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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...

Complexation Equilibria: The Chelate Effect

Complexation Equilibria: The Chelate Effect

In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...

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...

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...

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Related Experiment Video

Updated: Dec 30, 2025

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

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Three-Dimensional Network Structures Based on Pyridyl-Calix[4]Arene Metal Complexes.

Carmelo Sgarlata¹, Giovanna Brancatelli², Cosimo G Fortuna¹

¹Dipartimento di Scienze Chimiche, Università di Catania, viale A. Doria 6, 95125, Catania, Italy.

|January 21, 2020

Summary

New supramolecular assemblies formed using 3-pyridylmethyl-calixarenes and copper or zinc ions. Steric crowding and metal coordination influence the formation of diverse complex structures, including monomeric and polymeric species.

Keywords:

calixarenes metal-directed assemblies self-assembly solid-state structures titrations

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Area of Science:

Supramolecular Chemistry
Coordination Chemistry
Materials Science

Background:

Calixarenes are versatile macrocyclic hosts with tunable properties.
Metal-organic complexes offer diverse structural possibilities.

Purpose of the Study:

To synthesize and characterize novel supramolecular assemblies.
To investigate the influence of steric and electronic factors on complex formation.
To explore the structural diversity of metal-calixarene complexes.

Main Methods:

Synthesis of 3-pyridylmethyl-calixarene ligands.
Complexation reactions with copper (II) and zinc (II) ions.
Characterization using spectroscopic (NMR, IR, UV-Vis) and crystallographic techniques.
Solution and solid-state analysis.

Main Results:

Formation of novel supramolecular assemblies through the interaction of 3-pyridylmethyl-calixarenes with Cu(II) or Zn(II) ions.
Characterization of complexes in both solution and solid states.
Demonstration that steric crowding at the calixarene lower rim and metal coordination modes dictate the final architecture.
Observation of monomeric, dimeric, and oligomeric/polymeric species depending on reaction conditions.

Conclusions:

The steric environment of calixarenes significantly impacts the self-assembly of metal complexes.
Diverse coordination modes of metal ions lead to varied supramolecular architectures.
This study provides insights into the rational design of complex supramolecular structures.