Molecular SymmetrydPart I: Point

Chapter
3
Group Assignment

1. INTRODUCTION: IS IT NECESSARY TO LEARN

MOLECULAR SYMMETRY?
Nature created shapes, and humans have classified them into groups or
patterns. Whether in biology, mathematics, arts, engineering, physics, or
chemistry, these classifications were created to simplify the objects or
the world around us. Similarly, chemists classify molecules based on their
symmetry and the collections of symmetry elements, such as points, lines,
and planes that intersect at a single point, to form a “Point Group”. Obvi-
ously, in nature’s cycle of events, geometry of a molecule points to a sym-
metry group leading to group representation that determines the structural
properties based on the geometry of that particular species. Thus, for any
molecule’s symmetry, one can predict important properties leading to mo-
lecular identity, such as space group of any crystalline form, chirality (op-
tical activity) or lack of chirality, overall polarity (dipole moments),
infrared spectrum, and Raman spectrum. One must admit that symmetry
is the consistency, that is, the repetition, of an object in space and/or in
time as we normally observe in a wall drawing/painting, wings of a butter-
fly, flower petals, musical notes, and even the repetition of day and night
and the seasons on our planet. Since symmetry is an important aspect of
nature, we must learn about its mystery.

2. ELEMENTS OF SYMMETRY
2.1 Symmetry operations
1. The shape of a molecule is described by indicating the spatial arrange-
ment of the atoms.
a. For simple symmetric molecules, the terms trigonal planar, tetrahe-
dral, octahedral, etc. are useful descriptions. However, for more

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32 CHAPTER 3 Molecular SymmetrydPart I: Point Group Assignment

complex molecules not having a great deal of symmetry, a better

way of describing the stereochemical arrangement of the atoms is
needed.
b. Example: Consider the pentagonal bipyramidal molecule PCl3F2
(Fig. 3.1). There are three ways to arrange the atoms.

F F Cl
Cl Cl F
Cl F Cl
Cl Cl F
F Cl Cl
I II III
n FIGURE 3.1 Possible isomers of PCl3F2.

c. All three structures have a trigonal bipyramidal structure. Of the

three, I is the most symmetric, whereas II is the least symmetric.
This ordering is done on the basis that in I, all three Cl’s are equiv-
alent, as are the two F’s. In III, two Cl’s and two F’s are equiva-
lent, whereas in II, only two Cl’s are equivalent. Therefore, one
can use symmetry to describe molecular shapes.
2. Only four symmetry operations are needed to define a structure. These
consist of rotations, reflections, inversion about a point, and rotation
and reflection in a perpendicular mirror plane.
3. If one carries out a symmetry operation and obtains an equivalent
(indistinguishable) structure, the molecule is said to possess that partic-
ular element of symmetry.

2.2 Operations and elements

1. Rotation about an axis.
a. The symbol Cn will stand for “n” number of rotations by an angle
of 360 degrees (2p/n).
i. C1 ¼ rotation by 2p (360 degrees). This is a trivial operation.
C2 ¼ rotation by 2p/2 (180 degrees).
C3 ¼ rotation by 2p/3 (120 degrees).
C4 ¼ rotation by 2p/4 (90 degrees).
ii. A single rotation by 2p/n ¼ Cn.
A rotation by 2(2p/n) [carry out the operation twice] ¼ C2n.
A rotation by 3(2p/n) [carry out the operation three times] ¼
C3n.
iii. The various C4 operations are shown for the vertices of a
regular octahedron (Fig. 3.2).
 2. Elements of Symmetry 33

1
1
2
5 3 5
4 2
4
C4 3
6
C4 4 = E C4
6
1
C4 2
5 3 C4
C4 3 4
6 C4 2
1
1
3 4
2 4 3 5
5 C4 2
6 6

n FIGURE 3.2 Illustration of rotation about an axis.

iv. If one applies Cn n times (Cnn ), it will have a total rotation of

2p (360 degrees).
This will give not an equivalent structure, but an identical
structure.
This operation is called the identify operation and has the
symbol E.
b. If one carries out the operation Cn and obtains an equivalent
structure, the molecule has an n-fold proper axis of symmetry. The
symbol for this element of symmetry is Cn. Since the symmetry
element and the operation have the same symbol, we will use bold
lettering to indicate the operation.
c. The element Cn generates n operations [Cn, C2n , C3n , . Cnn (¼E)].
2. Reflection in a mirror plane.
a. s ¼ reflection in a plane.
s2 ¼ reflection twice ¼ E.
b. If one carries out the operation s and obtains an equivalent struc-
ture, the molecule is said to possess a plane of symmetry. The sym-
bol for this element is s. An example is shown in Fig. 3.3 (dashed
lines connect the atoms in the mirror plane).
1 1
2 4
σ
5 3 5 3

4 2
6 6
σ
n FIGURE 3.3 Illustration of reflection in a mirror plane.
c. Each element s generates only one unique operation since s2 ¼ E.
34 CHAPTER 3 Molecular SymmetrydPart I: Point Group Assignment

3. Inversion through a point.

a. i ¼ inversion.
Note that i2 ¼ E.
b. If one carries out the operation i and obtains an equivalent struc-
ture, the molecule has a center of inversion as shown in Fig. 3.4.

1 6
2 4
i
5 3 3 5
4 2
6 1
i
n FIGURE 3.4 Illustration of center of inversion.

The symbol for this element is i.

4. Rotation þ reflection in a perpendicular mirror plane.
a. Sn ¼ rotation by 2p/n followed by reflection in a plane perpendic-
ular to the axis of rotation. Such a plane is called a horizontal
plane (sh).
b. If one carries out this operation and obtains an equivalent structure,
the molecule has an n-fold improper axis of rotation (Fig. 3.5).

1
6
2
5
5 3 S
4 2
4
3
6
S4 1
S4 4 = E
1
S4 2
5 3 S4
4
6 S4 2
S4 3
6 1
3 4
2 4 3 5
S4
5 2
1 6

n FIGURE 3.5 Illustration of improper axes of rotation.

The symbol for this element is Sn.

c. The element Sn gives rise to n operations (Sn, S2n S3n , S4n , . Snn ).
 2. Elements of Symmetry 35

2.2.1 Examples
Example 1. Symmetry elements and operations for PBr5.
PBr5 is a trigonal bipyramidal molecule with two axial and three equatorial
Br’s (Fig. 3.6). We will number the positions to see the results of symmetry
operations.

Br 1
Br 2
Br P
Br
= 4
3
Br 5

n FIGURE 3.6 Atom numbering surrounding the central phosphorus.

Note the axial positions are 1 and 5, whereas the equatorial positions are 2,
3, 4.
1. Proper axes of rotation
There is one C3 and three C2 axes. These axes and their related
operations are shown in Fig. 3.7.

1 5
C3 C2 '
4 2
3 3
2 4

1
5

1 1 1 5
C32 C 2'
2 3 C2
4 2 3
2 4
3 4
4 C2
2
3
5 1
5 C 2"
C3
1 5
2 "
4 C2 4
2
3
C33 = E 3

5 1
n FIGURE 3.7 Illustration of proper axes of rotation.
36 CHAPTER 3 Molecular SymmetrydPart I: Point Group Assignment

The proper axis of rotation with the highest symmetry is taken as the
main symmetry element (for PBr5 it is the C3 axis). All other
symmetry elements will be referred to this element. Note that each
C2 axis generates only one unique operation since C22 ¼ E, and E
was already listed as C33. The four symmetry elements generate six
unique symmetry operations.
2. Mirror planes
a. There are four mirror planes. One is perpendicular to the C3 axis
and is called a horizontal plane (sh). The other three contain the C3
axis. The intersection of these planes define the C3 axis; they are
called vertical planes (sv).
These planes and their operations are shown in Fig. 3.8. A
dashed line is used to connect the atoms in the particular plane.

1 5
1 σv ' 1
2
σh 2
σ v'
σh 4 4 2 2
4 3
3 3
3 4
5 1
5 5

1 1
1
1 σv"
σv 3 2 4
2 4 2
σv 4
4
3 3
3 2
5
σv " 5
5 5

n FIGURE 3.8 Illustration of mirror plane of symmetry.

b. Since s2 ¼ E, each element generates on one unique operation.

3. Center of inversion
The molecule does not possess a center of inversion, as the “i”
operation at the point of intersection does not give an equivalent
structure.
4. Improper axes of rotation
a. There is an S3 axis coincident with the C3.
b. This element generates only one unique operation, S3 (Fig. 3.9).
 2. Elements of Symmetry 37

n FIGURE 3.9 Operation of improper axes of rotation.

5. Summary
The molecule has nine symmetry elements (C3, 3C2, 3sv, sh, S3) that
generate a total of 11 unique symmetry operations.
Example 2. The elements and operators for the isomers of PF2Cl3
(Fig. 3.10).

n FIGURE 3.10 Isomers of PF2Cl3.

1. Isomer I
This isomer has all of the symmetry elements and operations of PBr5 out-
lined earlier.
In PBr5, there were two sets of Br’s: the two axial atoms and the three equa-
torial ones. No symmetry operation can interchange the axials with equato-
rials. Therefore, nothing changes if the axial groups and the equatorial
groups are different.
38 CHAPTER 3 Molecular SymmetrydPart I: Point Group Assignment

2. Isomer II of PF2Cl3 (Fig. 3.11)

F F
Cl (1) σ Cl (2)
F F
Cl (2) Cl (1)
Cl Cl
n FIGURE 3.11 Reflection in isomer II of PF2Cl3.

This isomer has only a plane of symmetry containing the two axial groups
and the one equatorial F.
Reflection in this plane interchanges the two equivalent Cl’s, Cl(1) and
Cl(2).
3. Isomer III of PF2Cl3 (Fig. 3.12)

Cl (1) Cl (3)
C2 F (2)
F (1)
C2 Cl Cl
F (2) F (1)
Cl (3) Cl (1)
Cl (1) Cl (3) Cl Cl
σv σv
σv Cl F F F(1) F(2)
Cl σv Cl Cl
F F F (2) F (1)
Cl (3) Cl (1) Cl Cl
n FIGURE 3.12 Rotation and reflection in isomer III of PF2Cl3.

This isomer has a C2 axis and two sv planes.

3. POINT GROUPS
3.1 Introduction
1. All symmetry elements intersect at a point, the center of symmetry of
the molecule.
a. This point has all the symmetry of the molecule.
b. On the basis of symmetry, one can classify molecules into point
groups.
2. Molecules with the same symmetry are in the same point group. We
will describe the shape of the molecule by assigning it to a particular
point group.
 3. Point Groups 39

3.2 Rules for assigning point groups

1. Look for proper axes of symmetry. If none exists and there is only:
a. a plane of symmetry, then the point group is Cs.
b. a center of inversion, then the point group is Ci.
2. If proper axes exist, pick the highest symmetry axis as the major axis.
If no uniquely high axis exists, pick one with some special geometric
property, e.g., being colinear with some unique bond, as the major axis.
If there is no obviously unique axis, just pick one and stick with it.
3. Once the major Cn is found, look for an S2n axis coincident with it. If
one is found and no other element of symmetry exists (other than i),
the point group is Sn (n will always be even).
4. If no S2n exists or if other symmetry elements exist, then:
a. look for a set of n C2 axes perpendicular to Cn. If such a set exists,
the point group is Dn, Dnh, or Dnd.
b. if a set of n C2 axes does not exist, then the point group is Cn, Cnv,
or Cnh.
5. If the molecule is one with a D point group:
a. look for a mirror plane perpendicular to the major Cn (this is called
a horizontal plane and has the symbol sh). If this plane exists, the
point group is Dnh.
b. if no sh plane exists, then look for a set of planes bisecting the C2
axes (these planes are called dihedral planes and have the symbol
sd). If these planes are found, the point group is Dnd.
c. if neither sh nor sd planes are found, the point group is Dn.
6. If the molecule is one with a C point group:
a. look for a sh plane. If one is found the point group is Cnh.
b. look for a set of n sv planes (planes vertical to and containing the
Cn axis).
If a set is found, the point group is Cnv.
c. if neither sh nor sv planes exist, the point group is Cn.
7. Special groups (these should be considered first):
a. CNv: Linear molecules that do not possess a plane of symmetry
perpendicular to the CN axis (example is HCl).
b. DNh: Linear molecule possessing a plane of symmetry perpendic-
ular to the CN axis (example is CO2 or Cl2).
c. Td: Tetrahedral molecules (example is CH4).
d. Oh: Octahedral molecules (example is SF6).

3.3 Examples
1. PBr5 and PCl3F2 are D3h (have C3 þ 3C2’s þ sh symmetry elements).
2. NH3 is C3v.
3. H2O is C2v.
4. Unfavorable isomers of PCl3F2 (Fig. 3.13).
40 CHAPTER 3 Molecular SymmetrydPart I: Point Group Assignment

n FIGURE 3.13 Isomers of PCl3F2.

A selection of a number of molecules and their point groups determined

with the accompanying flowchart (Table 3.1; reproduced from the book

Table 3.1 Symmetry and Group Flowchart

The following flowchart will help you place molecules into the point groups C1, Cs, Cn, Cnv, Dn, and Dnh.
Does Cn exist?

No Yes

σ? nσv?
No Yes No Yes

⊥
nC2 ?
C1 Cs Cn
No Yes
(E only) (E, σ only) (E, Cn only)
σ h?
Cnv
No Yes
(E, Cn, nσv )

Dn Dnh

⊥ ⊥
(E, Cn , nC2 only) (E, Cn, nC2 ,σ h +
others)

An Introduction to Inorganic Chemistry, K. F. Purcell and J. C. Kotz; Saun-

ders College Publishing, Philadelphia, 1980. 637 pp) as well as the structures
are shown in Table 3.2 [reproduced from the Website funded under
 3. Point Groups 41

Table 3.2 Symmetry and Point Group

Number of
Stereochemically
Active eL Pairs Example Point Group

2 DNh
2 H C N CNv
3 D3h

3 C2v

3 CS

4 Td

4 C3v

4 C2v

Continued
42 CHAPTER 3 Molecular SymmetrydPart I: Point Group Assignment

Table 3.2 Symmetry and Point Group continued

Number of
Stereochemically
Active eL Pairs Example Point Group

5 D3h

5 C3v

5 C2v

6 Oh

6 D4h

6 C4v

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