Symmetry and Shape in Inorganic Chemistry

Prof. Phil Gale Office 30:4028 philip.gale@soton.ac.uk

Topics to be covered
Symmetry elements and operations in molecular
and ionic species

Predictions of molecular shape Valence Shell Electron Pair Repulsion Theory Isoelectronic principle Isomerisation

Outcomes for this component of the course

By the end of this component of the course you should be able to:

Identify the symmetry elements present in a

particular structure. molecular shape. species.

Use VSEPR theory to rationalize a particular Use VSEPR theory to predict the shape of a simple Sketch the possible geometric isomers of a
molecule or ion.

Resources
In addition to the lectures, a workshop will be held in
week 3, at which time there will be an opportunity to consolidate your learning, and to discuss any problems with the tutors. course is contained within the standard text (Inorganic Chemistry - Shriver and Atkins) but this book deals with some topics in more detail than is required at this stage. See Chapter 7 Section 7.1 S&E 4th Edition p196

All the lecture material for this component of the

Web resources
There are numerous websites that cover molecular
symmetry and shape. Some good ones are:
http://symmetry.otterbein.edu/jmol/index.html http://winter.group.shef.ac.uk/vsepr/

Symmetry elements and operations in molecules

A symmetry element is a feature which permits a symmetry operation to be performed. i.e. a symmetry operation is an action that leaves the molecule unchanged. A symmetry element is a point or line or plane through which an operation is performed. There are five types of symmetry element in discrete molecules:

Proper Axis of Rotation: Symbol Cn Plane of Symmetry: Centre of Symmetry: i Rotation-Reflection (or Improper Rotation) axis: Sn The Identity: E

Proper axis of Rotation Cn

C2

Element: n-fold rotation axis

180 O

Operation: rotation by 360/n Symbol: Cn

H

C3
A

C3
120 A

C3
120 A

C3
120 A

120

C3
120 A

120

Cn: n = 4, 5, 6

90

72

60

Mirror Plane:
Element: mirror plane Operation: reflection Symbol:

Mirror Plane:
v vertical, i.e. parallel to the rotational axis h horizontal, i.e. perpendicular to rotational axis d dihedral, i.e. additional planes parallel to the
rotational axis

e.g. Hexagon

e.g. Hexagon

C6

e.g. Hexagon

e.g. Hexagon
v

e.g. Hexagon
v

e.g. Hexagon
v

e.g. Hexagon
h

e.g. Hexagon

e.g. Hexagon
d d

e.g. Hexagon

e.g. Hexagon
v

e.g. Hexagon
v

Centre of symmetry: i
Element: centre or point Operation: inversion through centre Symbol: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i

Centre of symmetry: i
So for a point on a Cartesian set of axes with a centre of symmtery at the origin the inversion operation will translate it from (x, y, z) to (-x, -y, -z)

Axis of Improper Rotation: Sn

Element: n-fold axis of improper rotation Operation: Rotation by 360/n followed by a
reflection perpendicular to the rotation axis

Symbol: Sn

S4 axis in CH4

The Identity: E
Dont do anything! The identity operation does nothing to an object - it

is necessary for mathematical completeness as you will see in the second year when you do group theory...

Some examples...

Examples of shapes or molecules which contain a centre of symmetry

Examples of shapes or molecules which contain a centre of symmetry

CO2 staggered-ethane

Location of the symmetry elements in:

H 2O NH3 CH2Cl2

Location of the symmetry elements in:

XeOF4

A methodical route for identifying symmetry elements

Step 1: Look for proper axes of rotation....symbol Cn
remember that it is not uncommon to find more than one axis rotation.

Step 2: Select the highest order axis. The direction

of this axis defines vertical.

A methodical route for identifying symmetry elements

Step 3: Look for planes. These will be horizontal or
vertical depending on their relationship to the highest order axis. A plane of symmetry which is perpendicular to the highest order axis(sometimes called the principal axis) is a horizontal plane. A plane of symmetry which contains the highest order axis is a vertical plane.

A methodical route for identifying symmetry elements

Step 4: What else could be present? (a) is there a centre of symmetry? (b) are there any rotation-reflection axes? (symbol
Sn) These are the hardest symmetry elements to spot. If present, they are likely to be co-incident with one of the Cn axes - usually the principal axis. Remember that the rotation - reflection operation does two things: the rotation and the reflection

Step 5 Finally there is always the identity E.

Worked examples.

Molecules with an innityfold axis: C

Linear molecules such as carbon dioxide, nitrous
oxide or acetylene (ethyne) have an internuclear axis around which rotation by any angle generates an equivalent position.

Mathematically, an equivalent position is generated

by rotation through an infinity of infinitesimally small angles. The axis defines vertical and there are an infinite number of vertical planes of type v.

Molecules with no symmetry

Many molecules have little or no symmetry apart
from the identity E.

This is the structure found, for example in CHFClBr

Octahedron
Can you work out all the symmetry elements
present in an octahedron?

OH2 H2O
2+ Ni

OH2 OH2 OH2

H2O

C4, C2, S4 C3, S6

C2

i C2

C3, S6