Symmetry, Point Groups, and Character Tables

Symmetry operations and their importance for chemical

problems
 A Symmetry Operation. Point Symmetry

C2 C3 C4 C5 C6
During all symmetry operations, which can be applied to a
molecule, at least one point in the molecule, the center of
gravity, remains unchanged. Symmetry of this kind is
therefore called point symmetry.
During a 360o rotation around the z-axis of the molecules I-V, I repeats itself twice, II,
three times, III, four times, IV, five times, and V, six times; the z-axes in these molecules
are thus called a two-fold, three-fold, four-fold, five-fold, and six-fold rotation axes,
respectively. If the angle through which the molecules must be rotated in order to secure
the superimposable image is designated , the molecules have 360/ -fold rotational axes.
The rotational axis is usually denonted as Cn, where the C is for cyclic and where
n = 360°/.

The subscript n is thus the number of times the superimposable orientation appears during
a 360o rotation. It should be understood that the symmetry operation we have been
discussing is rotation around an axis, while the symmetry element is the rotational axis Cn.

The symmetry operation Cn, frequently also is called a proper rotation, and the symmetry
element Cn, a proper rotational axis.

Molecules I-V all are planar and the z rotational axis in each case is normal to the
molecular plane.
Symmetry Operations and Symmetry Elements
Rotation About an Axis; Rotational Axis, Cn

Non-planar molecules ---

Although it may appear to be

trivial, it is nevertheless
important to recognize that all
molecules have an infinite
number of C1 axes, since a
360o rotation around any or
all axes passing through the
center of gravity of the
molecule returns it to its
original position.

C2 C3 C3 C3 C4 C4
All linear molecules such as C2H2 and CO (and hence also
all diatomic molecules) possess C∞, since rotation about the
internuclear axis by any angle gives an orientation identical
with the original.
The Identity Operation, E: The operation which leaves a molecule unchanged and
hence in an orientation identical with the original is called the identity operation. It is
desirable to distinguish between identical and equivalent orientations.

An operation which leaves the molecule identical to the original is called the identity
operation, denoted by E (from the German Einheit meaning unit or loosely identical) and
thus C33 = E; C22 = E; C1 = E, and since all these operations by definition leave the molecule
unchanged, doing nothing to the molecule is also an identity operation.

Class and Order:

CHCl3: C3 x C3 = C32 = C3ʹ (ʹ refers to counterclockwise rotation). Furthermore, C3 and C3'

give equivalent but not identical orientations; these two operations are said to belong to the
same class and we say that chloroform has 2C3 axes where 2 is called the order of the class.

CH4: Since the tetrahedron has four faces, there are a total of 8C3. All of the 8C3 are said to
belong to the same "class“.
 Inverse Operation
If two or more operatiom performed in sequence return the molecule to an orientation
identical to the original, the product of the operations is equal to the identity.

Another very simple way to return a molecule to its original position after a symmetry
operation consists of simply reversing the operation. Thus, the C3 or clockwise
rotation of the molecule CH4. Now if this were followed by C3' or C3–1, the inverse of
C3, the molecule would be returned to its original orientation.
Reflection of a Plane: The Mirror Plane,  (sigma)

If a molecule is bisected by a plane, and each atom in one half of

the bisected molecule is reflected (the operation) through the plane
and encounters a similar atom in the other half, the molecule is
said to possess a mirror plane (the symmetry element). The
operation and the element are denoted by  (probably derived from
the first letter in the German word Spiegel = mirror).
All planar molecules of course have at least one plane of symmetry, the molecular
plane. Thus, the xy plane is a horizontal mirror plane in all of the molecules I-V.

BF3, II, has in addition three vertical mirror planes, each including one BF bond and
bisecting the angle between the other two B-F bonds. [PtC14]2–, III, has four vertical
planes, the planes along the x- and y-axes and diagonal planes which are perpendi-
cular to each other and which bisect the angles between the x- and y-axes.

Benzene, V, has six vertical planes, a set of three which pass through opposite atoms
and which may be designated 3v , and a set of three bisecting opposite C-C bonds,
which may be designated 3d.
Inversion at a Center of Symmetry: Center of Symmetry, i

When a straight line is drawn from any atom in a molecule through the center of the molecule and,
if continued in the same direction, encounters an equivalent atom equidistant from t,he center (the
operation), and if the same operation can be performed on all atoms, then the molecule possesses
a center of symmetry, designated i for inversion.

Since each atom is thus reflected through the center into an equivalent atom, atoms must occur in
pairs (with the exception of any atom which may lie on the center itself) with the members of the
pair equidistant but in opposite directions from the center. Thus, molecules I, III, V, and XI have i,
but II, IV, and VI-X do not.
 Rotation about an Axis, followed by Reflection of a Plane
Norma1 to this Axis: Rotation-Reflection Axis, Sn
If a molecule is rotated around an axis and the resulting orientation is reflected in a plane
perpendicular to this axis (the operation) and if the resulting orientation is superimposable on
the original, the molecule is said to possess a rotation-reflection axis (the element).

The axis around which the rotation was performed is the rotation-reflection axis, and it is
designated as Sn, where n, as usual, is the order. This axis is also called an alternating axis or
improper axis, and is thus distinguished from a rotational or proper axis, Cn.
In trans-dichloroethylene, I, the x-axis is an S2 axis, since, e.g., the lower right H atom
on a 180o rotation around the x-axis followed by reflection in the yz plane (which is
normal to the x-axis) places the H atom on top of the upper left one in the original. The
other atoms are similarly transposed.

It should be noted that in this example the S2, axis which coincides with the x-axis is
not a C2 axis, which here is the z-axis. It should also be noted that the S2 operation
achieves exactly the same result as i.
 Actually, any axis through a molecule having a center of symmetry is an S2 axis.

In the chair form of cyclohexane, XII, the vertical axis which passes through the center
of the molecule is a C3 axis (e.g., clockwise 120o rotation transforms hydrogen 1 into
5, 5 into 10, and 10 into 1, as well as 2 into 6, 6 into 9, and 9 into 2), but this axis is also
an S6 axis (e.g., clockwise 60o rotation followed by reflection in the normal plane takes
1 into 4, 4 into 5, 5 into 8, etc.). A vertical axis through the carbon of methane, XIII, is a
S4 axis.
Thus, the most outstanding symmetry property of the chair form of cyclohexane is
its six-fold alternating axis, S6, which transforms all axial hydrogens into each
other, as well as all equatorial hydrogens into each other, and thus the twelve
hydrogens in C6H12 belong to two sets of six chemically equivalent hydrogen
atoms. The S4 operation on CH4 transforms all H atoms into each other and hence
the four H atoms in CH4 constitute one set of chemically-equivalent atoms.

The S axis is called an alternating axis because the equivalent atoms transformed
by the operation lie alternately above and below the plane of reflection.

It should also be pointed out that not only is i equivalent to S2 but  is equivalent to
S1. Usually it is easier to find the plane of symmetry than the S1 axis, but the S1 axis
will be any axis perpendicular to the plane of symmetry. Thus, in chloroethylene,
XIV, the x-axis is an S1 axis; rotation of 360o around x followed by reflection in the
yz plane gives a molecule identical with the original
Some Applications of Symmetry Operations:
Optical Activity
Dipole Moment
Some Applications of Symmetry Operations Optical Activity: The
criterion for optical activity of a molecule involves the test of superimposability of its mirror
image on the original; if the mirror image can be superimposed, the original and the mirror
image are identical and the molecule is inactive (unresolvable). If the original cannot be
superimposed on its mirror image, the compound is active.

1,2-Dichlorocyclopropanes: XV, cis-isomer; XVI, trans-isomer: resolvable into the

optically active enantiomorphs, XVI and XVII.
 All molecules which lack a rotation-reflection axis of any order (fold) (Sn) are said to
be dissymmetric and are optically active, i.e., the molecule and its mirror image
cannot be made to coincide in space by any kind of rotational or translational motion
of the whole molecule.

It will be recalled from our earlier discussion that a mirror plane is equivalent to S1
and a center of inversion is equivalent to S2 and hence molecules possessing these
symmetry elements have mirror images that are identical with the original and hence
are inactive.
If we examine trans-1,2-dichlorocyclopropane, XVI,
we see that there is a C2 axis in the plane of the three-
membered ring passing through the bond between the
chlorine-bearing carbon atoms and the methylene
carbon atom. Since the molecule does not possess an Sn
axis, however, it is active. On the other hand, because
XVI and XVII have a C2 axis, they do not lack
symmetry, i.e., they are dissymmetric but are not
asymmetric. The only symmetry that dissymmetric
(optically active) compounds possess are one or more
Cn axes; although many common dissymmetric
compounds have C2, most optically-active compounds
are asymmetric as well as dissymmetric and hence have
only C1.
 Operations
O E C2(z) v (xz) vʹ(yz) Repre-
H H
C2v
senta-
z tion

y s +1 +1 +1 +1 A1 z, x2, y2, z2
x px +1 -1 +1 -1 B1 x, xz
py +1 -1 -1 +1 B2 y, yz

pz +1 +1 +1 +1 A1

Tx +1 -1 +1 -1 B1
Ty +1 -1 -1 +1 B2
Tz +1 +1 +1 +1 A1
Rx +1 -1 -1 +1 B2
Ry +1 -1 +1 -1 B1
Rz +1 +1 -1 -1 A2 xy
 C2v E C2(z) v (xz) vʹ(yz)
A1 1 1 1 1 z, x2, y2, z2
A2 1 1 -1 -1 xy
B1 1 -1 1 -1 x, xz
B2 1 -1 -1 1 y, yz

Down the left side are various letters which we shall use as labels. Associated
with each label is a row of numbers, with one number for each type of
symmetry operation. The rows of numbers are each called "irreducible
representation" (of the group) and the letters are just a shorthand way of
indicating which set of numbers (which irreducible representation) we are
talking about. The numbers themselves are called "characters"-hence the name
"character table."
 L Orbital Symmetry
L L
C4v E C4+ C4- C2 v v d  dʹ
M
(xz) (yz)
L L
s s s s s s s s s
x pz z z z z z z z z
px x y -y -x x -x y -y
y py y -x x -y -y y x -x
z z2 z2 z2 z2 z2 z2 z2 z2 z2

x2-y2 x2-y2 -(x2-y2) -(x2-y2) x2-y2 x2-y2 x2-y2 -(x2-y2) -(x2-y2)

xy xy -xy -xy xy -xy -xy xy xy

xz xz yz -yz -xz xz -xz yz -yz
yz yz -xz xz -yz -yz yz xz -xz
 E C4+ C4- C2

(x, y) 1 0 0 1 0 -1 -1 0
(xz, yz) 0 1 -1 0 1 0 0 -1
2 0 0 -2

v (xz) v (yz) d dʹ

1 0 -1 0 0 1 0 -1
0 -1 0 1 1 0 -1 0
0 0 0 0
 Operations grouped by class Down the left side are various
C4v E 2C4 C2 2v 2d letters which we shall use as
labels. Associated with each label
A1 +1 +1 +1 +1 +1 z, z2 is a row of numbers, with one
A2 +1 +1 +1 -1 -1 number for each type of symmetry
operation. The rows of
B1 +1 -1 +1 +1 -1 x2-y2 numbers are each called
B2 +1 -1 +1 -1 +1 xy "irreducible representation" (of the
E 2 0 -2 0 0 (x, y), group) and the letters are just a
(xz, yz) shorthand way of indicating which
set of numbers (which irreducible
representation) we are talking
about. The numbers themselves
are called "characters"-hence the
name "character table."
Irreducible representation /Labels
E: 12 + 12 + 12 + 12 + 22 = 8
(the number of symmetry operations)
 An octahedron (a figure with eight triangular faces, twelve edges
and six corners) shows considerable symmetry.
Three distinct fourfold axes, passing through
opposite pairs of corners. We have coincident
fourfold and twofold axes, with two distinct
fourfold rotation operations (denoted 2C4) and a
single twofold rotation operation (denoted C2) – a
total of 6C4 and 3C2 operations.
Passing through each pair of opposite edges of the
octahedron are twofold axes quite distinct from
those found earlier. Since there are six pairs of
edges there are six twofold axes, denoted 6C2', the
prime distinguishing these twofold axes from the
others.
Perpendicular to each pair of opposite faces of the
octahedron and passing through the midpoint of
them is a threefold axis. Since there are four such
pairs of faces there are also four threefold axes –
a total of 8C3 operations.
px, py, pz : E = 3 (= 1 + 1 + 1)
px, py, pz : 6C4 = 1 (= 0 + 0 + 1)

px, py, pz : 3C2 = -1 (= -1 -1 + 1)

px, py, pz : 8C3 = 0 (px  py  pz  px)

px, py, pz : 6C2ʹ = -1 (= 0 + 0 -1)

 dx2-y2: 0
dz2 = (z2-x2)+ (z2-y2)
dz2: (-1/2) + (-1/2)
= 2z2-x2-y2
= 0 -1 = -1
E
E
E

dz2, x2-y2
(xy, xz, yz)

dz2: (dz2-x2) + (dz2-y2)

 C2H4

g/u 1/2/3 A/B