Geometry of PF

5 molecule
The outer electronic configuration of
phosphorus, the central atom, is 3s2
3p3 which may be represented as
shown in fig.1.24 (a). It has three
unpaired electrons in the ground
state:

fig 1.24 - Formation of PF5 molecule

involving sp3d Hybridization
To explain the pentavalency of
phosphorus in PF5, one of the
electrons in 3s orbital is promoted to
the higher 3d orbital so that it has five
unpaired electrons. This is called the
excited state of phosphorus and is
represented in fig.1.24 (b). These five
orbitals hybridize to form five sp3d
hybrid orbitals, which adopt trigonal
bipyramidal arrangement. Each of the
sp3d hybrid orbitals overlaps with 2p
orbital of fluorine forming five P-F
bonds as shown in fig.1.25.

fig 1.25 - Structure of PF5

Thus, PF5 molecule has trigonal
bipyramidal geometry. It may be
noted that all the bond angles in
trigonal bipyramidal geometry are not
equivalent. Three bonds lie in one
plane at an angle of 120o to one
another as in a triangular planar

arrangement. These bonds are termed

as equatorial bonds. Of the remaining
two bonds, one lies above and other
below the equatorial plane both
making an angle of 90o with the plane.
These bonds are called axial bonds. It
may be remembered that this
geometry is not symmetrical. The
axial bonds have been found to be
larger than equatorial bonds. For e.g.,
in case of PF5 molecule each P - F axial
bond = 219 pm and each P - F
equatorial bond = 204 pm. As the
axial bonds suffer more repulsion, the
axial bond will be slightly elongated
when compared to equatorial bond.

Geometry of SF

molecule
The geometry of SF6 molecule can be
explained on the basis of sp3d2
Hybridization. In SF6 the central
sulphur atom has the ground state
configuration, 3s23p4 as shown in
fig.1.27 (a).
6

fig 1.27 - Formation of SF6 molecule

involving sp3d2 Hybridization
To account for the hexavalency in SF6
one electron each from 3s and 3p
orbitals is promoted to 3d orbitals as
shown in fig.1.27(b). These six orbitals
get hybridized to form six sp3d2hybrid
orbitals. Each of these sp3d2 hybrid
orbitals overlaps with 2p orbital of
fluorine to form S-F bond.
Thus, SF6 molecule has octahedral
structure as shown in fig.1.28. The
dotted electrons represent electrons
from F-atoms.

fig 1.28 - Octahedral geometry of SF6

molecule
This involves the mixing of one s three
p and three d-orbitals forming seven
sp3d3 hybrid orbitals having
pentagonal bipyramidal geometry. The
geometry of IF7 molecule can be
explained on the basis of sp3d3
Hybridization.

Geometry of IF

molecule
The outer electronic configuration of
iodine atom is 5s2 5p5. To make seven
bonds, one s and two p orbitals are
promoted to the higher vacant 5d
orbitals as shown in fig.1.29 (b).
7

fig 1.29 (b) - Pentagonal bipyramidal

geometry of IF7 molecule
These seven orbitals are then
hybridized to give seven sp3d3 hybrid
orbitals. Each of these sp3d3 hybrid
orbitals overlaps with 2p orbitals of
fluorine to form IF7 molecule having
pentagonal bipyramidal geometry.
In this geometry, all the bond angles
are not equal. Five F- atoms are
directed towards the vertices of a
regular pentagon making an angle of
72o. The other two F-atoms are at
right angles (90o) to the plane. Due to
different bond angles, the bonds are
different in length. The axial bonds are
larger than equatorial bonds.
In addition to above types of
Hybridization, dsp2 type of
hybridization is also known
particularly in case of transition metal
ions. The orbitals involved in this type
of Hybridization are dx2- y2, s and two
p. The four dsp2 hybrid orbitals adopt
square planar geometry.
2-

Geometry of [Ni(CN)

]
The complex ion [Ni (CN) 4]2- involves
dsp2 Hybridization as explained below.
In this case, the oxidation state of
nickel is +2. The outer electronic
configuration of Ni2+ is 3d8 as given in
fig.1.30 (a).
4

fig 1.29 (a) - Formation of IF7 molecule

involving sp3d3-Hybridization

fig 1.30 - Formation of [Ni(CN)4]2involving dsp2 Hybridization

fig 1.31 - Structure of [Ni(CN)4]2In the formation of the complex ion,

the two unpaired d electrons are
paired up making one 3d orbital
empty. The four empty orbitals (one

3d, 4s and two 4p) hybridize to form

four dsp2 hybrid orbitals, which point
towards square planar arrangement.
Each one of the four CN- groups
donates lone pair of electrons to
vacant hybrid orbitals forming four Ni CN bonds. Thus, [Ni(CN)4]2- has square
planar arrangement as shown in
fig.1.30.