Chemistry 3820

1.

Answers to Problem Set #2

The symmetry of the following molecules (with HC models):

C2v

C3v

D2h

C2

2.

Td

D3d

D2d

D3h

C2v

Distinguish between the concepts of (a) symmetry operation, (b) symmetry element, and (c)
symmetry point group.
(a) Symmetry operation: an action, such as a rotation through a certain angle, that leaves the molecule
apparently unchanged.
(b) Symmetry element: a point, a line, or a plane with respect to which the symmetry operation is
performed.
(c) Symmetry point group: All of the operations that leave at least one point of the molecule unmoved.

3.

Draw sketches to identify the following symmetry elements: (a) a C3 axis and a v plane in the NH3
molecule; (b) a C4 axis and a h plane in the square planar [PtCl4 ]2 ion.

4.

Which of the following molecules and ions has (1) a center of inversion (i), (2) an S4 axis: (a) CO2 , (b)
C2 H2 (acetylene), (c) BF3 , (c) SO4 2
(a) CO2 has neither i or an S4 axis (point group C2v )
(b) C2 H2 (acetylene) has i but not S4 (point group D2h )
(c) BF3 has neither i or an S4 axis (point group D3h )
(d) SO4 2 has S4 but not i (point group Td)

5.

Determine the symmetry elements and assign the point group of (a) NH2 Cl, (b) CO3 2- , (c) SiF4 , (d)
HCN, (e) SiFClBrI, (f)BF4 . State the symmetry elements that imply that a molecule is nonpolar. Use
these symmetry criteria to determine whether each of (a) (f) is polar. State the symmetry criteria for
chirality. Use these criteria to determine whether each of (a) (f) is chiral. (Chiral molecules may be
optically active, so long as they are stable to racemization reactions in the medium that they exist in.)
(a)
(b)
(c)
(d)
(e)
(f)

NH2 Cl: E, . Point group Cs. Achiral and polar

CO3 2-: E, C3 , 3C2 , h , S3 , 3v . Point group D3h . Achiral and nonpolar
SiF4 : E, 4C3 , 3C2 , 3S4 , 6d. Point group Td. Achiral and nonpolar.
HCN: E, . Point group Cv . Achiral and polar
SiFClBrI: E. Point group C1 . Chiral and polar
BF4 : (square planar) E, C4 , 4C2 , S4 , i, h , 2v , 2d. Point group D4h . Achiral and nonpolar.

The sets of symmetry elements that independently require that a molecule is nonpolar are (i) a Cn axis
and a perpendicular C2 axis (i.e. a D point group), (ii) a Cn axis and a h plane(i.e., a Cnh point group),
(iii) a center of inversion, i, or (iv) multiple non-collinear axes with n>2.
The symmetry criterion for chirality is the absence of an Sn element of symmetry. Recall that S1 =
and S2 = i. (Point groups Dnh , Dnd, Td, and Oh all contain an Sn axis, and as such are achiral).
6.

For the following molecules and ions, provide the Lewis structure, VSEPR geometry, and assign the
point group (the central atom(s) are underlined). Include any resonance, and show all non-zero formal
charges. Indicate approximate bond angles around the central atoms. And clearly indicate the isomers
you choose if isomerism is possible.
SF5 Cl (C4v)
CH3 F (C3v) HSSH (C2 )
NHF2 (Cs )
XeF6 (Oh )
ICl3 (C2v)
BeH2 (D h )
NO2 F (C2v) GeH4 (Td)
XeO3 (C3v) TeF6 (Oh )
SeCl4 (C2v)

OCS (C v)
IF4 (D4h )
[NH4 ] (Td) [BrBr2 ] (D h ) BrNO (Cs )
KrF2 (D h )
2
2
SO4 (Td)
[TeCl6 ] (Oh ) NNO (C v) IF5 (C4v)
OSO (C2v)
SCN (C v)

7.

For each of the following molecules or ions, the chemical formula and a perspective sketch of the
molecule is shown. In some cases lone pairs are added for clarification of the VSEPR-derived
geometry. For each molecule: (i) determine the correct point group; (ii) identify and locate as many
symmetry elements as you can. Separate sketches can be made to show the location of these elements if
you feel this is necessary.
Br

F
b)

a)

F
c)

..
Ni

d)

D3h
C2h

C2v

S8

Br

..

F
F
e)

P
F

Cl
F

f)
Br

Br
Cl

g)

C2h

D3h

j)

D 3h

a) E, C2 , h , i.
b) E, C3 , 3C2 , 3v , h .
c) E, C4 , S8 , 4v ,
e) E, C3 , 3C2 , 3v , h . f) E, C2 , h , i
g) E, 4C3 , 3C2 , 3S4 , 3d,
i) E, C3 , 3v
j) E, C3 , 3C2 , 3v , h .
k) E, C3 , h
8.

O
CS

k)

C3v

Td

F
i)

h)

Si H
H
H

O
H
C3h

d) E, C2 , 2v
h) E,

Determine the symmetry elements of (a) an s orbital, (b) a p orbital, (c) a dxy orbital, and (d) a dz2
orbital.
(a) An s orbital, which has the shape of a sphere, possesses an infinite number of Cn axes where n can
be any number from 1 to , plus an infinite number of mirror planes of symmetry. It also has a
center of inversion, i. A sphere has the highest possible symmetry.
(b) The + and lobes of a p orbital are not equivalent and therefore cannot be interchanged by potential
elements of symmetry. Thus, a p orbital does not possess a mirror plane of symmetry perpendicular
to the long axis of the orbital. It does, however, possess an infinite number of mirror planes that
pass through both lobes and include the long axis of the orbital. In addition, the long axis is a Cn
axis, where n can be any number from 1 to (in group theory this is referred to as a C axis).
(c) Unlike a pz orbital, a dz2 orbital has two large + lobes along its long axis, and a torus (or
doughnut) around the middle. In addition to the symmetry elements possessed by a p orbital (see
above), the infinite number of mirror planes that pass through both lobes and include the long axis
of the orbital as well as the C axis, a dz2 orbital also possesses (i) a center of symmetry, (ii) a
mirror plane that is perpendicular to the C axis, (iii) an infinite number of C2 axes that pass
through the center of the orbital and are perpendicular to the C axis, and (iv) an S axis.

9.

Sketch the shapes of AsF5 and its complex with F (use VSEPR if necessary) and identify their point
groups. What are the point groups of F3 B-NH3 and Al2 Cl6 ? (This question is about Lewis Acid-Base
adducts, or course!)

F
F

As
F

F
F

D3h

F
F

Oh

F
F

As

Cl

H
B N

H
H

F
C3v

Cl

Cl
Al Al

Cl
D3d

Cl
Cl