The determination of point groups of molecules

only one rotational axis = C2 two v but no h mirror planes means

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 plus n 2-fold axes at right angles to it

A C indicates only one rotational axis

C3

C3v

D4d
4-fold principal axis

D4h
d = no h mirror plane h indicates a h mirror plane

3-fold rotational has v but axis no h mirror planes in a C group

Naming point groups (contd.):

A subscript h means that there is a h mirror plane at right angles to the n-fold principal axis:

C4

principal axis

C3

principal axis only one of the three v planes is shown

D4h

D3d

A subscript d (or v for C groups) means there is no h mirror plane, but only n v mirror planes containing the principal Cn axis.

Naming platonic solids:

Platonic solids: T = tetrahedral = 4 three-fold axes O = octahedral = 3 four-fold axes I = icosahedral = 6 five-fold axes

bucky-ball or Fullerene

C60

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
C
flow-chart, and can see that the CO2 molecule is linear, and has a center of inversion
(i) so it is Dh. Note the C principal rotation axis.

Dh

Other linear molecules:

The top row of linear molecules all have a center of inversion (i) and so are Dh.

Dh

N2

O2

F2

H2

HCN The bottom row have no i and so are Cv

HI

CO All have a C axis

Cv

The Platonic solids:

tetrahedron octahedron icosahedron

Td

Oh

Ih

C60 buckyball

The Cs point group:

Cs
F F

I C

Cl
chloro-difluoro-iodomethane

Most land animals have bilateral symmetry, and belong to the Cs point group:

Cs

Mirror planes ()

Cs

The C1 point group:

Molecules that have no symmetry elements at all except the trivial one where they are rotated through 360 and remain unchanged, belong to the C1 point group. In other words, they have an axis of 360/360 = 1-fold, so have a C1 axis. Examples are: I I
Cl Br C Cl F H N

C1

C1
chloro-iodo-amine

Bromo-chloro-fluoro-iodomethane

The division into Cn and Dn point groups:

After we have decided that there is a principal rotational 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 have no other O symmetry elements, iodine the Cnv point groups have also n mirror planes F containing the Cn rotational axis, while the Cnh point groups also have a h 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

C2

C2

there is no h plane at right angles to the C2 axis, but there are two v planes containing the C2 axis.

The point group of the water molecule is C2v

Other Cnv molecules:

water ammonia

v
C2v C3v

C4v

Vanadyl tetrafluoride (VOF4)

Some more C2v molecules:

C2

v
S

C2

C2

v
Phosphorus iodotetrafluoride (PF4I) sulfur tetrafluoride (SF4)

v
carbonyl chloride (COCl2)

The Cn point groups:

These have a Cn axis as their only symmetry element. They generally resemble propellers which have the front and back different. Important examples are (hydrogens omitted for clarity): triphenyl phosphine viewed down C3 axis

C3

C3
C3

Cobalt(III) tris-glycinate viewed down C3 axis

C3

C3
triphenyl phosphine viewed from the side

C3
Cobalt(III) tris-glycinate viewed from the side

The Dnh point groups:

C4 principal axis

four C2 axes at rt. angles to C4 axis

mirror plane at rt. angles to C4 axis

C2

C2

C2

C2

D4h

Examples of molecules belonging to Dnh point groups:

C2
C3 C3 C3

C4

D2h
C4

D3h
C5

D3h
C5

D3h

D4h

D4h

D5h

D5h

Benzene, an example of the D6h point group:

C6 principal axis

C2

C2

C6

C2 v

C2
v

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
N C [Cu(en)2]2+ complex with H-atoms omitted for clarity. (en = ethylene diamine)

C2
N

Cu

C2

D2

Some further views of the symmetry elements of [Cu(en)2]2+, point group D2 :

C2 principal axis

D2
C2 principal
axis

C2

[Cu(en)2]2+ complex with H-atoms omitted for clarity. (en = ethylene diamine)

C2
C2 C2 principal
axis

C2 principal
axis

C2

C2

C2

C2

C2

Some views of the symmetry elements of [Co(en)3]3+, point group D3.

C2

C2

C3 principal axis

C2

C3
principal axis view down the C3 axis of [Co(en)3]3+ showing the three C2 axes.

D3

C2
axis view down one of the three C2 axes of [Co(en)3]3+ at right angles to C3

Other examples of the D3 point group

C3 C2 C2 C2 C2

C2

C2

principal axis

D3
[Co(oxalate)3]3[Co(bipyridyl)3]3+

D3

Some cobalt(III) complexes belonging to the D3 point group:

C2
H2N H2N NH 2 NH 2 H 2 N

3+

C2
N N N

C2
3+
H3C O

CH 3 O O CH 3

Co
N H2 N

Co
N N H3C

Co
O O CH 3 O CH 3

tris(ethylenediamine) cobalt(III) cation

tris(2,2-bipyridyl) cobalt(III) cation

tris(acetylacetonato) cobalt(III)

D3

Comparison of C3 and D3 tris(chelates)

no C2 axis at this point

C2

D3
3+
NH2 H 2 N H2N

C3
O H2 N O NH2

H2N H2N

Co
NH2 N H2 O

Co
O O

tris(ethylenediamine)cobalt(III) tris(glycinato)cobalt(III)

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 v planes contain the principal axis

D3d
Staggered form of ethane

D5d
Staggered form of ferrocene

The D4d point group:

C2 C2 C4 principal axis

v v

C2

C2
C2

C4
principal axis

[ZrF8 Square antiprism

]4-

C4
principal axis

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 v 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

C2

C2

principal axis

C3 principal axis

K+
C2

v
C2

C2
C2

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 v mirror planes that contain the C3 axis, but no h mirror plane (because its not flat, as seen at center), so is D3d.

Some Point groups