Point Groups

Point Group = the set of symmetry operations for a molecule

Group Theory = mathematical treatment of the properties of the group which
can be used to find properties of the molecule
Assigning the Point Group of a Molecule
1. Determine if the molecule is of high or low symmetry by inspection
A. Low Symmetry Groups
B. High Symmetry Groups
2. If not, find the principle axis
3. If there are C2 axes
perpendicular to Cn the
molecule is in D If not, the
molecule will be in C or S
4. If h perpendicular to Cn then
Dnh or Cnh If not, go to the next
step
5. If  contains Cn then Cnv or Dnd
If not, Dn or Cn or S2n
6. If S2n along Cn then S2n
7. If not Cn
The determination of point groups of
molecules
only one rotational two σv but no σh mirror planes means
axis = C2 point group is C2v

The point group of the water molecule is C2v

 Naming point groups:
The name of the point group has information about the
symmetry elements present. The letter is the rotational group
and the subscript number after the letter indicates the order
of the principal rotational axis (e.g. 3-fold or 4 fold etc.):

A ‘D’ indicates an n-fold

principal rotation axis
A ‘C’ indicates only plus n 2-fold axes at
one rotational axis right angles to it

C3 C3v D4d D4h

3-fold rotational has σv but 4-fold d = no ‘h’ indicates
axis no σh mirror principal σh mirror a σh mirror
planes in a C group axis plane plane
 Naming point groups (contd.):

A subscript ‘h’ means that there is a σh mirror plane at

right angles to the n-fold principal axis:

C4 principal axis C3 principal axis

only one
of the three
σv planes
is shown

σh σv

D4h D3d
A subscript ‘d’ (or v for C groups) means there is no σh mirror
plane, but only n σv mirror planes containing the principal Cn axis.
 Naming platonic solids:
Platonic solids: Five special polyhedra: Tetrahedron, Cube,
Octahedron, Dodecahedron, and
Icosahedron
Their faces are all exactly the same.
The same number of faces meet at each vertex.
T = tetrahedral = 4 three-fold axes
O = octahedral = 3 four-fold axes
I = icosahedral = 6 five-fold axes

C60
‘bucky-ball’
or ‘Fullerene’

Td Oh Ih
Flow chart for determining point groups.
The point group of the carbon dioxide
molecule
i We start at the top of the
flow-chart, and can see that
C∞ the CO2 molecule is linear,
and has a center of inversion
(i) so it is D∞h. Note the C∞
D∞h principal rotation axis.
 Other linear molecules:
The top row of linear molecules all have a center of
inversion (i) and so are D∞h.

i D∞h i

N2 O2 F2 H2

HC≡N HI C≡O
The bottom row have no C∞v All have a C∞
i and so are C∞v axis
 The Platonic solids:
tetrahedron octahedron icosahedron

Td Oh Ih C60
‘buckyball’
 The Cs point group:
I σ
Cs
C
Cl chloro-difluoro-iodo-
F methane
F
Most land animals have bilateral symmetry,
and belong to the Cs point group:

Cs Mirror planes (σ)

 The C1 point group:

Molecules that have no symmetry elements at all except

the trivial one where they are rotated through 360º and
remain unchanged, belong to the C1 point group. In
other words, they have an axis of 360º/360º = 1-fold, so
have a C1 axis. Examples are:
I
I N
Cl
C H
Br
Cl
C1 F C1
Bromo-chloro-fluoro-iodo- chloro-iodo-amine
methane
The division into Cn and Dn point groups:

After we have decided

that there is a principal
rotation axis, we come
to the red box. If there
are n C2 axes at right
angles to the principal
axis, we have a Dn point
group, If not, it is a Cn
point group.

Dn

Cn
 The Cn point groups:
The Cn point groups all have only a single rotational
axis, which can theoretically be very high e.g. C5 in
the complex [IF6O]- below. They are further divided
into Cn, Cnv, and Cnh point
C5 groups. The Cn point
groups O have no other
symmetry
iodine elements,
the Cnv point groups have
also n mirror planes
F containing the Cn rotational
axis, while the Cnh point
groups also have a σh mirror
F plane at right angles to the
[IF6O]- principal rotational axis.
The point group of the water molecule

We start at the top of the

flow-chart, and can see that
the water molecule is not
linear, and is not tetrahedral (Td),
octahedral (Oh), or icosahedral,
(Ih) so we proceed down the chart
C2 Yes, there is a principal Cn axis,
so we proceed down the chart, but
in answer to the next question, there
are no further C2 axes at right angles
to the principal axis, which is the only
axis, so we proceed down the chart
 C2 there is no σh plane
C2 C2
at right angles to
σv σv the C2 axis, but
there are two σv
planes containing
the C2 axis.

The point group of the water molecule is C2v

 Other Cnv molecules:

water ammonia
σv

C2v
C3v
σv

C4v V
σv

Vanadyl tetrafluoride (VOF4)

 Some more C2v molecules:

C2 σv C2 σv C2 σv

P S
C

σv σv σv
Phosphorus iodo- sulfur tetra- carbonyl
tetrafluoride (PF4I) fluoride (SF4) chloride (COCl2)
 The Cn point groups:
These have a Cn axis as their only symmetry element. Important
examples are (hydrogens omitted for clarity):

triphenyl C3 Cobalt(III)
phosphine tris-glycinate
viewed down viewed down
C3 axis C3 C3 axis

C3 C3
C3 C3
triphenyl Cobalt(III)
phosphine tris-glycinate
viewed from viewed from
the side the side
 The Dnh point groups:

C4 four C2
mirror plane
principal axes at
rt. angles at rt. angles
axis to C4 axis to C4 axis

C2
C2 σh
C2 C2

D4h
Examples of molecules belonging to Dnh point
groups:
C2 C3 C3
C3

D2h D3h D3h D3h

C4
C5
C4 C5

D4h D4h D5h D5h

Benzene, an example of the D6h point group:
C6 C2
principal axis C2

C2 C2
C6 σh
σv σv

D6h

C6
principal axis
C6
principal axis
 The Dn point groups:

these have a principal

n-fold axis, and n
2-fold axes at right
angles to it, but no
mirror planes.

C2 principal axis
C
N
C2 [Cu(en)2]2+ complex
Cu
N with H-atoms
omitted for clarity.
(en = ethylene
diamine)
C2 D2
 Some further views of the symmetry elements
of [Cu(en)2]2+, point group D2 :
C2 principal axis
[Cu(en)2]2+ complex
C2 with H-atoms
D2 omitted for clarity.
(en = ethylene
diamine)
C2 principal C2
axis
C2 C2 principal C2 principal
axis axis
C2 C2 C2
C2 C2
 Some views of the symmetry elements of
[Co(en)3]3+, point group D3.

C2
C3 principal axis
C2

C2

C3 D3 C2
principal axis axis

view down the C3 axis view down one of the

of [Co(en)3]3+ showing three C2 axes of [Co(en)3]3+
the three C2 axes. at right angles to C3
 Other examples of the D3 point group

C3 C2
C2 C2 principal axis

C2
C2

C2

D3 D3
[Co(oxalate)3]3- [Co(bipyridyl)3]3+
Molecules belonging to the Dnd point groups

These have mirror planes parallel to the principal

axis, but not at right angles to it.
C5 axis
C3 axis σv planes
contain the
principal
axis

D3d D5d
Staggered form
of ethane Staggered form of ferrocene
 The D4d point group:
C4 principal axis σv
C2 C2 σv σv
C2 C2
C2 σv

C4 C4
[ZrF8 ]4- principal axis
principal axis
Square antiprism D4d
As predicted by VSEPR, the [ZrF8]4- anion has a square anti-prismatic
structure. At left is seen the C4 principal axis. It has four C2 axes at
right angles to it, so it has D4 symmetry. One C2 axis is shown side-on
(center). There are four σv mirror planes (right), but no mirror plane at
right angles to C4, so the point group does not rate an h, and is D4d.
 [K(18-crown-6)]+, an example of a D3d
point group:
C3
principal axis C3 principal axis σv
C2 C2
K+
σv
C2
C2 C2
C2 σv
D3d
The complex cation [K(18-crown-6)]+ above is an important structure that
has D3d symmetry. It has a C3 principal axis with 3 C2 axes at right
angles to it, as well as three σv mirror planes that contain the C3 axis,
but no σh mirror plane (because it’s not flat, as seen at center), so is D3d.
Some Point groups