3.

4 Isomers of coordination compounds

Study Figure 9.7 MFT322

• Isomers are molecules with identical composition, but with different
arrangement of the atoms in the molecules.

• Isomers could be divided into to two groups:

1. Configurational- or stereoisomers
• The same atoms in the isomer are bonded to one another.
• But the arrangement of/and bonding of the atoms differ.

2. Constitutional- or composition isomers

• Atoms which are bonded to one another differ from one
another.
 Diastereomers or geometrical
Yes isomers
Stereo- or configuration
isomers. Is each identical
with its mirror image?
Yes No Enantiomers or optical isomers

Two or more
molecules with
identical formula.
Are the bonds
Hydrate isomers
between the same
atoms?
No
Ionisation isomers
Constitutional or
composition isomers.

Coordination isomers

Bond isomers
 Diastereomers or geometrical isomers
Could have conformation isomers (different turn or
Yes Nee
bend of bonds)
/ No
Stereo- or configuration
isomers. Is each
identical with Its mirror
image?

No
Enantiomers or optical isomers
Chirality, non-super imposable mirror images

Selfstudy pp 50 – 51 Class notes

 Diastereomers or geometrical
Yes isomers
Stereo- or configuration
isomers. Is each identical
with its mirror image?
Yes No Enantiomers or optical isomers

Two or more
molecules with
identical formula.
Are the bonds Ionisation isomers
between the same
atoms?
No
Hydrate isomers
Constitutional or
composition isomers.
Coordination isomers

Bond isomers
 Ionisation isomers
Example - the ligand ions and counter ions are changed
around [Cr(H2O)5Br]SO4 and [Cr(H2O)5SO4]Br

Hydrate isomers
Example - special cases of ionization isomers where the
ligand is water

[Cr(H2O)4Cl2]Cl.2H2O = green; [Cr(H2O)5Cl]Cl2.2H2O =

bluegreen; [Cr(H2O)6]Cl3.2H2O = purple
Constitutional or
composition isomers
Coordination isomers
Example - both the cation and the anion complexes
[Co(NH3)6][Cr(CN)6] vs [Cr(NH3)6][Co(CN)6]

Bond isomers
Example - occurs if a ligand that contains two different donor
atoms as in NO2- and SCN-
M-ONO = nitrito-O, M-NO2 = nitrito-N,
M-SCN = thiocyanato-S, M-NCS = thiocyanato-N
[Co(NH3)5ONO]Cl2 = red and [Co(NH3)5NO2]Cl2 = yellow
3.5 Symmetry

Application categories of symmetry:

1. Construction of molecular and hybrid orbitals.
2. Interpretation of spectroscopic properties (e.g. vibrational
and electronic).
3. Determination of chirality of a molecular species.
3.5.1 Symmetry operations and symmetry elements (MFT75)
Symmetry Symbol Symmetry operation Symbol Representation
element

Axis C rotation around the axis with 1/n Cn C5

rotation.

Plane s reflection through the plane as a s

a
mirror c
b
b

Point i reflection through inversion i

a1 a2
point. b2 c1 b1 c2
i i
c2 b1 c1 b2
a2 a1
a1=a2; b1=b2; c1=c2
Improper axis S improper rotation= rotation with Sn S6
1/n rotation+reflection through
the plane perpendicular to axis
of rotation

identity E None E

https://people.unica.it/mariacarlaaragoni/files/2
https://youtu.be/PzLD41m68jk 012/04/Housecroft_Introd-Mol-Symm.pdf
Study the chapters on symmetry operations in the textbooks until
you can identify the possible symmetry operations of complexes,
make sketches of the symmetry operations and indicate them with
appropriate symbols.
3.5.2 Point groups (MFT80-89)

Yes
JA Lowsimmetrie?
Lae symmetry?

C1 , Cs, Ci NEE
No

Yes Hoë
Highsimmetrie?
symmetry?
JA
Td, O h, C¥ v, D¥ h, Ih NEE
No

Hoogste orde
Highest order rotation axis
rotasie-as

Cn

Yes Perpendicular
Loodregte CC No
D groups 2 axes
2 -asse? C CoforS2n
JA NEE - groups
S2n
D-groepe?
groepe?

s h? s h?
Yes No
JA NEE
Yes
JA No
NEE
Cnh sv?
Dnh s d? Yes
JA No
NEE

Yes No
NEE Cnv S2n?
JA
Yes No
Dnd Dn JA NEE
S2n Cn
Study the schemes and tables for the deduction of the point group
for a molecule to enable you to deduce the point group of a given
coordination compound. Work through the examples from HCl to
dodecahydro-closo-dodecaborate, MFT82, Figure 4.8

http://symmetry.otterbein.edu/
Application categories of symmetry:
1. Construction of molecular and hybrid orbitals.
https://youtu.be/OGJa40gE3nA

2. Interpretation of spectroscopic properties (e.g. vibrational

and electronic).
https://youtu.be/1Q45PpodjJY

3. Determination of chirality of a molecular species.