Geometrical Isomerism

The phenomenon of existence of more than one compound having

identical structural formula but differing in spatial arrangements of
groups or atoms owing to the restricted rotation about a double bond
( C=C, C=N etc) or about a ring is known as geometrical isomerism. In
brief Geometrical isomerism arises due to restriction of rotation either
by multiple bond or ring formation.
Conditions for Geometrical Isomerism
Molecules must have restriction in rotation and restricted atoms must
have different substituents.
General cases for geometrical isomerism
1. Along with C=C,
2. Along with C=N,
3. Along with N=N,
4. Along with C=O,
5. Along with C=S,
6. Along with cycloalkane either homocyclic or heterocyclic
7. Cycloalkene with C > or = 8
Along with C=C
Along with C=N
Along with N=N
Along with C=O
Along with C=S
Along with cycloalkane either homocyclic or
heterocyclic
Cycloalkene with C > or = 8
Configurational Nomenclature of Geometrical Isomers
There are three common methods
1. Cis and trans method: for carbon double bond carbon and
cycloalkanes which have at least one substituent is same
2. E and Z method: for carbon double bond carbon and cycloalkanes
which have all substituent are different.
3. Syn and Anti: for carbon double bond nitrogen (along with H)
nitrogen double bond nitrogen (wrt lone pair of electron)
Cis and trans method
The geometrical configurations of simple molecules having two
identical substituents, one on each involved atom, may also be
designated as cis, indicating like substituents on the same side of the
rigid part, and trans indicating those on the opposite sides of the part.
Specification of configuration of geometrical isomers
To specify configuration of geometrical isomers by Cahn-Ingold-Prelog method
following procedures are adopted:
1. the structural formula for the molecule is drawn on the plane of the paper clearly
showing the double bond or the ring with their substituents attached to the
involved atoms of the rigid part.
2. priority of the substituents on each of the involved atom is then determined (by
the priority rule) and marked accordingly by assigning number 1 to the higher
priority substituent and number 2 to the lower priority substituent.
3. if the higher priority substituents are found on the same side of the double bond
or the ring, the configuration of the molecule is said to be Z (Z is the first letter of
the germen word, Zusamen meaning together ) ; on the other hand if the higher
priority substituents are placed in the opposite sides of the double bond or the
ring, the configuration of the molecule is described as E ( E is the first letter of the
German word, entgegen meaning opposite) .
Stability of cis and trans isomers
The stability of geometrical isomers is due to steric hindrance of bulky groups on
the cis-isomer because the bulky groups are present on the same side of double
bond. but in trans-isomers, bulky groups lie on the opposite side of the double
bond. Hence, trans-isomer is more stable
Priority sequence rule
Cahn-Ingold-Prelog developed a system, in this system the groups and atoms
attached to the double bond atoms and to the chiral atoms are assigned priority
following certain rules as given below:
I. Higher the atomic number of the atom attached to the involved atom, higher is
its priority, e.g. N has priority over C, O over N, Br over Cs, I over Br etc.
II. for isotopes, the atom with higher mass has the priority, e.g. C14 over C12,
deuterium over hydrogen.
III. if the first bonded atom is identical in at least two groups, the priority is
determined by considering the next atom or atoms present in those groups,
e.g. ethyl group has priority over methyl group as the next atom in methyl is a
H, but that in ethyl group is a C atom. the increasing priority order amongst
different butyl groups is:
IV. in assigning priority to multiple-bonded atoms the following changes are made: