Ambo University Faculty of Natural & Computational Science Department of Chemistry

Inorganic Chemistry III (Chem. 4081) Lecture Note

AMBO UNIVERSITY
COLLEGE OF NATURAL AND COMPUTITIONAL SCIENCE
DEPARTMENT OF CHEMISTRY
INORGANIC CHEMISTRY III
(CHEM 4081)

Unit 1
Symmetry and Group Theory
1.1

Introduction

What Is Symmetry?
The term symmetry is derived from the Greek word “symmetria” which means “measured
together”. An object is symmetric if one part (e.g. one side) of it is the same* as all of the other
parts. Symmetry is the notion that an object of study may look the same from different points
of view. For instance; A sphere is more symmetrical than a cube because it looks the same after
rotation through any angle about the diameter. A cube looks the same only if it is rotated
through certain angels about specifc axis, such as 90o, 180o, or 270o about an axis passing
through the centers of any of its opposite faces, or by 120oor 240o about an axis passing through
any of the opposite corners.
When we say that a molecule has symmetry we mean that certain parts of it can be interchanged
with others without althering either identity or the orientaion of the molecule. The interchangeable parts are said to be equivalents to one another by symmetry, for example, a
Trigonal bipyramidal molecule such as PF5.
In this molecule we can see that, the three
equatorial P-F bonds to F1, F2 and F3 are
equivalent. They have the same bond
strength, bond angle, and the same type of
spacilal relation to the remainder of

1
Compailled by Kebede Humnessa Gemeda (MSc, Inoganic Chemistry),2014

the molecule. Any permutation of these three bonds are among them selves leads to a molecule
indisistinguishible from the original. Similarly, the axial P-F bond F4 and F5 are equivalent. But
axial and equatorial bnds are different types (eg. They have different length and bond angle), and
if one of each were to be interchanged , the molecule would be noticiably , on an intuitive bases
You know intuitively if something is symmetric but we require a precise method to describe how
an object or molecule is symmetric.the first set of tools is a set of symetry operation.
Here are also examples of different molecules which remain the same after certain symmetry
operations: NH3, H2O, C6H6, CBrClF. In general, an action which leaves the object looking the
same after a transformation is called a symmetry operation. Typical symmetry operations
include rotations, reflections, and inversions. There is a corresponding symmetry element for
each symmetry operation, which is the point, line, or plane with respect to which the symmetry
operation is performed. For instance, a rotation is carried out around an axis; a reflection is
carried out in a plane, while an inversion is carried out in a point.
1.2Symmetry elements and operations
A symmetry operation is an action that leaves an object looking the same after it has been
carried out. For example, if we take a molecule of water, H2O (HOH), and rotate it by 180°
about an axis passing through the central O atom it will look the same as before. It will also look
the same if we reflect it through either of two mirror planes, as shown in the figure below.

The square planar PtCl42- ion is said to be a highly symmetric ion because it contains a large
number of symmetry elements. Each symmetry operation has a corresponding symmetry
element, which is the axis, plane, line or point with respect to which the symmetry operation is
carried out. The symmetry element consists of all the points that stay in the same place when
the symmetry operation is performed. In a rotation, the lines of points that stay in the same place
constitute a symmetry axis; in a reflection the points that remain unchanged make up a plane of
symmetry.
The symmetry elements that a molecule may possess are:
1. The identity- E. The identity operation is equivalent to doing nothing or rtation about
360o (C1 operation) and has no symmetry element but it is a required member of each
symmetry group, and the corresponding symmetry element is the entire molecule. Every
molecule has at least this element. Thus, operation with E will change neither the positions of
the atoms nor the phases of the pz-orbitals. Consider the following description;

The trasformational matrix for identity element is a unit matrix, or unit matrix given above in
squere bracket. The example; of the molecule which has only the identity symmetry
operation is C3H6O3, DNA and CHClBrF.
2. An n-fold axis of rotation - C n. Rotation by 360°/n leaves the molecule unchanged.
Particularly, the operation C1 is a rotation through 3600 which is equivalent to the identity E.
H2O molecule has one twofold axis, C 2. NH3 molecule has one threefold axis,C3, which is
associated with two symmetry operations: 1200, rotation C3 and 240o (or -1200) rotation
C23.C6H6 molecule has one six-fold axis C6, and six twofold axes C2. All linear molecules
including all diatomics has C∞ axis because rotation on any angle remains the molecule the
same. Some molecules have more than one C axis, in which case the one with the highest
value of n is called the principal axis, and is designated as the z-axis. Note that by
convention rotations are counterclockwise about the z-axis. Thus the z-axis in PtCl42- is
perpendicular to the plane of the ion. This axis is actually three symmetry elements since
rotations by π/2, π, and 3π /2 about this axis all result in no change in the molecule. These
three axes are referred to as C4, C42 = C2 and C43, respectively.
The proper rotation (clockwise direction) about the z axis can be described by the following
matrix equation.

3. A plane of symmetry (refelection) -σ. Reflection in the plane leaves the molecule looking
the same. Reflection can be made through three different types of planes: vertical plane
(σv) contain the principle axis, horizontal planes (σh) are perpendicular to the principle axis
and dihedral planes (σd) contain the principle axis and bisect two C 2 axes. The distinction
between vertical and dihedral is often unclear. Where appropriate, planes bisecting bond
angles will be designated as dihedral while those containing bonds will be designated as
vertical. See figure

Figure I-3. The
reflection through
planes on the atoms

effect of
the symmetry
and the

chlorine pz orbitals

in PtCl42-

In PtCl42-, the
planes
containing the zaxis (σv and
σd) will not
change the
phase of the pz
orbitals
while reflection
through the
plane
perpendicular to the z-axis (σh) does invert them (figure I-3). Thus, PtCl42-contains: σv(XZ ) and
σv(YZ ), σh(XY) and σd(a) and σd (b) or five planes of symmetry. Note that a and b planes are

defined as those planes perpendicular to the plane of the ion and containing a and b rotational
axes.
If the mirror plane coincides with the xy, xz, or yz Cartesian planes, they can be described by the
following matrix equations:

σxσ=E
4. A centre of symmetry (inversion) -i. Inversion through the centre of symmetry leaves the
molecule unchanged. A Center of Inversion (i) takes all (x,y,z) → (-x,-y,-z). This operation
can be performed by a C(z) which takes (x,y,z) → (-x,-y,+z) followed by a σ(xy) which
inverts z, i.e., i= C2σh = S2. Since i and S2 are equivalent, S2 is not usually used.
Inversion consists of passing each point through the centre of inversion and out to the same
distance on the other side of the molecule. An example of a molecule with a centre of inversion
is shown below.

Figure I-4. The effect of improper rotations on the atoms and the chlorine in PtCl42-

The inversion operation changes the sign of all the x, y and z coordinates:

5. An n-fold improper rotation (also called a rotary-reflection) -Sn. The rotary reflection
operation consists of rotating through an angle 360°/n about the axis, followed by reflecting
in a plane perpendicular to the axis.that is, (Sn) is a Cn followed by a σh. Note that Sn1 is the
same as reflection and S is the same as inversion. The molecule shown above has two S 2
axes. SincePtCl42- is a planar ion; the Z-axis is an element for both proper and improper
rotations. See figure I-4. Note that an S4 results in the same numbering as a C4, but the
phases of the p orbitals are changed.
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 to 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, Sn.
The improper rotation about the z axis can be described as a proper rotation followed by
changing the sign of the z coordinate.

When n is even, Sn generates n operations.
When n is odd, Sn generates 2n operations.
Snn is equivalent to σ, and Sn2n is equivalent to E.
S1 = σh;
S2 = i
A note on axis definitions: Conventionally, when imposing a set of Cartesian axes on a
molecule (as we will need to do later on in the course), the z axis lies along the principal axis of
the molecule, the x axis lies in the plane of the molecule (or in a plane containing the largest
number of atoms if the molecule is non-planar), and they axis makes up a right handed axis
system.
1.3. Point Groups and Molecular Symmetry
It is only possible for certain combinations of symmetry elements to be present in a molecule (or
any other object). As a result, we may group together molecules that possess the same
symmetry elements and classify molecules according to their symmetry. These groups of
symmetry elements are called point groups (due to the fact that there is at least one point in
space that remains unchanged no matter which symmetry operation from the group is applied).
There are two systems of notation for labeling symmetry groups, called the Schoenflies and
Hermann-Mauguin (or International) systems. The symmetry of individual molecules is usually
described using the Schoenflies notation, and we shall be using this notation for the remainder of
the course1.
Note: Some of the point groups share their names with symmetry operations, so be careful you
don’t mix up the two. It is usually clear from the context which one is being referred to.
The molecular point groups are listed below:

1. C1 – contains only the identity (a C1 rotation is a rotation by 360° and is the same as the
identity operation E) e.g. CHDFCl.

2. Ci- contains the identity E and a centre of inversion i.

3. Cσ - contains the identity E and a plane of reflection σ.

4. Cn – contains the identity and an n-fold axis of rotation.

5. Cnv – contains the identity, an n-fold axis of rotation, and n vertical mirror planes σv.

6. Cnh- contains the identity, an n-fold axis of rotation, and a horizontal reflection plane σh
(note that in C2h this combination of symmetry elements automatically implies a centre of
inversion).

7. Dn - contains the identity, an n-fold axis of rotation, and n 2-fold rotations about axes
perpendicular to the principal axis
8. Dnh contains the same symmetry elements as Dn with the addition of a horizontal mirror
plane.

9. Dnd- contains the same symmetry elements as Dn with the addition of n dihedral mirror
planes.

10. Sn - contains the identity and one Sn axis. Note that molecules only belong to S2 if they have
not already been classified in terms of one of the preceding point groups (e.g. S n is the same
as Ci, and a molecule with this symmetry would already have been classified).
High order point groups:-There are several special point groups. Molecules having three or
more high symmetry elements may belong to one of the following: Molecules with multiple
higher-order rotation axes, the cubic groups T, Th, Td, O, Oh and Ih.

The following groups are the cubic groups, which contain more than one principal axis. They
separate into thetetrahedral groups (Td and Th) and the octahedral groups (O and Oh). The
icosahedral group also exists but is not included below.
11. Tetrahedral; Td:- species with tetrahedral symmetry. Eg. CH4. Contains all the symmetry
elements of a regular tetrahedron, including the identity, 4 C. C2 axes, 6 dihedral mirror
planes, and 3 S4 axis; e.g. CH4.

12. Tetrahedral; T - as for Td but no planes of reflection. Contains all the symmetry elements of
Td without σh.

Eg. C(CH3)4
13. Tetrahedral;Th– Contains all the symmetry elements of Td with σh. as for T but contains a
centre of inversion

14. Oh – the group of the regular octahedron e.g. SF6.

15. Octahedral: O - For O group, symmetry elements are E, 3C4, 4C3, and 6C2 as for Oh but with
no planes of reflection. And symmetry operations are {E, 8C3, 3C2፣ 6C4, 6C2} . The order
of O group is 24.

16. Icosahedral, Ih:-contains 6C5 asis and a total of 120 symmetry elements.

Dodecahedron

Icosahedrons

17.Highly symmetrical molecules:A few geometries have several, equivalent, highest order axes. Two geometries most
important:
Linear molecules: C∞v, and D∞h
Do infact fit in to scheme but they have an infinite number of symmetry operations.
Molecular axis ia C∞v-rotation by any arbitirary angle (360/∞)o, so infinite number of rotations.
Also any plane containing axis is symmetry plane, so infinite number of planes of symmetry.
Divide linear molecules into two groups:
i. Molecules with no centre of symmetry; This point groups conyains a C∞axis and an infinite
number of σv planes eg, NCN, OCS and hetrodiatomic molecules.

ii.

Molecules with centre of symmetry: eg. CO2, and homodiatomic molecules.D∞h.

The final group is the full rotation group R 3, which consists of an infinite number of C n axes with
all possible values of n and describes the symmetry of a sphere. Atoms (but no molecules)
belong to R3, and the group has important applications in atomic quantum mechanics. However,
we won’t be treating it any further here.
Table 1.1 Common Point Groups and Their Symmetry Elements
Point Group
Symmetry Elements Present
C1
E
Cs
E, σh
Ci
E, i
Cn
E, Cn
Dn
n = odd
E, Cn, nC2
Dn
n = even
E, Cn, n/2C2´, n/2C2´´
Cnv
n = odd
E, Cn, nσv
Cnv
n = even
E, Cn, n/2σv, n/2σd
Cnh
n = odd
E, Cn, σh, Sn
Cnh
n = even
E, Cn, σh, Sn, i

Dnh
Dnh

n = odd
n = even

Dnd
Dnd

n = odd
n = even

Sn
T
Th
Td
O

n = even only

Oh
I
Ih
Kh

E, Cn, σh, nC2, Sn, nσv
E, Cn, σh, n/2C2´, n/2┴C2´´, Sn, n/2σv,
n/2σd, i
E, Cn, nC2, i, S2n, nσd
E, Cn, nC2´, S2n, nd
E,
E,
E,
E,
E,

Sn, Cn/2 and i if n/2 odd
4C3, 3C2
4C3, 3C2, 4S2n, i, 3h
4C3, 3C2, 3S4, 6d
3C4, 4C3, 6C2

E,
E,
E,
E,

3C4, 4C3, 6C2, 4S6, 3S4, i, 3h, 6d
6C5, 10C3, 15C2
6C5, 10C3, 15C2, i, 6S10, 10S6, 15σ
infinite numbers of all symmetry

elements
Once you become more familiar with the symmetry elements and point groups described above,
you will find it quite straight forward to classify a molecule in terms of its point group. In the
mean time, the flowchart shown below provides a step-by-step approach to the problem.

Once you become more familiar with the symmetry elements and point groups described above,
you will find it quite straight forward to classify a molecule in terms of its point group. In the
mean time, the flowchart shown below provides a step-by-step approach to the problem.
1.4 Classification of Molecules into Point Groups

Procedure for Identification of Molecular Point Groups:Case 1:-The molecule is linear. In this case only two groups are possible: D∞h or C∞v. The
decision is easily made after ascertaining whether the molecule has or has not a centre
of symmetry.
Case 2:- The molecule has a regular geometry, suggesting type 3 symmetry group. In that case
we must identify more than one high order rotation axes Cn (n≥3). The Td group will be
indicated by four C3 axes, the 0h by three C4 axes and the Id by twelve C5 axes. . .
Case 3:- The low‐symmetry type of group is indicated by the presence of only one symmetry
element (Cn, σ or i). If the molecule has no symmetry elements, it belongs to the C1

group. If it has only one rotation axis Cn, the Cn group must be considered. The
presence of only one reflection plane corresponds to the C3 group, and the identification
of only one inversion centre indicates the Ci group.
Case 4:- The molecule does not display the type 3 symmetry, but rotation axes are associated
with other symmetry elements. In that case the type 2 symmetry group is apparent. The
group is found by stepwise examination, in the following way:
Step 1:- The highest rotation axis has an even order. Determine if this proper rotation is
not associated with an improper rotation Sn of a higher order. If that is the case
and no other symmetry elements can be identified, group will be Sn'
Step 2:- The rotation axis is also associated with mirror planes. This may indicate the Cnv
group. To make sure, identify the n vertical mirror planes.
Step 3:- The rotation axis Cn; is perpendicular to the molecular plane. If that plane
contains no C2 axes, the Cnh group must be ascribed to the molecule.
Step 4:- If the rotation axis Cn is perpendicular to the molecular plane and this plane
contains nC2 axes, the molecule belongs to the Dnh group.
Step 5:-The molecule is not planar, but the C, axis is associated with nC2 axes
perpendicular to it. The Dn elements are present here. The Dnh group being
excluded (the molecule is not planar), look for diagonal planes, which indicate the
Dnd group.

START

A simpler approach:

1.5Uses of point group symmetry and physical properties
Carrying out a symmetry operation on a molecule must not change any of its physical properties.
It turns out that this has some interesting consequences, allowing us to predict whether or not a
molecule may be chiral or polar on the basis of its point group.
1.5.1 Polarity
For a molecule to have a permanent dipole moment, it must have an asymmetric charge
distribution. The point group of the molecule not only determines whether the molecule may
have a dipole moment, but also in which direction(s) it may point.
If a molecule has a Cn axis with n>1, it cannot have a dipole moment perpendicular to the axis of
rotation (for example, a C2n rotation would interchange the ends of such a dipole moment and
reverse the polarity, which is not allowed – rotations with higher values of n would also change
the direction in which the dipole points). Any dipole must lie parallel to a Cn axis.
Also, if the point group of the molecule contains any symmetry operation that would interchange
the two ends of the molecule, such as σh mirror plane or a C2 rotation perpendicular to the
principal axis, then there cannot be a dipole moment along the axis. The only groups compatible
with a dipole moment are C2n, Cnv and Cs. In molecules belonging to Cn or Cnv the dipole
moment must lie along the axis of rotation is a polar molecule.
Therefore; a molecule cannot be polar if it has:
1. a center of inversion
–any group with i
2. an electric dipole moment perpendicular to any mirror planes
–any of the groups D and their derivatives
3. an electric dipole moment perpendicular toany axis of rotation

4. –the cubic groups T, O, the icosahedral I, and their modifications
1.5.2 Chirality
One example of symmetry in chemistry that you will already have come across is found in the
isomeric pairs of molecules called enantiomers.

Enantiomers are non-superimposable mirror

images of each other, and one consequence of this symmetrical relationship is that they rotate the
plane of polarised light passing through them in opposite directions. Such molecules are said to
be chiral*, meaning that they cannot be superimposed on their mirror image. Formally, the
symmetry element that precludes a molecule from being chiral is a rotation-reflection axis S.
Such an axis is often implied by other symmetry elements present in a group. For example; point
groups that have Cn and σh as elements will also have Sn. Similarly, a centre of inversion is
equivalent to S2. As a rule of thumb, a molecule definitely cannot have be chiral if it has a centre
of inversion or a mirror plane of any type (σh, σv or σd), but if these symmetry elements are
absent the molecule should be checked carefully for an Sn axis before it is assumed to be chiral.
Therefore; a molecule is not chiral if:
1. It possess an improper rotation axis S
2. It belongs to the group D
3. It belongs to Td or Oh
Summary of symmetry elements and their Matrix transformation: