I-2: Geometrical Isomerism |1

 Number of Geometrical Isomers

 GI in Cyclic compounds
 GI in Allenes, Cumulenes and Spiro compounds
 GI in Biphenyls
 GI in C=N (Aldoximes & Ketoximes) and N=N (Azo compounds)
 E-Z nomenclature, CIP rules

Number of Geometrical Isomers

Non-symmetrical molecule:
Example-1: Find the no. of GIs of following molecule:

Solution: {CT So, 21 = 2 Isomers

Example-2: Find the no. of GIs of following molecule:

{
CC
CT
Solution: So, 22 = 4 Isomers
TC
TT

Example-3: Find the no. of GIs of following molecule:

{
CCC
CC T
CT C
CT T
Solution: So, 23 = 8 Isomers
TCC
T CT
TTC
TT T

In general, we have 2 Isomers for each Stereogenic area, i.e., Cis and Trans. So, total number of
Geometrical Isomers for non-symmetric molecule with n stereogenic areas = 2 ×2 ×… × 2=2n
 I-2: Geometrical Isomerism |2

Symmetrical molecule:

Example-1: Find the no. of GIs of following molecule:

Solution: {CT So, 21 = 2 Isomers

Example-2: Find the no. of GIs of following molecule:

{
CC
CT
Solution: As, (C T) and (T C) are same due to symmetry. So, total 3 Isomers.
TC
TT

Example-3: Find the no. of GIs of following molecule:

{
CCC
CC T
CT C
CT T
Solution:
TCC
T CT
TTC
TT T
Due to symmetry:
(C C T) and (T C C) are same (Palindromes) ; (C T T) and (T T C) are same (Palindromes)
Hence, total no. of isomers = 6

In general, we need to count one for each pair of palindromes. As, a result halving straightforward
 I-2: Geometrical Isomerism |3

n
2 n−1
we get =2 ,but we need ¿ add theterms deleted by straightforward halving .
2
So , final result is as follows :

{
n −1
n−1 2
N= 2 +2 if n is odd ; n=no . of stereogenic areas
n−2
2n−1 +2 2
if n iseven
Example-4: Find the no. of GIs of following molecule:

Solution: 4 valid SGA, not symmetrical. n = 4, N = 24 = 16

Example-5: Find the no. of GIs of following molecule:

Solution: 3 valid SGA, not symmetrical. n = 3, N = 23 = 8

Example-6: Find the no. of GIs of following molecule:

Solution: 3 valid SGA, not symmetrical. n = 3, N = 23 = 8

Example-7: Find the no. of GIs of following molecule:

Solution: 2 valid SGA, not symmetrical. n = 2, N = 22 = 4

 I-2: Geometrical Isomerism |4

GI in Cyclic compounds

Revisiting hybridisation at C-atom:

 Due to Tetrahedral geometry of sp3 hybrid orbitals if two substituents (same or different) are
attached to two different sp3 carbon atoms then this type of substituted cyclic compound
can exhibit GI.

 sp2 geometry is trigonal planar, so, trans configurations are not possible in cyclic compounds
having sp2 hybridised carbon atom.
This is clear from the following case of trans configuration. Geometry in trans configuration
is too much deviated from trigonal planar and results in a large angle strain. So, trans
configuration is highly unstable and do not exist:

 Cyclooctene is the smallest ring that can show both cis and trans isomers because it is
flexible enough to twist into the trans conformation. The cis and trans isomers of
cyclooctene are shown below:
 I-2: Geometrical Isomerism |5

So, in cyclic molecules follow the following steps:

(1) Mark the probable Stereogenic area(s) (SGA)
(2) Confirm the validity of SGA(s) in ring. Possible SGA locations in a Ring can be as follows:
 Two substituents area. If SGA has one of the C-atoms with sp2 hybridisation then it is not a
valid SGA.

 Double bond area: unless until ring comprises 8 or more carbon atoms, double bond area is
not a valid SGA. So, cyclooctene onwards exhibit GI.
(3) Confirm the validity of SGA(s) outside the ring by checking the possibility of cis-trans
Configuration as follows

Example-1: No valid SGA. n = 0. GI not possible

Example-2: 1 valid SGA, n = 1, N = 21 = 2

Example-3: 1 valid SGA, n = 1, N = 21 = 2

 I-2: Geometrical Isomerism |6

Example-4: 1 valid SGA, n = 1, N = 21 = 2

Example-5: 1 valid SGA, n = 1, N = 21 = 2

Example-6: No valid SGA. n = 0. GI not possible

Example-7: No valid SGA inside the Ring. 1 valid SGA outside ring. n = 1, N = 21 = 2

Example-8: 1 valid SGA inside the Ring. n = 1, N = 21 = 2

 I-2: Geometrical Isomerism |7

Example-9: 1 valid SGA inside the Ring. n = 1, N = 21 = 2

Example-10: 2 valid SGA in Ring. No valid SGA outside Ring (why?). n = 2, N = 22 = 4

Example-11: 1 valid SGA in Ring. No valid SGA outside Ring (why?). n = 1, N = 21 = 2

Example-12: 1 valid SGA in Ring. 1 valid SGA outside Ring (why?). n = 2, N = 22 = 4

 I-2: Geometrical Isomerism |8

Exercises:

Find the umber of GIs in following:

(1)

(Ans: No GI)
(2)

(Ans: No GI)
(3)

(Ans: No GI)

(4) Draw Isomers also

(Ans: 2)
(5) Draw Isomers also

(Ans: 2)
 I-2: Geometrical Isomerism |9

(6) Draw Isomers also

(Ans: 2)
(7) ) Draw Isomers also

(Ans: 2)
(8) ) Draw Isomers also

(Ans: 3)

(9) ) Draw Isomers also

(Ans: 2)
(10) Draw Isomers also

(Ans: 2)
(11)

(Ans: 2)
(12)

(Ans: No GI)
(13) Draw Isomers also

(Ans: 2)
(14)
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 10

(Ans: No GI)
(15)

(Ans: n = 2, N = 22 = 4)
(16)

(Ans: n = 1, N = 21 = 2)

(17)

(Ans: No GI)
(18)

(Ans: n = 2, N = 22 = 4)
(19)

(Ans: n = 2, N = 22 = 4)
(20)

(Ans: n = 2, N = 22 = 4)

(21)
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(Ans: n = 3, N = 23 = 8)
(22)

(Ans: n = 3, N = 23 = 8)
(23)

(Ans: n = 3, N = 23 = 8)
(24)

(Ans: n = 2, Symmetrical, N = 22-1 + 20= 3)

(25)

(Ans: n = 2, Not Symmetrical, N = 22 = 4)

(26)

(Ans: n = 2, Not Symmetrical, N = 22 = 4)

(27)

(Ans: n = 2, N = 22 = 4)
(28)

(Ans: n = 2, N = 22 = 4)
(29)
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(Ans: n = 1, N = 21 = 2)
(30)

(Ans: 4)
(31)

(Ans: 2)

(32)

(Ans: 4)
(33)

(Ans: 4)

(36)

(Ans: 8)
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GI in Allenes, Cumulenes and Spiro compounds

Allene: Consecutive Diene

Consecutive pi-bonds lie in planes perpendicular to each other. Left pi-bond in XY plane while right
pi-bond is in YZ plane. From this geometry we can conclude that aerial distances a and b are same.
So, both positions are same with respect to A. Hence, cis-trans configurations not possible. So,
Allene does not exhibit GI.

Cumulenes: Compounds with Carbon chain having more than two consecutive double bonds

Due to change of plane in consecutive pi-bonds we can conclude the following:

 I - 2 : G e o m e t r i c a l I s o m e r i s m | 14

 Even cumulene does not exhibit GI

 Odd cumulene exhibit GI

 Only one SGA corresponding to Odd Cumulene. So, we can consider all bonds in Odd
Cumulene inside a single SGA

Spiro Compounds: Compounds with consecutive rings connected by single atoms. Like pi-bonds of a
Cumulene, consecutive rings in Spiro compounds also lie in perpendicular planes:

So, for GI considerations, we can assume an equivalent Cumulene against a Spiro compound by
squeezing each Ring into a double bond.

Example-1: n = 2, N = 22 = 4

Example-2: n = 1, N = 21 = 2

Example-3: n = 4, N = 24 = 16

Exercise:

Find the umber of GIs in following:

(1) Draw Isomers also.
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 15

(Ans: 2)
(2)

(Ans: 4)
(10)

(Ans: 4)

(11)

(Ans: 8)
(12)

(Ans: n = 3, Symmetrical, N = 22 + 21 = 6 )
(13)

(Ans: 2)
(14)

(Ans: 4)
(15)

(Ans: 8)
(16)

(Ans: No GI)
(17)

(Ans: 2)
(18)
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 16

(Ans: 2)
(19)

(Ans: 22+21 = 6)
(13)

(Ans: 2)

(14)

(Ans: 22+21 = 6)
GI in Biphenyls
Biphenyl: Two benzene rings connected by a single bond. Both Rings in same plane:

No GI possible as cis-trans not possible due to identical atoms.

Biphenyl rings with substituents: Two benzene rings connected by a single bond. If substituents are
attached on both rings like in following diagram. Then, to minimise the Steric interaction, rings orient
themself in perpendicular to each other. Cis-trans configurations not possible in perpendicular
orientation of rings (same reasoning as for allenes). Hence, biphenyls do not exhibit GI.

GI in C=N (Aldoximes & Ketoximes) and N=N (Azo compounds)

C=N compounds (Aldoximes & Ketoximes):
Aldehyde + Hydroxyl Amine  Aldoxime
Ketone + Hydroxyl Amine  Aldoxime

Examples:
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 17

Note the following:

 GI Isomers of Aldoximes and Ketoximes are known as syn and anti in place of cis and trans.
 GI Isomers of Aldoximes and Ketoximes are defined with respect to OH group. It is clear from
the below examples:

 In case of Ketoximes, out of two groups, one is syn w.r.t. OH and other is anti w.r.t. OH. So,
same Ketoxime can be expressed in two different ways like the following:
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 18

N=N compounds (azo compounds): GI Isomers of azo compounds are known as syn and anti in place
of cis and trans. Following examples explain it:

E-Z nomenclature, CIP rules

E-Z convention:
Consider the following molecule. There is an ambiguity in defining cis and trans configuration for this
molecule:

To avoid the ambiguity, E and Z designations are used in place of cis and trans. Following steps are
involved:
(1) Assign priority to each group relative to each other on left and right of SGA.
(2) Use the following convention:
Z (Zussman in German): High priority groups on same side
E (Entgegen in German): High priority groups on opposite sides (Ent = Anti)

CIP priority system (Cahn-Ingold-Prelog system):

 I - 2 : G e o m e t r i c a l I s o m e r i s m | 19

Assigning priority is the first activity to be done for determining E / Z configuration. Based on CIP
system, following rules need to be followed to assign priority to groups attached to SGA:
(1) Assign priority to two groups of each atom SGA based on atomic weights. Higher
atomic weight receives higher priority.
(2) If two atoms have same atomic weight then priority is decided by looking to next atoms and so
on. To decide the priority of an atom write down the attached atoms in decreasing order of
atomic masses. For example:
(Cl C C) has higher priority in comparison to (F C C)
(Cl H H) has higher priority in comparison to (O C C), Note that, we do not go for H vs C.
(3) Convert double bonds and triple bonds to equivalent single bonded structures by introducing
Phantom atoms or Phantom groups. Then, decide the priority accordingly.
(4) Lone pair of electrons is always have lowest priority.

(In the following examples: Red-> High Priority; Green->Low Priority)

Example-1: Rule-1

Example-2: Rule-1

Example-3: Rule-2: Tie at first atoms directly connected to pi-bond C-atoms. So, we go to atoms
connected with tie-atoms:

Example-4: Rule-3: Converting triple bond to single bonds through the use of Phantom atoms:
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 20

Example-5: Rule-3: Converting double and triple bond to single bonds through the use of Phantom
atoms:

Exercise:

Determine E or Z configuration in following:

(1)

(Ans: Z)
(2)

(Ans: Z)
(3)
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 21

(Ans: Z)
(4)

(Ans: E)
(5)

(Ans: Z)
(6)

(Ans: (a) cis (b) E)

(7)

(Ans: Bi-phenyl, No GI)

(8)

(Ans: Z)
(9)

(Ans: Even Spiro, No GI)

(10)

(Ans: Z)
 I - 2 : G e o m e t r i c a l I s o m e r i s m | 22

(11)

(Ans: Z)
(12)

(Ans: E)
(13)

(Ans: cis)
(14)

(Ans: Z)

(15)

(Ans: trans)
(16)

(Ans: Z)
(17) Arrange the following groups in the order of priority:
- OH, - NH2 , - COOH, - C= C, - CHO, - CH3, H, - COOCH3
(Ans: - OH > - NH2 > - COOCH3 > - COOH > - CHO > - C= C > - CH3 > H)

(18) Assign the priority 1 to 4 in following compound:

 I - 2 : G e o m e t r i c a l I s o m e r i s m | 23

(Ans: 1- Cl, 2- F, 3 – H, 4 – LP)

(19) Assign the priority 1 to 4 to the groups attached to Carbon attom marked *:

(Ans: 1- SH, 2- C=O , 3 – COOH, 4 - CHO)