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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.

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...

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...

VSEPR Theory and the Effect of Lone Pairs

VSEPR Theory and the Effect of Lone Pairs

Effect of Lone Pairs of Electrons on Molecule Geometry

Metallic Solids

Metallic Solids

Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many...

Structural Isomerism

Structural Isomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...

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Related Experiment Video

Updated: Jun 13, 2026

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

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Published on: May 28, 2014

A Two-Dimensional Layered Bismuth Coordination Polymer Based on a Lone Pair-π Interaction.

Haruto Yamaoka¹, Kazuya Otsubo^1,2

¹Department of Chemistry, Faculty of Science, Tokyo University of Science, Shinjuku-ku, Tokyo 162-8601, Japan.

Inorganic Chemistry

|June 12, 2026

Summary

Researchers synthesized a novel coordination polymer (CP) using bismuth ions and protocatechuic acid. This CP exhibits a unique 2D layered structure driven by cation-based lone pair-π interactions, influencing its electronic properties.

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Published on: May 12, 2023

Area of Science:

Materials Science
Crystallography
Solid-State Chemistry

Background:

Metal-organic frameworks (MOFs) and coordination polymers (CPs) are versatile materials with diverse applications.
The design of novel CPs relies on understanding metal-ligand interactions and coordination geometries.

Purpose of the Study:

To synthesize and characterize a new coordination polymer based on bismuth ions and protocatechuic acid.
To investigate the crystal structure and electronic properties of the synthesized CP.
To explore the role of cation-based lone pair-π interactions in CP assembly and properties.

Main Methods:

Single-crystal X-ray diffraction (XRD) for structural analysis.
Optical absorption spectroscopy for electronic property evaluation.
Density Functional Theory (DFT) calculations to understand electronic interactions.

Main Results:

Synthesis and structural determination of Bi(PCA)(H2O) CP, featuring a 2D layered structure.
Identification of an unusual six-coordinated geometry for Bi3+ ions due to a stereochemically active 6s2 lone pair.
Observation of cation-based lone pair-π interactions and π-π stacking driving the assembly of 2D layers.
Detection of a characteristic absorption band linked to lone pair-π interactions.

Conclusions:

The study reports the first CP utilizing cation-based lone pair-π interactions.
The findings demonstrate the potential of exploiting unique metal ion coordination for designing novel CPs with tailored structures and electronic properties.
This work opens new avenues for MOF and CP research by leveraging specific electronic interactions.