Stereochemistry of
Coordination compounds with
different coordination
numbers
Ms.A.Jerli Auxilia,
Assistant Professor,
Department of Chemistry
Stereochemistry of Coordination compounds
The ligands adopt a definite geometry around the
central ion depending upon the coordination number
of the ion. The arrangement of the coordinated ligands
is such that the electrostatic repulsion between them is
minimum. The stereochemistry of the complexes with
coordination numbers varying from 2 to 9.
Coordination Number 2
Two arrangements are possible for compounds
with coordination number 2: i) Linear ii) Bent
When the central ion utilizes the two hybrid
orbitals for bonding with the ligands and does not
contain any lone pair of electrons, it forms linear
complexes.
when the central ion utilizes, apart from the two
hybrid orbitals, one or more additional hybrid orbitals
for accommodating lone pairs of electrons, it forms
bent complexes.
Ex:
[CuCl2]-, [Au(CN)2]-, [Ag(NH3)2]+
Coordination Number 3
This coordination number is uncommon, rather
rare. Several compounds which from their
stereochemistry appear to be 3-coordinate, are found
upon examination to have higher coordination
numbers.
Ex:
K[Cu(CN)2]
Coordination Number 4
The two principal geometries encountered are
i) Tetrahedral
ii) Square planar
Tetrahedral geometry
This geometry is complexes of transition as well as
non-transition elements.
Ex:
[BeF4]2-, [BF4]-, [ZnCl4]2-, [Cd(CN)4]2-, [MnCl4]2-
Square planar geometry
This geometry is complexes of transition
elements only.
Ex:
[PtCl4]2-, [Ni(CN)4]2-, [Cu(NH3)4]2-, [PdCl4]2-
Coordination Number 5
Complexes with coordination number 5, with
coordination number 3, are rather rare. Complexes in
which the metal ion was considered to be having
coordination number 5 to have the metal ion with
different coordination number.
Ex:
(NH4)3[ZnCl5] in which the complex ion [ZnCl5]3-
Two principal geometries in the compounds in which
this coordination number 5 has been established are
i) Trigonal Bipyramidal
ii) Square Pyramidal
Trigonal bipyramidal geometry:
[Fe(CO)5], [MoCl5]-, [CuCl5]3-, [SnCl5]-
Square bipyramidal geometry:
[SbF5]2-, [VO(acac)2] and [Ni{(C6H5)P}2Br3]-
Coordination Number 6
The regular geometric arrangement is
octrahedral due to distortions the geometry changes to
tetragonal.
Ex:
[Cu(NH3)6]2+, [FeF6]3-, [TiF6]2-, [PtF6]4- and [SbF6]-
Coordination Number 7
Three geometrical forms are as follows:
i) Pentagonal bipyramidal
[UO2F5]3-, [UF7]3- and [ZrF7]3-
ii) Distorted octahedrom
[NbOF6]3-
iii) Trigonal prism
[NbF7]2- and [TaF7]2-
Coordination Number 8
Three types of geometries of compounds are
i) Cubic
ii) Square Antiprism
iii) Doedecahedral
Cubic geometry: The most symmetrical arrangement is
simple cubic. Ex: [UF8]3-
Square antiprism geometry: This depicts a distortion in
the cubic geometry which is adopted to minimise the
repulsion between the anions. Ex: [TaF8]3-, [ReF8]2-
and [Zr(acac)4]
Doedecahedral geometry: [Mo(CN)8]4- and [Zr(ox)4]4-
Coordination Number 9
There is only one symmetrical arrangement
known for this coordination number. This is derived
from a trigonal prism by placing the three additional
atoms outside the centres of the three vertical faces.
Ex:
[Nd(BrO3)3].9H2O which contains [Nd(H2O)9]3+
as the complex ion in which the central ion Nd3+ has
coordination number 9.
