HCl , CO, NO, HD ,HF, HCN, SiH, KH, HSe, etc belong to C∞v point group. These
molecules have C ∞, ∞ σv . Fig.10 gives some symmetrical figures which belong to D∞h point
Φ

group.

C∝

n-gonal prisim

Fig.10 Symmetrical figures belonging to D∞h point group

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory
MODULE No.9 : Classification of molecules into point group part- II
 10
_________________________________________________________________________________________

(ii) Kh group: This point group characterizes the sphere. This geometry is possessed by all free
atoms. All possible symmetry elements belong to this point group. Free atoms, H, D, He, Cl., Ca,
belong to this point group. Figure .11 shows symmetry of perfect sphere.
z

x
Fig.11 Symmetry of a perfect sphere

5. Classification of molecules in point groups

The success of the quickest method of classification of molecules into point groups depends upon one’s
ability to recognize the symmetry elements present in the molecules. The skill can be developed by
continuous practice.
Before going through the scheme of classification it is very necessary that you are familiar with the
shapes of molecules. Table.1 gives some of the shapes/geometries of the molecule according to VSEPR
theory.

Table.1 Some common shapes of the molecules

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 11
_________________________________________________________________________________________

Molecule Geometry Shape

trigonal planar Y
XY3
X
Y Y

pyramidal X
XY3 Y
Y Y
Y
X
XY4 Tetrahedral Y Y
Y
Y Y
XY4 Square planar X
Y Y
Y
Y
XY5 triangular bipyramidal X Y
Y
YY
Y Y
XY5 square pyramidal X
Y Y
Y
XY6 Y Y
Octahedral X
Y Y
Y

5.1 Different ways of classification: Two ways of classifications will be discussed. You are directed
to look at the shape of the molecule and answer the question as asked and go through the various steps to
arrive at the point group of the molecule.
In first way various steps involved are:

(I) Find whether the molecule belongs to special point groups ie very high symmetry point groups Td,Oh,
Ih , C∞v, D∞h as described earlier.

(II) For all remaining molecules, find whether the molecule has rotation axis of any order, if yes go to
step IV otherwise go to Step III.

(III) (i) Molecule does not have any symmetry element---C1 point group

(ii) Molecule has only one σ------------------------------Cs point group

(iii) Molecule has only ‘i’ ---- ------------------------Ci point group

(IV) Look for nC2 axes perpendicular to Cn axis. If these are there go to step V.

If these are not there , look for σv, σh , no symmetry element , or only S2n colinear with Cn axis

(i) if only σv is there it is -------------------------------------Cnv point group

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory
MODULE No.9 : Classification of molecules into point group part- II
 12
_________________________________________________________________________________________

(ii) if σh is there it is -----------------------------------------Cnh point group

(iii) if no other symmetry element except Cn axis , see whether it has S2n axis colinear with Cn axis , if S2n
is there point group will be S2n otherwise it is simply Cn point group.

(V) If molecule has nC2 axes perpendicular to Cn axis it belongs to Dn group

.
(i)If molecule also has σh -------------------------- Point group is Dnh.

(ii) If molecule besides Dn group has σd also ------ Point group is Dnd

(iii) If neither σh nor σd is there molecule will belong to Dn group

5.2 Flow chart scheme and flow chart: In the second scheme of classification of molecules into point
groups follow the following flow chart given in fig.1 and answer the questions as asked in boxes in Yes
or No simply. The answer to each question will take you to next question until a point group is finally
determined.
The first question is whether the molecule is linear or not. Yes or No to this will direct you to next
question and so on. Presence of each and every symmetry element must be verified before you are certain
about the point group of the molecule. This second scheme of classification of the molecules into point
group is very simple and easy to follow provided you are well aware the shape of the molecule in
question.

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 13
_________________________________________________________________________________________

START

yes yes
D∝h is there i ? linear?

No No

C∝v

are there

yes
yes yes two or more
Ih is thereC5? is there i ? Cn with n>2 ?

No
No No
Oh
Td

See is there
yes yes
yes highest order
Cn axis and aCn ?
Dnh is there σh? nC2 ⊥ to it?
No No
No yes
yes Ci is there i ?
Dnd is there σd? yes
is there σh ?
Cnh No
No No
yes
Cs is there σ?
yes
Dn Cnv is there σv?
No
No
C1
yes
S2n is therS2n
colinear with Cn?

No
Cn

Fig.1 Flow chart for the scheme of classification of the molecules into point groups

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 14
_________________________________________________________________________________________

Point groups O,T, Th, Ih, and I, have not been included in the scheme as these are not very common point
groups.
5.3 Examples of molecules
Let us classify molecules into point groups using this flow chart.
(i) Example of CHFBrCl
H

Br Cl
F

Let us start using flow chart CHFBrCl

Is it Linear?
No
Does the molecule contain
two or more unque C3 axis, ie n>2?
No

Does molecule has proper axis?

No
Does molecule has σ?
No
Does molecule has i ?
No

Molecule belongs to
C1 point group?

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 15
_________________________________________________________________________________________

(ii)Example of trans -1,2-bromoethylene

H Br
C C σh

Br H
C2

Is it linear? Does molecule

C2H2Br2 No contain two or moreCn axes n>2?
No
Does molecule
contain Cn axes ?
Does molecule
Molecule belongs contain σh ?
Yes
yes ,C2 axis as shown
to C2h point group
but does not have ⊥nC2 axes

(iii)Example of dichloromethane CH2Cl2

C2,2σv
CH2Cl2
Is molecule H H
linear ?
No C
Does the molecule
contain two or more Cn>2 ?
Cl Cl

Does the molecule

No contain nC2axes ⊥ to Does molecule
Does the molecule NO
yes ,of Cn axis ? contain σh?
contain Cn ? No
order 2 ie C2

Does molecule
molecule belongs to yes contain σv?
C2v point group

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 16
_________________________________________________________________________________________

C3
F
F
(iv)Example of PF5
F P C2
F
F
Is molecule Does the molecule Does the molecule
linear ? contain two or more Cn>2 ? contain Cn ?
PF5 No No yes of
order 3 ie C3

?
is
ax
n
C
to
es e
2 ax cul
⊥
nC ole
m
nta he
co oes t
in
Does molecule D
contain σh?
molecule belongs to yes
D3hpoint group
yes , it has 3 C2 axes⊥ toC3

C4 C4
Cl Cl
(v) Example of WF5Cl F F
Is molecule linear? F W F F W F
F F
No F F
Does the molecule contain
two or more Cn axes of order n >2?
Does the molecule has
4C2 axes ⊥ to Cnaxis?
NoDoes it contain Yes it is of order C4 No
along ClWF ?
σh
Cn axis? ve
e ha
ul
Does the molecule ec
molecule belongs
has σv ol
to C4v point group Yes it has 4σv
as shown in structure
No es
M
Do

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II
 17
_________________________________________________________________________________________

(vi)Example of PF4Cl ( Cl equatorial)

F
F Cl
P
Is molecule linear?
F C2
F
No
Does the molecule contain
two or more Cn axes of order >2?
Does the molecule has
2C2 axes ⊥ to C2 axis?
Yes it is of order C2
No Does it contain along ClP bond
Cn axis?
Yes it has 2σv Does the molecule No
molecule belongs containing axial FPF bond and PCl bond have σv does molecule have σh?
to C2v point group and bisecting one of the∠FPF No
and second σv is
the equatorial plane having 2F's
and Cl

6. Summary
o Point groups of type III and type IV discussed
o Examples of type III point groups Dn, Dnh, Dnd discussed and explained
o Examples of type IV point groups Td, Oh, Ih mentioned and discussed
o Examples of some more special point group, C∞v , D∞h , kh discussed
o In all diagrams are given and where ever possible symmetry elements present in them
are also shown
o Different geometries of the molecules given in table form to give quick view of the
geometry of the molecule
o Two scheme of classification of the molecules into point group discussed
o Flow chart for the second is given
o With the help of the chart number of example of molecules taken and their point group
determined
o Example of PF4Cl in different geometries discussed in detail and point group determined

CHEMISTRY PAPER No.13 : Applications of molecular symmetry and group theory

MODULE No.9 : Classification of molecules into point group part- II