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Lookup NU author(s): Emeritus Professor Bill CleggORCiD, James Holcroft, Nick Martin
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Reaction of copper(II) salts with pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid) and bases using slow vapour and gel diffusion techniques produces a variety of complexes containing copper and pyromellitate ions and solvent molecules, both coordinated (usually as terminal ligands) and uncoordinated. In some cases molecules of base are also coordinated, and organic or alkali metal cations may be present. Most of the complexes are 2- or 3-dimensional polymeric networks as expected, though there are also some discrete molecular complex ions, which are unusual for pyromellitate complexes of metals. Coordination of copper(II) is most often square pyramidal with a long apical bond, but with some examples also of square-planar coordination supplemented by additional secondary interactions with carboxylates or solvent molecules above and below the plane to give distorted octahedral geometry. Pyromellitate is fully deprotonated in all but one product, and usually coordinates to 2, 4 or 6 copper ions, and additionally to 8 alkali metal ions where these are present. Hydrogen bonding plays a significant role in all the structures, its role ranging from formation of discrete clusters of coordinated and uncoordinated water molecules to extensive 3-dimensional networks. The impressive structural variety arises from the combination of rigidity of the benzene ring and individual carboxylate groups with torsional flexibility in the connections of these groups, together with the availability of different coordination geometries for copper(II). The results illustrate the considerable structural versatility of pyromellitate ligands and the unreliability of structural design in benzenepolycarboxylate coordination chemistry.
Author(s): Clegg W, Holcroft JM, Martin NC
Publication type: Article
Publication status: Published
Journal: CrystEngComm
Year: 2015
Volume: 17
Issue: 14
Pages: 2857-2871
Print publication date: 14/04/2015
Online publication date: 09/03/2015
Acceptance date: 09/03/2015
Date deposited: 20/01/2015
ISSN (electronic): 1466-8033
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/C5CE00470E
DOI: 10.1039/C5CE00470E
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