Chapter 1:

Symmetry elements
and operation

Dr Nur Atiqah Nasir

atiqahnasir@usim.edu.my
The term symmetry is associated with:

• 1. Beauty
• 2. Regularity
• 3. Periodicity
• 4. Harmonicity
• 5. Systemization
In geometrical objects.

(Molecules for chemist)

Geometrical Object
And the monuments
Beautiful molecule structure and
colloidal nanoparticles
 The qu es tion is ----
How to qu an tify thi s be au ty a spe ct?

SYMMETRY ELEMENTS AND OPERATIONS

• Symmetry elements are geometrical entities such as a plane, an axis (of

rotation), centers (of inversion), etc., through which a symmetry
operation can be performed.
• Symmetry operation - an operation performed on an object which leaves
it in a configuration that is indistinguishable
- a movement of a body such that after the
movement has been carried out, every point of the
body is coincident with an equivalent point
 Elements of Symmetry
• Five main classes of symmetry operations:
• Identity (E). “do nothing”
• Proper Rotation (C ) or axis of symmetry
n

• Reflections (σ) or plane of symmetry

• Inversion (i) or centre of symmetry
• Improper rotation” (S ) or rotation-reflection axis
n
The identity E and rotations Cn are symmetry operations that could actually be carried out on a
molecule. For this reason they are called proper symmetry operations.

Reflections, inversions and improper rotations can only be imagined (it is not actually possible to7
turn a molecule into its mirror image or to invert it without some fairly drastic rearrangement of
chemical bonds) and as such, are termed improper symmetry operations.
 Symmetry Operations and Symmetry
Elements
Symmetry Operation Symmetry Element

Identity (E) E itself “do nothing”

Rotation (Cn) Axis of rotation (principal and non-principle)

Reflections (σ) Plane of reflection (σh, σv, σd)

Inversion (i) Center of inversion

Improper rotation (Sn) Rotation followed by reflection

8
 Identity, E —the easiest element
to see
• The “E” element of symmetry. Do ABSOLUTELY nothing. It
is simplest of all symmetry elements.
• All molecules have Identity. It is the only element/ operation
possessed by all molecules.
• The molecule looks exactly the same because you’ve done
nothing.
• For example:- CHBrFCl (1-chloro-1-bromo-1-fluoromethane)

Note- some chemists do not consider

this as an symmetry operation. 9
 Proper Rotation Axis, Cn
n-Fold Rotations: Cn, where n is an integer

rotation by 360°/n about a particular axis defined as the n-fold rotation axis.

C2 = 180° rotation, C3 = 120° rotation, C4 = 90° rotation, C5 = 72° rotation,

C6 = 60° rotation, etc.

Rotation of H2O about the axis shown by 180° (C2) gives the same molecule
back.
Therefore H2O possess the C2 symmetry element.

10
 Proper Rotation Axes Cont.

• Other molecules—BF 3 like we’ve seen F

rotate 120
F

already B B
F F F F

• BF3has a 3-fold rotation axis, coming out of

the plane C2

F F

B
• Also has THREE C
B

2 axes IN the plane, as

F F F F

shown 11
 Examples of Proper Rotation

• platinum tetrachloride; PtCl4 adopts a square planar geometry. Two

different rotation axes C2

Cl Cl C2
Cl
rotate 90 Cl Pt Cl
Cl Pt Cl Cl Pt Cl C2

C4 Cl
C2
Cl Cl

• Principal Axis—largest value of ‘n’ is called the principle rotation axis (we
normally denote this as the z-axis). So the principle axis of PtCl 4 is C4
12
 Rotational axes of BF3
principal axis
(highest value of Cn)

C3 C3 C2 C2

three-fold axis three-fold axis two-fold axis two-fold axis

viewed from viewed from viewed from viewed from
above the side the side above
13

Note: there are 3 C2 axes

n-fold Rotation

Water has a 2-fold axis of rotation.

When rotated by 180o, the hydrogen
atoms trade places, but the molecule
will look exactly the same.

14
 n-fold Axis of Rotation

Ammonia has a C3 axis. Note that there are two operations

associated with the C3 axis. Rotation by 120o in a clockwise or a
counterclockwise direction provide two different orientations of
the molecule. 15
 Reflections (σ) —Mirror Planes

“line” and “plane”…same thing. These represent PLANES of symmetry

You can also sort of view them as C2 axes

16
 Going back to water
O
H
• There are two different types of mirror plane.
H

– Parallel with principle rotation axis

– Perpendicular to PRA O
rotate 180 °
O

• First graphic establishes the principle H H H H

rotation axis (C2) mirror plane

through the
– Second shows a mirror plane between 3 atoms, no O
3 atoms
O
obvious movement
HH HH
– Third—another mirror plane, looks a lot like the C 2
axis (and has the same effect).
mirror plane

• Because these mirror planes are parallel to C

through the
oxygen
2 O O
(PRA), they are ‘vertical’ mirror planes—v H H H H
17
Reflections (σ)

The reflection of the water molecule

in either of its two mirror planes
results in a molecule that looks
unchanged.

18
Reflections (σ)

The subscript “v” in σv, indicates a

vertical plane of symmetry. This
indicates that the mirror plane includes
the principal axis of rotation (C2).

19
 Reflections (σ)

 The benzene ring has a C6 axis as

its principal axis of rotation.
C6.
The molecular plane is
perpendicular to the C6 axis, and is
designated as a horizontal plane, σh.

20
 Reflections (σ)

 The vertical planes, σv, go

through the carbon atoms, and
include the C6 axis.
C6.

 The planes that bisect the bond

angles of two neighboring C2 axis
are called dihedral planes, σd.

21
 Reflections (σ) —Mirror Planes

 In case of symmetrical molecule with center atom, the reflection planes

are shown as follows:
 Reflections (σ) of BF3:
Mirror planes can contain the principal axis (σv) or be at
right angles to it (σh). BF3 has one σh and three σv planes:
(v = vertical, h = horizontal)
σv σh
mirror plane C3 mirror plane
principal axis C3
principal axis

23

σv mirror plane σh mirror plane

contains the C3 axis is at right angles to the C3 axis
 Platinum tetrachloride—v and h

• In addition to having a C4 and 4 C2’s, PtCl4 also has

several mirror planes—4 v and another mirror plane IN
the plane of the board. v
v
Cl

• This one is a little harder to see Cl Pt Cl

v

Cl v

• It’s also  to our PRA (in/out plane

of the board), so we denote that as h.
24
 Inversion (i)
• The inversion operation takes a point through the center of
symmetry of the molecule to a equal distance on the side.

center of center of symmetry

symmetry

(Note: The center of symmetry is important in deciding whether orbitals are g or u)

 Inversion (i)
• Inversion (i) is the inversion of ALL atoms through the center of
the molecule
Note: the center of a molecule isn’t necessarily an atom
• Consider ethane (the staggered form). Pardon the color
explosion…but they distinguish each hydrogen and where they
go. center of
inversion
H H H H
H H
C C C C
H H
H H H H 26
 Inversion (i)
The inversion operation projects each atom through the center
of inversion, and across to the other side of the molecule.

27
 Improper Rotation Axis, Sn
• The improper rotation axis is invariant to rotation by 360/n,
followed by reflection through a plane at right angles to the
rotation axis.
• This symmetry element is less important than the others, and is
necessary to create the complete group. Most rotation axes that
can be identified are also proper rotation axis.

** The S4 improper rotation axis here is also a C2 axis

** The S4 improper rotation axis here is also a C2 axis
 Improper Rotation axis, Sn

• Harder to see…but this symmetry element combines two other operations

—rotation followed by reflection  to the axis.
• Again…consider ethane—staggered.

H H
H H H
C6 H
C C C C
H H
H H H H
rotation by 60 °

H H H H
H H
C C C C
H H
H H H H
structure LOOKS the
same, but the H's occupy
different locations--S6

Note that 30
S1 is the same as reflection, σh and
S2 is the same as inversion, i.
 Improper Rotation axis, Sn
Summary:
i) Improper rotation operation is 360/n, followed by reflection in a plane
perpendicular to the axis of rotation
ii) n refers to the improper rotation by 360/(rotation degree) and reflection
iii) Sn exist if the movement Cn followed by σ h (or vise versa) bring the object to the
equivalent position.
iv) If both Cn and σ exist then Sn must exist.
h

v) Neither Cn or σ need exist for Sn to exist.

h
THE END