Structure of organic molecules

Molecular structures of organic compounds depend upon the

chemical bonds. Formation of bonds may take place in
different ways depending upon the arrangement of electrons
in the outermost shell of combining atoms. The different type
of bonds may be classified into the following categories:
(i) Ionic Bonding:
This type of chemical bonding is formed as a result of
complete transfer of one or more electrons from one
atom to other so that both atoms acquire inert gas
electronic configuration (i.e. 1s2 or ns2 np6 outermost
electronic configurations). The atom that loses the
electron becomes positively charged. For example in
the formation of sodium chloride, sodium atom loses
its electron to acquire a stable octet and chlorine
accepts the electron to complete eight electrons.
Thus,
Na x cl Na x
cl
2,8,1 2,8,7 2,8 2,8,8

+ –
Na cl

Nacl
(ii) Covalent Bonding:
This kind of bond is formed by mutual sharing of
electron pairs between the atoms of the same or
different elements. It is essential for sharing that the
two electrons must have opposite spins.
For example: the formation of chlorine, two chlorine
atoms combine to form a molecule by sharing a pair of
electrons.

Formation of oxygen molecule.

Formation of nitrogen molecule.

Formation of water molecule.

The covalent bond is termed as single, double and

triple bond when one, two and three pairs of electrons
are shared respectively between two atoms.

The number of electrons which an atom can share

with others is known as the covalencyof the element.
Thus hydrogen, oxygen and nitrogen have covalencies
of 1, 2 and 3 respectively.
Orbital concept of covalent bond:
Chemical bonding in organic compounds is concerned
only with s and p orbitals.
An orbital is that region in space where the electron
charge density or probability of finding the electron is
greatest by their geometric shapes.
The S - atomic orbital is spherically symmetrical about
the nucleus whereas the P atomic orbitals have a shape
resembling a “dumb – bell” with two lobes disposed
symmetrically about the nucleus along a line. This line is
referred to as the orbital axis. The two lobes of the orbital
have a position concentric with the atomic nucleus where the
probability of finding an electron is zero.
This point is called a node and the plane passing
through it and perpendicular to the orbital axis is called
nodal plane.

The three p – orbitals differ not only in shape from the s

– orbital but also in directional properties. They are oriented
perpendicular to each other along the three axes and
therefore, are designated as px, py and pz orbitals.
 Now according to orbital concept, a covalent bond is
formed between two atoms when a half – filled valence
orbital of one atom overlaps a half – filled valence orbital of
another. It is essential that the two electrons which are
involved in bond formation should have their spins in
opposite directions.
Thus a covalent bond is formed as a result of the
progressive overlapping of the combining orbital. The atomic
orbitals actually merge together to form a new orbital called
molecular orbital. This orbital contains both the electrons
which have now got paired.
Types of covalent bonds: Two Types of covalent bonds are
visualized as follow:
(1) Sigma ( σ) bond (2) Pi ( π ) bond

(1) Sigma bond: A single bond formed between two atoms

by end to end overlap or by linear overlapping of orbitals
along their axes is known as sigma bond.
Therefore sigma bond can be formed by linear
overlapping of:
(i) s – s orbitals (ii) s – p orbitals
(iii) p – p orbitals, as shown in the diagram given below.
s – s overlap

s – p overlap

p – p overlap
 (2) Pi ( π ) bond :The bond formed between two atoms by
the lateral or sidewise overlapping of atomic orbitals is
known as a Pi bond.
Therefore the Pi bond is formed by lateral overlapping of:
(i)Py – Py orbitals
(ii) Pz – Pz orbitals as shown in the diagram given below.

Py – Py overlap

Pz – Pz overlap

π Bond is weaker than a sigma bond. This is because of a

relatively poor overlap of orbitals and thus the energy
decrease in π bond formation is less than in sigma bond
formation. Both sigma and Pi orbitals contain two electrons
but the Pi electrons are easily attacked than the electrons in
a sigma orbital. This is the reason why a double bond is more
reactive than a single bond.

HYBRIDIZATION AND TETRA VALENCY OF CARBON

1. It is clear that the orbital theory does not offer a
convincing explanation for the geometry of the
molecules, since the formation of the compounds of
carbon cannot be simply explained by the number of
unpaired electrons in orbitals. The tetra valency of
carbon in most of its compounds presents in intriguing
problem and the attempt to describe the bonding in
methane further brings up issues which are far more
intriguing and cannot be solved easily.
2. Electron promotion approach: since the electronic
configuration of carbon is 1s2 2s2 2p2, carbon has only
two half – filled orbitals. Hence, according to the orbital
theory carbon should be divalent and a compound
having formula CH2 should be known.
However, this is not so, it is a very reactive and unstable
product.
In actual practice carbon is always tetravalent and forms
a very large number of stable compounds. In all those
compounds, carbon has a covalency of four. To explain its
tetravalency, it has been suggested that under the
conditions of bond formation the electrons in the 2s
orbitals of carbon atom are unpaired and one of them is
promoted to the empty 2p orbital. This gives rise to the
electronic configuration 1s2, 2p1, 2p3 as shown below.
 Therefore in the excited state, the carbon atom has four
half – filled orbitals which would be available for the
formation of four covalent bonds. Thus carbon atom
would exhibit a covalency of four.
Although the process of electron promotion justifies the
tetra valency of carbon, the problem is still not solved
because the four half – filled orbitals of carbon are not
equivalent. A carbon atom has three p orbitals and one s
orbital. It may be clearly explained by considering the
formation of methane molecule.
Here four hydrogen atoms form a single bond with the
carbon. Now one of these bonds would involve the
overlapping of 1s orbital of hydrogen with the 2s orbital
of carbon to form one s – s bond while each of other
three bonds would involve the overlapping of 1s orbital
of hydrogen with a 2p orbital of carbon to form three s -
p bonds. But, in actual practice all the four bonds are
found to be equivalent to one another in all respects and
are directed towards the corners of a tetrahedron.
3. Hybridization, to explain the equivalence of the four
valencies of carbon, Pauling introduced the concept of
hybridization. In this process, the four orbitals of carbon
namely the 2s and 2px, 2py, 2pz combine together, losing
their individuality and produce four new orbitals
equivalent to each other in all respects. The new
equivalent orbitals are called hybrid orbitals which have
identical shape, size, energy and orientation is space.

Hybrid Types of
Orbit Mixing Natur
orbital hybridizati Orientation
al orbitals e
produced on
Pure X Spherically
S X X
Symmetrical
P X X Pure X Inclined at an
 angle of 90°
Sp S+p Two sp Hybri Sp Linear angle
Sp2 S+p+p Three sp2 d Sp2 180°
Hybri Triangular
d plane, angle
120°
hybri Sp3 Tetrahedral,
S+p+
Sp3 Four sp3 d angel 109°
p+ p
28.

Thus by mixing s and p, two equivalent sp orbitals are

obtained. By mixing s, p, p, three equivalent sp2 orbitals
are obtained and by mixing s, p, p, p, four equivalent sp3
orbitals are obtained.

The characteristics of hybridized orbitals are as follows:

1- The number of hybrid of orbitals produced is equal to
the number of atomic orbitals taking part in
hybridization.
2- A hybrid orbital, like the atomic orbitals, cannot have
more than two electrons in it, which two of opposite
spins.
3- While distributing themselves in space, the hybrid
orbitals assume the direction of the dominating orbitals.
Since s orbital has no directional character of its own,
the mixing p orbitals largely determine the shape and
the direction of the resulting hybrid orbitals.
Types of Hybridization
Hybridization, the process of redistribution of energy in
orbitals of an atom, is of following types:
(a) Sp hybridization :
The process of mixing of one s and one p – orbital to
form two new hybrid orbitals is called sp – hybridization.
 The characteristics of sp – hybrid orbitals are as follows:
(i) The two sp – hybrid orbitals are linear i.e. lie in one
plane.
(ii) The angle between the two sp – hybrid orbitals is
180°.
(iii) Each sp – hybridized orbital possesses 50 % s –
character and 50% p – character.
(iv) The 2py and 2pz orbitals remain perpendicular to the
sp – hybridized orbitals.

2
(b) Sphybridization:
The process of mixing of one s – orbital and two p –
orbitals of an atom to form three equivalent hybrid
orbitals directed towards the corners of an equilateral
triangle is called sp2 hybridization.
The 2s, 2px and 2py orbitals hybridize before bonding to
give three sp2- hybrid orbitals.
The characteristics of sp2 – hybrid orbitals are as follows:
(i) The three sp2 – hybrid orbitals lie one plane.
(ii) The angle between any two sp2 – hybrid orbitals is
120°.
(iii) All the three sp2 – hybrid orbitals are equivalent.
Each sp2 – hybrid orbital possesses ⅓ s – character
and ⅔ p – character.
(iv) The remaining 2pz orbital which is left in its original
state is oriented in a plane at right angles to the
plane of the sp2orbitals.

(c) Sp3 hybridization:

The process of mixing of one 2s orbital and three 2p
orbitals to form four new equivalent orbitals directed
towards the corners of a tetrahedron is called sp3
hybridization. Thus in CH4, C2H6, C3H8, CCl4, CHCl3,
CH3OH etc. hybridization of carbon is sp3.
 The characteristics of sp3 – hybrid orbitals are as
follows:
(i) The four sp3 – hybrid orbitals of carbon are directed
in space towards the corners of a tetrahedron.
(ii) Each bond angle is 109° 28’.
(iii) All the hybrid orbitals are equivalent. Each hybrid
orbital possesses 25% s- character and 75% p-
character.

Now the different types of hybridization can be easily

understood by following examples.
The number of sigma bond on one carbon atom of a
compound will indicate the type of hybridization. If a
functional group is present in a compound then the total
number of sigma bonds on the carbon atom of functional
group or the carbon atom attached to functional group or a
double or triple bond will indicate the type of hybridization.
1. For example in acetylene the number of sigma bonds
on carbon atom attached to triple bond is two, hence
there is sp hybridization.
In the formation of acetylene molecule, the sp hybrid
orbital of one carbon atom overlaps with that of the other to
form a σ bond (sp – sp overlap). The other sp hybrid orbital of
each carbon atom overlaps with s orbital of H atom to form
another σ bond. The remaining two pure 2p orbitals (i.e. 2py
and 2pz) along with one sp – orbital on each carbon atom are
now available for side wise overlapping to form a π bond.
 2. Formation of ethylene:

H H
C C
H H
Number of sigma bond between two carbon atoms = 1.
Total number of sigma bonds in the molecule = 5.
Number of sigma bonds on one carbon of ethylene = 3.
.
. . Hybridization sp2
Shape triangular.
2
Here two sp hybridized carbon atoms form one sigma
bond by head – on overlap. The remaining two sp2 orbitals of
each carbon form σ bonds with H- atoms. The unhybridized
2pzorbitals of the two carbon atoms undergo a sidewise
overlap forming a π bond.