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Issue 14, 2015
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Copper pyromellitates: a complex story

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Abstract

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.

Graphical abstract: Copper pyromellitates: a complex story

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Publication details

The article was received on 06 Mar 2015, accepted on 09 Mar 2015 and first published on 09 Mar 2015


Article type: Paper
DOI: 10.1039/C5CE00470E
Citation: CrystEngComm, 2015,17, 2857-2871
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    Copper pyromellitates: a complex story

    W. Clegg, J. M. Holcroft and N. C. Martin, CrystEngComm, 2015, 17, 2857
    DOI: 10.1039/C5CE00470E

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