lNTRODUCTION 3

1.2 SYMMETRY ELEMENTS AND SYMMETRY OPERATIONS

As discussed above, symmetry of a mo lecule can be defined in terms of symmetry ele ments and
symmetry operations. But, before these are to be defined, some fundamenta l aspects of coordinate
system and mathematical operators are to be understood to make the idea of molecular symmetry as
useful as possible. The following three points criteiion will be adopted for further discussions throughout
the book:
(i) The centre of the molecule (often termed as centre of gravity of the molecu le) is considered
to be coincident with the centre (origin) o f the Cartesian coordinate system [Fig. l. 3(a)
and (b)], which will follow the Right Hand Rule. In this conventi on the positi ve directions
of the three Cartesian axis are defined in the same way as the thumb, index finger and
middle fingers of the 1ight hand. It can be understood in this way: If we hold our right
hand in such a manner that the thumb is pointing up, index finger pointing like a gun and
middle finger points in such a way that it is perpendicular to the other two (index finger
and thumb), then the thumb, index finger and middle finger now wilJ represent the z, x and
y directions of the Cartesian coordinate system respectively, as shown in Fig. l .4(a) o r
alternatively, if paJm is rotated such that it faces up, to present the z-axis in its usual
perpendicular direction [Figs. l.3(b) and l.4(b)].
z z

or
-----A'------+ X

(a) (b)
Fig. 1.3

or

(a) (b)
Fig. 1.4 Right Hand Rule
 q

JN CHE MISTRY
4 SYMMETRY AND GROUP T HEORY
a function is trans1o &

the ma tic al ope rat ors · An operator gives a rule by which nn~
(ii) Ma ·
· dx d ( x 2) • here, dx
d 1s .
a mathematical
. n. for exa mp le, wh en we wn te
mto ano the r fun ctio
2 ted, it is transfonn~
wh ich car ry out diff ere ntia tion of x , and when differe~tia
operato r,
x. + ~e operators which car
ries out additio
2x. Sim ilar ly, +, - ,
to another fu nction n one operators ;
, mu ltip lica tion and div isio n, respect:Ively. When more tha
subtraction ording to which operations
we sho uld foll ow the con ventions of ~p~rat~r algebra.' acc
the re, rations).
ried out fro m righ t to left (thi s 1s discussed m combined ope
are to be car
a circumflex (cap) is written
a sym me try ope ration from symm~try element,
To disting uish ent is indicated
(iii )
bol of the sym me try ele me nt. The eXIstence of~ symmetry elem
over the sym re to
rato r on the mo lec u~ ar wa ve ~unct~on or_on geometrical figu
by the effect of an ope original one. Now,
an ano the r fun ctio n or figu re equivalent or 1dent:1cal with the
result into rations?
wil l disc uss wh at are sym me try elements and symmetry ope
we (or in any object)
me nt is an im agi nar y lin e, pla ne or po int in a molecule
A symmetry ele means
try ope rat ion s are car rie d out. Here, symmetry operation
me
abo ut wh ich one or more sym ed after the operation is indistingu
ishable from the
(ge om etri cal for m) obt ain
that the config uration ion, etc .) about a symmetry
s her e me an, mo vem ent (ro tati on, reflection, invers
. Op era tion y are quite
original one
nt and sym me try ope rati ons are closely interrelated, but the
element. Symmetry ele me may be defmed as a
beg inn ers, it cre ate s con fusion. A symmetry operation
differem. For the figuration
h tha t it bri ngs the ob j ect int o an equivalent con
movement of an obj ect suc nec ess arily be identical wit
h the original one,
con fig ura tion ). It ma y not lecule. If
(indistinguishable n int erc han ged. For example, take H2 mo
ts ma y hav e bee
because some equivalent par ugh the centre of the covalent bon
d (as shown by
ima gin ary line pas sin g thro her
it is rotated about an get equ iva len t configuration, but if this is furt
le of 180 °, we
dotted line in Fig. 1.5) by an ang we get identical configuration. Here
Ha and Hb are
gin ary line by 180 °,
rotated about the same ima them as Ha and Hb (to
and are ind isti ngu ish abl e, for convenience, we have written
Hydrogen atoms
ms on rotation).
understand the movement of ato

Rotation Rotation
Hb .-- --1 --- Ha 1ao 0
180°

Identical
Original configuration Equivalent configuration configuration

Fig. 1.5
. . mo re synunetrY
Therefore, a symme try I
e em en
t.
IS a hoe , po mt or pla ne ab ou t wh ich on e or diflierent
operations can be rn.ed ou t whereas sy t • mo vem ent s of the
ea mm e ry op era tio ns are the
par ts of a molecule ab t th try ele me nt to giv e indistinguishable configura
tions
e sym me
(equivalent) from origin:lu one.
f
Now, we will describe the kindhs O symmetry elements that a molecule may possess and
the
generated b visualize
symmetry operati ons try ele me nts . Here, students are advised to .
lecy It e sym me
three dimensional model of mo u e to understand th e operatton • s. Further, the symmetry operauons
should be earned out within the molecuJe and not outside the molecule. because operation out51a.e
the mo lecule will lead to the translation motion of the molecule. which is not the pan of OU:
discussion. ln symmetry operations, at least one point in the molecule remain unaffected by all the
symmetry operations. All the symmetry elements intersect at this poinL This point maJ' be the
centre of mass of the object and due to this the description of symmetry of moJecu.Je is also
called Point-group symmetry.
In all , there are five types o f basic symmetry e lements and they are summarizec in the
Table 1. I.

Table 1.1

Symmetry Element Symmetry Operation Symbol

I. Ax is of symmetry Rotation by an angle C
(proper o r principal) 8 = 360/n about the axis "
2. Plane of symmetry Reflection in the plane a
3. Improper axis of symmetry Rotation about the axis fol.lowed Sn
by reflection in a plane
perpendicular to rotation axis
4. Centre of symmetry lnversion through the ce ntre i
of symmetry
5. Identity No operat.io n £
I
Proper or Principal Axis of Symmetry (CJ
Axis of symmetry is an imaginary line in a molec ule about which if the molec ule is rotated b) such
a mini mum angle (0) that after rotation, indistinguisha ble config uration of the molecule is obtained .
Then, those imag inary line s are cal led Rotational Axis of symmetry and the rotation by an angle a
about this li ne is called symmetry operation. Here we choose clockwise rotation as positive and
anticlockwise rotatio n as negati ve. T he symbol for the axis of rotation is Cn, where n is the o rder o f
the axis of symmetry and it can be expressed as, n = 36018 or 2rr/8. When n = 2, 3, 4 , then it is called
two-fold, three-fold , tetra-fold, axis of symmetry, respectively. It means that n is the number of
times the molecule can be rotated to reach at identical configuration .
For example, in H2 molecule we have (Fig. 1.6)

1so 0
1so
0

Rotation Rotation

(a and b subscripts are written for convenience

only otherwise they are Indistinguishable)

Fig. 1.6
Here, the dotted line is the Axis of symmetry whose order (n ) is 2 because by rotating the
molecule about this line twice by 180°, identical configuration is achieved. Therefore, this line is two-
fold axis of symmetry and designated as C 2. Similarly, take the case of BF , a triangular planar
3
molecule . (Fig. 1.7) We can have the following symmetry operations:
 6 S YMMETRY AND GROUP T HEORY 1.N C IIEMISTRY
. . t·itcd hy a n an g le of 1200 about a line passing through
I
.1· h lcc ul c ,s ro ,
Here , we see that t c mo d . . hr the molec ular pl ane (i.t'., plane of the paper), it
. ,d pcqJc ll tl:ll ' 10
1 . .
the ce ntre of the Boron at()m ~ . ( P) there fore , this lin t· i-; a three-fol d ax is of symmetry (C )
3
gives an indistingui shable con I ,g ur:tlJCll l . ·(Q) is n bt·iincd if the molec ule is rotated by 180" about
. . . I bl c )Jltiguration , ' . . (C ) Th
and another rnd1stmgu1s ia c 1 . • line is c1 two-fo ld ax is o f .-.y rnrnetry 2 . u~. this
• t1 11 d thc relo n I11c
a line passing along 13- l· 0 • , . . f . . . .
... . C , J th ree C 2 .,xcs O ff there arc C axes of different orders, then highest
molecule (Bl· 1 ) have o ne I 111 L • N n . . p .
• . cf cular to C 2 axis. ow order axis will he the Pnoc,pal or roper ax,~ of
symmet1y. Here. C, •~ perpcn , nber of axes , mmctry
. 1· I . ·11--· more n111 ~Y .
questio n a11:--e:- th,11 i t ie1e_, l,; is the proper o r L - - - - - -- - -- - . - - - - - - - J .
of symmetri prese nt. which o ne .' e ntio n is this that highest order ax is of symmetry 1s
- : . . ? Fo r this, the conv . f . h
Princip:il axis ot symmeu y· c • case of BF molecule, the C 3 axis o symmetry 1s t e
. ry There,ore, m 3
called Principal ax is of symmet ·
Principal Axis of symmerry. (b)
(a)

Fig. 1.7

Problem : Find out the principal axis of symmetry in

Benzene, PtCI~-and NH3.
Solution : Benzene, has a hexagonal planar structure
2
oecause al l the six carbons atoms of the benzene are sp
hybriaized. It has six C 2 axes (as shown by, dotted lines Fig .
J .8J and one C 6 axis, which passes through the centre of
the molecule and perpendic ular to the plane of the molecule. I

Therefore, principal axis of symmetry is C 6 . Similarly, PtCl! - C2

and .\IH 1 have C4 and C 3 as principal axis of symmetry, Fig. 1.8
respccti vel y
Now, if we try to fi nd ax is of symmetry in ethy lene molecule, C2 C
I 2
again it is a planar molecu le (beca use both carbon atoms are sp2 ~~
H I / / H
hybridized), a nd it ha'> three C 2 ax es of symmetry as shown in Fig .
1.9 by dolled lines. Now, question arises that which line is the
- - -~c ''c - - - -) c2
H/ ,' I '-H
/ I
proper axis of symmetry because o rder of all the three axes of / I
/ I
symmetry 1s :-,ame. Here, in s uch cases, the conventio n is this that I I

when there are more number of axes of symmetry the same Fig. 1.9
order, then that axis which passes through maximum number
 f_N TRODIJCTI UN 7

of atoms of the molecuk is principa l axis of symmetry. So, in th i5 case. the dolled line which is
in all
passing through the two carbons of the molecule is the princi pal axi s of symmetr y. Further.
Th is
molecule s. the principal axi s of symmetry is take n as ~-axi s in the Cartesian coord inate ,;y,;1em.
es like
element of symmetr y is a lso co mmonly called Ro tation axis of symmetry . For linear molec ul
H2 • CO~. HCL COS this axis of symmetr y can be C..,, he re the order (n ) of the axis is infinite. It means
g ive
that rotation about this ax is by the s mallest possible fraction of angle (tending to 0°) will
ity.
equivalen t o rientation of the molecule and we recall that when 0 tends to zero, n tends to infin
line
(when 0 ➔ 0. n ➔ oo). For example, in case of HCl, OCS, HCN, H 2, CO2 etc. molecul es, the
along the bond is C.., as shown in Fig. 1.10.

0 - 0----
Fig. 1.10
y
Now, as we know that each symmetry element generates some symmetr y operation s, i.e., symmetr
t how
operation s can be carried out on each symmetr y e lement. Obvio usly, the question arises tha
y
many symmetr y operation s are generated by the axis of symmetr y (C,,) or how many symmetr
the nth
operation s can be carried out on this element of symmetry . The answer lies in the fact that
take a
rotation of a molecule will bring back the molecule to the original orientatio n. For example,
simple molecule like 1½0, whjch is V-shape and has a C 2 axis of symmetr y.
The first rotation by J 80° once (C;) gives Fig. Rotation by 360/n carried out in successio n of
1.11 (b) and second rotation by I 80° about the axis c; m times is represente d by a symbol c:,"where
gives Fig. 1.11 (c) which is the orig inal orientatio n of n and m are integers.
the water molecule. Tha t is, by rotating twice by
two
180° (C;), the identical configuration of the molecule is generated . Therefor e, here we have
operation s on C 2 axis of symmetry and these are C~ and c; but C~ operation produces identical
configura tion therefore it is not a separate operation (as we see later that it is included in Identity
that is
operation ). Therefor e, the distinct operation possible on C 2 axis of symmetr y is one only and
c;. Similarly on C 3 axis of symmetr y, two distinct operation s are possible and they are C and
1 C2
because again c; operation wi ll produce the original orientatio n of the molecule (which is ~ncluded
in Identity symmetry element). O n C 4 , three distinct
symmetr y operatio ns can be carried o ut to get C,, axis of symmetry generates (n - J) distinct
equi valent config urations of the molecule. Therefor e, symmetry operations.
it can be understoo d that axis of symmetr y of order n
(C,,) has n - J symmetr y o perations.

I I
I I
I
I . I
I .
I C2 I Cz
0 0 0

Hb
/i"" Ha
I
I
/ i""Hb
Ha I
I
/ ~Ha
Hb
C2

(a) (b) (c)

Fig. 1.11
 8 SH,IMETRY .\.",1> GROUP TIiEORY c-; CHEMISTRY

, . . seen that there are many equivalen

be easily . t operation
. s possible, for example,
I ;-.;~w ~t ~anJ c' = c:! = c!. etc. and c~ = E wher~ E IS the !dent'. ty e~ement of symmetry. As
C.-' = ¼· C} = rC6. here
4
2 • . ns are carried out in clockw1se d1rect1on, one can argue that
the rotauo
mentioned ear ier. . al
. . muon may so g1•ve equivalent configura. tion. then they are also symmetry
·1 operation.
.
anttclocK\\ 1se ro t"ons For example tn BF molecule, we can eas1 y. recogru,;e that
\so symmetry opera 1 · ' 3 .
Yes. the) 8'.e a . b 120 0 2:ives Fig. 1.1 2(b), whereas, same configuration 1s obtai ned by
anticlock\, ise r~tauon . Y th
.· . 1 twice rotaung e mo~lecule by 120° about .
C proper axis of symmetry. Hence, we can
3 ·
succe:,~t\
. c -1 e Y ,
== c- and therefore. c -1 is
• not to be considered as a separate operation .
\\ nte ~ - 3 3 1

-1 0
(C 3 ) , 120

Anti- Clockwise
clockwise

120°

(b) (a) Fa 1 Clockwise

"'
(c)
Fig. 1.12
Problem: How many rotational axis of symmetry a re p resent
in PtCI~- and Clf5 and which is the p roper axis of symmetry in
these molecules?
Solution: PtCI\- has square planar geometry and
cyclopentadienyl anion (C5H;) is also planar.
As we see here, one four-fold axis (C ) which is passing
4
through the centre of Platinum atom and perpendicular to the plane
of the molecule and four two-fold axes of symmetry, which are
perpendicular to C4 . So PtCl~- has 1C + 4C ..L C . The highest
4
order axis is C4, therefore, C4 is the principal2 axis of
4
symmetry .
Similarly, the geometry of Ci½ is shown here.

I
\
\

© ---
'

I
I

-;(

I
I
\

Fig. 1.14
 1,,,woen,o:'11' 9

· known
It can be eas1\v · species
that this · 1c + SC 1 C The principal axis of symmetry
· contain
5 - 2· -L. s·
·1s ·
C 5 perpendicular· to the plane ot· c H- anion.
· pass111g
· ti1rou a0 h the centre of the molecule.
5 5

Plane of Symmetry (o)

It• there exists :ln 1mag111ary
· · ·
plane 111 the mo lecu 1e a bout w h'1c h the reflecti. on
. o f the molecule. is carried
.
· · · - · · · d ' ·
out and after retlection 1f conftgura11on 1s 111 1s1mgms a · h b le from the ono111al o ne then the 1ma 17
tnary
e · . . e
· ·
plane (or rnmor plane) 1s called a Plane o t· symmetry. Th' . is
e lement of sy mmetry 1s particularly
important in the discussion o n the optical activity of organic compounds.
For example. in H~O we can have a plane perpendicular to molecular plane pass ing thro ugh
oxygen atom and bisecti-ng the angle betwee n two 0-H bonds. . .
Figure l.15(a) and I. 15(b) are indistinguisha ble, therefore, the plane (cr.c) about which reflecuon
operation was carried out is a plane of symmetry.
z

- - - - - + --+y

Molecular
plane
(crxy) (Reflection)

Plane of symmetry

(a) (b)
Fig. 1.15
Here, H2 0 molecu le is planar, therefore, molecular plane (cr_n.) which contains all the a toms of
the molecule is also a plane o f sy mmetry because reflection thr0tig:h this plane will kave aH atoms
unshifted and we get indisti ng uis hable configuration . Whereas, reflectio n through crc leaves oxygen
atom at the same place but the two H-atoms are exchanged. It is ve ry easy to recognize that the
operation of reflection produce equivalent configuration but if the o peratio n is c~uned ou t twice.
origina l configuration is obtained. Hence. a plane o f symme try (cr) generates o nly one uistinct operation.
Therefore, we ca n wi-ite, cr" = cr, if II is odd.
cr • cr = cr2 = E and cr'' = E, if n is eve n.
Here E s tands for Ide ntity e le me nt.
T here are three types of planes of sy mme try:
(i) Vertical plane of symmetry (o,,): II is a plane of sy mme try passing through (ll, cni1Kidi11g
with) the principal axis or
symmetry anu o ne o f the subs idiary a xis (if prt'st'nt). In t)lht'r
words it is a plane c on tain ing Principal Axis o f Sy mmetry.
(ii ) Horizontal plane of symmetry (o,,) : It is a pla11~ nf sy mm~Lry \\'h id1 is papt.·11di1.: ular !()
the principal axis of sy 111111et1') .
10 'SYMMETRY AND GROUP THEORY IN C 11EMIST RY

(iii) Dihed ral plane of symmetry (ad): JI is 1he plane o

f symm etry . r _assing through the
. ·, - . u· ,, . 1 bisccri ng 1he angle betwee n two subs1<.11ary axes (C2 -axes)
rinc ·, pal
c clX IS O 1 symm e y 11 u · . . • ·
P 'h d
LI
,, 0 •ire those planes . which bisect the angle between two
. .
In Otl1er word s. d 1 e ra 1 p 1111 ~ .., d' •
is bisected by a c 2 axis,
• C -ax is.. Al -1- 11 e ang le betwee n a set of two. planes . .
so, 1 1
succes sive 2
. . · 1.0 desigi nted as oer· or we can. say that c.Jihedral planes (ad >
t hen t h1s set o1 p 1anes 1s a s · •
C2 axes.
are those cr s which bisecl the ang le betwee n two succes sive
. ,. f H lecule o and cr are vertica l .planes of symme try (cr f)
C 2- " '
F or examp le m case o 2O mo '
symm
xz
etry
xy
(C
. .
S1m1la rly rn Pt 1 we can see that it
· . . . is of 2 ) . 4
1
b ecause both planes contai ns pnnc1pa ax
contai ns l 0 1,, ~cr,. and 2od (Fig. 1.1 6).

_ _ _ _ .,.c,

- ----- i~ CI

Cl ""-1-- ---.J
Cl

Fig. 1.1 6
is Allene (C3 H 4 ) . The geometry
A good example to describe the dihedr al plane of symm etry (ad)
of the molecule is shown below in which the centra l carbon is
sp hybrid ized, where as the termin al ·
in perpen dicula r planes (Fig. 1.1 7).
carbon s ¥e sp hybridi zed. The H-atom s of termin al carbon s lie
2

Fig. 1.17
 l l'<TRODUCTION 11

· . h J I axis C (-) is present in w hich one

Here we see that a set o f planes passing throug mo ecu ar 2 .. ·
is a plane containing three carbon ato ms. H I and J-1 ·
2 • ,.e.,
C -
-
C = CH 2 and second plane
d"h d
· ·
contammg three carbo n atoms, H1 and H4 . i.e.,
·
CH
2
· b. .
= c = c·
d b
These two planes are I e ra 1 p 1anes
· h .
C" a x is as well as t e-,e p 1anes 1sect
b. .
of symmetry because the ang le be tween the m 1s 1sccte Yn 2 ·
the angle between two successive C-i-axe:-. . - -- - -- - - - - - - - - -- - ,
/\. verticnl plane which bi~t two l. C 2
In Benzene (Fi~. 1.1 8), accordi ng 10 de finition of a,1
~ a xe,; is called a d ihedral plane.
and a,. all the ,ix planes of symmetry arc di hedra l p la~es
as well as ve rtical plane or sy mmetries. Now the quesu on
ari se , whic h planes arc to be designated as di hedral ~ )
an d ,, hich are venical (a,.) planes. Some authors assume I
(JI
\
I
that those planes wh ich are passing through greater number \
\ I
\ I
of carbon ato ms are a d w hereas those passing through the I
. \ I

centres of opposite edges are a,.s. Just reverse convention '--.---'

1s abn popul ar in many authe ntic books where a v are planes
cnnt..tining 2:reater number of atoms or to contain proper (or
pnnci paJ)- ~ is o f a reference Cartesian co ordinate syst~m - - - - - - -
l r o r \" a.xis). The difference of convention, i.e., knowing
wheth~r a p lane is to be called a v or a d is not so crucial to
apply symmetry operations. Whatever convention is used ,
the analysis or treatment of a chemical problem is to use
the standard character tables for a particular symmetry, so
that the resu lt remain unaffected. So in Benzene, we have
3cr and 3crd. Dihedral planes are present only in those Fig. 1.18
mo lec u les w hich have more tha n one C 2 - ax i s .
Generally accepted convention about ad is this that when both a v and ad occur in the same system.
cr, will contain greater number of atoms and a d planes will contain bond angle bisectors. i.e., a 1 are
those ai which bisect the angle formed by a pair of horizontal C 2-axis and may contain mirnmum
number of atoms of the molecule.

Centre of Symmetry or Centre of Inversion (1)

The centre of 5ymmetry is an imaginary point in the molecule which is also the centre of gnn IC) or'
the molecule about which inversion operation is carried out to get indistinguishable configuration of
the molecule. By inversion we mean that if we take any point in the molecule arid join this p,"lmt from
an/ atom and then extend the line to the same distance in opposite directi on it m ust meet 1Jet1~al
atom. Thi~ should be true for a ll atoms of the molecule. If this h appen. w e say char mole..:u l. .· has
centre of symmetry. This po int is us ua lly taken as the origin of the Cartesian coordinate ,) s tem. If
in ver.,1,;n exists m the molecu le, then for every po int (atoms of the m nlecule ) \\ ith .:0on➔ 11 uce
(x, ), zJ. there; will be an equi valent po int at coordinate (-x. -y, -z). For example, in H,. \\e see that
there e/1st a point exactly at the mid poi nt of two H-atoms, about which inven.il)fl op.:r.1 1\m 1::- l-arri ed c
rJut and an 111dist1nguishabl e (eq uivalent) configurati on is o btained . The refore. rhe poin t i~ centre of
!iymmetry <F, g. 1.19 ).
Inversion

Centre o f symmetry
Fig. 1.19
 to poin t ou1 that_ thcre ex 1, 1 no ce ntre of symrr
H., ry
But if ,,e lake HCi I Ft~ 1 20 then 11 jc;. ea<.~ ·>.e '>e:e
,hahle confij!urat,on ,,f ~~Cl m<,le cule. Here
bel.'au, e .1ftt'r m, e£"'1t'n ,,~r.H ll'O \\t' gel J,<.1 rngu, ved. 1nere fore •
, .· '"\ ,r, , ,, , !"- r..1.h). '1 1, , •lm t:,-- I l iul I\\ I\.C · rhc orig inal vm figur at, on ,., achie • -.e

") mme try. the centr e <A ,ymmetry r.;i

jp·l... , 1:

.:an "-,•c · _ l ldt·iit il, 1 Jliu, li ~c a mirro r plane of Jri, •"-,

one centr e of ,,.• mme trv 1 rnol~ ule
tn an'-
>u· 1 th t·r•· Jr Ix· l,nh •
~ ' 1 "'~ u , u n ~ ,
~ p,.._. J • 1 n I) , ~ •
ZJ. there .:re
,..:-:J.ti~d.- ABf\ J ,c 21 lnl' c.. uk
,t:rl.' ,~L ,cc thJt along t:ach of 1he three aJ(C'> (A.,,.
~'-, 1\J. ~n !lh'm , 8) ht· , qu1u1 , 1.1n1 tn p0, tlJ\(.' and n~g,l ll\C dtr ectt o n
s

Not a ce11 ;re ol S)TTVTI-elfY

Fig. 1.20

8.

9~
'' '' /
/

' /

' '
/
'' /
/

/ '' /
''

\
--;/A
/

' /
/
' /
/ A

Q;mre of
S)'i:"l/l lS1,Y /

ao
B2
B3
/ \
B,. B,

Fig. 1.21

Eci-~e staggered conformation). Ptc1-_?. and C6 H6

(Fi g. 1.21 ) have centre of symm etry. :\ifo lecules
cule (methane,.
r,;, ,.H:- :-a, e cem:re of symmetry
are called cenrros) mm etric . The tetrahedral AB~ mole
C -~ pl.1r.ar pentagon . cis-dichloroethene
do not have cent re of sym metry. Simil arl). 1rans-
compounds ha,·e centre of S) mme try. Benzene and
fr
- · -: « c~0ethcne. rrans-AB: C: (square planar) tituted benze r.f:
- - • • ~t;:-d .x::-,zene ha\e centre of symmetf)
but mono -subs tituted and ortho . meta -subs
_ n!.:il, - c _e,,tre of ' ) n:met1
cemre
' ~ I! 1s :lear '1<:1t ,ince centre of
1 S} mmetr:, is a point. only one atom will be at the
ation is carri ed out. All lhe other arom..-
' r.:mau: un,h1fted "-hen inversion or an) other oper
cules \loruch contair.
--w~m pa1. ~ Therefore. \l,e can not ha•.e .i centre of symmetry in mole
ber of more than one atoms.

lmpr0per Axis of Sym metry or Rotatio n-R

efle ctio n Axis (S ,J
in a plane perpend icula r to that axi:, iillJ
!f ric: c, ~ a r u1uona1 a,;n and v,e CillT) out rene ction .it1::
c L ng •he<,(: t...,o peratJOn\ lroLlttion fir,t and
then rdlec11on J if \\c eet indic;tineuic;hablc configurJt
tion- Reflcction a-x1-, of , , m--metn . and 1! h l-..ille ...
f •hen ,fe(. e lhc:n m 1 lec ult: 1!> ,a,d ro h,J\c a Rorn
..:r: Jrripr p,.:r Al( < f ~)mmclr). h I'> dei;1gnatcd b)
'>)mbol \,. \\her e 11 = 360/ 8 (or 2rr/0 J. For e'<amplt'.
,n trw .. h..t1 r x:ltlcnc v. c ha , , ( J \ i ( f ig f 22

d
 l.'l r JIOLJU<'1 ION JJ

Cl H
'\ / 1no·
s., c=c -- •
no1c1llon
/ '\
If Cl

(a)

Cl H
'\ /
c=c
/ '\
H Cl
(c)

Fig. 1.22
passing through two carbons
Here. if imagine the molecule is rotated by 180° about the line
uratjon from original one, therefore
atoms we get Fig. l.22(b), which is not a indistinguishable config
an axis of rotatio n only. But when
trus dotted line is not necessarily a axis of symmetry but it is
line is carried out, we get the
second operation of reflection in a plane perpendicula r to this
is S2-Jmproper axis of symmetry. The
inrustinguishable configuration Fig. 1.22(c). Therefore, this line
Rotati on (C11) and Reflection in a
existence of Improper axis of symmetry implies two operations-
plane perpendicular to C11, i.e., crh, so we can write
s
fl
=&
- "
c n
nt is a result of comb ination
Here, first C11 and then cr" operations are carried out. So this eleme
tand is that the existence of S11 does
(product) of two operations. Here one thing important to unders
nts separately.
not necessarily require the presence of C,, and crh symmetry eleme
I

~
H
H

ah
H ~

goo ah
Rotation
I H
--, --
I
H
I
I
/
I
H H
H
\

Fig. 1.23
-
ts inc.lt:pendcml) :-,() there mu,1
for <.:xamplc in PtCI .1 (A/3 11 , <,quar<.: plwia1 J, horh C' 1 and''" l'"<i<,
(IL'lr :tlwdr al AB) (Fig. 1.2'.I J, S 4 l' \ i~1, hur
al<,o ex,.,t \. 1;ince 11<, both part., are pn·.,ent , hut in Cf 11
the molec ule CH 11 doc., not have inder endenl ex i -,1enc:e of C'.1 and
a" in ihe l f. Thal is. neilht· r C 1 nor
lh<.: student can learn ahout impropt'r
cr" oreration<, result in a incfoting ui , hahle configuration-;. Now
nnation..;. In ec: lip,ed co11for m a 11un.
ax il> of <,y111111 e1ry by preparing a hall , rid model of l.!l ha11c confo
plane. Tl1erl·l'ore . 1hl.'1r nist, a .S 1
rhere i-, a C i ax i., collin ear with 1hc C C hond and a C\ mirror
 14 P THEORY lN CHEM/S1RY
SYMMETRY AN D GROU
. . but C3 ax is ex i sts. Also ·
is collinear ·th C ge red co nfo rm at10n , the re 1s no crh
.
ax 3 , wh ere as
in s tag . . re e • . in
d
w1
• . re ex
.
ist S co l 1,ne ar wi th C3 ax is altho ug h the XIS t llCJ!her
I sta gg e ane, the
t 1e re co n1 o rrn at1011 of eth
6

c 6 no r a h. th
n (if n is even) as 1·0 e ca ,e 0 f
ne rateu by SII ax is• will also be
To tal nu mber or op era tio ns 11c is od d th
. e
2 , c.i.. .. 11 (C'11 = E). n opern11011s
are gene rated. Bu t if n en what
C
11
.
ax ,s wh ere ,, c' . c
11 ,,
c
11 11
h rx a111plc.
ap pe ns. \\ e c:in \\ rile fur
C 1) (c.1ccorui11g to the ue
Dn itio n of s)
S ·1l = (CT/, l (a/,c) c ) (a1
l I
11

= (cr" a"J a" • c, · c_ l · c1

= E. a". c: (be ca use CT,, · a11 = E)
C = E)
11

= E . CJ/, • E (beca use II

= identical
(Jh
=s:: bu t if n is od d the n s;:
= cr1, an d so to reach at the
he re n is od d) axi s, i e
ev en, E
It me~u 1s that when n is tio ns are to be ca rrie d on S11 (w
era
i s can be see n by actua·ll;
lec ule , tot al 2n op
co nfi gu rm ion of the mo ne rate _211 op era t'.ons. Th 1 s2 sJ
with od d 11 :'i ll ge
s;,~= E (if n is od d). Therefore,thS11a mo lecule, for ex ample, 111 BF1 (Fig. 1.24) we can ha ve ~~nt~~ s
ca in i ng our the operatio
ns wi ssi ng through the
di
llin ea r with C3 an d pa
S~. s~.
-S ~. operations possi
pe rpe nd icu
ble
lar
on
ro
S3
the
which is co
mo lec ula r pla ne (pl an e
of pa per he re).
Bo ron ato m and

Fig . 1.2 4
. . . .
re, it n be no tic ed that only SI . d 5 5I are the u1 s1m ct ·
ns ge ne rnrccJ by S ,Lx 1s
He Ci:l 3 an opern r,o 1
) lh · 0 2 _ 2 ~ 1 cr
- .
beca.u ,c we '>CC in the r,, 11 _ ( 1 24
e, a, ,1 l - Ci • s
I = s" - c' r

1 and S
6
.1 = E. Th es e res ul ts ca n als o
"' 1 -
 INTRODUCTION 15

be mathematically worked out (witho ut taking models) as fo llows:

SJ= a n CJ° a,, C3 = (a,,• an ). Cj = E·Ci = c;

54 3 I
.1 1 · a,, Ci- a,, CJ° a,, c3 = (a ,,· a,, ) (a ,,• a,, )· C 3 · C3
= a,, C_
= E · E ·E · C31 -- CJ1
In case of AB4 square planar mo lecule (like PtCl-42, Ni(CN)4 , etc. (Fig. 1.25) there exist C4 , and
~- wi.th
S.i is co Ir_me.tr
. · it. " 11 = 4 (even), the possible operations on S are S l , S 2 , S3 and S4 (=E).
' Now 1or
4 4 4 4 4
But S4 wil! generate only two distinct operations, S!
and S~. This can be verifi ed by actually performing
the operauons on the molecule first C 4 and then a1,, we have ,

84 81

1•'l.(\";;7/
S4= crh C4 ;~

83 82

84 81

2 , ' I 2.
S4 = (crhC4) ~
(\";;7/
83 82

Fig. 1.25

We can verify here that resulted configuration of s;

operation is also obtained by C~ operation,
which is already present in the molecule AB 4 (Fig. 1.26).

Fig. 1.26

Therefore 5 2 =
' 4
c4'2 and c42 is also equal
.
to the inversion operation (i). This can be verified easily
2 2 .
When the inversio n operati on i, is earned out. T herefore, 5 4 = C .i = 1. (T here results can be
mathematically obtained as done earlier in case o f 5 3)

Now, for 5 3 =
4
(6- I, C4 ) 3' look at the Fig. 1.27.
Here we have seen that the resulting configuration o f S~ operatio n is exactly same as obtained
by C~ operation, therefore,
S43 = C43 (or c -41)
 IN Ct111MIS Il<'r
16 SYMMETRY AND GROUP THEORY
c·"' 111Ci lll ~ c·,, npcral1011 Lw11 1"d
.. . S"'
•

_,, = E.. Thcn·lorc, ,, = ' ,, • ,, ·

A

r''" s~.
u
,
i t:
• • •
,. L
l n any planar ltgure. u •rutionH gcncru, 1c,1 11y eve n t)f(kr
• .1111 wri te 1hc ope,nly two d1st . 1
. 1nc r r,pcrat,on~. ,c,
·
out III t1111es. So for Al3,1 square plan
ar 11H 1b:u lc. we t:
1· Tl •rel'orc· rllcr•c• urc < c"4 <.i1. and 4
. . ' S1 =(, ,~ =,.. S, , =C, ~1 and S,,14 = ~- i c , opcmli ons hccau~c
1 1
S4 axis 1s Sot. 4 .
1 . , • , 1 111id( '· J1s11nc
, · lwv c ( ,1 ,1
and s:i generatl:d by s~ :I \I S (Ith Oil ( ., \Vl'

C! = E).

Oh

-
I
82 83

@
, B, j/'
0 s, 81

@
82

84
Fig. 1.27
of symmetry
(E): This is the simp lest trivial element present in all objects. Thi s element
Identity by not doin g any~hin ~.
to the molecul e (lea ve it alone) then
s present when we do not do any thing ope ration is
1
guis habl e (exa ctly iden tical ) con figuration of the molecule. Therefore. no
we get indistin ent in all the molecules
ratio n for the Iden tity elem ent of symmetry. So this element is pres
the ope ry operations
s that it is not imp o11an l, but it has importance when we con side r symmet
(objects). It seem ng certain requ irements
form a mat hem atica l grou p. The need of identity ope ratio n arises for sati sfyi
to successive (one by
Normally, we des ignate the results of
of group theory (as we will see later on). is rotated by 360°
bine d oper atio ns by thei r equi vale nt configuratio ns but if a molecule
oneJ or com origi nal one . Therefore.
gct exa ctly identical configuration to
or reflected twice or inverted twice, we clement (E). So.
oper atio ns are iden tifie d and hen ce the name identity is give n to the
result of such
we can writ e,
C1 = E. a = E, i2 = E.
2

ini ' l I · rsc, c11·

The mvc
Here it is nccc.<.,!>ary Lo dctinc the ex isten · ce of · of a .sy,i c ry e emc1 nt.·
inve rsl!
l · 1· ·
of the elctnL:llt ••ind 1·1s. ·inve rse s11ou1u give 1l entit y. ' lH
.
ry elem ent ,~ such rhat the rrou uct
a symmet . .
example, J/ we have CI/ , then
 l NTRO DUCI1 0N 17

1
(C,,) (C,,r = E t:- I
Here (C n )- 1 1s
•- h ·
t e mver se of C11 axis of symm etry.
For exam ple, in case of BF_ 1 mole cule,
we have C~, c;
opera tions on C3 axis of symmetry. If
tions one by one), then the resulting configuration
we take th e prod~ ct (actually carry ing out the opera
ng to the molecule (Identity).
of the mole cu le 1s same as obtained by doing nothi
C2 I c2
c :ll I -I
= c1 :l or C3 C 1 = E.
:l ·

. . Therefore, C ~ is inverse of andc; c;is inverse of C~.

If produ ct of two opera t ions of an
that o is
Similarly, we have seen tha1 er . er = E. It implies
is that elem ent is ident ity the n the two
inverse of itself. So inverse e leme nt or operation operations are inverse of each other.
result
opera tion which when comb ined with the operation,
ined with
into Identity. Seco ndly if Identity elem ent is comb
i.e., ECn = Cn or E · cr = crE = a , ESn = Sn E =
any opera tion it always result the same operation,
Sn.
ents
Some Important Inter-Relations of Symmetry Elem
(i) C~ = E (if n = even or odd)
(ii ) S~ = E (if n = even)
S~ = a,, (if n = odd)
S~ = E (if n = odd)
( iii) a" = E (if n = even )
= cr (if n = odd)
(iv) i'1 = E (if n = even )
= i (if n = odd)
(v) s: = c; (when m = even and m < n)
s: = c;- (when m = even and m > n)
n
and a centre of symm etry (i)
(vi) If Sn (n = even) exists, then there always exist Cn12
independently.
If Sn (n = odd) exists, then there exists C n and cr11
(Vii) Some deductive relations: Thes e relati
ons can be derived without actually perfo rmin g the
write as:
mathematics, we can
operations. With the basic know ledge of simple
(a ) On C II axis of symmetry, total n symm
etry operations are
1
C~, C~, c~. .... , c;,·, ....., C"~ . c; (= E).
NOW, C"
n
+ I = C"
n
CIn = E . CIII = CIn

Therefore, the serie s of operation lasts up to c;.

(b) In c;,if n/m is an integ er (k) then,
cmfm _ C
fl/m - Ir.

axis.
It impli es that Ck axis is alwa ys collin ear with C 11
the following opera tions :
For example, on C 6 -axi s of symmetry, we have
ci3, cJ6 = cJ/3 ci2
c61, c62= c 212
6/2 = 6/3 =
c~ = c4:Z = c;, Ci and c! = E
 RY IN C111!.MISTRY
SYMM l: I RY /\ND GROI IP T 111!0
18 5 2
. 1· 1i11cl operations arc C~ ' C~, C2' C6. C3 and E. Also,
•rhcrc 1· • I it·tl ~,x l I~ . f symm t (C ) C an
Oi l:. < ' • • illc princ ipal axis o e ry 2 u
, · I1 • · llincar Wtl 1 1 6 .
( 1 axes will ~ ui . . iced that on c axis. total seven operations are possib •
' 'I ·ly tl Cll ll hl lkt1l 7 le.
•Slllll lll h'
• • I vc II opcra11011s, ' I
w ,c l are
' c·) ()11 S ol even II . we Ht
I ,,
s' s~ 1
s· 1 s·'
. ...... S""- I , S',,I and S"II = cr"
I,
c·"
II
11 11 11
11· • ' =E· E=E

• 511 • I -
"
S,,
s' -_ E . s' = s 1 (repeated). IL implies that beyond n, it will not
Therc lorc. 11 - "
II II

generate any new element. .

S axis the total operations are
For examp Ie, on 4
S4' = c'4 . cr, = S J 4
1

S2
4 =
c24
cr2" = c'2 . E = c2'
S43 = c34 cr3
I,
-- c3
4
. crI, = s43
S44 = C44 cr4I, = E . E = E
Ss4 = cs4 aI, = c 4 • cr1I = S~ (repeated)
5 1

Therefore, maximum four distinct operations are possi

ble and they are E, C2, S~-
and S43.
If we have S,, with odd 11, then it will generate 2n distinct
symmetry operations.
' s2
Sn' s3 s11n -- s"+ 1 s" +2 s2n(_
II ' II' •..• , ah' fl ' ,, ' •• • • , n - E) .

Now sn211 + 1 = S2n" •S

1
= E • Sn1
(repeated) ' therefore, after 2n operations, no new
,r

element is generated. For example, on S axis of symm

5 etry, we have following
operations:
s; = c; · a,, = s; (by definition)
s2
5
= c25 cr2,,= c2
5 '
E= c2
5
sJ5 = c 3s cr31, = CJ
5 · a,, = 53 (
5 because
2
crh = E)
54 = s cr,, = s . E = Cs4
C4 4 c 4
5
ss5 = css · cr,,5
= E · cr,, = cr,,
56 = C 6 6 C5 I
5 5 , a,, = 5 ' C5 ' E = E · c~ · E = c~
57 = c 1 a1 = c2
5 5 " . - s2 .
5 a,, - 5 (this should be read as S 2 and then a )
S8 8= 8
5 cs · 0 ,, = c~• E = c~ 5 "
s95 = c~ . a~' = c5 . a - s4 < h.
" - s t is shoul d be read as Sol and then a )
SIO -
5 -
CIO 10 ~ 5
s 0 ,, = E · E = E h

s''5 = c'; cr 11
- C1
· 1, - 5 · a,, = S5I (repeated).
 Tht·rd\ m·. tolul I() opt·rnlillns 1111 . \ axis will bl'
s~ s'.-; . \s'~ · c"~ - c·~
s'~ -'-~,1o. .~ . c' ·•, ,
~- c~ ~
,, and 1•:.

(S~ ~• 1- o,,) a,, ). H.:sr rr11vc

· 1y.
11 t·rc. ,s 2, nmt ..l•"
. . , are uc111111ly nnd (S "~ +
Si 111ilnrly. st11dt·111 rnn verify 111111 on S 1, tilt· upcrntions mt·
s' s ' = , ,.! s 1
' \. '- I
s" ( ,I S'l : •SJl II~ •"'~•<•I -- r:,e ,
\. .\ ' \ I O' I,• ' I I•

S·i = (a,, c,, f = 0 1, er,, cr,, CT,, a,, c 1 c, r , C\ C1 =- a;:·a,,· ( i' · C;

= E · cr,, · E . C'~ (h ,•cr111.1·<1 cr;: = E 1111d C: = E)

= cr,, -C~ - (s1+a,,) (because c.~= S.~ )

(d) s2= ,.
((') 111 case of CII of even order 11 > ,..,- · S,, -axis
.
is wtlinea r with CIIn· For exampl e. S,. colline ar \I

with C6 also has S3 colline ar with it. Therefo re. besides s~ and sg. two more operati ons

s~(c~+cr,,) and 5~(c~+ cr,,) are also possibl e. In case of S4 (colline ar with C.i >·

5~ (cJt- cr,,) is lhe inversio n operati on and it is not a new operati on.

(j) In general . the inverse of C,",' is C"II - "' and lhe inverse of 5"'
II
is 5II11 - 111
if n is even and

5 2II " - "' if n is odd.

Problem: What is the inverse of C~ ?

t is identity (E ).
Solution: We know that if the produc t two operati ons of a symme try elemen
lhen they are said to be each other's inverse and also we know that c~
= E. Therefo re, c~ must be

the inverse of c~ becaus e c! .c! = c: = E.

Problem: How many symmetry operations are there in CH4 ''

''
nwlecule?
Solution: T he geomet ry of Lhe CH4 is tetrahedral, meanin g
by, four trigonal equilate ral faces, four comers and six edges as
~hown in Fig. 1.28. Carbon is at the centre of the cube and Lhe four
hydroge n atoms are at opposite corners of two opposit e faces. Now H3
we analyse this geomet ry for symme try elemen ts (operat ions). Fig. 1.28
(i) As all molecu le contain identity, so it has also E.

(ii) There are 4C 3 axis of symme try each passing through the
carbon atom. one hytlrog en atom

and the centre of the opposit e trigonal face and o n eac h C 3 a.xis. C~,
~ operati o ns c;. c
for each C 1 -axis
are possibl e but C~ = E (Identit y) which is already present. Therefore!.
e on ..ic, i.s ➔ x
of symmetry, we have two distinct operati ons. So total operati ons possibl
2 = sc 3.

<iii) There arc 3C2 axe.~ of symme try passing th rough centres
of two opposi te etlges. One
passe~ betwee n H 1H 2 and H 3 H4 , second through H 2 H; and H 1H 4 and
third is passing
 SYMMETRY AND GROUP T11F.ORY IN C 11EMISTRY
20
. ml 11 11 Each C7-ax i~ of symmetry c an generate o nly one di~tinct <
bct\, ccn 11 ~ l l , ·1
• , , ,J
1 1· • c - be 3 x I :::: 3C'PcrarJr!TJ
1: T here fo re LOtul opcral1ons on -3 2 w111
/ c., c~ bccau:,.c ( , - ,. ' 2·
. ho cx i~t coll inear w ith C 2 axi'> and a~ we have 1-cen
li\') 1S J ,\ \ C:,. ol :,.) ll\lllCII y .1 , . -I • 51 . ' ' earlier r
, . 1\, two new o pe rauom, (S 4 c1nd 4) arc generated. Henc.: f ,r1
S ,,-i,ot ,,111111cll \ . Oll J
1
~ e, Orth
•
c
• . •
tot ·\I d1:-1111ct
. ' ,
• · • 3S ·s • x 2 = 6S 4 .
opcr,111n11s on . 4 i. 3 rC<:
.l \ ,l l ~. l •

, . . . )f synimctry (O) . eac h passing throug h one edge and th

l ,., 1 here C\1:-ts :-1>. p 1.11ii;:- < · . ~ c centr .
,,1 the uppl)!\llC Cl1g,c., .cl~1 c.1 eac h plane o f symme try gene rates o nly one operati<m . So lr,t.;,j
e1
,1pcmt1ons on 60 arc 6 x I = 6 · .
Hence. the total 24 symme try o perations are possible for CH 4 m olecule and they ar~
1E, 8C1 , 3C 2 , 6S 4 , 6crd
. , ·larly student can ve rify that for octahedral geometry, there ex ist~ 48 '>yrnrr
S 1n 1 , h . . .ti . 1etr.
operations. For any regular polyhedra, Euler s t eorem 1s JUSt1 1ed which states that, ·
V + f-e = 2
where V = vertices,

J = faces and
e = edges. I
I 1\\ ~
\
I \ '-
fo r octahedral geometry, for example, we know that there /
B2 r:-- - -- - . .\,, --_~.
' Bl
\
are eight trigonal equivalent faces, 6 comers and 12 edges, \

satisfying the condition of Euler 's formula. Octahedral

geometry is fo und in AB 6 type of molecules for example,
(Fig. 1.29).
[Co(NH 3 \ ] 3+ , [PtCl 6 ]2- B.

In icosahedron geo metry, ( F ig. 1.30), there are 20

equilateral faces, and total number of symmetry operations
B5
are 120 . for example, Dodecaxborane B 12 is an H~; Fig. 1.29
icosahedron.

1.3 SYMMETRY POINT GROUPS

If <,omeone asks what is the geometry of a m olecule, it can

be ea\il} answered, but if the questi on is asked like that what is
'-: mm<.:try of a molecule? Then, we need first to arbitrarily fix
rhe Cartesian coordinates and then we have to e xam ine the
eh::rm:nt-. of '> ymmetry pre~ent in the molecule. For this purpose
fi r'>t we -.ee a ll po:-.sible symmetry ax is a lo ng the Cartes ian
coordinates or in the planes of the coordinate a xis. Then principal
axi'i of '>ymmetry (C 11 ) (gene rall y highest o rder axis of symmetry)
i<, selected and designated a" z-axi:-. . T he n w ith re fere nce to this
z-axi s, the planes of '>ymmetry like o ,,, o ,, , o ti are e xami ned and
then the pre~ence or ah~enc.;e of centre of symmetry (i) in the
molec ul e i:-. c hecked . Fig. 1.30

I
 fNTROOUCn ON 21

The rnlki.;11011 ol' 1111 sy1111t1l'l ry l'lc111cnls (opernlion s) possessed by a molecule constitute a
grnup. I kn· I his gt11up ol' .~y11111tl'lry l'll'111c1111, L~ ulso a rna1hcmu1ical group, it means that it also satisfy
Cl'l'tain rnnd itions for a 11111lhl·111111ic11I group. One 1hi11g i1, very dear thut all symmetry elements of
11 111olcrnk pass thrnugh II fixed poi111 i11 1hc 111oleculc (usually 1he centre
of mass of the molecule).
Thi~ pui111 n·11111i11 unshilh:d during all the sy11u11elry opera tions. Therefore, a sci of (collection of) all
sy111111l'try opl'l'llli1111s 11111y ht: classified in to II group known as point group and symmetry of a
111ob:11k is called poinl sy111n1clry.
111 general. mosl of lhc 111olet:ules can be classified in to 32 (thirty-two) symmetry point groups
1111d lhey arc lahl'llcd by Schlinl'lics 1101a1ions. Cryslals arc classified
according to their symmetry in
to 230 space groups a11d symbols for this arc designated as Hermann Mauguin notations. We wil l
disrnss. hct'l' is this hook. only molecular point symmetry groups using Schonnies notations .
Now In de1cn11inc lhc poinl syrnmelry o f a molecule, or to know that the molecule belong to
which symnu.:lry poinl group, we have to follow a tlow chart which is shown below. (Fig. 1.31 ).

No Is there
any S 2n
Start collinear N
any cr o
with Cn
Is there any Cn(proper axis)

No Yes (n> 1) Yes

Is there
any o
Is there any
nC2 .1 Cn
J
No Yes
Yes
Point
Is there group Is
/exist
@di

Fig. 1.31
Now we can discuss one by one
(a) Groups wilh Proper /\xis of Symmetry.

(i) hir example, the poinl symmelry of H20 and

NI 11 molecules can be easi ly determined by
lol lowing Ilic above charl. In H20, we huve IC2
a11d 2a, therefore. ii belongs to C2,, point group
or we c;in say i1s sy111metry is C2,, symmetry. o,
Si111ilatly 1'01 Nll 1, tht.: geometry is Pyramidal
("fl' hyh, icli1a1io11 ) and 1he sy1111ne1ry ele111en1s
p, l'~l'llt i11 till' 111ob:ule arc IC 1 + 301• therefore,
lhl' 111ole<: ule helongs 10 C 1i poi 111 group. So
!!L'lll'1ally WL' rn11 wri tL' 1ltat if a11y 111<>keulc whit:h
ha, I: , ( ·11 1 11a, 1he11 i1-; sy1111netry is ~ J. Fig. 1.32
22 SrM ~IFl 'R\ AND GRc wr T111:
0R\' IN C11F~,11sTN.,

E + CII + CJh' tht'n poi111 ~,,roup will

IC:7.
be ~ Here one thi.a ~o
lii) lf :I mn b.-u k j)('S Sl'SS
also lhc point
be men tion ed is that if the mo kru k l'<mt:1ins blHh CJ1 and CT;, lhen
to Cl. tran.s- Hp 2•
. H_,BO_, (pl:.!n:ir). rrcm s-CHCl = CH
symmett") will he ( 111,· For t'x:unpk
l'tc. ha,·t' C nI1 s,·m mt'Lf'I• .
•
up. whi1.-~ is called
C l. e,,. it belongs to D11 point gro
(iii) lf :1 mo lecu k has E + C,, + 11 2 _pomt groups
dihedral group and the C2 axe's ..1. 10
enm' c:tlk-d dihedral axis . Dihed.ra.l trom Genn:m
ps are cyclic (the kne r C derin~d
are not l.'.yclic groups. whereas e,, grou nC: c l. C,, . then
:1Isl1 present in addition to C,, and
word "Cyclosch" ). If 11cr., planes are
Elhane tstaggered l.
tht' poim group will he ~ - for example. Aiknt'. Cycloht'xane.
D_:.., As we
e only rw0 point groups. i.e.. DM and
t".tc . Under D"·' poi111 groups, we ha\·
ah :tlso. lhen lhe p<1int group
will be ID~
procet".d for 0 4.1 and Dc-.r we h:1\·c'
.l en+ 11cr., => Dr.J and E + c,. +
nC: l. c,, +
Tht'refo re. We' C,Ul \\Til e' E + e,, + 11e:
ah => D,,,, point group.
(b) Gro ups with Improper Axi
s of S:, mmetry (S n).
is no oth~~ r
ecul e com ains S :1xis of s,·m mem . · coincident wilh Cn axis and mere
If the mol n .
As stated earlier
t'nt.s (t'xc ept i) then moh ·ule belo ng 1c1 S" point group s~1nmetry.
elem
ecule.
thar when S,, (11 = e\·e n) is there in mol are just
ent inde pen den th. When S., (11 = odd ) e:cists, point groups
Cn1:c. axis will also be pres y SJ. S6. SJ.
icu l~ the same as C,._~ poin1 groups. Onl
coll inear with S,,. bur cr planes perpend te.nce.
senr .... etc. h::iYe separa1e e..tis
ro C,, c. or S,, ::ixi s ,,·ill nor be pre , the pom · t
exa mpl es are there which belo no , uen 11 -- __
::- to S,, ::-!ITOup. \\"-
independt'nt . ly. A few
ups will be tem1ed
ed C; bec:1use Sc. -- 1·- From 11 = -t1 onwards . the pomt .!ITO
•
!rrou
~ p S , 1s call
- the S11 axis will
l number of operations gen era ted from
as 54· 56_- 5s e_rc. In th.is case. the tora · - Si (OCH 1 ) 4 and terraf1uoro
be.II · whc ch will be the el emems of th.i s pomt group. For example. -
up.
sp1rononane belong ro S4 poinr gro .
.
in the molecule then it irnPli es the independent presence ot a
If Sn axis ( 11 = odd ) exists . . _
plan e of symmetry (cr ) and total -" 1 operatio ns will be oene ed by S" (n = odd). ln su.. h
h rat
le will be C D ::-
•
cases. the synunetry of the molecu ,,. Dnh or Dn:t For e.,;ampl
e. eth:int'
l r:Ji•
(gauche conformation)· BF_; · naphtha ene. etc.
.
Special Point Groups·• (\J\ 1o1ecu1es of cubic and mear geometnes )· r .
Ml ries com ~ .
_o ecules of linear and cubic geomet es und er this cate gorv
of special point 0orou ps · L.mear mol . • - -
ecules with mve rsio n are
. ~ - cen tre of
clru,sified in to the special pom t gro up , D whi h • d. es the presence
~~ c m 1ca1
of C + ooC l c + cr For example. H,. CO,. NO
2 ✓ h·
- 2· XeF ,. etc. belono
•
-
D ooh pomt symmern.1 These molecules al -0 h
00

(O · - ::-
· M
· :s ave mfin .ite num ber of
vertical planes (CJ ) in add H1o.. . .-
. ' n to one cr . Here C,., axis l!:i also S . Llne.ar
re of h_
molecules w1th ouc cem n ha, e C . ""
. sym met (I)
, ,.e .. an a'tis of
. .- ,., + oocr
mfinHe ord er and infi nite vertica l PIane s The , ::tre , 1 'f e<l
lr 7 c ass1 I . in to the point
. For ex1mpl e, HC! , HC ~ i • Fig. 1.33
group ~
· NO, OCS . etc. ha,·e ,.,1 poim c
symmetry.

J
 )NTROD U ~ l3
Molecules with specially high symmetry belong to cubic group of symmetry. It includes mainly,
tetrahedral, octahedral, icosahedral or dodecahedral geometries, and they are classified as T" . O,,, lh
point groups, respectively. One can ask what is the symmetry of an atom? Atom is a spherical
geometry and contains infinite number of symmetry elements and they belong to ~ point symm.. : try
known as spherical symmetry. In cubic groups, mainly we come across tetrahedral and octahedral
compounds and few compou nds or molecules belong to higher symmetry like icosahedron or
dodecahedron. Let us first we find that how many symmetry elements are present in a simple cube?
It is rather strenuous to find out the symmetry elements in such geometry but if one tries to carry out
operations of rotation, reflection and inversion in mind, then it comes out that a simple cube contains
9 planes of symmetry, 13 axis of symmetry (3C + 4C + 6C ) and one centre of symmetry (i). These
4 3 2
total 23 elements of symmetry constitute a cubic point group. Therefore, molecules belonging to cubic
group must have two or more C11-rotation axis symmetry of order n ~ 3 or 4C 3 (if molecule has
geometry tetrahedral or octahedral), whereas, icosahedron or dodecahedron molecules must have
IOC3 and 6Cs-
It means presence of four or more C 3 axes of
A cube has 6 faces, 8 corners and 12 edges. It has
symmetry in a molecule indicates to look for cubic
13C11 , 9o and i.
point symmetry. The possible five regular polyhedra
is depicted here with their total symmetry elements and geometrical description satisfying Euler's
formula.

Table 1.2

Geometry Faces Vertices Edges Example Total Symmetry

Operations
Tetrahedron 4 (equilateral triangles) 4 6 CH4 , CCl4 24
Cube 6 (squares) 8 12 Cubane C8H8 48

Octahedron 8 (equilateral triangles) 6 12 SF6, CO(NH3 t 48

Al~-
6

Dodecahedron 12 (regular pentagons) 20 30 c20~0 120

Icosahedron 20 (equilateral triangles) 12 30 B12H~; 120

B12Cl~~

A regu lar tetrahedral molecule of type AB4 Regular geometries has equivalent face areas. I
has E + 8C3 + 3C2 + 6S 4 + 6ad symmetry operations equivalent vertices and edges.
(as we have seen earlier). Therefore,
molecules with regular tetrahedral geometry belong to [!J
point symmetry.
Total 48 symmetry operations are possible on a regular octahedron. This can be seen by drawing
an octahedral molecule in a cube (cube and octahedron are said to be dual to each other). If we
connect the midpoints of adjacent faces of a cube, we obtain an octahedron and vice versa. A regular
octahedral molecule (SF6) with a horizontal plane of symmetry is illustrated in Fig. 1.34.
 l~IIIY
24 SYMMETRY ANll G1m1•p TIIW RY IN CmM
z

F+-- ---, . Y

X
Fig. 1.34
presence of following symmetry elements
ven'fy the
b II stick model an dl 35).
Student ma) prepare a a ( Fig d . th
. . .
. ah dral geometry. see hrough opposite vertices of the octa he ron, 1.e., ey
tor the regu lar oci e try They pass t
~ ng the S-F bonds).
(il 3C.i-axes of symme ·es of oppos1·te faces of the cube (alo .
ass l.hrough the centr
the C4-ax1s of symmetry. th
..
p and 3S axes of symmetry collinear with
3C
111 1 4
faces of the octahedron. As ere
, iii) 4C : -axes passi ng through the centres
of two opposite
ar/ 8 such faces, there are 4C3 present.
1ii J 456.axes coincident with
4C3.
(r) 6C,-axes bisec ting opposite
edges.
<iiJ A ~entre of symmetry (or centre of
inversion) i.
e three
, 1iiJ 3oh: these are due to the presence of
three proper axes of _symmetry (3C4). Thes
. (Each ah is .1 to a C4).
horiwmal planes are perpendicular to C4 axes
11 ii1J 6od: Planes pass ing throu gh two
apices and bisecting opposite edges.
lar octahedral molecule will be E + 8C 3 +
_6C.i
Therefore. total symmetry operations for a regu operat10n s
operations. Molecules with these symmetry
~ 6C, + 3(, + i + 6S4 + 8S 6 + 3o" + 6crd = 48
btlong LO _2J poi nt symmetry.
dr~n
Th()~e molecule s, although very few are there
, which have regular Icosohedron or dodecahe
gec;mctf) belong to the highest symmetry (exc
ept D coh and C point group
)
QJ . The ion. 8 1:Hi~
lar icosahedral.
00

to understand it . B 12H212- is regu

and Fullerene\ (C6," 1J are the be~t examples ~
. 1.37). It 15
(Fig l.36J ..\hereiJ\ Fullerenc (C 60 ) has
truncated regu lar icosahedron geometries (Fig
s lie at the veitices of a regular icos ahed ron. This
dcpKtcd bdov . in which the twelve boro n atom poss ible for
The total number of symmetry operation s
ge{,mctry ha\ 2() ~uilateral triangular faces. In this. a
etry are E + 24C 5 + 24SJO + 20C + 20S 6 + 15C7 + 15cr + i = 120 operations.
thi, geom
C5 axl\ emerge, from each ap~x , whil e in
1
dodecahedron , a c 5
axis emerges from the centre of each
n, however, complexes Ii~~
face . At ,pre;"ent, m~Jlec. ul~\ w11h dodecahe dron symmetry are not know
they h:i1t
nd 1 ~hape but their symmetry is not 1,,, rather
[tyfo (C.I\Jx) a fl'.r \ J have dodecahedral
D2d symmetry.
 l N'TRODUC..'TIUN 25

I
I
I
F

F F

--- -- -- --- c~

Centre of
F F symm etry

@:;]- point symmetry

Fig. 1.35
also an
The soccer-ball shape d Buck miste r fuller ene (C60) is
net comp osed
example of I,, point symm etry. It consi sts of a spher ical
d by 20 six-
of 12 five- mem bered rings (pent agons ) surro unde
the langu age
membered rings (hexa gons) . There fore, C 60 in terms of
is show n in
of symm etry may be writte n as Ih- 60. The struct ure
with each pair
(Fig. 1.37) in which it conta ins six pairs of penta gons
and in a
of penta gon placed diago nally oppo site to each other
from each
stagg ered orien tation . A C 5 rotati onal axis emer ges
onal face.
pentagonal face and a C 3-axis emerg es from each hexag
becau se each
Here. it is to be noted that there exists no C 6 axis
and three
hexagon is surro unded altern ately by three penta gons
d mutu al
hexag o ns. Icosa hedro n and dode cahed ron are calle
The C 5 axis
polyh edra since they posse ss same symm etry eleme nts.
as they pass
pass through oppos ite vertices in icosahedro n, where
on, where as
through the centr es of oppo site faces in the dodec ahedr Fig. 1.36
pass throu gh the centre s of oppos ite faces in icosa hedro n
C3 axi s
vertices.
while in dodec ahedr on they pass through the oppos ite
is linear, then it has C ax is of symm etry
Molecu les may be linear or non-linear. If molec ule
00

er of vertical planes (oocr) . They belo ng to

which is along the mole cular axis and infinite numb
ule possess a centr e of symm etry
~ point symmetry, for example, HCN, HCI, etc. but if the molec
ndicu lar to C oo) and infini te numb er of C ,
in add ition to C c..o then it wil l also have a a,I (plan e perpe
ining one C2 axis. Then , is such case, point
ax is perpe ndicu lar to C There are infinite <1v5' each conta
00
•

),ymm etry wil l be ~ for example, CH = _CH, H 2

, CO2 , etc.

ule, which has lowes t symm etry eleme nt

In case of non-linear molec ule, we start with a molec
C point sy mmetry which is a trivial rotati on
with n = l , i.e., E (Identi ty) only. This is classi fi ed as 1
nothin g to the mo lecule is o ne and the same
axis of 8 = 360°, and there fore rotation of 360° or doing
Identity e le ment and no other e lements of
thing, theref ore, C = E. Molec ules which have o nly
1
 I

26 SYMMETRY AND GROUP T HEORY IN CHEMISTRY

. For example, lactic

. ca. ll ed Asymmetric.
symmetry me . sec-butyl alcohol, CIFSO, CHFCI Br' etc ·
. acid,
Some are shown in Fig. I .38.

Dodeca hedron
Icosahedron
Bukminster
fullerene C60

Fig. 1.37 Molecules of th point symme try

F,- -- - - -
''
''
''
''
'' Cl
Cl
Fig. 1.38 Molecules of C1 symmetry
. If O' and i are added
By adding symmetry elements, one by one, to E, we get other point groups
Cn) generate only one
separately to E, we obtain point groups of order two because cr and i (unlike
operati on each. Hence E + cr ~ [sJ (= S 1) and E + i ➔ [sJ (= S2
) . If cr is a molecular plane

ichloroethane, HOC! and

then C5 = cr 11, because cr .l C 1 (E) = crh. For example, 1,2-dibromod
2-Bromonapthalene, etc. belong to Ci and Cs point symmetry (Fig. 1.39).
Br

H\ / - , /Cl

I
I
I

I
I \

I
\

I
I
I
lo \
H Cl

Fig. 1.39
. . . E C
Hence, if C11 rotation ax is is added to E, it will result ·mto a cyclic pomt group, 1. e. . + ,,
.
~ [sJ' for example, cis- H20 2, stagge red 1,2-dichloroethane and 1,3-dichloroa
Jlene (Fig. I ,40).
 JNTROOUCTION 27

I Cl
I
I
I H H
I Cl
o+o
"c=
H
I \ H
H H
H
/

Cl
CIS - H2 O 2 Staggered 1 ,2-dichloroethane 1 ,3-dichloroallene

Fig. 1.40 C2 point symmetry

l 1n case of 1.3-dichloroallene, the terminal carbons are hybridized s/ Br H
and central carbon is sp hybridized, therefore, H and Cl atoms of terminal
carbons lie in perpendicular planes) all these molecules belong to C 2 point
symmetry.
Similarly. I, 1, 1-tribromoethane (gauche or skew conformation, where Br
O" < 0 < 60°) is an example of C 3 point symmetry (Fig. 1.41 ).
Br
In case of the molecules, having C11 + nC2 l. C 11 , we look for nad and
Fig. 1.41
C\. But if na d and crh are absent, then in such situation, molecule belong
to D" symmetry only. D11 point groups are rare. For example, ethane (gauche conformatjon) and tris
3
(ethylenediamine) Cobalt (ill) ion, i.e., [Co(en) 3] + are the examples of D 3 point symmetry.

5
NH2

H
H"' 1/H
---,,c-c,--- C 3

w"! ',H
H
Ethane (gauche)
en
6 NH2

(en = ethylenediamine)

Fig. 1.42 Molecules of D3 point symmetry

Point Symmetry in English Alphabets

Capital letter~ of English alphabets also possess certain point symmetry. lt is quite amusing and
interebting to clasbify not only molecules but also the Eng lish alphabets into various point groups
according to their symmetry, and the groups may be called "Alphabetical Point Groups•·. Table 1. 3
given below describe~ the symmetry elements present in the alphabets and the ir point groups.
 28 SYMMETRY AND GROUP THEORY IN CHEMISTRY

Tabe 13 .
Point Group
Alphabets Symmetry Elements -
ABCD Czv
EMTU E + Cz + 20 .,
VWY
- c.,
FGJK E +O
LPQR
Czh
NSZ E + Cz + i + 0"1,
D21r
HO IX z + 2av + ah + i
E + Cz(z) + 2Cz .l Cz()

---
A -B- ·C- ·D- -E- -,-C2
-
that if the mnth alphabe is
I
t
. 'I 'I ,I ,I ,I :
lt is interesting to observe d bottom of the ' ' : : : ,
.
written without ·
honzonta 1 rnes
I
at. the top andimenswnal . an d '
M '
+
u v W' y
letter, i. e.,
' I • h
' t en
treating this as one
C .l C + oo(J + ah + l
. ; '
' '
'
'
. .
cylindrical, it. contain . s E + C + boo I -? to D point group.
00 •
00 ".
'
'
,
'
,
'

Therefore Jt e ong oo/, • d I I I

symmetry elements. ' . I and so it is class1fie , , , .J
Also. the letter
·
'O' ·s not a perfect crrc e,
Jetry Same 1.
s true 'I or letter 'X' because, t e
h I..
v !
, - - - -"
C
in to D2h pomt symrn . · · an Je (90°). Here, we 2
Axis of symmetry
lines are not intersecting at exactly ng~t g t d by dotted
see that the principal axis of symmetry is represen e Fig. 1.43
lines as shown in Fig. I .43. h • of symmetry whereas those
I C oint symmetry do not ave axis ,
Alphabets, which be ong to s P. . •ng through the centre of inversion
belong to C 21r point group, have a principal axis of symmetry pass1
( i) and perpendicular to the plane of the letter.

Symmetry and Geometry

Jt is also interesting to observe that although geometry and symmetry are very much co~ne~ted but
they are different aspects. For some molecules, geometry may be same but symmetry IS d'.fferenl,
whereas for some molecules, symmetry is same but geometry is different. For example, consider the
following compound, CH4 , CH3Cl, and CH2Cl 2 the geometry of all the three molecules is same that
is tetrahedrn/, but point symmetry for CH4, CH3Cl and CH CI are T d, C v and C v, respectively. In
2 2 3 2
other situation, for example, BF3, PCl5 and ethane (eclipsed) have trigonal planar, trigonal bi pyramidal
and eclipsed geometries (conformations), respectively but all the three belong to same point sy mmetry.
i.e., D31,. Therefore, we can say that symmetry is a finer most aspect of geometry and geometry is a
crude lliipect of symmetry. Dodecahedron and Icosahedron are different geometries but belong to
same symmetry, 11,.

1.4 SYMMETRY AND OPTICAL ACTIVITY

The necessary and sufficient requirement (condition) for a compound to be t· • (Ch' 1·ty)
. . . . .
1s that its mirror image should be non-supenmposable on it From symmet p 1ca· 11 y active
O 1ra 1
f • ,
. . · ry pomt o view we comt:
across two terms, namely, asymmetric i:lnd d1ssymmetric. A compound or molecule is called Asymmetric
 lNTRODUcnON 29

ns absence
cxcepl ldenlily (E), whereas dissymmetric mea
if_it doe~ not_possess any sy111me1ry elcmenl nt, but
th111 dissymmelric molecules may have significa
ot Sn axis 01 symmetry of any order. 11 mea ns ,H
limited symmetry. /1
ic case s of dissy mme tric /
Asymmetric molc niks are lhc lcasl symmclr 1

man y htlllks. the cri1eriu11 fur a com poun d to be oplically active H3C- - 1
ones . ln
many compounds which are I

is 1ha1 comJXllllld musr be Asy mme1ric. Bui I

Therefore, a single criterion

I

!Hlt asymmetric bu1 lhcy arc optically aclive.

I
I
n by symmetry cons iderations
for :i compl.lllt1d lo be optically active is give
I

active if It does not possess ''

:md 1ha1 is. a ('Ompound will be optically spiran
'\ I
ple. a com poun d show n in Fig. 1.44 ' ,N
S,. axis of symmetrJ'. For exam y but the
of sym metr
which neither has a plane of symmetry nor
a cent re
ained only on the basis of H, (! I ,,CH3
~-ompoun d is oprically inac6ve. This can be expl
s~ mmetry criterion that this compound has
a S4 axis of symmetry that is H3 C ~ : H
ymm etric com poun ds are also optic aUy I
wh~ it is optically inactive. Diss I

plan ar cis-d imet hylk eto pipe razin e (Fig. I.45) is s.

J Cri \ e. for example. a
e it does not contain S4 axis
altho ugh not asymmetric but dissymmetric sinc Fig. 1.44 (Spiran)
cular to the
of symmetry but has only a C2 axis perpendi inacti ve
1.45 . The trans-isomer of this compound is optically
plane of the ring as shown below in Fig. optic ally active
s-I ,2-cyclohexanedicarboxylic acid is an
because of the presence of S2 (= i). But tran
compound.
M'rror

HC"\ / : \ /CH3
3
I
I
:
: II
HN --L- C
I
0

\
en

,
(cJl( ) ,,
,, ,,

·D
I I \
C

,
///
C
\
I

:
I
/ ',,
'
I
I
I
I
en

H C ~NH H I
I
II I
I
I
I
I
en
0 I I
I I

c2 (Non-superimposable
mirror images)

Fig. 1.46 (Co(en)J3+

Fig. 1.45
for
and D,1 ~~i_nt groups are possi~le candidates
In other word , molecules belonging to C 1, C,, y and
ple, [Co(en)~] 10n belong lo 0 3 pomt symmetr
exhibning chira lity (opti cal acti vity). For exam
it i\ optically acti ve (Fig. 1.46).
w~ich Molecule with ans,. axis is optically inactive.
Although, in mos t or the case s (mo lecules), s,, axis, it
show opltcal If the molecule doc!'> not possess
belong 10 the chiral poinl groups (C 1, C11 , D,) s
and 2 = i. s
helong to . C2 muy bi! optically al'tivt. 1 = 0
activity but in rare cases like H20 ~, which . .
~o th~ tac1_
Point ~ym metry, i~ opticall y inacti ve. It is du~ nmp osab le on ti. Allenes
ll Its mirror imag e to be supe
that free rota tion around 0 - 0 bond will perm thumb
Cum ulen es are also optic all y inac tive beca use they possess S4 axis of symmetry. So, the
and S beca use
abse nce of S,1 axis of any order (including 1
rule for a com pound 10 be optically active is
axis of symmetry.
S1 == cr), how ever, molecule may contain C11
 30 Sn 1M ET RY AN o G EM ISTRY
ROUP TH EO RY IN CH

Symmetry and Di. pole Moment I t- · ·

I a rnu e dip ole
ss
y mo ecu e. posse
Th e kn ow ! c ct gc o t- sy mr nc t I·Y ·is• a Iso lie lrl·ul to dc ll.:r rni ne w he the r an it
-
11
.
certa.mly ha ve a
ps, w1
in o rn e n or not ll .,
t .
' m o 1,ec_u 1e .hd on gs
to (' . c. c111· or c- •· po int gr ou
• • •
d C gro ups '
de t~· •ttc Jip . · 11 .'
alo ng the C ax is 1n the C,, anI
ol c 11 , 111011Ic11I wi ll he I n_v
th centre
tn Hl mc nt. I lie dip ole 'llll g ro . ~J11ear mo ec u es wi
, ·,
'po II
.
· -11 , -· .. ilc hc lnn gs 10 c up
- d. I nt
Wh .
cr ea s1 1 lic ·s i11 I l <.: LtIrn1 pla ne 11 1111 i lcn
r 'mo lec ules w h.Ic h h av e ze ro ipo e mo me
l. an d lin ea no t
ot :,,v- m me tn- (') 1 11 1a , l' 1e ru dip \llc 1110I11cn
1 ' '··1
ule s, the ab ov e sta tem
en ts are
n- lin ea r mo lec ·
m us t c1..mtai n ce n tre
or sv 111111ctry (i) but for no nl ot· CC l4 is · ze ro b ut rt . d oes no t co nta in ce ntr e
· . ole mo me
· t n. I :-, Ilo Ill g on d . h1 r cx am rlc . the dip
ne-ce .-. :-.
ot :--:-, n1m et r:-, .
Po in t G ro up s
of M ol ec ul es Be lo ng in g to Va rio us
Ex am pl es
So m e In te re st in g F
Cl

H
Cl
H
H
I H
H
H

/ /\, F
Cl Cl Cl

(S}(= E)
Cl
-l~ D
r~ J(J
- - Cl Cl
Cl
@;]
co co co
~ / // co
o c -- c ,- -- -c r- -c o
c f \o ot1
2-
2
PtCl s-
Cr2(C OJ,o
(n- ele ctr on del oca lize
d) (staggered)
[§ J
@;]

© Fe
I

Sta gg ere d ferrocene

[§;]
Fig. 1.47
 f.NTRO DUCnoN 31

t the planes), T1I (T plus i), 0

In special point groups Like Tu_,,· Oh and II, • we also have T (Td withou
) point groups, but these point group s have
(01, less the centre and planes) and I (6C5 + 1oc3 + 15C2
cal compounds.
been omitted due to their little significance in dealing with chemi
ules and their point groups of
Table 1.4 given below shows the examp les of common molec
interest to chemists.

Table 1.4

Molecules Symmetry Elements No. of Symmetry Symmetry Point

Operations Group

CHCIBrF, CH3 C H (OH) COOH , E J C1

SiBrCIFI

E + C2 2 C2
HP2·
Gauche CHFI- CH2Cl,
trans- 1-2-dibromocyclopropane,
1.3-dichloroallene

HOCI. HCOCI , CH2CIBr, E+ CT 2 cs

POBrC 12, 2-Bromonapthalene
E+i 2 C;
CHFCJ-CHFCI (staggered)
E + C2 + 2crv 4 c2v
C8iCl 2, SO2, H2O, CJF3, CJO;
BClF2, cis-CHCI = CHCI,
SiCl 2Br2, Pyridin e, NO2 ,
2-butene (cis), Cyclohexane
(boat form), C6 H5 X, C6 H4 X2
(ortho or meta), Cyclopentadiene,
cis-[Pt (NH3\ CI/+,
cis-[Pt (NH3)2Cl 2], cis-H p2
E + C3 + 3crv 6 c3v
NH3, POCl3, CIO3, so;,
CH3X, CHX 3, S20 ;~
PH 3, PCJ 3, PF4 Cl, quinuclidine
E + C4 + 4 o-v 8 c4v
AX5 and AX4 (square pyramidal),
SF5CI (octahedral),
Mn (CO) 51, JF5 ,
[Co (NH3)4 C1HpJ2+-

HBr, NO, HCN,

E + C.. + oo(,v
00
c...
(infinite)
CO, HCI, OCS,
Np, SCN-, CIO-
E + C2 + 0-1, + i 4 Clh
1rans-2-butene,
lrans-H2O2
lrans-CHCI = CHCI ,
._glyoxal
-- -- -- -- - ~ - - - - - -- .. - - - - - - - -- -- - -
 Iii

-32- -SYM-- -
METRY AND GROUP THEO RY IN CHEMISTRY
- -r - -6 - - -- -- -
H _1B03 (Planar) - - - - - - - r-
E-+-C - -----
+ a,, 3CJh
bicyc lo (3.3. 3) unde cane.
I .'.t 5. trihy drox y benze ne 8
E + JCz (mutu ally l.) + S4
C yclooc ta tetrae nc.
coinci<.lcnl with one Cz
Biph enyl (twis ted ). + 2<J,1 (passing 1hrough
A llene . spiranc.
S4 axis ) DJd
12
E + C + 3C2 l. C3 + S6
J
Cyclohex ane (Cha ir form ). (coincident wi lh C3)
C 2 Hc, (stag gered )
+ i + 3<Jc1
P ~o t- tstag.gered )
S p t (s1:1ggered ) 8 D2Jr
E + 3Cz + 3<J +i
N 0 (Plan ar). B 2 H6 •
2 4 1_
, )2 Cl 2] , PlzCl 6,
trans- [ Pt (NH_
pnra -C H X • CH
6 2
4 1
=
CH 2 , Anthracene,
Naphthalene. Cumulene
(CH:, = C = C = CH2) ,
Pyrene 12
E + C + 3C2 l. C 3
3
PCl5. BFy co~: S03, + 3a., + a,,
NO j . ptanar-tribromobenzene,
C:,H (eclipsed). DAB CO
6
I A-diazabi cyclo (2.2.2) octane),
Borazole ([norganic benze ne), CH3 16 D4h
PrCJ ~: Ni(CN)~~
+ 4cr,, + cr,,
1rans -[Co( NH3) 4C12 t, + C 2 and S 4
square plan ar AX4 ,
(coin cident wi th C 4) + i
Cyclobutane. Xef 4
[AuCl.ir
E + C · + 5C2 1- C5 , 20
C
5
f15.
ferrocene (eclipsed), 5
Cyclo pentane, LF7 + 5cr,, + cr,, + C2
and S (coinciden t with C5 )
Rulhenocene (eclipsed) 5

c6 24 D6,,
Benz ene, dibenzene E + + 6C2 1- c6
Chromium (eclipsed), + 6cr" + cr,, + C2
Coronene and S (all coinc ident
6
with C6 ) + i

I 8eCl2 • Xef2 , CO2, E+C 00

+ ooC 2 _l_C 00
D"""
.
00
+
NO,, CH = CH H2' Cl 2' ' + oo<J,, + (JI, + i

I Br2, HgCJ 2. N;

CH , CCl4 , SiCl 4 , P4 , E + 3C 1 + 4C + 6cr 24

4 - 1
/7..n (CN)i , Ni(CO)4 , + 3S4 (coin cid.e nt with c )
, 2
S0 4
1 ,
, P0 , CI0 , adamantan e
- - - - 4 _ _ _ _ _ _ .J~ - - - - -
4
--
2
__ __ _... ___ ______ __
 b,rraoot·CTJON 33

, -- -- -- -
5ft. _[Co (\~ JJ ~ -
--- ~ - - - - -

E ~ J C ..1 ( mu tuall y .1)

- - - - -r- - - -

48
- - -

o.
- - -

PtCt·L~ PC1 ;. ~ 6: + 4C_~ + JS..1 and JC:

I Cuba ne. Ta.Ser,;. (coin ciden t " ith C..1>
Lr ,5 - 6C: + 9cr + 456
(coin ciden t " ith C_.) + i
120 1,.
[\lo( C~ ), J..!-. B r:>H~: E + 6C, (coinciden t with S 1o)
(dod ecab oran e). •IOC, (coin cidem with S6 )
dodecahed.ran e ( CH)20. +1 5C T 15cr + i
Fulle rene -Cw
I
I Spherical symm etry
00 K•
Free Atom s

their sym metr y

Ye pow er ro clas sify the mole cule s inro
Stud ent may now exer cise their imaginari sym metr y elem ents
metr y of the com poun d by know ing the
point grou ps or dete rmin atio n of the sym
present.
sy11v11erry
clas s(fy rhe .follo ll'ing mole cule s imo rheir
Exa mpl e: Der enni ne the s-ymm erry or
poinr groups.
(a ) 5 8 mole cule
(b J C ffloh e.wn e (cha ir fonn )
( c) Ocra cyan omo lybd are ( /\ ,
(d) CYc looc ra,e rrae ne
(e) Dich loromerhQJ1e
(f) B(O H) 3
(gJ IF,
(h J Spiropem ane.
s. The
is a zig- zag clos ed chai n of sulp hur atom
Solu tion : (a ) 5~ mol ecul e: The mole cule ).
w as irs top- ,·iew and side -,·ie w (Fig . 1.-.J.8
~trucrure of the mole cule is show n belo
i.e .. Td . O".
does nor belo ng to spec ial poin t grou ps.
(iJ First of alJ we see char the mole cule
I.
n
D ~r. . C x \ . etc.
e. It is clea r that
<ii) Then \\e find wea ther any prop er
axis of sym metr y pres ent in the mol ecul
gere d pair
pass ing t11rough the cent re's of the st;ig
a prin cipa l axis of sym metry C..1 exis ts
,·iew of the mole cule ).
of .,quare:, of sulp hur atom s (See the rop-
thes e lines .
there in the mole cule beca use if abou t
fiitJ The pre, ence of ➔ C _ C~ is :ilSl) ➔C ~ sht)Wn in !he
mole cule is roca1 ed b~ e get indis ting uish able cont igur a1io n. (
uw-- . \\
figu re ).
thrn ugh a pair
(i1•J Four a d plan es of~) mm et~
aho e xists in the mole cule . The se plan es pass
eithe r o f the squ,1re plan es.
of :,uJphur atom s :,itua ted diag onal ly on
:Lxis is also pres ent.
<i·J S axis of !>) mme lr). coll inea r with C~
11
 34 SYM METRY AND GRo t il' THEORY
IN OWM ISIR Y

Top-view

Side-view

Fig. 1.48
+ 4ad , which
So, now we have, E + 1C4 + 4C2 l. C4
.-.:o other elements of sym metry present.
clearl: rndicates that the molecule has ~
point symmetry.
n below
CJc lohe xane (C H ): The stru cture of the molecule in chair form is show
(bJ 6 12 n, these are axial
three pointing up and three pointing dow
(Fig. l.49). 6C-H bonds are parallel to CJ> d equatorial:
rem aining 6C- H bond s are nearly perp endicular to C3, these hydrogens are calle
bonds. The

Cent re of symmetry (i)

Fig. 1.49

l
,
 INrR llDl'C fl<lN 35

belong to any speclal point group.

(,) First of ell. the molecule does not
the centre
11
tii ) .·\ C_. a:\is f s~•11111w1ry is fll\.'Sl'llt
i11 1h1.· molcrn lc (as show n) passing through
ball
we ha ve
11 f tht· 11111k1.·11k (the sy111111L·1ry of' rllL• mnkL·uk will he umk rs1ood better if
uriun of 120 ° abo u1 thi s C 1 ge nera tes
:111d slid . 11h,ckl 111' lhl· 111ukr uk ). Roi ·
i11LI is1 i11~u isha hk c1111 fi gurar iun .
the middle
tiii) Alsn . .;c·~ l. C,. fH\.'sr111 in lhl' 111u
kcule. These C, axes are passing through
-
nf rite 1wo opp1>silt' C- C bonds.
planes.
tii ·) \\'c 11hst•n·c 1ha1 passing t11ruugh
1wo opposite carb on atoms. are the Jcrd
inversion
t 1·) .·\ L'L'lllr\' nf symmetry (i) is also
present in the mol ecul e (as sho wn) because
uishable configuratio n of the molecule.
thrnugh this l'l'nt1\' results into an indisting
ording to the
t 1·i) Thcrt'li.m.·. rile molecule contain
s E + IC •1 + JC-1 ..L C -1 + 3crt1 + i. Acc
p.
e belongs ro / D_i., / symmetry poin1 grou
scheme shown in rJ1e fl ow chm-r. the molecul
m geometry
omolybdate (IV) have the square antipris
t,·) .\lo( CN )~- _. In solutjon phase. octa cyan
:1~ :-hlm n in Fig. 1.50.
N
Ill
C

I
I
I
I
I
................ \,'
..... ......,......,,..
,.,,,..,,,.

N=c ~ ~ ~ 11 Mo,
I \ ' ' .._
I I '
I I
I I
I I
I I

I
I
I
I
I C
C2, ad Ill
N

Fig. 1.50

(i) The mol ecule (ion) does not belo

ng to any special poim group.
to the plane of
(ii) A C4 axis of symmetry pass ing
through the Mo atom and perpendicular
the paper exists.
(iii) 4C2 J_ C4 are present as shown
in the Fig. 1.50.
plane
are also present. The ion does not contain Oh
(iv) Four ad planes alon g the four C2 axis
.
o{ symmetry.
C + 4C2 ..L C4 + 4crd. It implies that the
ion has IT&;J
(v) Therefore, the ion contain s E + 4
the same symmetry.
poin t symmetry. TaFt ion also belongs 10
 36 SYMMr: 11n ANn G1u 1up T1tHlRY IN C'1111MIsr n v

(d) Cycloo crarerm ene (Cx Hx): Although gcncrall: we draw the
s tructur~ of _C 8 H8 as Q, but
Fig. 1.51 .
the ac tual three di me nsio nal config uration is o f Tub form as sho wn be low in
(i) Mo lecule does not be long to any special po int group.
(ii) It has a 5 ax is o f symme try as shown and colline ar with
this, there also exists a
4
C 2 -axis o f symme try.
(iii) 2½ ..l c (coll inear with S4 ) are also presen t in a plane perpen
dicular to S4-C 2-axis.
2
bonds and passing
(iv ) Two a d planes (vertical planes) of symme try bisectin g opposi te double
betwee n the C' -axes are also present .
2

Fig. 1.51

( v) a" is absent.
(vi) Therefo re, the symme try elemen ts presen t in cycloo ctate traene
is E + C 2 + 2½ ..l C2
I
+ 2ad , clearly ind icates the mo lecule belong s to 0 2d / point symme
try, student may
verify that twisted biphen y l a lso be longs to the same point group.
to sp 3 hybrid ization of
(e) Dich/o romethane (CH 2C I2 ) : Accord ing to VSEPR theory, or due
in Fig. 1.52.
carbon atom, the molecule has tetrahedra l geome try as sho wn be low

Cl

Cl

Fig. 1.52
.
(i) Now, the mo lec ule doc s no t be long 10 T " sy
are similar. · mme try as fo ur atoms auar he d 10 carbtin
110 1
 (/1) Wi · 11h111·1v1• 111111 111 · , 1111 111 111 11 y11111w11 y 111 111 1·1w111 1111 lw 1,11,l,·11111· wfii1I,1 1111i1.1•11 1h,1,1w fi
l11111d11 1111Hln1. 'I 11111 ( '1 P1 tl w 1,1dy
11 11 • 1·111 hon 11111 111 11 11d hl111·1 IN 111,· ( 'l ( · ( 'I it111I ff ( ' 11
11 x11• 11 f' 11 Y11 1t 111'11 y p11 •1,1·111 111·11• 1111d llll'l !'lnw , II /11 fl w ,,,1 111•lpsi
l II X IH 1,I ►1y11111wt1 y.
u l Hy11111w11y 111 1· 11111 111 1· 111:111 .
(111 ) Any 111 111 •1 _)( ', 111 ·q w11tl1nil111 111 tllf' pd1111p11I 11x 111
11 ( · 11 lu,11d'!
(11 ' )'l\vn o , m,· p11·s1·111 wll l1'11 1111HH1· ~ 1l11111, 1,1 fi ( 'I ( ' ( 'I 1111d
( l' ) l'lu,., . \\/\' lluw H I ( ·., I .~n ,, 1111d llll' rt' IIIII', Ifie 11111k c11 lc 1>1·11111 /(ll ,,,r' / j 111111,1 V flJll J',
111t· Hy111111cl1 y
,-.;1wh·111 111 11y v,·iif'y 111111 ryl'l11p1·11p\·111· 11IH11 11111-1 Ilic 1-111
(/) /i111i<' odd, II (011 ) 1: 'f'llt' 111111111 11111111 iM
.l'i hyh,idi:t,t:d 1111d llil'fl.: l111 c, 11111lec; 11 h; h:14 ;, pf:111:11
):1'111111'11\ .t:-- ~,1(1\\1 11 Ill f.'ig. I ..'U.
yi ,11111.:1, y.
(/) '1'111:-- 11111kt 11lt.: drn·,<1 11111 hclo11 g 1111111y Mpcci11I poi111 M
(ii) l'lh· 111ol1·c 11lt l't111111i11s 011c ( ' 1 axis of'
,<1y111111clry paMHi11,:
of' ' IJ - - 0
11111111 /,.:11 llit.: ll11r1111 a111111 1111d pcrpc 11dic11l11r 10 11,c plu11c
Ille 111ukl'lil1·. H'-. / \
0 H
(iii) No ( '2 I (' 1 1:x isl.<1, llicrcforc. docs 1101
hclon g lo D gro11p Fig. 1.53
sy1n111c1ry.
(ii') '1'111:rL· l'xis l onl y 011c plane . i.,·.. a1,,
which is rnolcc ulc.1r plane pcrpcndil:u lar Lo the
pri1ll'ipal ax is of sy111111c1ry ( ' 1•
lcs 1ha1 molec ule he longs to ~
Tl1crl'l'urL'. Wl' ha ve I i 1- (' 1 + CT1, , wh ich clearly indica
~) 111111L'l1 y poi 111 gro11p.
gw111clry of the F
(g) II \: Acco n li11g lo VSl-:PR lhcory. lhc
mnll'r uk is sq11are r,yra111idal as show n in Vi g. I .54.
(i) Molc rnk docs nol belon gs lo any special point group. --- -<> --- --- - F
One C',1 nxis of sy n11111:1ry passin g 1hrou gh 1he vertic
al
(ii)
I-' I bond and perpe ndicular lo the square plane ex ists.
(iii ) 4cr,'. arc also prcsc:111 bul no C2 axis is
there.

Therefore, 1hc cleme nts prcse nl in lhe molec ule arc E

+ C4
+ 4cr, indica ti11g 1he [ c.,l
poinl symmetry of Lhe molecule. Student
etry.
ran verify 1ha1 SI\ Hr al so hclon gs 10 1hc same symm
-------.:,/
(/1) J/Jim w11t<111e (C_ ~I 11J The structure of the spiropenlane F " - - -
hybridi zed. Fig. 1.54
",hown below in Fig. 1.55 in which each carhon is .\ 'f'':I
(i) The molec ule docs nol helong to any
special point group .

(ii) Thi :-- molec ule cunla ins a C2-axis of symm

etry as shown in the figure .

(iii) Also, there arc 2cr,, prese nt , which passes

through the C2-axis.

iii') Therefore. we have E + C2 + 2cr,, which

show s that the molecule belon gs to es:=J point
group .
 Tmm kY IN CHliMIS rRY
38 SYMM ETRY AND G ROlJP

H H

H
H

or

H
H
H
H
Fig . 1.55

T CO NC EP TS
SUMMARY OF IMPORTAN prc~eni in a
1 of ,;ym mel.f)' elcmenls
•
can bl! described by a sc
(i) Sy111me1 ry of mo kt:u les
mn k cult-.
me try d cmi:111 s an
... .. t d opera
d them. ·1ss oc1,1 e
tio ns are given below :
Symbol I
{ii) T he li ve sym
Operation
Elemt'llt

(a) ldt·111it y
No ope rati on.
Ro tati on abo ut the axis by
an
E
Cn (where n = 360/0) I
(hl A , i$ of sym me try
e is angle of rotation I
ar1gle 360°/11 .
(proper or Principal)
Reflec tion through the plane.
(1
I
(c) Plane of S) mm etry i
re of sym me try
Invers ion (or reflection) I
(d) Cem
thro ugh r11e centre .
Rotatio n abo ut the axis by
Sn (n = 360 /0 ) I
metry
(el Improper axis of sym
an ang le 36O/n foll owed by
(Ro1alion-retlec1ion axi s)
refl ection through a plane
perpendic ular to the axis.

e with putting a cap over the

m. i. e.. E. en. a. i
metry operati ons are sam
Symbob of sym
and S•. ate only one
sym me try op era tions. E. i and CJ each ge ner
aus e C: = E.
gen era tes
Each symme1ry eleme 111
( iii)
,Lx is of sym me try . C,, gen erates (n - l ) operatio n bec
operation. Proper ide ntical .
try ope ra1 ion s !?en er Jte d by C f ,1I and S IJ are alw ays
In J When n is odd . symme ber L1f
operations are equ al to num
'-'

ups . num ber of sym me try

11 J For c,. C, and C, poinr gro and two for Cs (E + CJh ) an d
one fo r CI(El.
.. two for C (E + i )
')m meuy ele ments. i.e
var ious syn un etry pc.1int
I

111 5 = C, = i = C,. To 1al symmetry opera tfo n for

> , =<1 =C, ~nd S, cr,,
le 1.5.
group~ are gJ\ en bel ow in Tab
 INTRODUCTION 39

Table 1.5

Point Groups en Dn Sn (11 = e11en) en,, or Sn cnv Dnd Dn1t

(n - odd)
Total No. 2n 2n 2n 4n 4n
11 n
of symmetry
operations
Symmc1ry including
Element~ Identity

l l 1 1
E I I I
n- 1 n-1 n-1 n- 1
C,, 11- l 11- l -
- - n n
11Cc l. Cn - n -
l - - l
- - -
t\
- n n n
11cr, na., - - -
n-I . - n (n-1 )
Remai nin!! operations - - (n-I)
I -
etry
(i·ii) Mole cules belon ging to point group shall alway s have an impro per axis of symm
Dnd
axi s will be
o f rhe orde r S 211 • The vario us n oper ation s gene rated by thi s
si2n • s3 s
2n • 5 211 • • ·
211 -
5 2n 1
·

(1·iii) The produ ct of symm etry opera tions mean s

succe ssive ly by perfo rming the opera tions one
after another.
(ix) A molec ule, to be a polar , must belon g to
Cn , C11v or Cs point group s and must not have
highe r symm etry.
per rotati on (S 11).
(x ) Chira l mole cule does not posse ss an axis of impro
(xi ) Highe st order axis is called princ ipal (or
prope r) axis of symm etry. If order s are same . then
atom s is called the princ ipal axis of
the ax is which passe s throu gh maxi mum numb er of
symm etry.
er that each point (or atom ) in a
(xii) An opera tion of inver sion is carrie d out in the mann
then out the same distan ce on the
molec ul e is move d to the centr e of the molec ule and
(for all atom s in the mole cules ) then
other side of rhe cen tre. If simil ar atoms are obtai ned,
the centre of the mole cule will be centr e of symm etry.
<xi ii) C6<{ Fulle rene is trunc ated regul ar icosa
hedro n geom etry and it belon gs to a speci al point
'>ymm etry W.
is the finerm ost aspec t of geom etry.
(xi v) Geometry is the crude aspec t of symm etry and symmetry
derivatives may be know n by the
The ~ym rnetry point group s o f molec ules like A B11
follow ing Table 1.6.
 -
40 SYMMETRY AND GROUP T1tl•.rnn IN Cl ll'MIS'l l<Y

Table 1.6
- . (')ymmetry )
/' oint ( ,rottp · ·
Geometry Molecr,/,• 1)'/JC
- - IJ ,,,
-
Planar AB ,
ABi X C2,,
ABX , Ci,,
AB 1 C i,.
~ram id :.11
AB 2X
C
'
A BX 2 C,

T,I
Tetrahedral AB 4

1X
AB _ Cl,•
A B 2X 2 Cz,

AB 4 D ,i1,
Sqtmre planar
AB 3X C2,·
AB 2X 2 (cis) C2,·
AB2X2 (trans ) D 21,
A

n x
A A
(A is apical) AB 4 C4,.

1nJx
Square Pyram idal

l\
AB 3X c., B - -·B
AB 2X 2 (sy n )
AB 2X 2 (anti)
c_,.
C2,,
!_
B
I --- !
B
I.
B (syn) X
X (anti) 8

X B
AB 5
AB 4 X (apical)
A B4 X (basal)
C4,.
c-1,,
C,

B
~8
3Zr
~A~I 1 ~~I
~A x B B B B
B
X is apical X 1s basal

Trigonal A B5 D 31,
Hipyrnmidal A B4 X (axial) C3,.
AB 4 X (cquitorial) c2,•
Ocwhedral AB 6 o,, Gcomclri1.:s uf mer- and fac -AB X an: a" fol low -, ·
X
X .1 I
AB~X (ax ial ) c4,•

!~ l rw r
A8 4 X 2 (ds) C2,,
AB 4 X 2 (trans) D-11,
A0 1X , (mer) C,_,
AB1X 1 (fac) c,,. / :~
B I B B
/ :~ I
X
I
I I
I
X B
(mer-)
(lac-) I
 fNI l(()l> lln/r)N 4J

. .
Here, now s1udc111ts· llla. y cons1n
1c1 1I
lllo
• , .
dcl s 0 1 lht 11111krnle 1111d l'IIJ oy lhc clear und cr-.u,nd,n J.!
tc ,
_. the symmetry .1 .
'sp ec s .,o.1 molec ules· wJIll: • ·I I , .
1 x:long lo l11g hcr sy1JJ1 netry. lo <.: 0111,tru
<.: r the model ,,
Of · . .
rd plastic lub es· 0 ,· <.1111c1c 111 colou rs •ind 11 YI011 sln1,1gs ol u lcw 111e1er length , iire required · h>r
ha ' · · '
.• d . . lo le IH,lrulc lire cx isle m.:e of 4('7 wh ich fie pcrpcnd1cufar 10 rhc
exa mp Ie, f11 a rea er 1s 1111crcs· tccl l IIHI
. lec ule ha vi 111, sn11 ·tr . .111 11· · 111 gco111c1ry, lhe n rhc rcquin.:d num hcr ol tube'> arc II N
C axis o . •a mo ' c • pns
u hy nylon <,Iring,._ pt.1<,<,in g
. (C' • '1

an urc hook ed ro. 011c ano the r

4 h in Jen ,11)
cu t to um lorr n size (== '.! inc g I
.
a111 the de -~•iI•Cd geo . 111e1ry. Model.~ ol 1he dod ecahedron , t1nd M.juarc antipri,;m
throueh cac I1 lll t)C.. 10 -ob1
·
~
are ~hown be low 111 Fig . 1.56 .

Square antiprism
C2
Dodecahedron
Fig. 1.56
and Cenco-Peterson
ma de bal l and stic k mo dels and foreign made Driedling
Indigenou sly constru cting
rke t but the y are cos tly and therefore, the above method of
mod els are available in ma
y cheaper.
the molecular model will be ver

PROBLEMS
operations?
metry elements and symmetry
1. What do you mean by sym
Hint. See the text. symmetry?
ons are generated by S3-axis of
2. How ma ny symmetry operati Sj, Sj, S~. S1. Sj
erate 2n distinct operations, namely
s (n = odd ) of symmetry will gen
Hin t. Sn-axi
and Sj (= E ) .
2
• • odd n, Sn " -- E.
w that for eve n n, S" = E an d 1or
Sho
3. n

Hint. See the text.

and equal to n/2 ).
4. Show tha t s; = i (m is odd
1

Hint. See the tex t. foll owing obj ects:

axi '> of sym me try and plane of symmetry present in the
5. Iden tify the dumb
h handle (no decora tion), (d) a
(a J a spo

bell.
on,

(e)
(h) butterfly, (c ) a ceramic coffee mu g wit

a tenni '> ball (including the \ea m.\

-o ne colour and no markin gs) ,
(fJ +· (g) fl:)
(h) a pen cil (no nob).
ele me nts.
&cnce of foll owing symme try
//int. Reader may enj oy the pre
(a J a (bJ a (cJ a (d ) C.,,
, C2, a, i (j) C2 (g) C 3 (It) C...
 Ii

42 Sn~IETRY Aso GROL'P T HEORY L"I CHEMISTRY

6. Sh ow that (for s~ II =odd) =a h.

Hint. See the text. molecule
is the procedure lo classify a
7 · What ~o you mean by symmetry point gro ups? Wh al
according to its symmetry? a molecule.
the flow cha rt for de1 enn ination of the poinr gro up of
Hint. See elemenr i.
. where II is even have the
S. Show that for Cnh gro ups pec1ively for even II and
1io n (C, ) cha nge s x and y to -.r and - y res
Hi nt. (Cn)n/2 = C, . this -0p era 1112
e, cr;, (C) " = (C11 ) a;, =
12 i.
nge s-.: to - z: so. we ha~
cr,. cha molec ule ? Find our
me try ele me nrs and sym metry operations exists in NH3
9. How many sym
molecule belongs?
the p-Oint group ro which this lec ule.
me nts and sym me try ope ration s are presenr in the mo
ele
Hi nt. FoUowing symmetry a pyramidal geometry in which
N a1om
VS EP R the ory . has
The NH 3 molecule. according has a C3 axis passing
to
;e N- H bon ds are at an angle of I 07 °. Molecule
is at the apex and tbn ms. Abou1
cen tre of equ ilat era l tria ngle contai ning rhree H ato
through the atom N and the °. we get indistinguishable con
figuration of the
lec ule is rotate d by 120 , i.e.. c!.
thi s line if the mo rat ion s are genera ted by this mo lecule
1.5 7. Thr ee ope
molecule as shown in Fig. ° and 36 0°. respectively. He
re Ci = E. Henc :.
Ci and cJ
signifyin g rotatio ns by 120 °. 240
cJ
~ and (= c_~).
there are 1wo distinct C3 operation s. i.e.. C_
ing the line
rain ing N ato m and one of the H atoms and bisect
Reflection in a plane con h cr,. will
ms , i.e. , a ~. a ~ and cr~, as shown in figure bel ow, eac
between remaining rwo H ato
e, cr2 = E.
generate one operation becaus
C3

H1.\E~
N •

I
I
I
I
I Cl
3

Fig. 1.5 7
 ..,
lNTRODUC.TION 43

six symm etry operations and five symm etry

So we have E + 2C_1 + 3a .,. and therefore,
to the now chart (given in the text) , the NH3
cle me nts arc prese nt in the molecule. Acco rding
gr~up.
mo lec ule belo ngs to / C1,, ) symm etry poin t
the following molecules (ions ) and assign them
10. Ide ntify the symm etry elem ents prese nt in
:
thc po int gro up (or deter mine their symm etry)
CJBr (d) cis-2 -bute ne (e) trans -2-bu tene
(a) Py ridin e ( b) etha ne (stag gere d) (c) CH 2
(/) trans -di chlo rocth ene (g) Cycl open tadie nyl
i~n (h) cis-[Co(en) 2C1 2 (I) Cycl ohex ane (boa
t t
(m) Cu(N 02)~ (n) Cycl opro pene (o) Benz
ene
form ) U) Xe02F2 (k) TeC14 (/) Cycl opro pane )
(p) Allene (q) O=C =C= C== O (r) Whit
e phosphorus P 4 (s) C6() (t) Ferro cene (staggered
1 (w) 1,2,4 -trif luor o benz ene (x) HF
( u) Fe rroc ene (ecl ipse d) (v) CDC 3

(y) PtCl !-(z) @ -- @ (perp endic ular phenyl ri'J\gs).

e
various symm etry elem ents prese nt in the abov
Hint. Stud ent may draw the geom etry and find the follows:
to their symm etry as
given mole cules and class ify then acco rding
(e) C 21, (j) C21, (g) D 51, (h) C 2
(a) C2v (b) 0 3d (c) Cs (d) C 2v
D21, (n) c2v (o) D6h (p) 0 2d
(i) c 2v U) c 2v (k) c 2v (/) D31, (m)
(u) D5h (v) c3v (w) c 2v (x) c ..,.
(q) D..1, (r) Td (s) Ih (!) D5d

(y) o" (z) 02d

etry
the CH4 mole cule and show that it has 24 symm
11. Ident ify the symm etry elem ents prese nt in
operations (in total).
Hint. See the text.
relations of oper ation s are correct:
12. Show that for H 20 mole cule, the follo wing

(i) a v (xz) · C2 = av (yz )

Ui ) c 2
. & (xz) = &" (yz )
11
A

(iii) a II xz · a" yz
A ( ) A ( )
= C2
carry out oper ation s and then see the equa
lities.
Hint. To verify the abov e relat ions, we have to g symm etry
v poin t grou p will have foll owin
So for H 0 mole cule, whic h belon gs to C 2
2
operations . (Fig. 1.58).
(0 z
+
crxz
I I
, ,'
,,
I I
62 ► o ~. (xz) o
0 ---- -- -► X
Rotation / ~ Reflechon/ ""'
H/2':"' ""
Ha Ho . Ha Ho
0 / I
,' : Ha
,' C2

Fig. 1.58
 44 SYMMETRY AND GROUP T IIEORY IN C 11t:MIS'I HY

Hence, 0 1· (xz) · C2 = o,.(_vz) is ve rified .

(ii)

~v(xz)
0 ►
Reflection / ~

Fig. 1.59

H ence , a~ ,, ( XZ ) • V;., y ( yz ) = C2 is verified.

In above operations, after two operatio ns , a config uratio n is resulted, (shown by small
straight arrows) which can be res ulte d by a sing le ope ration (shown as large curved arrows)
and hence the relations are justified.
NH molec ule is pyramidal, but had it be a planar, what would be its symmetry.

,
13.
3
Hint. In py ramidal config uration, of NH 3 , it has E + C 3 + 3av so it belongs to [g point group
but if it is planar, the n it possess E + C3 + 3C2 .l C3 + 3av + a" a nd therefore it belongs
to @;J point group.
14. If centre of symmetry (i) is added to the following po int groups, then find the resulted poim
group.
(a) 0 6 (b) S3 (c) C 4 v (d) C 2 (e) C 3 (j) Td (g) if ah is added to C 4 v.
Hint. (a) If centre of sy mmetry i is added to 0 6 the n the point group
resulted wil l be 0 61, as s ho wn in the Molecule of Benzene.
(Fig. I .60) (b) C6 1, (c) 0 41, (d) C 21, (e) Addition of i to C 3 will
bring th ree C2 axes and 3ad. Then sy mmetry will be 0 3d (structure
will be trigonal antipris m) . (j) As disc ussed in the text that in a
reg ular tetrahedron, ato m occ upie s oppos ite corners of two
opposite faces of a c ube. If we add i to T d, then all the atoms after
inversion throug h the centre must coincide with equivalent a toms,
which implies that the vacant corners of the c ube will also be
Centre of
occupied by same atoms . Then in such situation, molecule will symmetry ,
have c ubi c struc ture and symme try will be I . (g) Addition of a Cs
to C 4v produce four s ubsidiary axes and a a1 ."Then, the symmetry" Fig. 1.60
will be 0 4". '

15. If a mo lecule consists o f four atoms has a C J ax is pe rpe ndic ular to the m o lecular plane and
a l!->o, the mo lecul e has I a" and 3a,,\·. It also has SJ and 3c2 .l c . Find the symmetry of the
mo lecule and its struc ture? J
 IN rROll l1(7 ION 45

Hint. Molecul e is of the type AX 3 and ii belongs to o3" symmetry point group. Its structure \\,ill

be trigonal planar as ;)A -X

llc.
following objects (o) a 1es1 tube (/, ) a pipc
16. Determine the point symmetry or the
(c) scissors (d) a glass stoppered bure
tle (e) a pair of tongs.

Hint. (a) C..,,, (b) C.,.,. (c) C2" (d) C1 (e) C_,..
and
etry perpendicular 10 the plane of' the molc cuk
17. If a molecule possess C4 axis of symm sym metr y
axis and 4C2 axis then lind the point
also have 4cr,, and lcr". The molecule has S4
and struc ture of the molecule .
min e till'
in the text and using the flow chart 10 deter
Hint. From the desc ription of point groups p.
observation possess 0 41, symmetry point grou
symmetry point group, the molecule under g
therefore , if the molecule is of' AX 4 cons istin
Here. number of atoms have not been given, AX then
ar, but if molecule is of the type •
five atoms, then struc ture will be square plan
6

structure will be square bipyramidaJ.

and if' the.:
18. In a meta l-ligand complex ML6, ligan
ds are at the corners of a regular octahedron
the
sym metry of the resulted con fi guration after
following distortions are made, then find the
distortion s:
(i) if axia l ligands along z-axis are pulle
d equally

(ii) if one ligand along z-axis is pulled

(iii) if two ligands alon g x and y-axes
are pulled equa lly

(iv) if three ligands are pulled along the

trigo nal plane

(11) if sets of three ligands are pulled alon

(vi) if a set of three ligands only of a
the other trigo nal plane.
Hint. We know that ML6 has O;, point symmetr
equally, then the complex will have I Ciz
situation the com plex belongs to
g the two trigonal planes
lld 10
trigonal plane are rotated and brought para
pulled
y. Now, (i) if axial ligands along :-axis are
this
) + 4C2 l. C4 + 4cr1, + I er,, and hence in
[§ J point symmetry (Fig . 1.6 1).

Fig. 1.61
structure will be as shown in Fig. 1.62 .
(ii) If one ligand along z-axis is pulled then the
alon g :'.-ax is but 4C2 l Ci:: ) al'l' ahsl'nt.
Jn this situa1io11 the complex has a C,1 axis
Therefore , ii belongs 10 / C'.11, j point sy111111etr
y.
SYM Mht RY AND G ROU P T HfO RY 1N CIIE MIS mv

L~r/ L(n
L(z)

L/ i~L(~ L
I
I
I
I
C4
Fig. 1.62
one C 2-axis of
this situ atio n, the stru cture is sho wn belo w in Fig. 1.63 . It has
(iii ) ln betw een LML
g the C2 -axi s bise cti ng the ang le
symmetry and 2cr11 planes, one alon
ngs to ~
led L ) and othe r hav ing fou r ligands in xy plane. The refore, this belo
(pul
point symmetry.

L~I/ LM
L(z)

(~C,
L/ i~ L
L
Fig. 1.63
Fig . l .64 . Thi s
this c~e , the stru ctur e of ML6 will bec ome as sho wn be low in
(iv) I n .
sym met ry and 3 <J s, th e refo re, the po int sym metry
con fig uration possess a C3-axi s of 11
. ,r7
will be ~

Fig. 1.64
 I NTROD UCTIO N 47

n below in Fig. 1.65.

(v) The struc ture of ML6 in this situat ion is show
H~re, this struc ture posse ss I CJ + JC2 J_ CJ + Jcrd
and there fore, it belon gs to / D 3c1 I
point symm etry.
L ..::--- - - -~ L

L- - - - - _ _ _ , , L
Fig 1.65

(vi ) Jn this disto rtion , the struc ture will be as

show n below in Fig. J.66.

Here, it has JCJ + 3C2 ..l CJ + 3crd and one ah. There fore, it belon gs to ~ po int
symm etry.
L - - - -- ~ L

L
Fig. 1.66
ound is relate d? What is the symm etry
19. How docs symm etry and optic al activ ity of a comp
h of the follo wing mo lecul es are optic ally
criterion of a mole c ule to be optic ally activ e? Whic
aclivc ?
(a) Spira nc (b) Allen e

H'TH
Br Cl Br
(J) (g) H - ; ~H
Br/ -
H
H"lilt. y inac tive whe reas mole cules not havi n o
Mole cules with a S11 -axis of symm etry are optic a ll
if we ana lyse rhe abov e g iven m o lecul et
S,,-ax is sha ll be optic a lly active . With this crite rion,
(d) inac tiv e ( e) in activ e (j) acti v~
we _find th at: (a) in ac tive (h) inac ti ve (c) a c tive
(x) inacti ve.
48 SYMMF.I RY /\NU GROUP TIIEORY IN C11EMIS m
Y
W. hat· is· the ,·eI·Jli·on betwccn symmetry
and
di po le moment o a
20. di po le m oment f t m o Iecu Ie.? ExpIam the zero
of the 11111lccules lik ·
To deter m e. CH,, CO , and ethane (S
ine th e sy n,mc trY po aggered).
int group of a molecule,
Hiut. the fo llo wi ng flo w
chart may also be
Stallo
fo 11we
ingd.from the top (m
ol ecule), one ca n fo
llo w this ch art and
reach to the point sy
mmetry
mentioned in ~q ua
rc .
START

Is molecule L- -_N_o
Yes _.
linear?

Fig. 1.67

oCJCl
 2
G R O U P THEORY

GROUP?
2.1 WH AT DO WE ME AN BY A
into symmetry point
sified on the basis of symmetry elements
\\ e ha\ e seen rhat molecules can be clas atics
t grou ps are also mat hem atic al grou ps. Group theory is a branch of mathem
p-oup:,. These poin e the entities are
h a grou p is defi ned as "a set of enti ties that satisfy certain conditions". Her
::: "hic called the order of the
group and total number of members is
.:a.led the member (or element) of the ain symmetry
by h ) . It is inte rest ing to note that all molecules which belong to a cert
;re .. p I deno ted triatomic molecule .
metry operations. For example, in a bent
point group have the same type of sym rdle ss of their nature.
.-iB:. the symmetry point group is 2
C ,, and therefore, those molecules, rega
r these symmetry
belo ng to C , poin t grou p, wi ll hav e same symmetry properties. To disc ove
11.hich hem atic al groups and
so it is essential to know about the mat
2
properties. group theory is very useful,
their propertie s.
of elements
A group in a mathematical sense is a set The symmetry operations which appl y
to
ted to each othe r by cert ai n rule s. The se rules
,. n1cn are rela a particula r molecule collecti vely poss
ess
are four in numbers. namely, closure,
identity, associativity p.
the properties of a mathematical grou
The 'ele men ts' here , need not hav e any on sym met ry
and reciproca lity. Gro up theo ry app lied
ry, in gen eral, is applied
Ph),ic.:al ,ign ifi canc e and the theo elements is calle d an algebra of geom etry.
to use sym met ry
t<J ab,trac.:t groups. Our concern here is
) of a molecule as
'Jperation, (not the ,ym metry elements
that to determin e
element\ of the grou p. A-; we have seen
th t ,ymmet ry of a molecu le, the geometry of a mol ecule is ry
see that gro up theory can be Symmetry operations (not the sym met
rJur direc t conc ern and we will p.
elements) are the elem ents of a grou
ry. The alge brai c
c.:on:idered as an algebra of geo met
metry ope rations,
ma~ipulatiom, wil l be done usin g :-.ym
Whic h h·ave thcir · own operator algebra.
this set is said ro
ve a set of elements A, B. C ... then
Let u, come to the point that ii' we ha ents :
1
ema tica l grou p ii' fol low ing rule s (conditions) ,u-e obeyed hy these elem
orm a math
49
-
so SYM.METRv AND GR o UP T HEORY IN C HEMJSTHY
s t be an ele me nt of the
U) C los ure Rule: Th e pro duc l (co m bin alio n) o f any two ele me nts mu n must
n the res ult o f this com bin atio
ir lwo c lc me nls a rc co mb ine d, the
gro up. ft m ea ns that inv olv e add ition,
mb er o r lhe g rou p. In gro up the ory, com bin a ti on m ay
a lso be lhc me e in o ur case of_sy~ etr y
mu l lipl ica tio n, di vis io n in the a lge bra ic term s, but her
s ubt ra~ lio n. com bin atio n of
ule , mu ltip lica tion (no t in alg ebra ic sen se) m ean s
opc ral1ons or a mo lec
one afte r ano_ther in a
ns i.e. , can -yin g o ut the sym me try ope rati ons
'iym mc try o per atio
B are the ele me nts (s ym me
try ope r~t1on) of a
r. For exa mp le, if A and
par ticul ar ord e (sy mm e try ope ratw n) which
the ir com bi nat ion A . B sho uld res ult in to an ele me nt
gro up.
o f the g rou p, i.e.,
s hou ld a lso be the me m ber The pro duc t of bin ary operations
is also
the ele me nt of the
A · 8 = C , C sho uld also be an elem ent of the gro up.
ion , her e foll ow s the rule s of
gro up. In com bi nat
ht to left , i.e., if
o per ato r a lge bra , i.e., from rig m B firs t the n do A and if
the com bin a tion , A . B, the n it means tha t per for
we wri te mu st be one of the
the n do A firs t and the n do B . Sin ce the pro duc t AB
B . A is w ritt en, sed und er multiplication.
o f the gro up, we can say tha t a gro up mu st be clo
me m ber s nt of the gro up. For
the squ are of any ele me nt of the gro up is also an ele me
Ob vio us ly,
exa mp le, 54 . 54 = C. 2 , &1, . C.4
= 54 , e tc.
ted fro m one ele me nt, say
Gro up: If all the ele me nts of a gro up can be gen era 11 up
Cy clic
2 3 , X 4 ... , X" are the ele me nts of the gro up
w ith X = E (ide ntit y), the gro
X. and X , X X
sym me try poi nt gro ups are
,

cal led a cyc lk gro up of ord er n. For examp le, C 11 and D,,
is
cyc lic gro ups. te. If
A- B = B ·A , the n it is sai d th at two ele me nts com mu
Ab elia n Gro ups : If bin ary com bin atio ns
it sho ws tha t the ele me nts A and B do no t com mu te . AU
AB ¥. BA , then wh y the ord er of wri ting the
vari ous sym me try poi nt gro ups nee d not com mu te, tha t's
in
is importa nt. If in
com bin atio n of two ele me nts ation of
com mu tati ve law An y gro up in whi ch all com bin
a gro up, all eleme n ts foll ow to be Abe lian
the n the gro up is elem ents com mu te is said
(a ll the elem ents com mu te),
mp le, in cas e of gro up.
called Ab elian gro up. For exa
to C 2 ., poi nt gro up
H2 O mo lec ule , wh ich bel ong atio n of ele me nts
5 5 + 2cr. , , fo ur sym me try ope rati ons . We see tha t com bin
po.'> e -, E + 1C 2
ons ) do com mu te, e,
e.g ., . &., (yz) = &., (yz ).e, 2
(Fi g. 2. ]) and this
(5y mm etry ope rati 2
the ref ore , C 2,, is an
nom en~ n ex is t for all the ele me nts of the gro up,
com ~ut a ti ve phe lic ati ons commute
gro ~p. All cyc hc_ ~r~ ups are AbeJian since aU the ir mu ltip
Ab el,an
c
t is v an Ab elia n gro up?
Th en we hav e to app ly
tru e. If Jt ,s ask e d tha
but r ever se 1.c, not 3
in !his poi nt gro up C3 O"v # 0" 11 C 3 and hen ce C:i,· is a non-
A A

thi -, con cep t and we see tha t

A

abe lian g rou p.

 GROUP THEORY 51

c\ ,(xz) C2
►
/0\ " /0\
H8 Hb Hb Ha
Sam e
result
of two
com bina tion s

C2 c\,(xz)
' (xz)• C' =
cr, 2

/ !\
o ►
/0\ /0 \
I
Ha Hb Hb Ha
I
I
c2 CHRIST UN~VERSSTY UBAARY
. Fig. 2.1 BANGALOAE / / ~ ~ R
.
such that it can
Ru Je: This rule stat es tha t the re mu st be an element in a group,
(ii) Ide nti ty ment is called Identity.
leave them unchanged. This ele
com bine with eve ry ele me nt and h all other
st exi st in a gro up as an ele ment and it mu st commute wit
Identi ty (E) mu tten as,
Mathematically, this can be wri
ele me nts lea vin g the m unaltered.
of the
EA = AE = A E, A, B, C ... are the elements

EB = BE = B gro up and E is the identity

EC = CE = C ortant. Alt hou gh the

i com mu te me ans the ord er of multiplication is not imp
The tem is necessary.
ntity ele me nt doe s not do mu ch, but its presence in the gro up
Ide s should be
: The ass oci ativ e (ma y not be commutative) law of multiplication
( iii) Ass ociativity that if A, B, C are the
for all com bin atio ns of ele ments of the group. It means ssed
val id
up, the n C(B A) mu st be equ al to (CB)A or it can be e.~pre
ele me nts of the gro
ma the ma ti cally as
A(BC) = (AB)C
bination in
y of this rule , firs t tak e left hand side, i.e., A(BC). Then com
To see the validit bin ed with A
(BC ) is firs t per for me d and the result of this may then be com
parentheses from right to left).
ng in min d tha t the ord er of per for ming operations should be
(keepi n
d sid e, i.e., (A B)C . No w, firs t find the res ult of the combinatio
The n take the right han . If the
( AR ) and the n res ult of this combination and C are multiplied
in parentheses, i.e., dition is valid. ln
left han d sid e and righ t han d sid e are same, then this con
produc t of of ele me nts , i.e.,
the ass oci ativ e Jaw mu st hol d for the product of any num ber
gen era!,
E) (FG ) H = ABCDEFGH.
A(BC) (D E) (FG) H = (AB ) C(D
), which should
Eac h ele me nt of the gro up must has its invers e (rec iprocal
Uv) Inver se Rule: wh en multiplied
me mb er of the gro up. An inv ers e of an ele me nt is one which
be also the X is its inverse, which
ele me nt, wil l res ult into the Ide ntity (E). If A is an element and
by the
 \\ \ ,\
\ \ I \ I •\

11111•1·,1• ti f ,\
\I ' 11/ ,\ 1111 11 \ II Ill 111 •
1

1' h'.t1 111.1 1 ii \ 1:-. 111\ l'l,

I! I\ 1111, ,111 , y11111 ,. . 1, y 1• 1I 111, llh I·
1,c ,, ,1 11w d b, 1111 • dn 11l pll1111 11111 d1 · 1·1111 1,·1 ' 11
1'11t,• t tth' • ,· tn 1 1 1111 •
1 fl l11 v1•111 , ·, ,1 11 •11 ,, ll w ll 14 11 If
.1111 1, ll11 d 11111
., , 1111 111·111 I\ , 11 111• 11
1' \ .ltl tph -. !.t"-, ., pl.itll' ,11 l l

n l1 I·
ill \\.' tS1' ,,f (), h,•, ·.111 .,c· l'
1111 ,1· ,
S ,llll t' IS lltl t' "'' 1·1•1
1[11 · ,,, , , 1111111·11, (/), l1t •1
I·
, u, ,1 1,. 111,111,, 11
1 , 11! 11• , 1111· "· l,1111· 11111 ·.~ (l'1111d111t111•.J , tlw y 1111111 111
S 11, 11 11,·n rile ., er 1,, ,· l,·11,c·11 1 11 >,1 11111p dn 1p111 111•d f,y
111l w1 111 c· lc-11 w11 1. , ,,, 1 1 ~" 1"11 ." !Ill ' 11 1d ·1 1 1111·
:-:r oup . t'hc 1111.il 11t1 ., f ,
,1lw y ll11•N1' 111111 L1111dl111 111 1 1 11
h. 111 c·h' 111c· 11/s 1111 11111 11 .~ 1,111p, \\'h tdt 11l.,11 p
h . If 11 c 11 1 t' ,
. , 1• 11
: v1·1y 1m llg 1 11 11 111 •1
11 /,) .i.: 11111 11 ,, n ille d., ., 11h~11 111p 111 1l1l' g 11111p. l
rhi s hil l er p 111t-, (lli.1 111·111l y 1·11~·,11111/e ll'd l>n ·""
''
.1:, .111 t'lc·1 111· 111 l'lll ' .,11h ~ 1, 111p., 111 ,• 11111rc• f1t·q · hli. 11
( l : l •d W1 1
h:I\ (' l ~ l'III II~ ,· 11 J-t f'l111p 1l11·n1 y 1,, 11ppli1
~ ai,· \ "Gt } ' 11sC 't'1 ll in :-.i1 11pllt\•i11.~ 1111· pn 1hlc111s wh
1hc
dis l·ns:- ir l.1k r ,111 .
TS
ER AT IO NS (O PE RA TO RS ) AS GR OU P ELEMEN
2. 2 SY MM ET RY OP
v11rlo11 s sy 11111u•t1 y 1·lr 11w11h
1·t1:-.si11 11 i11 l 'lt. ,pr n I , 111 111 11tt1k1.:11ks p11ssL'ss
\\'c f...1H111 frll lll 11ur c:,r
lin d1:, t ka l l111w11,111,
1cd ll'il lt .11 1 11p crn h1r . Op l'fl ltu r.'l lll-'l.!d ,'lllll tl' 11wrlu.: 11111
n r is :1., s11l·1:1 wil l s huw 1l1111 11 11r1 nf
.111d t':ic h s_, 111mc11~ clc tttc l'ltL ' tdo rc, in rlti s ,' ll'l' lio n, WLl
l 1,1 lw :1,·1 nl 11p, 11t.
t her e rile ~L·n111c1riol f'i
~ tm.· i111 wo up h111 :1
., 1111 111', 'ttk 1.·111 1sritt1IL ' 11111 nn ly II sy111111ctry p11
cr:1111r., ) l, 11 11w . In II sy111111l'l1y
s~ llll llt' lr_, t1pcr:t riu11s (11p 1lw f't1trr c1111tlirio11s 11w111lrn1cd 11h
.,c11sc :1l.,1 1.. , :11 is(, i11.i.: :ill .~y11w11; 11 y
grl ittp in a 111:11hc111:t1 i1.·:tl d is ri11 L' I sy1 1111 1c1ry 11pc rn1lo11 s µc: m·r11 1c d hy
ttlc. 11 c i111·ludc Pill_ \'
po 1n1 gm up of' :t 111ollY ld 1101 he i11cl11dcd in
nll' . 1 ll'r c dis1 i111 .·r 11p L'nt ti1111s 111c:1111s 1h111 rhc:y s hou
c.'kmc111s p rc:-cnr i11 rite 111
nkr ck 111c111 ,
1:t h· rhc 1111 1111 n11i1 1 (N I I 1) 111olc c.:11lc . The ,'lynt111 c rry
. hir cx:1111pll'. 11Jd." of ., y11 11;ic11 y
lHh cr sy111111cr 1) o pL·r:tliPi1., i,~ 1hc 1-'ig . 2.2. No w C 1
I C, r .1CT • us sh11w11
111 :trc I~ + 1 E Wh c rc 11,-.. 1111c opl ' ral iwr
prc :-c111 in 1hi:-. '. : kr nk 111s . i.,·.. C: 1111d C'j hct:1111sc C 1 =
1

II 111 1111 l'lr~ • 1 1f'l'l ':tl i1

g l'llc.'f'it lc..':- I n d,s r cr S) ''.
c1ry (<T ) .
·lt 1·cr t 1l·:1I pla ne pf' .,_v 11 1111
1, gc11cr:11L'd h~ L':tl
... I.
\..:,_,Jc., n
CT,,
-

/ / :~~ I
I
H #
I

b
CT,

Fig. 2.2
 GROUP T HEORY 53

c2 (=c -1) nb nc . • Hence th e

tot~l dist inc t ope rati ons are E ci - ,
na
vv, v v , v v 1.e., SIX.
Therefo.re, the , 3 , 3 3
=
ch the amm oni a mo lecu le belo ngs, has the ord er 6 (i.e., h (C )
symmet ry_ pm ~t gro up C3v to whi Jv
. ectively
6). Now, 1t will be sho wn that th ese symmetry operations (elements of the group C3v) coll
. .
r I . up as follows :
form a mat hem atic al gro up · Fou ru es are to be obeyed by this gro
I · · n wh'1ch 1s· al so an element of
rat· ratw
(i) Com bin atio n of any two ope ions resu ts m to an ope
n then we have ' C 31 aa to
th e gro up. For example, if combination of c 3 and aav are take
1 v'
• the molecule NH and
h we first perform a a operation on
get t e resu lt of this combination, V
3
h CJ operati.on, as shown in Fig . 2.3.
t en 3

C3
I
I
I
I
I AB
I (JV

AC
(JV

Fig. 2.3
sym met ry
on of the amm oni a mol ecu le which result from two successive
The configurati result of
Cj, can be obt aine d by a single operation cr~. Therefore, the
operations er~ and s property
n C cr~ = cr~ and er~ is also an element of the same group. Thi
the combin atio 3 combination
tion can be app lied on any two members of the group. Now, take the
of com bina and then a a\I as sho wn
we wri te era . ab = ?• . Then first perform abl'
of cr 0
V
and crbV
i. e., V V

in Fig . 2.4.
one thing is ver y
ce, cr~ . at ci,
= whi ch is also an element of the group C3v. Her e
Hen cessively, the plane
performing reflection operations suc
impo1ta nt to keep in mind that in as such for exa mp le
ration of the molecule will remain
design ated initially in the configu Hb, N and He atom s,
which contain N and Ha, N and
here, cr~, er~, cri are those planes performing cr!. cr: is
ration of the molecule, so after
respectively in the initial configu iall y [in 2.4 (i)J in
as the same plane as design ated init
performed on (ii), considering er~,
the mo lecule.

(ii)
c'3
Fig. 2.4
s-i Sn1!.ffiTRy A::\'D GROUP TH EORY IN O-lEMISTRY
• rec ognize
we can eas ily
(ii ) Th e ex ist ence of Id e n ti ty (E) •rs ver y mu ch lhe re in C 3v bectha use I
. ·
1·orm mg · ns on e mo ecuI e.
era tio
fol low m o relat.r·o n ,
s b Y pe r the se op
the 0

EC3 = C3 E = C3,
Ecr ~ = cr" E= cr"
V V

Ecrt = cr,, E = O'b

b
V

2
EC 3 = c2
3
E= c2
3
me nts of the gro up. For
of mu ltip lic ati on is als o sat isf ied by the ele
(ii i) Th e ass oc iat ive law condition
ele me nts of the gro up C3 \ , the n, the fol low ing
ex am ple ' if we tak e 0 °V' 0 V
h and 0 V c

mu st be ob eye d. (a c
a(cr,,b. cr,,c) = cr,, . O'vb) cr.,
crv
LH S
to ve rif y thi s, firs t take
No w, L.H .S. (L eft han d
sid e) = cri (a~· a~)
fir st pe rfo rm cr: and
the com bin ati on in pa ren the ses ( crt · cr~) we
To ge t the res ult of
the n a b. op era tio ns can
I'
pe rfo rm an ce of cr~ an d cr~
Th e resu lt wh ich is ob tai
ned aft er s ucc ess ive
, crt . cr~ = c;. So,
be ob tai ned by a sin gle
op era tio n c;, as sho wn in Fig . 2.5 the ref ore
side.
we hav e in the lef t han d
ai (cr t· cr~) = cr~ -c ;

I
I
I
C3
Fig. 2.5
·
st pe -"o nn r am mo nia
cr,~ . C com bin ati on , fi•r
1
C 3 an d the n cr~ on the
No w, to get the res ult of
111
3 "

. 2 .6.
mo lec ule as sho wn in Fig
C3
I
I
I
I

H/.1:~
I
N
► /.N
C I Ha H, / ~ H,
I
I
I

Fig. 2.6
 GROUP THcOl<Y 55

so that the result (pro duct ) of 0 ° . c' is 0

b
V 3 V

Hen ce, L.H .S. = cr" (ab.(j c)

V V V

= cra
V
·CJ'
= (j b .
V

Now take R.H .S. (Rig ht Han d Side) = (a~•at)

a~, first of all we have to find the product of
,
the combination in the parenthese. So, we have

b 8
av av
N N
/,N ~
""1! """· I
H, / H 0 H1 ""Hc
I Hb Ha
Hb I
I
I
I
I
c13
I
I
C3
Fig. 2.7

(Ja · <Jb
V V
= C'3
Now, R.H .S. = (a ~ · ae)cr~
(jc
C 3l V

Now, perform cr: and then c;, we get c' 3

(J c
V
= abV (as show n in Fig. 2.8)
I
I
I
I C c1
3
I Ov
N

""1! """·
Hb
I
I
I
I
I
I
I
I
I
C3
Fig. 2.8

so R.H.S. = ( cr~ ·cre) a ~

= c'3 (jc V

= (jb .
V
this
propertie s are satisfied by the elem ents of
Hence, L. H.S. = R.H.S. there fore, associative
ideri ng othe r elem ents of the group also .
group. Reader may verify this property by cons
 56
s, ~"" ''" \'I
·'
1 ' lMI II I'
' I Ill PH \ IN ( 111 ~II ~ I I<\
111 ' "111 I,, . I
I 111
•
Iw •wr ,i a,
1
ol 1111' 11 111 1,p .i •, ' "
{iv ) ·nw ,,
""
, ,·.~1••11
..
l·•·, Il l
Ill\ l' I \l' 111 r11 d1
t· k11 11· 111

folio\ \ ~ Y:u,d 11 1'· rh,· ,,,,.,,,,,,.r

; ., tire 111 w 111, · of 1de 11 11 1
I' I F 1'11•1l'1 111l', 1d1· 1111ty

o l I hl' ~ , nu p.
r11cm,
1111d (' ~ urc i 11 VCf N(' o l c:ic lr ,,1l,c r and ;,re cl,·
(. ' • (.' I c\ c; E. 1hc: 1cf orl' , (' ~
' ' of 1hc group .

a ''I a ·'= E} arc lhc in verse o f 0:, <J~ and o:.

1hc rcfon: . a:'.. a'.'. und cr:,
I

a ,.• a ,.= L.: me nts o f the group .

' ' L.:, •
respec ti vely and arc lhc cle
a:·a:= E y (f-,J.
L11e cleme nt of lllc gro up and its in verse is the Ide ntit
ct of
He re. "e ~ce 1hat the produ up satisfi c~ all the four
. it is cle ar lhat CJ,, symmetry point gro
Fro m abo \'c descri ption mc try point
tica l gro up. Sim ila rly , it can be pro ved that all ~ym
charac teristi cs of a ma thema up s) in a mathe matic al sen se
als o.
lly gro ups (abstr act gro
gro up~ are actua

ON TA BL ES
2. 3 GR OU P MULTIPLICATI
ented
sym me try op era tio ns of a po int gro up can be rep res
combinations of m the group
Th e pro duct of all brn ary are kn ow n as gro up multiplication tables . Fro
ular fom1. Such tab les ati on s of symmetry
in rov. -ct,lumn tab ow the effec t of var iou s com bin
str aig h1 for wa rdl y kn the molecule
mu Joplicauon table one can ner, the sy mb ol for the po int gro up to which
e. a l llle top lef t cor me try op erations
oper..uon-.. Jn lllis 1abl on tal) and co lumn (vertic al), a ll the sym
n in the row (ho riz
bel on g,. 1-, \\.ri llen and the
wn bel ow for C3,. group.
are v.nrten ~h ~ho
First ope rat ion (pe rfo rm )

c' c 2 I .I

E *

C:
c' 1
*
0
't 't
c-;s -
~
g-~....
e *
"O ~
C: 0.
0 * *
'..J
~
V)
• t * * *

by the prod uc t (re s ult ) of the binnr~

the va< .:ant pla ce1:, 1.ho wn by * are 10 b·•... 1·1·11e,1 '"
~·ov. co o rdina tes of
mb ma tiu m ut ,ym me Lry operar · ·. Q ne 1/1mg ·
10 be rem e mb ere d he re is that the
<.:u I OIH · o ut fi r.;!
try plane1 . do no r hif
& t du rin g .iny • me try opera11 on . Al so , the op era tio n ca rri ed
':.)m me .
sym
d h fro m the left
h
1, ou
lcJ b c rea d fro m the up pe r ho ria nt · 1
row a~ I e sec on d opera tio n sh ou ld be rea d
od . ., .1 ·
colum n of the wble Th e, pr u<.: t cJcmen1 (opcra11un) is pu t ct! . 1h ·
e Jun c11on (*) of the row
an d co lum n.
· •
Th . Lll Jun · .· resul1 of co lum n op era tor mu ltip lie d by top row n perntor.
us 21 e c uo n, we 1,ho ulcJ pu1 rhe
 GROU P THE.ORY 57

For example, the product of the combination

c\ cr<'. is to be put at the junction (*) shown in the above C1
then
111hk. The product of this combination is
obt~1in;d by performing cr~ operation first and
point group.
opc:ra1ion on lhe molecule belonging to CJ,·
the
ation table. we have to find the product of all
Now. to construct lhe whole group multiplic carrying
uct of the combination is obtained by actually
binary combinations of the group. The prod
whic h belongs to the point group.
0111 1hc: symmci-ry operatio ns 0 11 the molecule
ry
can verify the product of the various bina
By 1he same example of NH:i molecule , we C! cr = crc,
result of c'J ,T a combination is crr i. e.,
0

combinations. As we have seen earli er that the "-

_, \1 V
V
V V
find the
and cr~ operations. Similarly, the student may
so cr;: will be pu1 at the junction (*) of c.~ operations
metry operations by actually performing the
rcsul1 s of Rl l the binary combination s of sym table
the junctions of the operations, the multiplication
on 1hc molecule and by putting the result at
n below.
for C_1,. poi11 1 group can be construc ted as show
? II b r
c,v E c'3 C.1 cr" cr"
b
crv
C
(Here, C32 = c 3-')
E E c'3 Cl crv" crv crv
J

r b
c'3 c') c2 E crv
II
crv crv
3

b r a
c 2 c J2 E c'3 crv crv crv
3

II a b
crv
r
E c'J c2
crv crv cr" 3

h b r
crv crv
a
c2 E c'3
crv crv J
?
a b
C
crv crv
('

crv crv c'J CJ E

table.
It is clear that each row and column does
not repeat any element in the multiplication
H O
table for C2v point group taking example of 2
Example: Construct the group multiplication
molecule.
ents.
point group and possess E + 1C2 + 2crv elem
Solution: We know that H20 belongs to C2v metr y
y operations are same. So total number of sym
Here , number of symmetry elements and symmetr
group is 4 (i.e., h = 4).
operations are four and hence the order of the
er
C v point group, we write at the top left com
Now, to cons truct the multiplication table for 2 we
first left column and on the top horizontal row,
the ~ymbol for the point group and then in the
the group as shown below.
have lo write all the sym metry operations of
E C2 crv(xz) cry(y z)
C2v
E EJ EJ EJ G

c2 EJ

cr"(x z) EJ

crv(y z) EJ
 58 SYM METRY AND GROUP THEORY
IN CH EMISTRY

To find the valu e at vacant places. we h duc t of all binary combination ~

.
have Lo fill d L c pro ·h wn by 8 are
symmetry operatio ns. One can easi.ly und .st. . I I . t J·u ncti on places s o same as Writt....
. ci cllll t ia . . .
f ny elem ent with ....u
on top hon zont al row and Ill . . I , sc com bina t10n Identity (£
the lc lt column Jccu u. o a . )
wil\ result the sa111 c clc111cnt. So we can . b the same operat10 ns as shoWn
directly fi ll in the 8 places y
below.

C) V E Cl a )xz)

Cl a )xz) a )yz)
E E

C, C,

a) xz) av(x z)

av(y z) ahz )
. o erat
Now. we find the result of other bmary (p ions by actually performing the symmetry operations
? For this purpose, first perf
on H10 molecule, e.g., the product of Cza ) _
orm a,. (xz) and then
v x~7 - .
C1 as- shown below in Fig. 2.9.

a,(yz)

I
I

crv(xz)
cf--+--~ X
Hb / i
y :
I
I
I

(ii)

Fig. 2.9
aJyz) is a plane containing y and z-ax
es and av(xz) is the plane containing x
and z-axes.
We see here that the resultant configuratio
n obtained (ii) by two successive symmet
(a Jyz) and C ) can be obta ined by ry operations
2 a single symmetry operation (a.,<xz))
a (xz) , similarly we can get the following prod . Hence, C 2criyz) :::
V ucts of various binary combinations of
this group.
C2 C2 = E, C2 av (xz) = av (yz), av (yz) C
2 = av (xz), av (xz) · a,, (xz) = E,
a V (xz) · a (yz) = C , etc.
V 2
Substituting the results of these binary ope
rations in vacant places we get the group
table for C v point group as show n belo multiplication
2 w:
 GJWIJI' TH!'J.ik'( J9

c2v E c2 aJx z) crJyz )

E E c2 aJxz) crJyz)

c2 ( 2 E av(Y z) <1jxz )

av(x z) aJxz) av(yz) E Cz

aJy z) av(YZ) aJx z) c2 E

to know direc tly the

Grou p mul_tipli catio n _tab~es are useful Grou p multiplication table can
t10n of sym metr y oper ation s. If grou p
produc~ of_ any bma'.y c?mb 111a be useful for u ~ ing the
1s with us, one can easil y verif y that the sym metr y
rnultipltcat10 11 table properties of a grou p.
tical grou p whic h satis fy all the four
point group is al so a math ema
rules of grou p theo ry.
loyed.
C v poin t group, anot her method may be emp
For cons truct ion of mult iplic ation table of 3 dina te system
this meth od, to see the effe ct of the vario us grou p operations, we have to set up a coor
ln us sym metr y
onia mole cule and then see the effec t of vario
whose origin is at the nitro gen atom of amm oper ation s, the
ts awa y from the origin. Here, sym metr y
operations on an arbi trary vect or that poin on) and only
rema in fixed in space, (no translation moti
symmetry elem ents and the coor dina te axes cipal axis of
is lies alon g the C 3-axis (which is the prin
the vector is trans form ed. Sinc e the z-ax to look dow n
mirr ~r plan es of sym metr y (avs). It is easy
symmetry) and lie alon g the inter sect ion of
the C -axis . Let us find the resu lt (pro duct
cr~.
) of C 3
3

cf;

----~---➔ Y

r1
Vecto r
a;
X
X
Clock wise
(rota tion of 120°)

cf,

Fig. 2.10
60 SYMMETRY AND GROUP THEORY IN CHEM
1STR Y

3
ation s is equi vale nt to a ~ - -- - - -
The end resu lt of the succ essiv e two oper
get C) 6-'V = 6-"V . Simi larly,
retle ction of r throu gh 6-" and therefore we
1 I' '

we can verif y that the prod uct of 6-"II . 6-'V = C'3 or we can assu me the NH3
mole cule as show n in Fig. 2. 11.
re plan ar) mole cule,
Example: Prove that the point group for AB4 (squa
is also a mathematical group. 2
+ 4IC + 4C .1 IC4
Solution: The squa re planar AB4 molecule has E 2
Fig. 2.11
etry elem ents and total symm etry oper ation s are
+ 4cr,. + Icr" + i + S4 symm
en oper ation s will constitute
t
E' 2C 4 • C 2 ' 2C'2 ' 2C"2 ' ' 2§ 4. 6-h ' 26-v and 2&d (= I6). Total sixte the group.
16). AU these oper ation s are the elem ents of
to the poin t group D4h of the order 16 (i.e., h =
to
also a math emat ical grou p. For this, we have
Now, we shall prove that D4h point group is
verify all the four rules mentioned earlier as.
inati on of symm etry oper ation s shou ld also be
the
(i) Clos ure Rule: The product of the comb
all the mole cule AB4 with axes and planes
element of the group. To verify this rule, first of
of symmetry are shown below in Fig. 2. I 2.
z

G;(2) , <Jd(2)
y, c; (2), cr,(2)

8
4

2
C (1 ), crd(1) Or

3 2
8
B
X, C'2 (1 ), crv(1)

s.
Fig. 2.12

• C4 -axis of symmetry, in (along z-axi s) thi s mole cule is p · thr

assm g ough the central atom
A and perpendic ular to the plane 0 f th e mole cule (plan f th . .th
e O e pape r). Collinear w1
this will be S4 and a c 2 axis.
. .

. .
• c; (1) and c;(2) are axis of symmetry pass ing throu h
g the diag onal s of the squar e
and are in the plane of the molecue. I
• c; (I) and c; (2) are axes passing through the ce ntres of oppo ·
. Site edge s of the square
and lie in the plane of the mol ecu1e. av and ad plane s of sym C'
metr y are alon g the :
and c; axe5, respective ly.
 GROUP THEORY 61

Product of two sy111111L'try upcra1io11s. say c!, .c; (

1) will be known by actually carrying
Fig. 2.13.
out these operations on AB4• so look al the
~J2)

c; .c;(1)
401
3
•
2
C4 •
A1 403 104
1
•
2
c~ .,
---- --...
2 3
(ii) (iii)
(i)

c2(2J
Fig. 2.13

Here. the resultant configuration of the com

bination (I) is the configuration c! .c;
symmetry operation c; (2) or <Jd (2). Hence,
we
(iii) whic h can be obtained by a single

can write as C~ · (!) = c; c;

(2) = <Jd (2) and c;
(2) or <Jd (2) are also members of
the group.
Same kind of results are also obtained for othe
r combinations. For example, S c; (I) = ? !.
in order from right to left, we see that,
then performin g these operations one by one
c; (2J

S~· G;(1)
4
0 •
1

2
c;(1) .,
_ _..
A1
S4 •
104 201
2 3 3 4
3

ay(2J

Fig. 2.14

S~ .c; (!) = c; (2) = <"., (2) which are also the elements of the same
So, we can write ,
group D-1,,.
62 OIO ,,.. lJIJ l\fl\ lRY
SYM MET RY AND GR Olil ' THt

401 o,(1)10 "---• '02

Ag ai n.

c,d(2 )
0

0, (1) ; d (2) - --
4 3
: _, 2 3
3

c'
d

Fig. 2.15
on of 90" in
two C • C~ ( I) and c; ' (= 4
C (2)), <=! (1) me ans rot ati
He re. "c hav e 4
dir ection . Similar!}.
n and c~' (2) me ans rota tion of 90° in ant iclo ckw ise
d(\ci.. ,, i~e dire ctio 1
(2) = ah \(
< 2) = ahC~ .
SJ are also two. On e (1) = s~ 61iC 4 (1) and oth er §4
me nt, her e, als o E is the
le: Sin ce all mo lec ule s or obj ect s pos ses s identity ele
pi) Identity Ru lea ve then
ch com mu tes wit h all oth er ele me nts of the gro up and
ide ntit y ele ment whi
unc hanged. mp le, we car
mu ltip lica tion s als o hol ds goo d for the gro up, for exa
(iii ) Ass ociativ e law of
, erif ) that

c! (c2· crv (1 )) = (c! ·c 2) cr,, (I) = c! (c 2

· a l. (I))

(b) (c)
(a)
dic ula r to mo lec ular
C! (C2 · crv (I)) , her e C is col lfo ear wit h C 4 i.e. , per pen
LH .S. = 2
-a (1 ) wh ich can be
n the par ent hes es, we hav e to fin d the pro duc t of C2
plane. To ope i· '

401
obLained as sho wn below.

3 2
:i. (2) 403
1 2
201
3 4

Fig. 2.16
(C2 . a v (I)), C-I1 on the res ult cl
and now to get the product of C! we sho uld ope rat e
C2 a , (/J operation \ i.e.,
2
, I
c◄
:: P(a) (result of (a)
combination)
3 4 4

Fig. 2.17

No w, rake (h) combinurion ,

i.e., (c~ ·C2)a v (I),
firs r we take C,4 C operations so rhe
product of c~.c?-
= C I
4
2
 GR 0111 Tnw n 6.1

3D' 2
,
c2
+ 20'
1 4
, I
c,
D'
4 3

c'
'
Fig. 2.18
) = c 4- Now. we have
e. fo r co m bi na tio n (b)
e ob ta
.
in ed th e re sult as 2 (c~•c 1.

Th er ef or ,w . as follow s (Fig . 2. / 9).

th e re su lt of c- 1 . • So le t us do It

403
to ch ec k 4 <J 11 (1)

3
401 2
civ (1)

1 2
3□ 2
4 1
= P(b) (result of
comb ination (b ))

Fig. 2.19
The product of C
, . a. , I J
bination (c) is
(C 2 . cr v (1)) . c;
H en ce, P(a) = P(
b) an d the co m
at is the configurat
ion
2 0 1 • So-n oi~ · C'
-
de te rm in edin Fig. 2.17 and th J ➔
has al re ad y been
. b
1s to e pe rf on ne

Cl4
201
d on this , we ha

•
ve

302
4 1
= P( c) (result of (c)
combina lion)

3 4
Fig. 2.20
tip lication
P(c). Hence asso
ciati ve Jaw of mul
ve seen that P(a)
= P( b) =
Therefore, we ha e group.
e elements of th ou ld also be the m
embe r
ar e valid fo r thes ou p an d th at sh
element of the gr ation. Ir is denote
d by
Th ere m us t ex is t in ve rs e of each an in ve rs e op er
(iv) n reversed , is verse of
of the gr oup. A
ny operation, whe ve rs e of C ! is C ,~ 1
• similarly in
the operator. In has its
pe r ri gh t script on at ion) of the group
purring - / at up element (s ym m et ry op er
n in
. H er e also each ~' = E as sh ow
.§~ is .§; 1 an d so on th e gr ou p. Fo r
ex am pl e, C ~ · C
is m em be r of

401
w hi ch

102
in ve rs e

401
Fig. 2.2 1.

3 2
4 3
3 2
= E

,
E

Fig. 2.21
 64 SYMMETRY AND GROUP THEORY £N CHEMISTRY

d b Lh are clements of the same grou P D4/i·

. ref ore, C 4 an C 4 are mversc ol each other an °
d -1 . .
. The
l

This 1s trne for all other elements also (verify it).

hich belongs to D4~ symmetry l>Oint •
H ence, we have seen that the square planar molccu Ie w .
. • . . .. . ., · -f
1 cs of the mathematical group
g10up, and tlus pomt group also sati sfies the lour charactens · ·
. 0 0 . to be remembered here 1.s that symme . try operations when performcd over the
One thm 0 a0 am mo] 1
. . d This may be an atom . of the h ecu e
molecule, leave a pomt 111 the molecular geometry unmove · f
. 1 At this point a 11 . axes ormmg t e basis 0f
or a pomt called centre of gravity of the molecu e. ' ) H . .
.. (' t'1ng at one pomt . ere m our dtscussi on
defimtion of the 0 eorneu·y of the molecule
0 meet mtersec .
. . t their geometnes, therefore, our concern is·
we are dealing with isolated molecules with reference O .
(operators) must
· ~ .. · b d II the symmetry operat10ns .
pomt group symmetry only. Hence, for a hmte o Y, a .
~ . · tated about non-mtersectm g axes or reflected
leave one point unchanged. Therefore, 1f molecu 1e ts ro
across non-intersecting planes, then this will introd uce . a No symmetry operation on a finite body
111
translation motion of the molecule, i.e., the body ~o~es produces any translational motion of that
space and cannot be brought into coincidence with itself. body.
Translation motion is not our concerned here, this is treated
by space groups.

2.4 SUBGROUPS
It has been observed that among the symmetry operations which form a symmetry point group, there
generally exist smaller set of symmetry operations (element) that also obey the four rules of a
mathematical group. These smaller groups of a large group are called subgroup of a group. In general,
if h is the order of a group, then, a subgroup of order g may exist such that h/g = k (k is an integer
greater than I ). In other words, the order of any subgroup must be an integer divisor of the order of
Lhe group. However, it is not necessary that subgroups for all the allowed order must exist For
~ pie, in case of C2 v_ point group, we have E + 1C 2 + 2crv, its order (h) is 4. This group has two
ssibl~ subgroup_s having order (g) 1 and 2. From the multiplication table of C 2 v point group, we
easily recognize the following subgroups:
C 1 = {E }
C2 = {E, C2l
Cs = {E, cr1i (xz) }
Cs = { E, crv (yz) }
It is clear that every value of h can be divided b 1 . .
element (E) therefore c whi'ch . Y (as an
· mteger) and every group has idenuty
, , 1 contains only E w1·u
H . . . necessanly be a subgroup of any other group.
ere, one can venf y that the sets {E C
group. These are also not groups . . 'h 2 ' ~ v}' {E, cr/xz), cr /yz) } arenotthesub groupsofC2,·
. . . . . in mat emat1cal sense Th
integer divisor of the group order (4) . , . . . . · ese sets have order 3 which is not an
• i. e., tf we d1v1de h b
For C3v point group, the reader can . . . Y g, we do not get an integer.
C eas11Y identify as
1 = {E) ,C3 = {E,C~,C~ } , C' == {E " rl) b many as five subgroups. They are
s ,crv),L . == {Ecr) ~ - {E C
All subgroups must cont . ·ct . s ' v , s - , a v}.
. . am I enttty E but th · ·1
commute whereas the I ' e elements of
always Ab I' l'k e ements of a subgroup do com mam group need not necessan y
of h but r: tan I e. One thing more is that the order ( ) ~ute essentially. Therefore, subgroups are
, verse may generally not true. Thus 1·r g o any subgroup must be an integral divisor
· • we have a • f
group of order 6, then the order 0