TKT2023 – noorshida mohd ali

Symmetry operations
Symmetry elements
Multiplication of symmetry elements &
operations
- commutative & non-commutative
Point groups (Schoenflies symbols)
 TKT2023 – noorshida mohd ali

SYMMETRY OPERATIONS

An operation perform on an object

which leaves it in a configuration
that is indistinguishable from and superimposable
on the original configuration

SYMMETRY ELEMENTS

A symmetry operation is carried out with

respect to LINES, POINTS or PLANES
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Axis of symmetry - Cn
A molecule having a Cn axis can be rotated by 360°/n
about the axis and the configuration will remain unchanged

Clockwise rotation about axis C1,C2,…Cn..C

Cn 360/n
C2
Cnn n(360/n) = E = C1
rotate by 180°
O O
H1 H2 H2 H1

Axis lying in the plane of the paper

e.g: H2S, SO2 , H2O2
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F1 F3

C3 rotate by 120°
B B
F3 F2 F2 F1

Axis perpendicular to the plane of the paper (passing through

the central atom)
e.g: BCl3, SO3, AlCl3, [NO3]-, NH3, PBr3, [SO4]2-

C3
F

B
F
F
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C4

Cl2 rotate by 90° Cl1

1 Cl 4 Cl
I I
Cl3 Cl 2
4 Cl 3 Cl

Axis passing through the central atom in the molecule [ICl4]-,

e.g: XeF4, [PtCl4]2- C4

Cl 2
1 Cl
I
Cl3
4 Cl
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C5H5- C6H6 H1 H1 C7H71

H1
H2 H2
C H7 C
C H6 H2 C
C C C C
H5 C C H3
C C C
H3 C
C H3 H6
H5 C C
C
H4
H4
H4 H5

Axis is perpendicular to the plane of the

C8H8 2-
paper & passing through the centre of the
H1 H2
ring of carbon atoms
C C
H8
C C
H3 C5

C C
H7
H4
C C

H6 H5
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C
e.g : linear molecule
(Symmetrical) (Asymmetrical)

H N N H C H C N C
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Cnm m(360/n)
+m = clockwise rotation
-m = anti clockwise rotation

C3
Cnm
F
C31 = C3-2
B C32 = C3-1
F
F
C2
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C4

Cl
Cl
I
Cl
Cl C2

C41 = C4-3
C42 = C4-2 = C2
C43 = C4-1
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Plane of symmetry - 
A molecule having a plane symmetry  is unchanged in
configuration if all the atoms are reflected across the plane
Vertical reflection plane Dihedral / diagonal reflection plane

•Passing through the origin & •Passing through the origin & the axis with
the axis with the highest the highest symmetry
symmetry •Bisecting the angle between the two-fold
d
C4 axes perpendicular to the symmetry axis
C2
v
C2
F F
h
d
Xe C2
Horizontal reflection plane
•Passing through the
F F origin
v C2
•Perpendicular to the axis
with the highest symmetry
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C2 The plane in which

the molecule lies C2

O v’
O H
H1 H2 H
v’

The plane bisects

the molecule
C2 C2
v
O v’
O H
H1 H2 H
v’
v
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Centre of symmetry - i
If the molecule has a centre of symmetry i, reflection of
the position of the all atoms through this centre that
changing all their positions from (x, y, z) to (-x, -y, -z) will
leave the configuration of the molecule unchanged

e.g : 1) i = S2

C6
i centrosymmetric molecule

H Br Cl
2) Staggered conformation
i
CHClBr-CHClBr
Cl Br H

3) H F
C i C
F H
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4) F F 5) F F
C i C i
Xe
F F
F F

6)
F
F F
Si
F F
F
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H
O
H
O
O
CH3
Fe
N
O
O C N
N N C
H
O
H CH3
O Fe

centrosymmetric molecule
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Rotation-reflection axis of symmetry - Sn

 clockwise rotation by 360°/n about the axis
 reflection by across a plane perpendicular to axis
 and passing through the centre of the molecule

H H H

C C C
C2 i
C C C

H H H

Two-fold rotation-reflection axis  S2

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C3

F
F

B
F B
F F
F

B
F
F
Three-fold rotation-reflection axis  S3
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C4

H H H H H H
C C
C
H H H H
H H

Four-fold rotation-reflection axis  S4

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ferosena Fe(C5H5)2 – staggered conformation

C10

Fe i.e Fe

Ten-fold rotation-reflection axis  S10

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Identity element of symmetry – E

All molecules possess the identity element of

symmetry, E that is rotation of the molecule
through 0° leaves the configuration
unchanged

E = C1
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SYMMETRY ELEMENTS SYMMETRY OPERATIONS

Proper rotation : Clockwise rotation about axis
Rotation axis (Cn) C1,C2,…Cn
Cn 360/n
Cnm m(360/n)
Cnn n(360/n)
Reflection plane () Reflection in plane (v, h & d)

Centre of symmetry (i) Inversion at centre (i)

Improper rotation : Clockwise rotation about axis &
Rotation & reflection reflection in a plane perpendicular
axis (Sn) to the axis S1,S2,…Sn

Identity (E) or (I)

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MULTIPLICATION OF
SYMMETRY ELEMENTS AND OPERATIONS

Symmetry operation A and B

This multiple operation is written B x A
(Carry out operation A first and then operation B)

there are four symmetry operations which are : A, B, C and D

AxB=CxD
then the right and left operations are said to
commute or to be commutative
But if A x B  C x D
then the right and left operations are said to
do not commute or are non-commutative
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e.g: NH3 C3 x v(H(2)-N) = S3 x h

commutative and non-commutative ?

1H N
2H H3
C3 C3
v h

3H N 1H H3
2 H H1 2H N

C3 S3

2H N 2H N
1H H3 3H H1
C3 x v(H(2)-N)  S3 x h
non-commutative
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e.g: PF5 C2(F(3)-P) x v(F(2)-P) = C3 x h

commutative and non-commutative ?

F4 C3
v F2 h
F4 1F P F5
F3
F2 F2
3F P C2 F5 1F P
F1 F3
F5 F4

C2 C3
F5 F5

F1 F1
3F P 3F P
F2 F2
 C2(F(3)-P) x v(F(2)-P) = C3 x h
F4 F4
commutative
 TKT2023 – noorshida mohd ali

Schoenflies symbols
The complete set
C1, Cs, Ci,
of symmetry
elements in any POINT Cn, Cnv, Cnh, Cv,
particular GROUPS Sn,
molecule Dn, Dnd, Dnh, Dh,
Td & T, Oh & O, Ih

 Groups with low symmetry (C1, Cs, Ci)

 Groups with an n-fold rotational axis (Cn, Cnv, Cnh, Cv)
 Dihedral groups (Dn, Dnd, Dnh, Dh)
 Groups with very high symmetry (Td, T, Oh, O, Ih)
 TKT2023 – noorshida mohd ali

 Groups with low symmetry (C1, Cs, Ci)

Point groups Examples
1.  One symmetry element : E = I = C1
C1 = E = I
 all molecules possess C1

Point groups Examples

2.  Contain a plane of symmetry
Cs

Cs=C1v=C1h Br F
bromofluoromethanediol

O O 
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Point groups Examples

3.  Contain a centre of inversion i
Ci
Br
S2 = i Br Cl H Cl H

i i.e H Cl
H Cl Br Br
staggered conformation CHClBr-CHClBr
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 Groups with an n-fold rotational axis (Cn, Cnv, Cnh, Cv)

Point groups Examples

1. C2
Cn
Molecules containing only one axis
e.g: molecule gauche H2O2 ( axis C2 lies in
the plane of paper)
C2

H
H
111°

O O

hydrogen peroxide
 TKT2023 – noorshida mohd ali

Point groups Examples

- axis perpendicular to the paper (not
C3
planar)
C3
P

triphenylphosphine

Point groups Examples

2. 
Cnh C1h = C1v = Cs
h
rarer system A plane perpendicular to the Cn axis
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Point Examples
groups

C2h

h

 Contains one C2 axis of symmetry

A plane perpendicular to the C2 axis
C
hnecessarily contains
2
 If n is even the point group a centre of
symmetry (i)H Cl
C2
C i C Ni F
F N
Cl H h

trans-1,2-dichloroethene
trans-N2F2
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Point groups Examples


C3h

C3

O H

H B
O h
O
H

Orthoboric acid : B(OH)3

 TKT2023 – noorshida mohd ali
Point Examples
groups

3. Cnv  Contains one C2 axis of symmetry

n v plane that containing the C2 axis

C2v C2

C2 O

Cl Cl
H
H
v’
v
H H dihydrogen oxide
v’
Cl H
H H
C2
Cl H v’
v
H H
dichlorobenzene
v
 TKT2023 – noorshida mohd ali
Point groups Examples

 C3v C3
C5v & C6v
e.g : all the trigonal v
rarer system pyramidal in shape H N
ammonia
- PCl3, phosphine (PH3), H H
arsine (AsH3)

v v
C4v C4
d F v
F IF5
F
I
F
e.g : all the trigonal
F bipyramidal in shape

d - BrF5, XeOF4
v
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Point groups Examples

4.
Cv
 ∞ (infinite) plane of symmetry v
 Contain one C∞axis
 All linear molecule (non symmetry /
asymmetry) – without a centre of
symmetry (i)
 e.g: HCl, O=C=S

v v

H C N C I Cl C
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 Dihedral groups (Dn, Dnd, Dnh, Dh)

Point groups Examples
1. No mirror plane 3+
Dn
N
D3
N N
C3 Co
tris(ethylenediamine)cobalt(III) cation
N N
2. N

Dnh

h
 possessing nC2 axes 2
Molecules
nC Cn
perpendicular to the principal axes Cn
 Cn
1
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Point groups Examples

D2h- 2 C2 C2 C2 C2
- C2
h
-1 
3  - 2 v H
C i C
H
C2
H H
- if n = 2 : (i)

C2  
C2
ethylene
C2 
i

 naphtalene
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Point groups Examples

D3h 3 C2 C3

- C 3 h
- 1 v
C3 carbonate ion CO32-
- 3 C2
v
C2
O

C
O h
O
v
C2
v
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Point groups Examples

D3h 3 C2 C3

- C 3 h
- 1 v
C3
- 3
C2 v
F

F
F P C2
h
F
C2 v F

v

phosphorus pentafluoride
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Point groups Examples

D4h 4 C2 C4 - if n = 4 : (i)
+
Cl

H3N NH3 - C4
H3N
Co
NH3 h
- 1
Cl v d C4
- 2 and 2
trans-tetraaminedichlorocobalt(III) cation
d C2
v
d C2
Cl

H3 N i NH3 h
Co C2
H3 N NH3

Cl C2

v
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Point groups Examples

3.  Molecules possessing nC2 axes
Dnd
perpendicular to the principal axes Cn

n C2 Cn
 Cn
 S2n
 n d plane
 if n = odd number : (i)
allene
D2d 2 C2 C2
C2
C2
H d
H
 S4 C C C C2
d H
 C2
H
 2 d
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Point groups Examples

D3d 3 C2 C3

 C3
 S6
C3
 3 d d
H
 if n = 3 : (i)
C
H
C2 H
i d
H
C2 H
C

H
d
staggered ethane

C2
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Point groups Examples

Dh

 linear molecule with centre of symmetry (i)

(symmetrical)
C2 C

v
 
h C2
1
h
 e.g: O2, H2, Cl2
F i
Be F C
C2 v
h v
H Ci C H C
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 Groups with very high symmetry (Td, T, Oh, O, Ih)

(Cubic point group)
Octahedral
Tetrahedral
Oh : 4C3, 3C4, 6C2, 3h,
Td : 4C3, 3C2, 6d, 3S4
6d, 4S6, i =S2, 3S4
T : 4C3, 3C2
O : 4C3, 3C4, 6C2
(only containing
rotation of Td) (only containing rotation
of Oh)
Icosahedral
Ih : 6C5, 10C3, 15C2, 15,

6S10, 10S6, i =S2

e.g: - CH4
e.g: - SF6
- CCl4
- [Fe(CN)6]3-
- [Co(CN)6]3-
e.g: - [B12H12]2- hexacyanocobaltate(III)
anion
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Tetrahedral e.g: - CH4

Td : 4C3, 3C2, 6d, 3S4

T : 4C3, 3C2
(only containing rotation of Td)
Top view:
Side view:
C

C3

H
C3
C


H C
C C
H H
 TKT2023 – noorshida mohd ali
Side view:
Top view:
C2
H H H

H C2 C2
C
C H C2 H
H
C C2 H H

H
H H
H H H

H C2
C
C C2
H
H H

H Position of H atoms
H in the cubic C2
H H
above
H
C2 C
C bottom
H centre
H H

H
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Side view:

C2 H H
H

H H H
C2
C C C C2
H H H

H H H

d Hd
H d H

H d H dH
C C
C
H H
H
d H
H
H d
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S4
Side view:
H H
C

H
H

C4
H H H H H H
C Reflection h C
Rotate 90º
C
H H
H H H H
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Octahedral e.g: - SF6 F

Oh : 4C3, 3C4, 6C2, 3h, F F
6d, 4S6, i=S2, 3S4 S
F F
O : 4C3, 3C4, 6C2 F
(only containing rotation of Oh)
Side view: F
F

F
F
F F S
S F
F
F F

i = S2
F
F
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Top view: Side view:

C4
F F

F F F

S F S F
C4
F
F F
C4
F
F

F F
h
F F
C3 , S6 F
S F S F

F F h
F

F
h F
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Side view: C2
d
F
C2 h
C2 d F

h F
C2 d
F S F
F
F S
F F

F
d
F
F
C2
d
F
C2

F
F S F

F
h

d F
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Icosahedral
Ih : 6C5, 10C3, 15C2, 15, e.g: - [B12H12]2-

6S10, 10S6, i=S2

C5
C3 C2