TOPICS
& Symmetry operators and symmetry elements
& Point groups
& An introduction to character tables
& Infrared spectroscopy
& Chiral molecules
B B B
F F F F F F
Fig. 3.1 Rotation of the trigonal planar BF3 molecule through 1208 generates a representation of the structure that is
indistinguishable from the first; one F atom is marked in red simply as a label. A second 1208 rotation gives another
indistinguishable structural representation.
passing through the boron atom; the axis is an example of a example, in square planar XeF4 , the principal axis is a C4
symmetry element. axis but this also coincides with a C2 axis (see Figure 3.4).
Where a molecule contains more than one type of Cn axis,
A symmetry operation is carried out with respect to points, they are distinguished by using prime marks, e.g. C2 , C2 ’ and
lines or planes, the latter being the symmetry elements. C2 ’’. We return to this in the discussion of XeF4 (see Figure
3.4).
Rotation about an n-fold axis of symmetry
The symmetry operation of rotation about an n-fold axis Self-study exercises
(the symmetry element) is denoted by the symbol Cn , in 1. Each of the following contains a 6-membered ring: benzene,
3608 borazine (see Figure 12.19), pyridine and S6 (see Box 1.1).
which the angle of rotation is ; n is an integer, e.g. 2, 3
n Explain why only benzene contains a 6-fold principal rotation
or 4. Applying this notation to the BF3 molecule in Figure axis.
3.1 gives a value of n ¼ 3 (equation 3.1), and therefore we
2. Among the following, why does only XeF4 contain a 4-fold
say that the BF3 molecule contains a C3 rotation axis; in
principal rotation axis: CF4 , SF4 , [BF4 ] and XeF4 ?
this case, the axis lies perpendicular to the plane containing
the molecule. 3. Draw the structure of [XeF5 ] . On the diagram, mark the C5
axis. The molecule contains five C2 axes. Where are these
3608
Angle of rotation ¼ 1208 ¼ ð3:1Þ axes? [Ans. for structure, see worked example 1.14]
n
4. Look at the structure of B5 H9 in Figure 12.23b. Where is the
In addition, BF3 also contains three 2-fold (C2 ) rotation C4 axis in this molecule?
axes, each coincident with a BF bond as shown in Figure
3.2.
If a molecule possesses more than one type of n-axis, the
axis of highest value of n is called the principal axis; it is Reflection through a plane of symmetry
the axis of highest molecular symmetry. For example, in (mirror plane)
BF3 , the C3 axis is the principal axis.
If reflection of all parts of a molecule through a plane
In some molecules, rotation axes of lower orders than the
produces an indistinguishable configuration, the plane is a
principal axis may be coincident with the principal axis. For
plane of symmetry; the symmetry operation is one of reflec-
tion and the symmetry element is the mirror plane (denoted
by ). For BF3 , the plane containing the molecular frame-
work (the yellow plane shown in Figure 3.2) is a mirror
plane. In this case, the plane lies perpendicular to the vertical
principal axis and is denoted by the symbol h .
The framework of atoms in a linear, bent or planar
molecule can always be drawn in a plane, but this plane can
be labelled h only if the molecule possesses a Cn axis perpen-
dicular to the plane. If the plane contains the principal axis, it is
labelled v . Consider the H2 O molecule. This possesses a C2
axis (Figure 3.3) but it also contains two mirror planes, one
containing the H2 O framework, and one perpendicular to it.
Each plane contains the principal axis of rotation and so
may be denoted as v but in order to distinguish between
them, we use the notations v and v ’. The v label refers to
the plane that bisects the HOH bond angle and the v ’
label refers to the plane in which the molecule lies.
Fig. 3.2 The 3-fold (C3 ) and three 2-fold (C2 ) axes of A special type of plane which contains the principal
symmetry possessed by the trigonal planar BF3 molecule. rotation axis, but which bisects the angle between two
Chapter 3 . Symmetry operations and symmetry elements 81
Fig. 3.4 The square planar molecule XeF4 . (a) One C2 axis coincides with the principal (C4 ) axis; the molecule lies in a h
plane which contains two C2 ’ and two C2 ’’ axes. (b) Each of the two v planes contains the C4 axis and one C2 ’ axis. (c)
Each of the two d planes contains the C4 axis and one C2 ’’ axis.
82 Chapter 3 . An introduction to molecular symmetry
(3.7) (3.8)
Show that B2 Br4 has one less plane of symmetry than B2 F4 Self-study exercises
which is planar.
1. Draw the structures of each of the following species and
3. Ga2 H6 has the following structure in the gas phase: confirm that each possesses a centre of symmetry: CS2 ,
[PF6 ] , XeF4 , I2 , [ICl2 ] .
2. [PtCl4 ]2 has a centre of symmetry, but [CoCl4 ]2 does not.
One is square planar and the other is tetrahedral. Which is
which?
3. Why does CO2 possess an inversion centre, but NO2 does not?
4. CS2 and HCN are both linear. Explain why CS2 possesses a
centre of symmetry whereas HCN does not.
(3.3) (3.4)
Identity operator
All objects can be operated upon by the identity operator E.
This is the simplest operator (although it may not be easy to
appreciate why we identify such an operator!) and effectively
identifies the molecular configuration. The operator E leaves
(3.5) (3.6) the molecule unchanged.
Chapter 3 . Symmetry operations and symmetry elements 83
3608
Fig. 3.5 An improper rotation (or rotation–reflection), Sn , involves rotation about followed by reflection through a
n
plane that is perpendicular to the rotation axis. The diagram illustrates the operation about one of the S4 axes in CH4 ; three
S4 operations are possible for the CH4 molecule. [Exercise: where are the three rotation axes for the three S4 operations in CH4 ?]
First draw the structures of cis- and trans-N2 F2 ; both are 5. The consequence of the different types of C2 axes,
planar molecules. and the presence of the v plane in the cis-isomer, is
that the symmetry planes containing the cis- and
F
trans-N2 F2 molecular frameworks are labelled v ’ and
N N N N h respectively.
F F F
cis trans Self-study exercises
1. The identity operator E applies to each isomer. 1. How do the rotation axes and planes of symmetry in Z- and E-
CFH¼CFH differ?
2. Each isomer possesses a plane of symmetry which con-
tains the molecular framework. However, their labels 2. How many planes of symmetry do (a) F2 C¼O, (b) ClFC¼O
differ (see point 5 below). and (c) [HCO2 ] possess? [Ans. (a) 2; (b) 1; (c) 2]
3. The cis-isomer contains a C2 axis which lies in the plane
of the molecule, but the trans-isomer contains a C2 axis
which bisects the NN bond and is perpendicular to
the plane of the molecule.
Worked example 3.2 Symmetry operations in NH3
The symmetry operators for NH3 are E, C3 and 3v . (a) Draw
the structure of NH3 . (b) What is the meaning of the E opera-
tor? (c) Draw a diagram to show the rotation and reflection
symmetry operations.
(b) The E operator is the identity operator and it leaves the In addition, BCl3 contains a h plane and three C2 axes
molecule unchanged. (see Figure 3.2).
(c) The C3 axis passes through the N atom, perpendicular to
a plane containing the three H atoms. Each v plane
contains one NH bond and bisects the opposite
HNH bond angle.
Fig. 3.6 Successive C3 rotations in NH3 are distinguished using the notation C3 , C32 and C33 . The effect of the last operation is the
same as that of the identity operator acting on NH3 in the initial configuration.
Similar statements can be written to show the combined character tables (see Sections 3.5 and 4.4) which are
effects of successive operations. For example, in planar widely available.
BCl3 , the S3 improper axis of rotation corresponds to rotation Table 3.1 summarizes the most important classes of point
about the C3 axis followed by reflection through the h plane. group and gives their characteristic types of symmetry
This can be written in the form of equation 3.4. elements; E is, of course, common to every group. Some
S3 ¼ C 3 h ð3:4Þ particular features of significance are given below.
C1 point group
Self-study exercises
Molecules that appear to have no symmetry at all, e.g. 3.9,
2
1. [PtCl4 ] is square planar; to what rotational operation is C42 must possess the symmetry element E and effectively possess
equivalent? at least one C1 axis of rotation. They therefore belong to the
C1 point group, although since C1 ¼ E, the rotational
2. Draw a diagram to illustrate what the notation C64 means with
respect to rotational operations in benzene. symmetry operation is ignored when we list the symmetry
elements of this point group.
H
3.4 Point groups Br
C
F
The number and nature of the symmetry elements of a given Cl
molecule are conveniently denoted by its point group, and
give rise to labels such as C2 , C3v , D3h , D2d , Td , Oh or Ih . (3.9)
These point groups belong to the classes of C groups, D
groups and special groups, the latter containing groups C1v point group
that possess special symmetries, i.e. tetrahedral, octahedral C1 signifies the presence of an 1-fold axis of rotation, i.e. that
and icosahedral. possessed by a linear molecule (Figure 3.7); for the molecular
To describe the symmetry of a molecule in terms of one species to belong to the C1v point group, it must also possess
symmetry element (e.g. a rotation axis) provides information an infinite number of v planes but no h plane or inversion
only about this property. Each of BF3 and NH3 possesses a centre. These criteria are met by asymmetrical diatomics
3-fold axis of symmetry, but their structures and overall such as HF, CO and [CN] (Figure 3.7a), and linear poly-
symmetries are different; BF3 is trigonal planar and NH3 is atomics (throughout this book, polyatomic is used to mean a
trigonal pyramidal. On the other hand, if we describe the species containing three or more atoms) that do not possess
symmetries of these molecules in terms of their respective a centre of symmetry, e.g. OCS and HCN.
point groups (D3h and C3v ), we are providing information
about all their symmetry elements. D1h point group
Before we look at some representative point groups, we
emphasize that it is not essential to memorize the symmetry Symmetrical diatomics (e.g. H2 , [O2 ]2 ) and linear poly-
elements of a particular point group. These are listed in atomics that contain a centre of symmetry (e.g. [N3 ] ,
86 Chapter 3 . An introduction to molecular symmetry
Table 3.1 Characteristic symmetry elements of some important classes of point groups. The characteristic symmetry elements of the
Td , Oh and Ih are omitted because the point groups are readily identified (see Figure 3.8). No distinction is made in this table between
v and d planes of symmetry. For complete lists of symmetry elements, character tables should be consulted.
Cs E, one plane
Ci E, inversion centre
Cn E, one (principal) n-fold axis
Cnv E, one (principal) n-fold axis, n v planes
Cnh E, one (principal) n-fold axis, one h plane, one The Sn axis necessarily follows from the Cn axis and h plane.
Sn -fold axis which is coincident with the Cn axis For n ¼ 2, 4 or 6, there is also an inversion centre.
Dnh E, one (principal) n-fold axis, n C2 axes, one h The Sn axis necessarily follows from the Cn axis and h plane.
plane, n v planes, one Sn -fold axis For n ¼ 2, 4 or 6, there is also an inversion centre.
Dnd E, one (principal) n-fold axis, n C2 axes, n v For n ¼ 3 or 5, there is also an inversion centre.
planes, one S2n -fold axis
Td Tetrahedral
Oh Octahedral
Ih Icosahedral
CO2 , HCCH) possess a h plane in addition to a C1 axis observed electronic spectra of tetrahedral and octahedral
and an infinite number of v planes (Figure 3.7). These metal complexes (see Section 20.6). Members of the
species belong to the D1h point group. icosahedral point group are uncommon, e.g. [B12 H12 ]2
(Figure 3.9d).
Td , Oh or Ih point groups
Determining the point group of a molecule
Molecular species that belong to the Td , Oh or Ih point
or molecular ion
groups (Figure 3.8) possess many symmetry elements,
although it is seldom necessary to identify them all before The application of a systematic approach to the assignment of
the appropriate point group can be assigned. Species with a point group is essential, otherwise there is the risk that sym-
tetrahedral symmetry include SiF4 , [ClO4 ] , [CoCl4 ]2 , metry elements will be missed with the consequence that an
[NH4 ]þ , P4 (Figure 3.9a) and B4 Cl4 (Figure 3.9b). Those incorrect assignment is made. Figure 3.10 shows a procedure
with octahedral symmetry include SF6 , [PF6 ] , W(CO)6 that may be adopted; some of the less common point groups
(Figure 3.9c) and [Fe(CN)6 ]3 . There is no centre of sym- (e.g. Sn , T, O) are omitted from the scheme. Notice that it is
metry in a tetrahedron but there is one in an octahedron, not necessary to find all the symmetry elements (e.g. improper
and this distinction has consequences with regard to the axes) in order to determine the point group.
Fig. 3.7 Linear molecular species can be classified according to whether they possess a centre of symmetry (inversion centre) or
not. All linear species possess a C1 axis of rotation and an infinite number of v planes; in (a), two such planes are shown and
these planes are omitted from (b) for clarity. Diagram (a) shows an asymmetrical diatomic belonging to the point group C1v , and
(b) shows a symmetrical diatomic belonging to the point group D1h .
Chapter 3 . Point groups 87
Fig. 3.10 Scheme for assigning point groups of molecules and molecular ions. Apart from the cases of n ¼ 1 or 1, n most
commonly has values of 2, 3, 4, 5 or 6.
Self-study exercises 2. S6 has the chair conformation shown in Box 1.1. Confirm that
this molecule contains a centre of inversion.
1. Show that CHCl3 possesses C3v symmetry, but that CCl4
belongs to the Td point group.
2. Assign point groups to (a) [NH4 ]þ and (b) NH3 .
[Ans. (a) Td ; (b) C3v ]
3.5 Character tables: an introduction
A1 1 1 1 1 z x2 , y2 , z2
Self-study exercises A2 1 1 1 1 Rz xy
B1 1 1 1 1 x; Ry x; xz
1. Copy diagram (a) above. Show on the figure where the C4 axis B2 1 1 1 1 y, Rx y, yz
and the four C2 axes lie.
90 Chapter 3 . An introduction to molecular symmetry
Table 3.3 The character table for the C3v point group. For The next two sections deal briefly with the consequences of
more character tables, see Appendix 3. symmetry on observed bands in infrared spectra and with
the relationship between molecular symmetry and chirality.
C3v E 2C3 3v In Chapter 20, we consider the electronic spectra of octa-
hedral and tetrahedral d-block metal complexes and discuss
A1 1 1 1 z x2 + y2 , z2 the effects that molecular symmetry has on electronic
A2 1 1 1 Rz
E 2 1 0 (x, y) (Rx , Ry ) (x2 – y2 , xy) (xz, yz) spectroscopic properties.
Infrared and Raman spectroscopies are both concerned with subject to the rule of mutual exclusion which states that in
the study of molecular vibrations, and while IR spectroscopy such a molecule, a vibrational mode which is IR active is
is used routinely in the practical laboratory, Raman spectro- Raman inactive, and vice versa. Thus, for a molecule with
scopy is a more specialized technique. When radiation of a an inversion centre, a ‘missing’ absorption in the IR spectrum
particular frequency, (usually from a laser source), falls may be observed in the Raman spectrum. However, the pre-
on a molecule, some radiation is scattered. The scattered sence of symmetry elements other than the inversion centre
radiation is of two types: does result in some exceptions to the rule of mutual exclusion
and it must be applied with caution. We exemplify the rule
. Rayleigh scattering involves radiation of frequency, 0 ,
with reference to CO2 (Figure 3.11). The two vibrational
equal to that of the incident radiation, and
modes which are asymmetric with respect to the inversion
. Raman scattering involves radiation of frequencies 0
centre (i.e. the carbon atom) are IR active and Raman inac-
where is a fundamental frequency of a vibrational mode
tive, while the symmetric stretch is IR inactive but Raman
of the molecule.
active. Thus, the value of 1333 cm1 for this latter vibration
The selection rules for Raman and IR active vibrations are can be confirmed from a Raman spectrum.
different. A vibrational mode is Raman active if the polarizabil-
ity of the molecule changes during the vibration. Changes in For more detailed accounts of the Raman effect, see:
polarizability (for Raman spectra) are not as easy to E.A.V. Ebsworth, D.W.H. Rankin and S. Cradock (1991)
visualize as changes in electric dipole moments (for IR Structural Methods in Inorganic Chemistry, 2nd edn,
spectra) and in most cases it is necessary to use group theory Blackwell Scientific Publications, Oxford, Chapter 5.
to determine whether or not a mode will be Raman active. K. Nakamoto (1997) Infrared and Raman Spectra of
A combination of IR and Raman spectroscopic data is Inorganic and Coordination Compounds, 5th edn, Wiley,
often of great use. Molecules with a centre of symmetry are New York.
same energy and could be represented in a single diagram Selection rule for an infrared active mode of
with the understanding that one vibration occurs in the vibration
plane of the paper and another, identical in energy, takes
place in a plane perpendicular to the first. One of the important consequences of precisely denoting
molecular symmetry is seen in infrared spectroscopy. An
IR spectrum records the frequency of a molecular vibration,
Self-study exercises
but not all modes of vibration of a particular molecule give
1. Using VSEPR theory to help you, draw the structures of rise to observable absorption bands in the IR spectrum.
CF4 , XeF4 and SF4 . Assign a point group to each molecule. This is because the following selection rule must be obeyed:
Show that the number of degrees of vibrational freedom is for a vibrational mode to be IR active, it must give rise to a
independent of the molecular symmetry. change in the molecular dipole moment (see Section 1.16).
[Ans. Td ; D4h ; C2v ]
For a mode of vibration to be infrared (IR) active, it must
2. Why do CO2 and SO2 have a different number of degrees of
give rise to a change in the molecular electric dipole moment.
vibrational freedom?
3. How many degrees of vibrational freedom do each of the In the discussions of IR spectroscopy that follow, we are
following possess: SiCl4 , BrF3 , POCl3 ? [Ans. 9; 6; 9 ] concerned only with fundamental absorptions, these being
the dominant features of IR spectra.
Fig. 3.11 The vibrational modes of CO2 (D1h ); in each mode of vibration, the carbon atom remains stationary. Vibrations (a)
and (b) are stretching modes. Bending mode (c) occurs in the plane of the paper, while bend (d) occurs in a plane perpendicular
to that of the paper; the þ signs designate motion towards the reader. The two bending modes require the same amount of energy
and are therefore degenerate.
92 Chapter 3 . An introduction to molecular symmetry
The transition from the vibrational ground state to the first Worked example 3.8 Infrared spectra of triatomic
excited state is the fundamental transition. molecules
Fig. 3.13 The vibrational modes of SO3 (D3h ); only three are IR active. The þ and notation is used to show the ‘up’ and
‘down’ motion of the atoms during the mode of vibration. [Exercise: Two of the modes are labelled as being degenerate: why
is this?]
their IR spectra. The IR spectra of anions such as [NO3 ] 2. In the IR spectrum of NF3 , there are four absorptions. Why is
and [CO3 ]2 may also be recorded, but the counterion may this consistent with NF3 belonging to the C3v rather than D3h
also give rise to IR spectroscopic bands. Therefore, simple point group?
salts such as those of the alkali metals are chosen because 3. The IR spectrum of BrF3 in an argon matrix shows six absorp-
they give spectra in which the bands can be assigned to the tions. Explain why this observation confirms that BrF3 cannot
anion. have C3v symmetry.
A set of normal modes of vibration similar to those shown
in Figure 3.13 can also be drawn for a C3v XY3 species such
as NH3 , PCl3 , AsF3 , [H3 O]þ or [SO3 ]2 . Each mode is IR
active and so we expect to observe four absorptions in the
IR spectrum of such a species. XY4 molecules with Td or D4h symmetry
Differences in the IR spectra of XY3 molecules possessing An XY4 molecule with Td symmetry has nine normal modes
C3v or D3h symmetry is a method of distinguishing between of vibration (Figure 3.14) but only six of them are IR
these structures. Further, XY3 molecules with T-shaped active. The IR spectra of species such as CCl4 , TiCl4 ,
structures (e.g. ClF3 ) belong to the C2v point group, and OsO4 , [ClO4 ] and [SO4 ]2 exhibit two absorptions because
vibrational spectroscopy may be used to distinguish their of degeneracies.
structures from those of C3v or D3h XY3 species. There are nine normal modes of vibration for a square
Fax planar (D4h ) XY4 molecule but, as can be seen from Figure
3.15, there are only three IR absorptions. Among com-
pounds of the p-block elements, D4h XY4 structures are
Cl Feq rare; the observation of absorptions at 586, 291 and
161 cm1 in the IR spectrum of XeF4 is consistent with the
structure predicted by VSEPR theory.
Fax
See also Figure 1.30
(3.10)
Self-study exercises
For the C2v molecules ClF3 (3.10) or BrF3 , there are six
normal modes of vibration, approximately described as 1. The IR spectrum of gaseous ZrI4 shows absorptions at 55 and
equatorial stretch, symmetric axial stretch, asymmetric 254 cm1 . Explain why this observation is consistent with
molecules of ZrI4 having Td symmetry.
axial stretch and three deformation modes. All six modes
are IR active. 2. The [PdCl4 ]2 ion gives rise to three absorptions in its IR spec-
trum (150, 321 and 161 cm1 ). Rationalize why this provides
evidence for a D4h rather than Td structure.
Self-study exercises
3. SiH2 Cl2 is described as having a tetrahedral structure;
1. The IR spectrum of BF3 shows absorptions at 480, 691 and SiH2 Cl2 has eight IR-active vibrations. Comment on these
1449 cm1 . Use these data to decide whether BF3 has C3v or statements.
D3h symmetry. [Ans. D3h ]
94 Chapter 3 . An introduction to molecular symmetry
Fig. 3.14 The vibrational modes of CH4 (Td ), only two of which are IR active.
Observing IR spectroscopic absorptions: 3.15) where two of the three IR active vibrational modes
practical problems are below 200 cm1 ; a specialized far-infrared spectrometer
may be used to observe such absorptions.
We have just described how to establish the number of Samples for IR spectroscopy are often prepared in cells with
vibrational degrees of freedom for a simple molecule with optical windows which themselves absorb within the 4000 and
n atoms, how to deduce the total number of normal modes 200 cm1 range; common materials are NaCl and KBr and
of vibration, and so determine the number of absorptions these materials ‘cut off’ at 650 and 385 cm1 respectively with
expected in its IR spectrum. Our premise for using IR the effect that absorptions (due to the sample) below these
spectroscopy to distinguish between, for example, an XY3 values are masked by the absorption due to the optical win-
molecule having C3v or D3h symmetry, depends upon being dow. ‘Solution cells’ are used, not only for neat liquid samples
able to observe all the expected absorptions. However, a but for solutions of the sample in a suitable solvent. This adds a
‘normal’ laboratory IR spectrometer only spans the range further problem, since absorptions due to the solvent may mask
between 4000 and 200 cm1 and so if the vibration in ques- those of the sample; in regions of strong solvent absorption, the
tion absorbs outside this range, the corresponding band transmitted radiation is essentially zero and so no absorptions
will remain unobserved. An example is [PtCl4 ]2 (Figure at frequencies due to the sample may be detected.
Fig. 3.15 The vibrational modes of [PtCl4 ]2 (D4h ); only the three modes (two of which are degenerate) shown in the lower row
are IR active. The þ and notation is used to show the ‘up’ and ‘down’ motion of the atoms during the mode of vibration.
Chapter 3 . Chiral molecules 95
Fig. 3.16 A pair of enantiomers consists of two molecular species which are mirror images of each other and are non-
superposable. (a) Helical Se1 has either a right- or left-handedness. (b) The six-coordinate complex [Cr(acac)3 ] contains
three identical didentate, chelating ligands; the labels and describe the absolute configuration of the molecule (see Box 3.2).
The nomenclature of chiral compounds is complicated. In order to describe the absolute configuration of an organic
Historically, compounds were described in terms of the molecule, the Cahn–Ingold–Prelog system was introduced.
sign of the rotation of plane-polarized light; the rotation The descriptors R and S refer to the absolute arrangement
was denoted (þ) or d for dextrorotatory, and () or l for of the groups about a centre. A complete description of a
laevorotatory. The sign and magnitude of rotation are molecule will include both the sign of the rotation and the
often dependent on the wavelength of light and this was absolute configuration, e.g. (þ)589 -(R).
incorporated in the descriptor: ()589 or ()D (where D Unfortunately, the Cahn–Ingold–Prelog rules are not
stands for the sodium D-line at a wavelength of 589 nm). directly applicable to most inorganic systems. For
Whilst this system is useful provided that the wavelength is example, the three chelating ligands in [Cr(en)3 ]3þ (en ¼
specified, it is purely defined in terms of an observable (the H2 NCH2 CH2 NH2 ) are identical and ‘priorities’ (an integral
rotation); there is no direct relationship with the absolute part of the Cahn–Ingold–Prelog rules) cannot be assigned to
configuration of the molecule. individual nitrogen-donor atoms. Descriptions based upon
This problem was first addressed in organic chemistry the observable rotation are, of course, useful, for example,
where a chosen reference compound, glyceraldehyde, was (þ)589 -[Cr(en)3 ]3þ and ()589 -[Cr(en)3 ]3þ . However, these
arbitrarily assigned, one absolute configuration to the (þ) convey no information about the absolute configurations
and the other to the () enantiomer. The (þ) form was of the complexes.
assigned a D absolute configuration and the () form, an L A number of schemes have been introduced to describe
configuration. Chemical transformations between organic the configurations of such compounds, the most useful of
molecules then allowed the assignment of D or L absolute which is the IUPAC recommended and system. This is
configurations to be related to the arbitrarily assigned glycer- exemplified in Figure 3.16b with the structures of the
aldehyde configuration. A consequence is that, for many enantiomers of [Cr(acac)3 ].
organic molecules, the () enantiomer may possess a D (not For further discussion: see Box 19.2 and Section 19.8.
an L) configuration! Additionally, it is not always easy to
relate a D or L configuration of a highly complicated organic
Further reading
molecule back to the configuration of glyceraldehyde. As a
matter of interest, the original arbitrarily assigned configura- Basic Terminology of Stereochemistry: IUPAC Recommenda-
tion to (þ)-(D) glyceraldehyde has been shown to be correct tions 1996 (1996) Pure and Applied Chemistry, vol. 68,
by anomalous dispersion X-ray experiments. p. 2193.
Chapter 3 . Glossary 97
The importance of chirality is clearly seen in, for example, Are there 3 C2 axes Yes; one runs vertically
dramatic differences in the activities of different enantiomers perpendicular to the principal through the Fe centre in
of chiral drugs.† axis? diagram (b)
A helical chain such as Se1 is easy to recognize, but it is Is there a h plane
not always such a facile task to identify a chiral compound (perpendicular to the
by attempting to convince oneself that it is, or is not, non- principal axis)? No
superposable on its mirror image. Symmetry considerations Are there n d planes
come to our aid: a chiral molecular species must lack an (containing the principal
improper (Sn ) axis of symmetry. axis)? No
STOP
A chiral molecule lacks an improper (Sn ) axis of symmetry.
The point group is D3 .
Another commonly used criterion for identifying a No centre of symmetry or planes of symmetry have
chiral species is the lack of an inversion centre, i, and plane been identified and this alone is sufficient to confirm that
of symmetry, . However, both of these properties are molecular species in the D3 point group are chiral.
compatible with the criterion given above, since we can rewrite
the symmetry operations i and in terms of the improper Self-study exercise
rotations S2 and S1 respectively. (See problem 3.25 at the
By referring to the character table (Appendix 3) for the D3 point
end of the chapter.) However, a word of caution: there are a
group, confirm that the symmetry elements of the D3 point group
few species that are non-chiral (achiral) despite lacking an
do not include i, or Sn axis.
inversion centre, i, and plane of symmetry, .
character tables with useful additional notes and symmetry D.F. Shriver and P.W. Atkins (1999) Inorganic Chemistry, 3rd
diagrams. edn, Oxford University Press, Oxford – Contains a clear
R.L. Carter (1998) Molecular Symmetry and Group Theory, and concise introduction to symmetry and symmetry-related
Wiley, New York – An introduction to molecular symmetry topics.
and group theory as applied to chemical problems including A.F. Wells (1984) Structural Inorganic Chemistry, 5th edn,
vibrational spectroscopy. Oxford University Press, Oxford – A definitive work on
F.A. Cotton (1990) Chemical Applications of Group Theory, 3rd structural inorganic chemistry; Chapter 2 gives a concise
edn, Wiley, New York – A more mathematical treatment of introduction to crystal symmetry.
symmetry and its importance in chemistry.
G. Davidson (1991) Group Theory for Chemists, Macmillan, Infrared spectroscopy
London – An excellent introduction to group theory with E.A.V. Ebsworth, D.W.H. Rankin and S. Cradock (1991)
examples and exercises. Structural Methods in Inorganic Chemistry, 2nd edn, Black-
J.E. Huheey, E.A. Keiter and R.L. Keiter (1993) Inorganic Chem- well Scientific Publications, Oxford – Chapter 5 deals with
istry: Principles of Structure and Reactivity, 4th edn, Harper vibrational spectroscopy in detail.
Collins, New York – Chapter 3 provides a useful, and readable, S.F.A. Kettle (1985) Symmetry and Structure, Wiley, Chichester
introduction to symmetry and group theory. – Chapter 9 deals with the relationship between molecular
S.F.A. Kettle (1985) Symmetry and Structure, Wiley, Chichester symmetry and molecular vibrations.
– A detailed, but readable, account of symmetry and group K. Nakamoto (1997) Infrared and Raman Spectra of Inorganic
theory. and Coordination Compounds, 5th edn, Wiley, New York –
J.S. Ogden (2001) Introduction to Molecular Symmetry, Oxford Part A: Theory and Applications in Inorganic Chemistry –
University Press, Oxford – An Oxford Chemistry Primer that An invaluable reference book for all practising experimental
provides a concise introduction to group theory and its inorganic chemists, and including details of normal coordi-
applications. nate analysis.
A. Rodger and P.M. Rodger (1995) Molecular Geometry,
Butterworth-Heinemann, Oxford – A useful, clear text for
student use.
Problems
Some of these questions require the use of Figure 3.10 planes of symmetry. Give appropriate labels to these
symmetry elements.
3.1 Give the structures of the following molecules: (a) BCl3 ;
(b) SO2 ; (c) PBr3 ; (d) CS2 ; (e) CHF3 . Which molecules are 3.7 Using the answer to problem 3.6 to help you, deduce which
polar? symmetry elements are lost on going from (a) BF3 to
BClF2 and (b) BClF2 to BBrClF. (c) Which symmetry
3.2 In group theory, what is meant by the symbols (a) E, (b) ,
element (apart from E) is common to all three molecules?
(c) Cn and (d) Sn ? What is the distinction between planes
labelled h , v , v ’ and d ? 3.8 Which of the following molecules or ions contain (a) a C3
axis but no h plane, and (b) a C3 axis and a h plane: NH3 ;
3.3 For each of the following two-dimensional shapes,
SO3 ; PBr3 ; AlCl3 ; [SO4 ]2 ; [NO3 ] ?
determine the highest order rotation axis of symmetry.
3.9 Which of the following molecules contains a C4 axis and a
h plane: CCl4 ; [ICl4 ] ; [SO4 ]2 ; SiF4 ; XeF4 ?
3.10 How many mirror planes do each of the following
(b) molecules contain: (a) SF4 ; (b) H2 S; (c) SF6 ; (d) SOF4 ;
(e) SO2 ; (f ) SO3 ?
3.11 (a) What structure would you expect Si2 H6 to possess?
(b) Draw the structure of the conformer most favoured in
terms of steric energy. (c) Does this conformer possess an
(a) (c) (d) inversion centre? (d) Draw the structure of the conformer
least favoured in terms of steric energy. (e) Does this
3.4 Draw the structure of SO2 and identify its symmetry conformer possess an inversion centre?
properties.
3.12 Which of the following species contain inversion centres?
3.5 The structure of H2 O2 was shown in Figure 1.16. Apart (a) BF3 ; (b) SiF4 ; (c) XeF4 ; (d) PF5 ; (e) [XeF5 ] ; (f ) SF6 ;
from the operator E, H2 O2 possesses only one other (g) C2 F4 ; (h) H2 C¼C¼CH2 .
symmetry operator. What is it?
3.13 Explain what is meant by an 1-fold axis of rotation.
3.6 By drawing appropriate diagrams, illustrate the fact that
BF3 possesses a 3-fold axis, three 2-fold axes, and four 3.14 To which point group does NF3 belong?
Chapter 3 . Problems 99
3.15 The point group of [AuCl2 ] is D1h . What shape is this (c) Locate three v planes in PF5 . (d) To what point group
ion? does PF5 belong?
3.16 Determine the point group of SF5 Cl. 3.27 Open the structure file for problem 3.27 which shows
the structure of NH2 Cl. (a) How many planes of
3.17 The point group of BrF3 is C2v . Draw the structure of BrF3 symmetry does NH2 Cl possess? (b) Does NH2 Cl possess
and compare your answer with the predictions of VSEPR any axes of rotation? (c) Confirm that NH2 Cl belongs to
theory. the Cs point group. (d) Detail what is meant by the
statement: ‘On going from NH3 to NH2 Cl, the symmetry
3.18 In worked example 1.14, we predicted the structure of the
is lowered’.
[XeF5 ] ion. Confirm that this structure is consistent with
D5h symmetry. 3.28 Open the structure file for problem 3.28: this shows the
structure of OsO4 , which has Td symmetry. (a) Orientate
3.19 Assign a point group to each member in the series (a) CCl4 , the molecule so that you are looking down an O–Os bond,
(b) CCl3 F, (c) CCl2 F2 , (d) CClF3 and (e) CF4 . O atom towards you. What rotation axis runs along this
3.20 (a) Deduce the point group of SF4 . (b) Is SOF4 in the same
bond? (b) The character table for the Td point group shows
point group? the notation ‘8C3 ’. What does this mean? By manipulating
the structure, perform the corresponding symmetry
3.21 Which of the following point groups possesses the highest operations on OsO4 .
number of symmetry elements: (a) Oh ; (b) Td ; (c) Ih ? 3.29 Open the structure file for problem 3.29: this shows the
3.22 Determine the number of degrees of vibrational freedom structure of [Co(en)3 ]3þ where en stands for the didentate
for each of the following: (a) SO2 ; (b) SiH4 ; (c) HCN; (d) ligand H2 NCH2 CH2 NH2 ; the H atoms are omitted from
H2 O; (e) BF3 . the structure. The complex [Co(en)3 ]3þ is generally
described as being octahedral. Look at the character table
3.23 How many normal modes of vibration are IR active for for the Oh point group. Why does [Co(en)3 ]3þ not possess
(a) H2 O, (b) SiF4 , (c) PCl3 , (d) AlCl3 , (e) CS2 and (f ) HCN? Oh symmetry? What does this tell you about the use of the
word ‘octahedral’ when used a description of a complex
3.24 Explain what is meant by the terms (a) chiral;
such as [Co(en)3 ]3þ ?
(b) enantiomer; (c) helical chain.
3.30 Open the structure file for problem 3.30: this shows the
3.25 Confirm that the symmetry operation of (a) inversion is structure of C2 Cl6 in the preferred staggered
equivalent to an S2 improper rotation, and (b) reflection conformation. (a) Orientate the structure so you are
through a plane is equivalent to an S1 improper looking along the C–C bond. You should be able to see six
rotation. Cl atoms forming an apparent hexagon around two
superimposed C atoms. Why is the principal axis a C3 axis
and not a C6 axis? (b) Explain why an S6 axis is coincident
Web-based problems with the C3 axis. (c) By referring to the appropriate
character table in Appendix 3, confirm that C2 Cl6 has D3d
symmetry.
These problems are designed to introduce you to the
website that accompanies this book. Visit the website: 3.31 Open the structure file for problem 3.31: this shows the
www.pearsoned.co.uk/housecroft structure of -P4 S3 . (a) Orientate the structure so that the
and then navigate to the Student Resources site for Chapter unique P atom is closest to you and the P3 triangle
3 of the 2nd edition of Inorganic Chemistry by Housecroft coincides with the plane of the screen. You are looking
and Sharpe. down the principal axis of -P4 S3 . What type of axis is it?
(b) Show that the molecule does not have any other axes of
3.26 Open the structure file for problem 3.26: this is the rotation. (c) How many planes of symmetry does the
structure of PF5 . (a) Orientate the structure so that you are molecule possess? Are they v , h or d planes?
looking down the C3 axis. Where is the h plane with (d) Confirm that -P4 S3 belongs to the C3v point group.
respect to this axis? (b) Locate three C2 axes in PF5 .