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Applications of Coordination Compounds
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Isomerism in Coordination Compounds

Last Updated : 18 Aug, 2023
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Isomerism in Coordination Compounds as the name suggests explores the concept of Isomerism in Coordination Compounds i.e., generally compounds formed by d-block elements. Isomerism is the phenomenon of exhibiting different molecular structures by the compounds with same molecular formula. The phenomenon of isomerism is quite significant in hydrocarbons however it is of no less importance in coordination compounds. Coordination Compounds are those chemical compounds in which a group of anions is attached to a central metal atom via covalent bonds. Coordinate compounds are also called coordinate complexes. The coordinate compounds having the same molecular formula but different arrangements of ligands are called isomers of coordination compounds and the phenomenon exhibited is called Isomerism in Coordination Compounds. In this article, we will learn about different types of isomerism exhibited by Coordination Compounds in detail.

What are Coordination Compounds?

Coordination Compounds are chemical compounds in which the central metal atom or ion is attached to the number of oppositely charged or neutral atoms more than its normal valency. The coordination compounds are formed by the combination of two or more simple and stable compounds that retain their identities. The central atom is usually a transition metal due to its nature of exhibiting variable valency properties as they have the presence of incompletely filled d-orbitals.

The Central Metal Atom has two types of valencies namely primary valency and secondary valency. The primary valency tells the oxidation number and the secondary valency tells about the coordination number. The d-block transition element to which negative or neutral molecules are attached is called the central atom and the neutral atom or the anion attached to the central atom is called ligand. The central atom and the ligand are written inside a square bracket and are often called Coordination Complexes. Coordination Compounds differ from Double Salt in the manner that double salt dissociates on dissolution while Coordination Compounds don't.

Coordination Compound Examples

Let's understand more about coordination compounds with the help of a few examples:

In [Co(NH3)6]Cl3 the central atom is Cobalt(Co), to which six neutral molecules of NH3 are attached which is called a ligand. These are attached to Co with primary valency and hence written inside the square bracket and the Cl3 which is written outside is the counter ion attached to the coordination complex that consists of [Co(NH3)6]3+ via secondary valency.

Learn More,

  • Nomenclature of Coordination Compound
  • Important Terms pertaining to Coordination Compounds

Isomerism in Coordination Compounds

The phenomenon of exhibiting different arrangements of ligands by the coordination compounds with the same molecular formula is called Isomerism in Coordination Compounds. The Coordination Compounds exhibiting isomerism are called isomers. There are two types of isomerism by coordination compounds

  • Structural Isomerism
  • Stereoisomerism

Let's learn them in detail.

Structural Isomerism

The property of coordination compounds having the same number of atoms of each type but showing different bonding patterns is called Structural Isomerism. The Coordination Compounds that have the same number of atoms of each type but show different bonding patterns are called structural isomers. The different types of structural isomerism are:

  • Ionization Isomerism
  • Hydrate or Solvate Isomerism
  • Coordination Isomerism
  • Linkage Isomerism

Let's discuss these types in detail as follows.

Ionization Isomerism

Ionization Isomerism takes place when a ligand that is bound to the central atom exchanges its position with the counter ion which is outside the Coordination Complex. The Coordinate Compounds formed by such exchange of place of the ligand with the counter ion are called Isomers. For Example, [Co(NH3)5Cl]SO4 and [Co(NH3)5(SO4)]Cl are ionization isomers. This is because the ligand Cl which is a part of the Coordination Complex in [Co(NH3)5Cl]SO4 exchanges place with the Counter ion SO4 and hence now Cl becomes the counter ion and SO4 becomes the ligand.

Solvate Isomerism

Solvate Isomerism is a special type of Ionization Isomerism in which the ligand is replaced by a solvent molecule and if the solvent molecule is water then it is called Hydrate Isomerism. For Example, [Cr(H2O)6]Cl3 is a solvate isomer. It is violet in colour. In this, we see that the H2O molecule is directly attached to the central atom Cr. [CrCl(H2O)5]Cl2.H2O is a grey-green coloured hydrate isomer. However, in this case, we see that water molecule is present inside and outside the square bracket. The water molecule inside the square bracket is directly bonded to the central atom while that outside the bracket isn't attached to the central atom and is called Water of Crystallization.

Water of Crystallization refers to the number of molecules of water attached to the compound but not part of the Coordination Complex. It is usually shown attached to the molecule by a dot(.)

Coordination Isomerism

Coordination Isomerism is exhibited when there is an exchange of ligands between a cationic and an anionic complex bonded together. In this, there is a Cationic Coordinate and an Anionic Coordinate Complex which are bonded together and there is an exchange of one or more ligands between them. For Example are [Co(NH3)6][Cr(C2O4)3] and [Co(C2O4)3][Cr(NH3)6] are Coordinate Isomers. In [Co(NH3)6][Cr(C2O4)3] (NH3)6 is attached to the Co atom and (C2O4)3 is attached to the Cr atom while in [Co(C2O4)3][Cr(NH3)6], Co is attached to C2O4 and Cr is attached to the (NH3)6.

Linkage Isomerism

Linkage Isomerism occurs when the ligand coordinates in more than one way. Such ligands that coordinate in more than one way are called ambidentate ligands. Examples of ambidentate ligands include SCN-/ NCS- and NO2- and ONO-. Examples of linkage isomerism include [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2. In [Co(NH3)5(NO2)]Cl2, Co is attached to NO2 and called Nitro isomer while in [Co(NH3)5(ONO)]Cl2, the central atom Co is attached to the ONO and called Nitrito isomer.

Learn more about Isomerism.

Stereoisomerism

Stereoisomerism refers to the phenomenon of exhibiting different 3D spatial arrangements of bonds but having the same molecular formula. The compounds exhibiting stereoisomerism are called Stereoisomers. Stereoisomers have even the same set of bonds but they differ in arrangement. There are two types of Stereoisomerism that are:

  • Geometrical Isomerism
  • Optical Isomerism

These two types are discussed in detail as follows.

Geometrical Isomerism

There are two types of arrangements possible under Geometrical Isomerism. These are called cis-isomers and trans-isomers. In cis-isomers, the two similar bonds are on the same side of the central atom while in trans-isomer the similar bonds are on the opposite side of the central atom. The image inserted below will give a clear idea of cis and trans-Geometrical Isomerism.

Cis and Trans isomerism

Geometrical isomerism is shown by square planar and octahedral-shaped molecules. Tetrahedral-shaped molecules don't exhibit cis and trans isomerism. Square-shaped molecules of type MX2L2 exhibit cis and trans isomers. An example of this type is mentioned above i.e. Pt[(NH3)2Cl2]. In this case, the ligands X and L are unidentate. A square planar molecule of type MABXL where M is the central atom and A, B, X, and L are ligands all different then it will exhibit three isomers out of which two will be cis type and one will be trans.

In the case of an Octahedral Coordination Complex of type MA2B4 the cis and trans isomerism is shown below in the attached figure. In this case, the ligand which is two in number is arranged in such a manner as to exhibit cis and trans isomerism.

Geometrical Isomers of [Co(NH3)4Cl2]

In the case of a Coordination Complex where the central atom is attached to a didentate ligand i.e. the ligand which has two electron donor atoms, the geometrical isomers are shown below in the picture. The compound is of the type [MX2(L-L)2] where M is the central metal atom, X is the unidentate ligand and L is the didentate ligand. In the picture attached below Co is the central atom, Cl is the unidentate ligand and en is the bidentate ligand which stands for Ethylenediamine whose molecular formula is C2H4(NH2)2.

Geometrical Isomer of [CoCl2(en)2]

In the case of an Octahedral Complex of type MA3B3, there two types of isomers formed known as Facial or fac-isomer and Meridional or mer-isomers. For Example, the fac-isomer and mer-isomer for [Co(NH3)3(NO2 )3] are given below. The facial (fac) isomer is formed when three donor atoms of the same ligand occupy adjacent positions at the corners of an octahedral face. The meridional (mer) isomer is obtained when the positions are centred on the octahedron's meridian.

Learn more about Geometric and Optical Isomerism in Coordination Compounds.

Optical Isomerism

Optical Isomerism is the phenomenon exhibited by molecules when they have similar bonds, and different arrangements such that their mirror images are non superimposable. The mirror images of molecules that can't be superimposed on each other are called Optical Isomers. Optical Isomers are also called Enantiomers. These molecules rotate the plane of Polarized light in a Polarimeter. Depending upon the direction of rotation they are classified as Dextrorotatory and Laevorotatory. The Dextrorotatory rotates the plane of light clockwise or in the right-hand direction while Laevorotatory rotates the light rotates the plane of light in Anticlockwise or left-hand direction.

The Optical Isomerism in Coordination Compounds is exhibited by Octahedral and Tetrahedral Coordinate Complexes but not by Square Planar. Hence, we see that Octahedral Coordinate Complexes exhibit both Geometrical and Optical Isomerism. In octahedral complexes containing didentate ligands, optical isomerism is common.

Optical Isomerism

In a coordination entity of the type [PtCl2 (en)2 ]2+, only the cis-isomer shows optical activity.

cis Isomer

Also, Read

  • Application of Coordination Compounds
  • Wener's Theory
  • Valence Bond Theory in Coordination Compounds

Isomerism in Coordination Compounds Examples

Example 1: Draw all geometrical isomers of [Fe(NH3 )2 (CN)4 ]–.

Solution:

geometrical isomers of [Fe(NH3 )2 (CN)4 ]–

Example 2: Indicate the types of Isomerism exhibited by the following complexes  

  1. [Co(en)3 ]Cl3  
  2. [Co(NH3 )5 (NO2 )](NO3 )2  
  3. [Pt(NH3 )(H2O)Cl2 ]

Solution:

  1. [Co(en)3 ]Cl3                                ----> Optical isomerism
  2. [Co(NH3 )5 (NO2 )](NO3 )2         ----> Optical isomerism, Linkage isomerism, Ionization isomerism
  3. [Pt(NH3 )(H2O)Cl2 ]                    ----> Geometrical (cis-, trans-) isomerism

Example 3: How many Geometrical Isomers will be possible in [Co(NH3)3(Cl)3]?

Solution:

Two geometrical isomer is possible for [Co(NH3)3(Cl)3]-

geometrical isomer for [Co(NH3)3(Cl)3]-

Example 4: What are Ligands in Coordination Compounds?

Solution:

Ligands are ions or molecules that are bound to the central atom/ion of the coordination entity. Simple ions like Cl–, small molecules like H2O or NH3, larger molecules like H2NCH2CH2NH2 or N(CH2CH2NH2)3 , and even macromolecules like proteins can fall into this category.

Example 5: Draw the geometrical isomers of [Pt(NH3)(Br)(Cl)(Py)].

Solution:

Geometrical Isomer of [Pt(NH3)(Br)(Cl)(Py)]

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Applications of Coordination Compounds

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  • Class 12
  • Chemistry
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  • Inorganic-Chemistry
  • Coordination Compounds

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    Sulfuric Acid or Sulphuric Acid is a mineral acid consisting of one Sulfur, four Oxygen, and two Hydrogen atoms. The chemical or molecular formula of Sulfuric Acid is H2SO4. Sulfuric Acid is one most important commercially used chemicals. It is also known as Mattling acid or Hydrogen Sulfate or Vitr
    8 min read
    Group 17 Elements: The Halogens
    The Halogens are the elements in the periodic table of Group 17 of the periodic table. Fluorine, chlorine, bromine, and iodine are examples of reactive nonmetals. Halogens are nonmetals that are extremely reactive. These elements have a lot in common in terms of properties. Group 17 elements are kno
    8 min read
    Chlorine (Cl)
    Chlorine is a chemical element that is represented by the symbol Cl. Chlorine is present in the 17th Group (Halogen Group) and 3rd Period of the Periodic table. Chlorine is the second lightest halogen that lies between Fluorine and Bromine in the halogen group. Chlorine is a yellow-green, pungent-sm
    6 min read
    Hydrogen Chloride - Definition, Preparation, Properties, Uses
    As a hydrogen halide, the compound hydrogen chloride has the chemical formula HCl. It is a colourless gas at ambient temperature that emits white fumes of hydrochloric acid when it comes into contact with air-water vapour. In technology and industry, hydrogen chloride gas and hydrochloric acid are c
    7 min read
    Oxoacids of Halogens - Definition, Properties, Structure
    The elements of Group 17 from top to bottom are fluorine, chlorine, bromine, iodine, and astatine. They are referred to as halogens because they create salt. This group's members are very similar to one another. They have a consistent pattern of physical and chemical features. The valence shell of e
    7 min read
    Interhalogen Compounds
    The p-block elements are known to be those elements in which the electron enters in one of the three orbitals of the p-block. There are 6 groups of p-block elements. The properties of p-block elements are that they are shiny and are good conductor of heat and electricity since they have free electro
    6 min read
    Group 18 Elements - Characteristics of Noble Gases
    The group's members have eight electrons in their outermost orbit (except helium which has two electrons). As a result, they have a stable configuration. Group 18 elements are gases that are chemically unreactive, meaning they do not form many compounds. Be a result, the elements are referred to as
    7 min read

    Chapter 8: d- and f-Block Elements

    Position of Elements in the Periodic Table
    The elements in the middle of the periodic table, from Group 3 to 12, are referred to as d-block elements. The name d-block comes from the fact that the final electron enters the d-orbital of the penultimate shell. These are frequently referred to as transition elements because their properties fall
    6 min read
    Electronic Configuration of the d-block Elements
    Electronic Configuration of the d-block elements are those that can be found in the contemporary periodic table from the third to the twelfth groups. These elements' valence electrons are located in the d orbital. d-block elements are sometimes known as transition elements or transition metals. The
    7 min read
    General Properties of Transition Elements (d-block)
    Elements with partially filled d orbitals are known as transition elements (sometimes known as transition metals). Transition elements are defined by IUPAC as elements with a partially full d subshell or elements capable of forming stable cations with an incompletely filled d orbital. In general, an
    7 min read
    Lanthanides - Definition, Configuration, Properties
    Lanthanides are the contemporary periodic table's rare earth elements, with atomic numbers ranging from 58 to 71 after Lanthanum. Rare earth metals are so-called because these elements are extremely rare (3 × 10-4 % of the Earth's crust). As lanthanide orthophosphates, they are accessible in 'monazi
    8 min read
    Actinides - Definition, Properties, Formation, Uses
    The d and f block mainly contains elements that include groups 3-12. The f block has elements in which 4f and 5f are progressively filled. These elements are placed below the periodic table in a separate table. The d and f block elements are majorly known as transition or inner transition elements.
    9 min read
    Some Applications of d and f-block Elements
    Transition metals are typically characterized as elements with or capable of forming partially filled 'd' orbitals. Transition elements are d-block elements in groupings of three to eleven. Inner transition metals, which include the lanthanides and actinides, are another name for the f block element
    6 min read

    Chapter 9: Coordination Compounds

    Important Terms pertaining to Coordination Compounds
    A coordination compound is made up of a central metal atom or ion that is surrounded by a number of oppositely charged ions or neutral molecules. All the ions or molecules in coordination compounds are connected with coordinate bonds to the central metal atom. When coordination compounds are dissolv
    6 min read
    Nomenclature of Coordination Compounds
    The ability of the transition metals to form the complexes is referred to as coordination compounds. This property is not only applicable to transition metal only but also shown by some other metals. Werner, in 1893 was the first scientist to propose the theory of coordination compounds and also pur
    10 min read
    Metal Carbonyls - Organometallics
    Carbonyls are coordination complexes that are formed by transition metals and the carbonyl ligand i.e. carbon-monoxide ligand. These are also termed homoleptic carbonyls. These complexes have a simple and well-defined structure which is generally tetrahedral and octahedral in nature. Nomenclature of
    5 min read
    Werner's Theory
    Werner's Theory of Coordination Compounds was proposed by a Swiss Chemist Alfered Werener in 1898. Werner studied the physical, chemical, and isomeric properties of several coordination compounds and postulated some theories. In this article, we will learn about, Werner's Coordination theory, its po
    8 min read
    Valence Bond Theory in Coordination Compounds
    There have been numerous approaches proposed to explain the nature of bonding in coordination molecules. One of them is the Valence Bond (VB) Theory. The Valence Bond Theory was developed to describe chemical bonding using the quantum mechanics method. This theory is largely concerned with the produ
    9 min read
    Crystal Field Theory
    A coordination compound consists of a metal atom or ion at the centre, surrounded by a number of oppositely charged ions or neutral molecules. A coordinate connection connects these ions or molecules to the metal atom or ion. When dissolved in water, they do not dissociate into simple ions. Crystal
    7 min read
    Isomerism in Coordination Compounds
    Isomerism in Coordination Compounds as the name suggests explores the concept of Isomerism in Coordination Compounds i.e., generally compounds formed by d-block elements. Isomerism is the phenomenon of exhibiting different molecular structures by the compounds with same molecular formula. The phenom
    10 min read
    Applications of Coordination Compounds
    Chemical compounds made up of an array of anions or neutral molecules linked to a central atom by coordinate covalent bonds are known as coordination compounds. Coordination compounds are also known as coordination complexes. Ligands are the molecules or ions that are bonded to the central atom (als
    7 min read
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