Organic Molecules

Structure of
5
H

1. CLASSICAL TREATMENT OF BONDING

STRUCTURE OF ATOM
which accepted today have developed from the classical
The views on the atomic structure are

Rutherford-Bohr theory. According to this theory, the atom is made of a central positively charged
nucleus containing positively charged particles called Protons, and neutral particles called Neutrons,
called Etectrons
both having unit mass. The nucleus is surrounded by negatively charged particles
which carry one unit negative charge and negligible weight.
the nucleus in fixed orbits or energy levels. While the
The electrons are said to revolve around
a definite quantity of energy and it neither emits nor
electron moves in such a level, it possesses
in the orbits so that the maximum number of electrons in
absorbs energy. The electrons are arranged
nucleus is 2, 8, 18, 32, 18, 8. The outermost orbit of
the various orbits starting from the one nearest the
is incomplete and the electrons in it are
electrons in different atoms (except those of inert gases),
known as the Valence Electrons.

WHY ATOMS COMBINE TO FORM MOLECULES?

The classical concept of formation of molecules, proposed by Lewis and Kossel, is based upon
electrons in the outermost
the electronic structure of atoms. The atoms of inert gases have either 2 or8
orbit. These gases do not enter into chemical combination and, therefore, are assumed to have complete
or stable orbits. The atoms of all other elements have incomplete outermost orbits and tend to complete
them by chemical combination with other atoms. GN. Lewis proposed that it is the urge of atoms to

complete their outermost orbits of clectrons as in the inert gases, which is responsible for chemical
 60A TEXTBOOK OF ORGANIC CHEMISTRY
combination. In other words, chemical combination
between two atoms results from the redistribution
of
electrons between them so that both the atoms complete their outermost orbits or acquire stable
electronic configuration possessed
by the inert gases.
YPES OF BONDSS
There are three basic ways in which
chemical combination occurs
(1) lonic or electrovalent bond
(2) Covalent bond
3) Coordinate bond
lonic or Electrovalent Bond.
lonic or electrovalent bonds are formed
clectrons from one atom to by transfer of valence
another. This type of bond unites two atoms one of which has
clectrons than the stable number excess
(2 or 8), and the other is short of electrons. Sodium chloride is a
typical compound formed in this way.
Here sodium atom (2, 8, 1)
the
attain a stable inert
transfers its excess electron to chlorine atom (2, 8,7). and thus both
gas type electron
neon (2, 8) and
becomes positively configuration. Sodium acquires the electron configuration of
8, 8). and becomes charged. Chlorine acquires the electron configuration
of argon (2,
negatively
force of attraction. This charged. These oppositely charged
ions are held together by electrostatic
type of bond is commonly found in
inorganic compounds.
1e 1e-
8e 8e
e 8e
2e 8e
( (CI
2e ( 2e
Na
Na 2eCI

Na CI

Sodium Chlorine Sodium chloride

lonic or clectrovalent
compounds are nonvolatile, soluble in water and
points. Their aqueous solutions conduct electric possess high melting
current.
Covalent Bond. Covalent bonds are formed
by mutual
which are short of electrons. The sharing
unites two atoms, both of of electrons. This
two atoms type of bond
and then share the contribute
resulting pair of electrons. Hydrogen is the one electron each
simplest compound formed
Here the two electrons H+H HH or
H-H
in this way.
are shared, and give toeach
This type of bond is hydrogen atom the configuration of
termed covalent bond and is indicated
found in by line. Covalent a helium
organic compounds. bonds are
commonly
Covalent compounds are volatile,
They possess low nelting and generally insoluble in water but
boiling points. Their solutions do not soluble in organic solvents.
Coordinate Bond. Coordinate bond is also conduct electrie
formed current
the two clectrons that
are
by mutual
shared come sharing of electrons but in this case
the same atom.
from A
of which has a
spare pair of electrons and the other Is short coordinate bond unites two
atom) contnbutes of atoms, one
electrons and the secondofatom
a
one
par (lone pair) of pair electrons. The tirst atom
After the formation of the (donor
bond, the lone of eles tuons is held n (acceptor atom)
represented by an arrow.
pau
common The
accepts it
hond
pointung away tromthe donor atom coordinate bond is
is found in the boron hy
drnde annmonia counplex Aneellent illustratuon of the coordinate
 STRUCTURE OFORGANIC MOLECULES 61

H H H H H H
HB NH H B:NH or H-B-N-H
X X
H HH H
VALENCE OF CARBON
The atomie number ofcarbon is 6 and its atomic weight is 12. Its clectron configuration is shown
in Fig. 5.1. t has four electrons in the last orbit and tends to gain four more electrons by forming four
covalent bonds with other hydrogen atoms. Thus, the structural formula of the simplest hydrocarbon
methane (CH,) can be writen as
H

+4Hx HCH or H-C-H

H H
Similarly in all organic molecules carbon atom is tetravalent. That is, it has a valence ot 4.
to Le Bel and van't Hoff the four
ACCording
valencies of carbon do not lie in one plane. They are directed
the corners towarus
of a regular tetrahedron so that the
angle between any two valencies is 109-28' (Fig. 5.2)
-4e-
2e.

10928

Fig. 5.1. Electron configuration Fig. 5.2. Four valencies of carbon are directed
of carbon. towards the corners of a regular tetrahedron. The
angle between any two valencies is 109°28'.

Carbon-Carbon Single Bond. Carbon atom has the wonderful property of uniting with other
carbon atoms through covalent bonds. This serves to construct the carbon structure of
organic
molecules. Thus the molecules of hydrocarbons, cthane and propane contain two and three carbon
atoms respectively linked by covalent bonds.

H--C-H H--C-c-H
H H H H
Ethane Propane
Carbon-Carbon Double Bond. In some compounds, two of the valencies of a carbon atom may be
satisfied by union with the two valencies of another carbon atom. Thus in
are united by two covalent bonds.
ethylene the two carbons
H H
H-C=©-H =c
Ethylene Carbon-Carbon
double bond
Such a union
involving covalent bonds between adjacent carbon atoms is called Double
two
Bond.
Carbon-Carbon Triple Bond. Sometimes two adjacent carbons are linked
covalent bonds. Thus acetylene molecule is represented as : together by three
H-C=-H -CEC-
Acetylene Triple bond
 62 ATEXTBOOK OFORGANIC CHEMISTRY
Such a union involving three covalent bonds between adjacent carbon atoms is called Triple
Bond.
Cyclic Structures. We have given above some examples of substances where the molecules
consist of carbon atoms joined together in chains that are free at both ends. There are numerous
compounds known where carbon atoms join to form closed rings. These are called Cyclic Compounds
or Ring Compounds.
H2

C-cH2 HC CH
H2C CH2 HC CH

Cyclohexane Benzene
BOND LENGTHS
hentwo atoms are bonded by a covalent bond, the distance between the centres of the two nuclei
is called bond length. Bond lengths are measured by X-ray crystallography and by microwave
spectroscopy. The unit of bond length is Angstrom (MÅ=103 cm). For most bonds the values are I to
2 A. Some typical bond lengths are
given in Table 5.1.
Table 5.1 SOME BOND LENGTHS
Bond Bond length (Ä) Bond Bond length (Å)
C-H 1.09 C-O 43
C-C 1.54 C-O 1.21
C-C 1.34 C-N 1.47
C=C 1.20 C-CI 1.77
0-H 0.96 C-Br 1.91
N-H 1.02 C-I 2.12

BOND ENERGIES
Bond energy or bond strength is defined as the amount of energy required to breaka bond in a
molecule. Bond energies depend upon the type of bond as well as the structural environment in which
the bond is situated. They are determined by quantitative measurements of heats of
chemical reactions
(calorimetry) and by spectroscopic methods. The unit of bond energy is kcal/mole. Some typical bond
energies are given in Table 5.2.

Table 5.2 SOME BOND ENERGIES

Bond Bond energy Bond Bond energy
(keal/mole) (keal/mole
C-H 99 C-O 86
C-C 83 C-0 179
C=C 146 C-N 73
C=C 200 C-CI 81
0-H 111 C-Br 68
N-H 93 C-I 51
 STRUCTURE OF ORGANIC MOLECULES 67

in their atoms are

electron contiguration of chemically stable inert gases shows that all the orbitals
completely filled. On the other hand, atoms of allother elements are known to bereactive and have
half-filed orbitals. During bond formation, the half-filled orbitals of such atoms tend to acquire
anotner
to stable orbitals in He, Ne, Ar, etc. Thus it is
electron in order become by having completely filled as

evident that only those atoms which have half-filled orbitals would combine with each other to form
molecules. In other words, in bond formation only the valence shell electrons and the orbitals
associated with them are of importance. In the valence shell only those orbitals take part in bona

formation which are half-filled, that is, which contain only unpaired electrons. The half-filled orbitals
involved in bond formation are often referred to as the Bonding Orbitals.
Ionic or Electrovalent Bond. The only difference the modern structure of atom makes to the idea
of ionic bonding is that we can now be more specific with regard to naming and indicating the
positions of the electrons that are transferred. Thus in sodium chloride, it is the 3s electron of sodium
that is transferred to the chlorine and it will occupy a 3p orbital in the chlorine atom.
Na 1s 2s 2pfas [Nal' 1s2s 2p° + e
Neon Configuration
Cl 1s2s2pas3p5+ e [CI 1s 2s*2p°3s*3p
Argon Configuration
Both Na" and C have attained a more stable electronic configuration of an inert gas (and thereby
lowering the total energy of the system). Nat has the electron configuration of neon. Ci has the
electron configuration of argon.
Covalent Bond. A covalent bond between two atoms results from the overlap of an orbital of one
atom with an orbital of another atom.
When two orbitals overlap they share the same region in space
and a new orbital, called a Molecular Orbital
(MO), is formed. The molecular orbital is a covalent
bond. Like an atomic orbital, a molecular orbital can accommodate
bond is formed only if:
only two electrons. A covalent
(1) the two combining orbitals are half-filled.
(2) the bonding orbitals approach each other in proper alignment
needed an for effective
overlap.
3) the electrons in the bonding orbitals have opposite spins.
TYPES OF COVALENT BONDS
There two main types of covalent bonds
are or molecular orbitals
(1) Sigma (o) bonds
) P i (T) bonds
Sigma Bond. A sigma bond is formed by the linear or end-to-end overlap of orbitals.
obtained: They may be
(a) By the overlap of two s orbitals,

S S
o Bond
(b) By the overlap of p, and an s orbital,

S
Px
(c) By the overlap of two p orbitals, o Bond

=
Px Px
Bond
 68 ATEXTBOOK OFORGANICCHEMISTRY
the two nuclei. They are represented
Sigma bonds are symmetrical around the line drawn between are called
that occupy a sigma bond
by a single ine drawn between the atomic symbols. The electrons
Sigma (o) Electrons.
Pi-Bond. Api (t) bond is formed by parallel or side-to-side overlap ofp orbitals. For example,

2-9
Py Py
t Bond

LIke the p orbitals from which it is obtained, a t bond has two lobes. One half of the t bond lies
above the plane containing the two nuclei and the other half lies below. The electrons that occupy Tt
bond are known as the Pi (Tt) Electrons.
There are two important differences between sigma and pi bonds.
(1) Pi electrons are loosely held than a pair of electrons in a o bond. They are of higher energy.
As a
result, T bonds are more easily broken and are more reactive than o bonds.
(2) Rotation of atoms is not possible around a t bond. If any attempt is made to do so, the lobes
of p orbitals will no longer be coplanar and will not overlap to fom the t bond. This restriction in
rotation around a t bond is responsible for Cis and Trans isomerism in alkenes.

AYBRIDIZATION
sp3 HYBRIDIZATION OF CARBON
Let us consider the electronic configuration of carbon in its ground or atomic state.
c (Ground state) =1s 2s 2p 2py'2p2°
Valence shell
In terms of energy level diagram, this electron configuration may be represented as in Fig. 5.13.
Since there are only two unpaired electrons (half-filled orbitals), it might be expected that only two
single covalent bonds will be formed.
On this basis, carbon would combine with two hydrogen atoms (H = 1s) to form a molecule CH2
The two C-H bonds would be formed by overlap of the 2p orbitals (p, and p,) with the 1s orbital of
each hydrogen atom. Since the angle separating the p orbitals is 90°, the C-H bonds would be at right
angles to each other. But from chemical analysis we know that the simplest stable compound that
carbon forms with hydrogen is methane (CH4) and this compound contains four identical C-H bonds.
Now let us assume that one of the 2s electrons in the ground state is moved or promoted to the
empty p, orbital. Since 2p, orbital is at a higher energy level than the 2s orbital, this promotion process
would require input of energy. This energy is supplied in the form of heat or light. This new state of
carbon is referred to as the Excited State. The electron configuration of the carbon atom in its excited
state is :
C Excited state) 1s 2s'2p, 2py 2p
-------*--***----**--------

Valence shell
In terms of energy level diagram, this electron configuration may be represented as in Fig. 5.13.
Since there are four unpaired electrons (half-filled orbitals) in the valence shell of the carbon atom in
its excited state, it might be expected that four covalent bonds will be formed. On this basis, carbon
would combine with four hydrogen atoms to forma molecule CH4. The three C-H bonds would be
formed by the overlap of three 2p orbitals (P. P, and p,) with the ls orbital of each hydrogen atom. The
fourth C-H bond will be formed by the overlap of the 2s orbital of carbon with the Is orbital of a
hydrogen atom. Since the angle separatingthep orbitals in an atom is 90°, the three C-H bonds may
be expected to be at right angles to each other. The fourth C-H bond involving the overlap of s orbitals
 STRUCTURE OF ORGANIC MOLECULES 69

will not have any directional characteristics because s orbitals are spherically symmetrical. This
of methane molecule. This
implies that two different types of C-H bonds are involved in the formation bonds that are
is not true. Experimentally, methane has been shown to contain four identicalC-H
directed towards the corners of a regular tetrahedron.
To form four identical bonds, carbon must contribute a set of four equivalent orbitals. 1This can be
achieved if the 2s and the three 2p orbitals (p,. P, and p,) in the excited state are mixed or hybridized
to give four new equivalent orbitals. Theseneworbitals are known assp (pronounced ess-pee-three)
hybrid orbitals or simply sp* Orbitals because they are formed by the interaction of one s and threep
orbitals. Mixing of a pure s orbital and three p orbitals is rather like mixing of a gallon of pure red paint
Tnd three gallons of white paint to give four gallons of pink paint. This process of mixing of pure
orbitals to give a set of new equivalent orbitals is termed Hybridization and the carbon is said to be in
Hybridized State. The electron configuration of the carbon atom in its sp hybridized state is:
C (Hybridized state) 1s2 2(sp)'2(sp)'2(sp$)'2(sp*)
---.-.---
Valence shell
In terms of energy level diagram, the above electron configuration may be represented as 1n
Fig.1 Mix
Px Py Pz Px Py Pz

2p 2p
2(sp)

2s 2s

1s 1s
(C) Ground state Excited state sp3-Hybridized state
Fig. 5.13. Formation of four equivalent sp hybrid orbitals of carbon.
The processes which lead to the formation of four equivalent sp3 orbitals are summarized in
Fig. 5.13.
Each sp orbital contains one electron. Since each sp? orbital is obtained from one s and three p
orbitals, it has 25% s-character and 75%p-character. As indicated, eachsp orbital has a large lobe and
*

a smalllobe (Fig.

Sp3
109.5
C

Fig. 5.14. Shape of an sps Fig. 5.15 Orientation of

hybrid ortbital. four sp hybrid orbitals.
The four new sp orbitals obtained above are identical (same energy and shape) but differ only in
their orientation in space with respect to each other. The four
sp' orbitals are arranged in such a way
that their axes are directed towards the cormers of a regular tetrahedron with carbon located at the
centre. The angle between any two orbitalsis therefore, 109°28'. The orientation of sp' orbitals is
shown in Fig. 5.15. The smaller lobes are not indicated because they do not extend sufticiently far trom
nucleus to participate in bond formation.
The tetrahedral arrangement is favored because it allows the sp' orbitals to stay as far away from
each other as possible and thereby reducing the electron electron repulsion. This is in keeping with
 70ATEXTBOOKOFORGANIC CHEMISTRY
the fact that each sp orbital contains an electron, and electrons stay as far apart as possible because
they have the same charge.
At this stage, the student should clearly understand that carbon does not necessarily undergO
bond fornation in its ground state. The electron configuration may change prior to bond rormauon
and the final arangement that it acquires would depend upon the number of other atoms or groups t
which it is attached.
Whenever carbon is bonded to four other atoms or groups (as in methane), it uses sp hybrid
orbitals.
Bonding in Methane. In methane carbon forms single covalent bonds with four hydrogen atoms
Since the carbon atom is attached to four other atoms it uses sp orbitals to form these bonds. Fig. 5.l16
shows how the bonds in methane are formed.
Each C-H covalent bond is the result of the overlap of an sp orbital from carbon and 1s orbital
from hydrogen. H

sp-s 109°.5°
- S p
1.09A
0 H

H
H
a Bonds

Fig. 5.16. Bonding in Methane.

Since the four sp orbitals are oriented in such a way that their axes are directed towards the
corners ofa regular tetrahedron with carbon located at the centre, the resulting C-H bonds are also
directed towards the vertices of a tetrahedron with carbon at the centre. Thus, the bond angles
in methane are the same as the angles between the axes of the sp orbitals, that is 109°28'.
The covalernt bonds formed by the overlap ofsp orbitals and s orbitals are sigma (0) bonds
because the electron density in each bond is symmetrical about the line joining the centres of two
bonded atoms. Thus, all C-H bonds in methane are sigma bonds.
Electron diffraction and spectroscopic studies have shown that methane has a tetrahedral structure
and all the C-H bonds are identical. They are the same length (1.09° A). Theenergy required to break
any of the four bonds is the same (102 kcal). The angle between any pair of bonds is 109°28'.
a Bonds

sp3-sp3
1 . 0 9 Ac

L54 A 109.5
s

S-Sp
Sp3sS
H
H H H
H H
Fig. 5.17 Bonding in thane.
Bonding in Ethane. In ethane there are six C-H covalent bonds and one C-Ccovalent bond. As
in the case of methane, each C-H bond is the result of the overlap of an sp* hybid orbital from carbon
and 1s orbital from hydrogen. The C-C bond arises from the overlap of sp* orbitals, one from each
carbon atom. Fig. 5.17 shows how the bonds in ethane are formed.
All C-H bonds and the C-C bond are sigma (o) bonds
 STRUCTURE OF ORGANICMOLECULES 71

Electron difraction and spectroscopic studies have given the following measurements for the
molecule ot ethane: HC-H and H-C-C bond angles are 109° 28', C-H bond length is 1.09A and C-

Cbond length is 1.54A.

sp HYBRIDIZATION OF CARBON
As in the case of sp" hybridization, we start with the carbon atom in its ground state.
C (Ground state) =
1s 2520, 2P,2P
Valence shell
The promotion of one of the two 2s electrons to the empty p, orbital gives the excited state.

C (Excited state) = 1s2 2s'2p,2p2p

Valence shell
At this point we follow a different course than that used for sp? hybridization, in which case one
2s and three 2p orbitals were mixed. Instead, the 2s electron and justtwo of three 2p orbitals are mixed
or hybndizced to give three new equivalent orbitals. Thesenew orbitalsare referred to as sp- (pronounced
ess-pee-two) hybrid orbitals or simply sp? Orbitals, because they are formed by interaction of one s
and two p orbitals. Third 2p, orbital is left unhybridized. The electron configuration of the carbon
atom in its sp* hybridized stateis
C (Hybridized state) = 1s 2(sp) 2(sp)'2(sp)'2P2
**no*****************-*********a**

Valence shell
The processes which lead to thhe formation of three equivalent sp2 hybrid orbitals are summarized
in Fig. 5.18.
Each sp orbital contains an unpaired electron. The shape of an sp? orbital is similar to that of an
sp' orbital

Mix

Px Py Pz Px Py Pz Pz

2p
2p 2P
2(sp )
2s 2s
1s 1s 1s
(C) Ground state Excited state sp2-Hybridized state

Fig. 5.18. Formation of three equivaient sp hybrid orbitals of carbon.

The sp? orbitals obtained above are identical (same energy and shape) but differ only in their
orientation in space with respect to each other The three sp* orbitals lie in the same plane with their
axes directed towards the corners of an equilateral triangle. The angle between any pair of orbitals is
thus 120°. The orientation of sp' orbitals with respect to each other is shown in Fig. 5.19 (a). The
smaller lobes are not indicated because they do not extend sufficiently far from nucleus to participate
in bond formation. The tigonal arrangement is favored because it allows the sp orbitals to stay as far
apart from cach other as possible and thereby reducing the electron-electuon repulsions
The unhybridized p, orbital is oriented along an axis perpendicular to the plane of sp' orbitals,
with each lobe above and below the plane of the sp orbitals. Fig. 5.19()indicates the position ofthe
unhybridized p, orbital in relation to the three spp orbitals
 72 ATEXTBOOKOF ORGANIC CHEMISTRY
Pz Pz

sp2

(a) (b) (c)

Fig. 5.19. (a) Orientation of three sp? orbitals. (b) The unhybridized Pz
orbital. (c) Orientation of the p, orbital in relation to the sp? orbitals.
lt should be remembered that whenever carbon is bonded to thrce other atoms or groups (as in
ethylene) it always uses sp hybrid orbitals and ap, orbitai to form its bonds.
Bonding in Ethylene. Each carbon atom in
T Bond
ethylene (HC=CH2), is attached to two hydrogen
atoms by single covalent bonds and to another carbon Pz Pz
atom by a double bond. Since each carbon is attached H
to three other atoms, it uses sp hybrid orbitals plus sp2-sp
an unhybridized p, orbital to form its bonds.
In ethylene there are four C-H single covalent S
SP

bonds and one C-C double bond. Each C-H bond is

a sigma (o) bond and results from the overlap of an H H
sp orbital from carbon and Is orbital from hydrogen. Bond
One of the two bonds in the double bond is also
ag bond and results from end-to-end (linear) overlap Fig. 5.20. Bonding in Ethylene.
of the sp orbitals, one from each carbon atom.
The second bond in the double bond is a pi (t) bond and results from side-to-side (lateral)
overlap of two unhybridizedp, orbitals, one from each carbon atom. It should be noted that p, orbitals
can overlap only when all six atoms lie in the same plane, that is, the plane of the o bonds. Like the p
orbitals from which it is formed, a Tt bond consists of two equal parts. One part lies above the plane of
the carbons and hydrogens and the other part lies below this plane. These two parts together make up
one (T) bond.
Although the C-C double bond inethyleneis represented by two equivalent lines, remember
that one line represents a a bond and the other the t bond (Fig. 5.22).

One half of the n Bond

Pz Pz
H ****** ******
T Bond

c.
H
H H
o Bond

The other half

Fig.5.21. Formation ofthe p bond in Ethylene. Fig. 5.22. The C-C double bond in
ethylene is represented by two
equivalent lines. One line represents
a o bond. The other line represents
the t bond
 STRUCTURE OF ORGANIC MOLECULES 73
Electron diffraction and spectroscopic studies have also shown that
molecule. All bond angles (H-C-H and H-C-C) are 120°. The C-H bond ethylene 1.09A.
is
planar (Tla) a

length The
bond length in ethylene is 1.34Å as compared to the C-C bond is C-C
length of 1.54A in
ethane. ns
shortening Is to be expected on the basis of additional orbital
overlap associated with the two Donds
sp HYBRIDIZATION OF CARBON
AS in the case of sp hybridization, we again start with the carbon atom in its ground state.

C (Ground state) 1s 2s
=
2px 2py 2P2°
***********************
Valence shell
The promotion of one of the two 2s electrons to the empty p, orbital gives the excited state.

C (Excited state) =1s2 2s'2p,'2py 2p2

------..--io.---
Valence shell
At this point we follow a different course than that used for sp? hybridization, in which case one
2s and two2p orbitals were mixed. Instead, the 25 electron and just one of the three 2p orbitals are
mixed or hybridized togive two new equivalent orbitals. These two new orbitals are referred to as sp
pronounced ess-pee) hybrid orbitals or simply sp orbitals because they are formed by interaction of
one s and one p orbital. The other two 2p orbitals (p, and p) are left unhybridized. The electron
configuration of the carbon atom in its sp hybridized state is:
C(Hybridized state) 1s 2(sp)'2(sp) 2Py 2P
=

Valence shell
Mix
Px Py Pz Px Py Pz Py Pz

2p 20 t t 2P
2(sp)
2s 2s

1s 1sL 1sL
(C) Ground state Excited state sp-Hybridized state
Fig.5.23. Formation of two equivalent sp hybrid orbitals of carbon.
The processes which lead to the formation of two equivalent sp hybrid orbitals are summarized in
Fig. 5.23. Pz
Each sp orbital contains an unpaired electron.
The shape of an sp orbital is similar to that of an sp sP Sp Sp
orbital.
The sp orbitals obtained above are identical
(same energy and shape) but differ only in their
orientation in space with respect to each other. They
lie in a straight line. The angle between the two sp (a) (b)
orbitals is thus 180° (Fig. 5.24a). The linear Fig. 5.24. (a) Orientation of two sp orbitals (b)
arrangement is favored because it allows the sp Orientation of the unhybridized p, and p, orbitals
orbitals to stay as far apart from each other as in relation to the sp orbitals
possible and thereby reducing the electron-electron repulsions. The unhybridized p, and p, orbitals
are at right angles to the line of the sp hybrid orbitals. Fig. 5.24(b) indicates the positions of the p, and
P orbitals in relation to the two sp orbitals.
 74ATEXTBOOKOF ORGANIC CHEMISTRY
Tt should be remembered
that whenever carbon is bonded to two other atoms or groups (as in
acetylene) it always uses sp hybrid orbitals and two 2p (p, and p,) orbitals to form its bornds.

T Bonds
Pz
Py
S-sp sp-sp
H
C

o Bonds

Fig. 5.25. Bonding in Acetylene.

Bonding in Acetylene. Each carbon atom in acetylene (H-C=C-H) is attached to one hydrogen
atom by a single covalent bond and to another carbon atom by a triple bond. Since each carbon is
attachedto two other atoms it uses sp hybrid orbitals plus two unhybridized 2p orbitals (p, and p.)to
form its bonds.
n Bonds
Pz
T Bonds

Sp-sp
H-SSp Sp-SH H- -c#
o Bonds
o Bonds
Fig. 5.27. The C-C triple bond in
Fig. 5.26. Formation of the two r bonds in Acetylene. acetylene is representated by
three equivalent lines. Two lines
represent the t bonds. One line
represents the o bond.

In acetylene there are two C-H single covalent bonds and one C-C triple bond. Each C-H bond
is a sigma (o) bond and results from the overlap of an sp orbital from carbon and 1s orbital from
hydrogen.
One ofthe three bonds in the C-C triple bond is also a obond and results from end-to-end (linear)
overlap of the two sp orbitals, one from each carbon.
The other two bonds in the triple bond are pi (t) bonds and result from side-to-side (lateral)
overlap of the unhybridized p orbitals on each carbon.
Although the C-C triple bond is represented by thre equivalent ines, remember that one line
represents ao bond and the other two the T bonds.
Electron diffraction studies have also shown that acetylene is alinear molecule. The H-C-Cbond
angle is 180°. The C-H bond length is 1.09 Ä. The C-C bond length is 1.20 A.
HYBRIDIZATIONS OF NITROGEN
Atomic number of nitrogen is seven. It has five electrons in the valence shell (outermost shel).
Like carbon, the nitrogen atom also undergoes sp', sp. and sp hybridizations. Fig. 5.28 illustrates the
formation of sp hybrid orbitals of nitrogen.
 STRUCTURE OF ORGANIC MOLECULES 77

P T Bond

H H..
s-SPC&C S P S p 2

-(
. .sn--ceno.
H H

Fig. 5.34. Bonding in Formaldehyde, H,C-O.

GUIDELINES

Drawing Molecular Orbital Structure of Organic Molecules

rememberT:
When you are asked to draw orbital structure of an organic molecule, always uses spP
in methane or ethane), it always
(1) Whenever carbon is bonded tofour other atoms or groups (as
hybrid orbitals to form its bonds. sps hybrid
Whenever carbon is bonded to three other atoms or groups (as in ethylene), it always uses
(2)
orbitals and ap orbital to form its bonds.
it always uses sp hybrid
(3 Whenever carbon is bonded to two other atoms or groups (as in acetylene),
orbitals and two p orbitals to form its bonds.

ELECTRONEGATIVITY
in a
Electronegativity of a n atom is a measure of its power to attract electrons that it is sharing
of electrons,
covalent bond.Ií a covalent bond A: B, ifB has greater power to attract the bonding pair
it is said to be more electronegative.
The electronegativity of an atom
Atoms of different elements have different electronegativities.
depends upon two factors
the magnitude of the positive charge on the nucleus.
(1) Atomic Number. That is,
distance of the valence electrons from the nucleus.
(2) Atomic Radii. That is, the
less atomic radius have higher electronegativities. The
Atoms with higher atomic number and
Table is rather regular. As you read to the right in a
trend of electronegativities in the Periodic
the elements become more electronegative. Likewise, as
particular horizontal row of Periodic Table,
vertical row, the elements become more electronegative. Electronegativity
you read up a particular
molecules are given below:
values of the elements commonly encountered in organic

2.1
Li Be B N
1.0 1.5 2.0 2.5 3.0 3.5
Na Mg A lSIPS C
1.5 1.8 2.1 2.5 3.0
0.9 1.2

0.8
Ce
1.0
Br
2.8

Increasing Electronegativity 2.5

 8 AEXTBOOK OF ORGANIc CHEMISTRY
The concept of electronegativity has
the properties of compounds. proved very useful in predicting the nature of bonds as aiso
POLAR AND NONPOLAR BONDS
When a cOvalent bond is
formed between two atoms with different
involved in the bond are not shared. The
atom with higher
electronegativities,
the
electrons
closer to it. In other words, the electron electronegativity pulls bonding elecurons
the
density in the molecular orbital would be
atom
with higher electronegativity. The result of this displacement of the moleculargreater around ne
orbital toward the
more
electronegative atom will be that the more
the less electronegative atom will electronegative atom will acquire a small negauve and
Let us now consider
acquire a small
positive charge.
the C-Cl covalent bond. Because chlorine is more electronegative tnan
carbon, he electron
around the carbon atom.
density in the molecular orbital would be higher around chlorine
atom than
Thus the chlorine atom acquires a small negative charge and the carbon atom
acquires a small positive charge. This may be indicated in the following way.
,.'

C CI or
-
C-CI Bond is a polar bond.
The Greek letter delta, 8, stands for smll. The symbol 8, means a small positive charge, and &
means a small negative charge. Such a bond which appears to have a positive end and a negative end,
is said to be a Polar Bond.
When a covalent bond is formed between two atoms with sanme electronegativities (C-C, H-H, and
F-F). theelectrons involved in the bond are shared equally. Electron density in the molecular orbital
binding the two atoms together is same around each atom. There is no positive and negative end.
Such a bond is said to be a Nonpolar Bond.

.
H H H-H

H-H Bond is a nonpolar bond.

POLAR AND NONPOLAR MOLECULESs
A molecule is said to be a polar molecule if it satisfies thefollowing two conditions:
(1) Themolecule must contain one or more polar bonds.
2) The polar bonds must be so directed that there are separate centres of positive and
charges in the molecule. negative
Carbon dioxide has two polar carbon-oxygen bonds, but the molecule is not polar. The carbon
dioxide molecule is linear, and the centre of the two negative charges is at the same
of the positive charge the carbon atom (Fig. 5.35).
-
place as the centre

CI
Center of Center of
Center of positive and
positive and
positive charge negative charge
negative charge H H CI
O=C=0
Center of
negative charge CI
Fig. 5.35. Carbon dioxide is Fig. 5.36. Water is a polar Fig. 5.37. Carbon tetrachloride
a nonpolar molecule. molecule. is'a nonpolar molecule.
 STRUCTURE OF ORGANIC MOLECULES 79
Water molecule has two polar oxygen-hydrogen bonds. The H-O-H bond angle is 104°.
of the positive charge is between the hydrogen atoms The
c e n t r e

(Fig. 5.36). As the centre of posiuve

eAnd the centre of negative charge do not coincide, water molecule is polar.
charge

Carbon tetrachloride has four polar carbon-chlorine bonds, but the molecule is not polar. The
rarbon tetrachloride is tetrahedral (all CI-c-Cl angles are 109 28), and the centre of four negative
charges is at the same place as the centre of the positive charge - the carbon atom (Fig. 5.37).
charg
Polar molecules behave like small magnets and possess a dipole moment. The dipole moment (4)
is the product of the magnitude of the charges and the distance between the charges.
Dipole Moment = Charge x Distance
Molecules that do not have a dipole moment are called Nonpolar Molecules.
Polar molecules have a great attraction for each other as also for ions, and thus acquire
characteristic physical and chemical properties.

Polar molecules
Nonpolar molecules
and polar
on the orientation
of nonpolar molecules
electric field whereas polar
The effect of an themselves randomly,
molecules orient the positive
molecules. Nonpolar ends point toward
themselves so that their negative
molecules orient plate.
ends point toward the negative
plate and their positive
RESONANCE CONCEPT one structure. For example,
cannot be accurately represented by
compounds
A number of organic
represented as :
benzene is ordinarily

carbon-carbon double bonds.

carbon-carbon single bonds and three
has three in benzene are identical
This structure that all carbon-carbon bonds
However, it has
been determined experimentally carbon-carbon bond length of (1.39 Å)
is
(1.39A). Furthermore, the
and have the same
bond length
double-bond length (1.34 Ä) and the normal
carbon-
between the normal carbon-carbon be written for
intermediate structures
two alternative
and (1
can 2)
Actually
carbon single-bond length (1.54 A).
benzene

Neither (1) nor (2) is a correct

These two structures differ only in the position of electrons.

somewhere between these two
structures.
actual structure of benzene lies
representation of benzene. The can be written for a compound
which involve
which two or more structures
This phenomenon in atoms is called Resonance.
identical positions of
 ATEXTBOOK OF ORGANIC
CHEMISTRY

-
The actual structure of the Benzene
2

molecule is said to be a
3
Benzene
structures. The alternative structures Resonance Hybrid of various possible altermatüve
are referred to
Forms. doubie headed
A as the
Resonance Structures or Canonical
arrow
resonance hybrid. Thus in the ( ) between the resonance structures is used to
structure of the
case of represent the
benzene, (1) and (2) represent the resonance structures. Actual
molecule may be
single structural formula (3). represented aas hybrid of these two
ened resonance structures, or by the
It should be
clearly understood that the resonance structures (1) and (2) are not actual
of the benzene molecule. structure
the molecule. In resonance
They exist only in theory. None of these structures
adequately represents
theory, we view the benzene molecule (which is of course a real entity) as
being hybrid of these two hypothetical resonance
structures.

Unicorn Dragon
Resonance structure Resonance structure

Rhinoceros
Resonance hybrid
Analogy beiwean e reesunance hybricd and artinoceros. TheiesOnarnce
siructures, iike the unicorn an the dragon, are not rea. They are
mythicai creaiures. nBy the rybriu iike ihe rh:noceYos, describes
the real structure.

blue with yellow is a good visual analogy to the resonance

A green mark produced by overprinting
to the resonance structures (canonical forms). and the green
concept. Yellow and blue correspond
structure.
corresponds to the hybrid
the
T h e resonance hybrid is more stable than any one of
in between
various resonance structures. The difference energy
the hybrid and the most stabléresonance structure is known
asS

can be determined
the Resonance Energy. Resonance energy
by the difference between the calculated and experimental heats
mole of 38 Kcal
of combustion (energy given off as heat when one
has
compound is burned) of the compound. For example, it
been calculated that the hypothetical structure (1) (2)
or would
have a heat of combustion of 797 kcal/mole. The measured
value for the heat of combustion of benzene is 759 kcal/mole.
Therefore, the resonance energy of benzene is (797-759) keal/ Fig.5.38. Resonance energy of
mole or 38 kcal/mole. The benzene is said to be "stabilized" by
benzene.
a resonance energy of 38 kcal/mole (Fig. 5.38).
 STRUCTURE OF ORGANIC MOLECULES 81
Anothe her species that is not
correctly represented by a single structure is the acetate ion. As in the
of benzene, acetate 1on is a
hybrid of
two resonance
:

cacetate ion are identical and have the same bond

structures. Both carbon-oxygen bonds
in
26 Å is intermediate between the length (1.26 Å). The carbon-oxygen bond
of normal
carbon-oxygen double-bond length (1.20 lengtn
rmal carbon-oxygen single-bond length (1.43 Å). (1 Ä) and the

CHa-C CH-C = CH-C

Acetate ion
o-h
Acetate ion
RULES OVERNING RESONANCE
The resonance concept is extremely useful in organic chemistry, and will come up a numDer o
aS times. The following are some important rules governing resonance.
(1) Resonanc. Occurs whenever a molecule can be represented by two or more structures
differing only in the arrangement of electrons, without shifting any atoms. Resonance only involves
the delocalization of electrons.
2) Resonance structures are not actual structures for the molecule. They are nonexistent and
hypothetical.
8) Resonance structures are interconvertible by one or a series of short electron-shifts. For
example,

Benzene

CHa-C CH-CS
Acetate ion
of the molecule. The structure of the
represents the actual
structure
(4) Resonance hybrid and is not a mixture of
intermediate between the various r e s o n a n c e structures
resonance hybrid is
them. ( ). This should not be
is represented by a double headed arrow
5) Resonance hybrid different compounds.
arrows (F2)used
to denote equilibrium between two
confused with the two forms (resonance structures).
Resonance hybrid is more stable than any of its contributing
(6) increases the stability of a molecule
and lessens its reactivity.
( Resonance always
e
HYDROGEN BONDING contain
molecules
attractive force which occurs in any compound whose
Hydrogen bonding is an for example, is
in water, alcohols, acids, amines, and anmides). The 0-H bond,
0-H or N-H bonds (as and pulls the bonding electrons
bond. Oxygen is more electronegative than hydrogen
the oxygen atom acquires a small negative charge (8)
a highly polar and
closer to it. As a result of this displacement,
the hydrogen atom a small positive
charge (8,).
More electronegative
than hydrogen

R-0: H or R-8-
bond will be attracted to each other by
Adjacent compound containing an 0-H
molecules of the
the Hydrogen Bond. Usually a
charges. This force of attraction is known as
virtue of these opposite
of
hydrogen bond is represented by a dotted line (Fig. 5.39).