TKT2013 – noorshida mohd ali

□Symmetry operations
□Symmetry elements
□Multiplication of symmetry elements &
operations
- commutative & non-commutative
□Point groups (Schoenflies symbols)
 TKT2013 – 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
C nn n(360°/n) = E = C1
rotate by 180°

Axis lying in the plane of the paper

e.g: H2S, SO2 , H2O2
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rotate by 120°
C3

Axis perpendicular to the plane of the paper (passing through

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

C3
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C4
2 rotate by 90° 1
1 4

3 2
4 3

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

2-
e.g: XeF4, [PtCl4]
C4
2
1
3
4
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1
C5H5 - C6H6 C7H7

Axis is perpendicular to the plane of the

C 8H 82- paper & passing through the centre of the
ring of carbon atoms
C5
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C□
e.g : linear molecule
(Symmetrical) (Asymmetrical)

H N N H C□
C□
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m
Cn m(360°/n)
+m = clockwise rotation
-m = anti clockwise rotation

C3 m
Cn
1
-2
C3
=
C3
2
-1
C3
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C4

C2

C 1 =C -3
4 4
C42 = C -2
4
=C 2
C 3 =C -1
4 4
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Plane of symmetry - σ
A molecule having a plane symmetry σ is unchanged in
configuration if all the atoms are reflected across the plane
Vertical reflection plane Dihedral / diagonal reflection plane
• Passing through the origin & the axis with
• Passing through the origin &
the axis with the highest the highest symmetry
symmetry •Bisecting the angle between the two-fold
σd axes perpendicular to the symmetry axis
C4
C2
σv
C2

σh
σd
C2
Horizontal reflection plane
•Passing through the
origin
σv C2 •Perpendicular to the axis
with the highest symmetry
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C2 The plane in which

the molecule lies C2

σv’

σv’

The plane bisects

C2 the molecule C2
σv

σv’

σv’ σv
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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 centrosymmetric molecule
i

2) Staggered conformation
i
CHClBr-CHClBr

3) H F

C i C
F H
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4) F F 5)
i
C i C
F F

6)

i
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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

C2 i

Two-fold rotation-reflection axis ∴ S2

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C3

Three-fold rotation-reflection axis ∴ S3

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C4

Four-fold rotation-reflection axis ∴ S4

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ferosena Fe(C5H5)2 – staggered conformation

C10

i.e

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
C m m(360°/n)
n
C n n(360°/n)
n
Reflection plane (σ) Reflection in plane (σv, σh & σd)

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 σv(H(2)-N) = S3 x σh

commutative and non-commutative ?

C3 2 3
σ C3
σh
v
3 1 3

2 1 2

C3 S3

2 2

1 3 3 1
∴C3 x σv(H(2)-N) ≠ S3 x
σh non-commutative
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e.g: PF5 C2(F(3)-P) x σv(F(2)-P) = C3 x

coσmhmutative and non-commutative
? 4 C3
σ 2 σh
4 1 5
v
3
2 2
5 1
3 C2
3
1
4
5
C2 C3

5 5

1 1
3 3
2 2
∴ C2(F(3)-P) x σv(F(2)-P) = C3 x
4 4
σh
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The complete set Schoenflies symbols

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

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

❷ Groups with an n-fold rotational axis (Cn, Cnv, Cnh)
❸ Dihedral groups (Dn, Dnd, Dnh)
❹ Groups with very high symmetry (Td, T, Oh, O, Ih, D∞h,
C∞v)
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❶ Groups with low symmetry (C1, Cs,

Ci)
Point groups Examples
1. ■ One symmetry element : E = I = C1
C =E=I
1 ■ all molecules possess C1

Point groups Examples

2. ■Contain a plane of symmetry
C
s

Cs=C1v=C1h
bromofluoromethanediol

σ
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Point groups Examples

3. ■Contain a centre of inversion i
Ci

S2 = i Br Cl H

i i.e
H Cl Br

staggered conformation CHClBr-CHClBr

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❷ Groups with an n-fold rotational axis (Cn, Cnv, Cnh)

Point groups Examples
1. C2
Cn
■Molecules containing only one axis
■e.g: molecule gauche H2O2 ( axis C2 lies
in the plane of paper)
C
2

H
111°
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Point groups Examples

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

triphenylphosphine

Point groups Examples

2.
C ■ C1 =h C = C 1v s
nh σ
■A hplane perpendicular to the Cn axis
rarer system
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Point Examples
groups

C2h
■ σ
h

■Contains one C2 axis of symmetry

■A plane perpendicular to the C2 axis
■If n is even the point group necessarily contaCins a
σ
2
centre of symmetry (i) h

C2
i

σh

trans-1,2-dichloroethene
trans-N F
2 2
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Point groups Examples

■ C
3h

C3

σh

Orthoboric acid : B(OH)3

 Point Examples TKT2013 – noorshida mohd ali

groups
3. ■ Contains one C2 axis of symmetry
Cnv ■nplane that containing the C2 axis
■
σv
C2v C2

C2
σv
σv ’

dihydrogen oxide

σv’
Cl H
C2
Cl H σv’
σv
H H
dichlorobenzene
σv
Point groups Examples TKT2013 – noorshida mohd ali

■ C3v C3
C5v & C6v
e.g : all the trigonal σv
rarer system pyramidal in
-shape
ammonia
PCl3, phosphine
(PH3), arsine (AsH3)
■
σv σv
C4v C4
σd
σv
IF5

e.g : all the trigonal

bipyramidal in shape
σd - BrF5, XeOF4
σv
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❸ Dihedral groups (Dn, Dnd, Dnh)

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

2.

Dnh

■
Moleσhcules possessing nC2
cipal
n C axes CnC
perpendiσcular to the
axes 2 n
■ Cn
prin
■1
■ other n
■ if n = even number : (i)
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Point groups Examples

D2h - 2C C2 C2
-C 2 C2
2
- 1σ
- 2
h
σ
3σ σv
- if n =
i C2
2 : (i)
σ
σ σ
C C2
2 ethylene
σ

C2

i
σ naphtalene
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Point groups Examples

3 C2 C3
D3h
- C3 σh
- 1σ
v
C3 carbonate ion CO3 2-
- 3
C2
σv
C
2

σh

σv
C2
σv
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Point groups Examples

D3h 3 C2 C3

- C 3σ h
- 1σ
v C
- 3 3

C2 σv

C2
σh

C2 σ
v

σv

phosphorus
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Point groups Examples

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

- C4
- 1 σh
- 2 σv and 2 σd
C4
trans-tetraaminedichlorocobalt(III) cation
σd C
σv
σ
2d C2

i σh
C2

C2

σv
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Point groups Examples

3. Dnd ■ Molecules possessing nC2 axes
perpendicular to the principal axes C n

■C n C2 Cn
n
■ S2n
■ n σd plane
■ if n = odd number : (i)
allene
D2d 2 C2 C2
C2
C2
■S σd
4
■ C2
C2
■2 σ
d
σd
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Point groups Examples

D3d 3 C2 C3

■C3
■S6 C3
■3 σd σd
■if n = 3 : (i)

C2
i σd

σd
staggered ethane C2
C2
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❹ Groups with very high symmetry (Td, T, Oh, O, Ih , D∞h, C∞v)

(Cubic point group)
Octahedral
Tetrahedral
Oh : 4C3, 3C4, 6C2, 3σh,
Td : 4C3, 3C2, 6σd, 3S4
6σd, 4S6, i =S2, 3S4
T : 4C3, 3C2 O : 4C3 , 3C4, 6C 2
(only containing rotation (only containing rotation
of Td) of Oh)

Icosahedral
Ih : 6C5, 10C3, 15C2, 15σ,
6S10, 10S6, i =S2

e.g: - CH4
e.g: - SF6
- CCl4 - [Fe(CN)6] 3-
- [Co(CN)6]3-
e.g: - [B12 H12]2- hexacyanocobaltate(III)
anion
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Tetrahedral e.g: - CH4

Td : 4C3, 3C2, 6σd, 3S4

T : 4C3, 3C2
(only containing rotation of Td)

Top view:
Side view:
C

C3

C3
C

C C
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Side view:
Top view:
C2
H H

C2 C2
∙
C2 C

C2 H H

H H

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

C2

C2
C2

σd σd
σd

σd σd

σd
σd
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S4
Side view:

C4

Rotate 90º Reflection σh

 TKT2013 – noorshida mohd ali

Octahedral e.g: - SF6

Oh : 4C3, 3C4, 6C2, 3σh,
6σd, 4S6, i=S2, 3S4

O : 4C3, 3C4, 6C2

(only containing rotation of Oh)

Side view:

i = S2
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Top view: Side view:

C4

C4

C4

σh

C3 , S6

σh

σh
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Side view: C2
σd

C2 C2 σh
σd
σh
C2 σd

σd

C2
σd
C2

σh

σd
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Icosahedral
Ih : 6C5, 10C3, 15C2, 15σ, e.g: - [B12 H12]2-
6S10, 10S6, i=S2

C5
C3 C2
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Point groups Examples

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

σv σv

C∞ C∞
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Point groups Examples

D∞h

■ linear molecule with centre of symmetry (i)

(symmetrical)
■ C∞
∞C 2
σv
■□
■1 C2
σh σh
■ e.g: O2, H2, Cl2

i C∞
C2 σv
σh σv
i C∞