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Coordination Number and Geometry

Coordination Number and Geometry

For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.

Coordination Compounds and Nomenclature

Coordination Compounds and Nomenclature

In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...

Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

Valence Bond Theory

Valence Bond Theory

Overview of Valence Bond Theory

Lattice Centering and Coordination Number

Lattice Centering and Coordination Number

The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is referred to as its unit cell. The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure then consists of this unit cell repeating in three dimensions. The three different types of unit cells present in the cubic lattice are illustrated in Figure 1.
Types of Unit Cells
Imagine taking a large number of identical...

Metal-Ligand Bonds

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...

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Related Experiment Video

Updated: Jan 17, 2026

Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

Published on: December 16, 2013

Does covalency decrease with coordination number?

Alexey O Shorikov^1,2,3, Dmitry M Korotin^1,2, Vladimir I Anisimov^1,2,3

¹M.N. Mikheev Institute of Metal Physics of Ural Branch of the Russian Academy of Sciences, 18 S. Kovalevskaya St., Yekaterinburg 620108, Russia.

The Journal of Chemical Physics

|September 15, 2025

Summary

This summary is machine-generated.

The degree of chemical bond covalency is not determined by coordination number, contrary to popular belief. Atomic properties and stoichiometry, not coordination, primarily govern bond ionicity and covalency in materials like ZnO, CO2, and NaCl.

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Published on: July 27, 2022

Area of Science:

Materials Science
Solid State Chemistry
Computational Chemistry

Background:

Traditional chemical theories suggest bond covalency decreases with higher coordination numbers.
Conversely, bond ionicity is expected to increase with coordination number.
This relationship has been widely accepted in chemical bonding principles.

Purpose of the Study:

To investigate the relationship between coordination number and the degree of covalency and ionicity in chemical bonds.
To challenge the traditional understanding of how coordination number affects chemical bonding.
To explore alternative factors governing bond characteristics.

Main Methods:

Utilized Bader charge analysis to quantify atomic charges.
Developed and applied a novel definition of atomic charges based on Wannier functions.
Examined zinc oxide (ZnO) in wurtzite and rock salt phases, carbon dioxide (CO2) in different phases, and sodium chloride (NaCl).

Main Results:

Observed that coordination number does not consistently correlate with ionicity in ZnO phases.
Found that covalency slightly increased in a higher-coordinated phase of CO2.
Demonstrated that bond ionicity in ZnO remained nearly identical across different coordination numbers.

Conclusions:

The degree of covalency and ionicity is primarily determined by the chemical nature of atoms and their stoichiometric ratios.
Coordination number is not the dominant factor influencing the degree of covalency or ionicity.
Revises the fundamental understanding of chemical bonding principles in materials.