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Issue 5, 2009
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From copper(II) carboxylate to copper(II) 4-pyridylsulfonate coordination polymers as a consequence of the copper(II)-assisted oxidative cleavage of the 4,4′-dipyridyldisulfide ligand

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Abstract

Five coordination polymers 1 {[Cu4(HCO2)6(OH)2(4dpds)2]·2CH2Cl2}n, 2 {[Cu4(CH3CO2)6(OH)2(4dpds)2]}n, 3 {[Cu(4dpds)2(H2O)2](4pySO3)2·2H2O}n, 4 {[Cu(4pySO3)2(4dpds)2]·2H2O}n and 5 {[Cu(4pySO3)2(dmso)2]·2H2O}n (where 4dpds = 4,4′-dipyridyldisulfide, 4pySO3 = 4-pyridylsulfonate) have been obtained during a study into the reactivity of basic copper(II) salts (formate and acetate) with 4,4′-dipyridyldisulfide (4dpds). The coordination polymers 1 and 2 consist of a repeated rhomboid structure in which analogous Cu4(RCO2)6(OH)2 cores are joined by two 4,4′-dipyridyldisulfide bridging ligands to generate two different chain topologies: planar ribbon in 1 and ruffled ribbon in 2. 4-Pyridylsulfonate ions appear as ligands or counterions in the coordination polymers 3, 4 and 5 due to oxidative cleavage of the 4,4′-dipyridyldisulfide under mild conditions. The coordination polymer 3 has been isolated repeatedly in several direct reactions of the copper(II) carboxylates with 4,4′-dipyridyldisulfide. However, the coordination polymers 4 and 5 have been obtained from 1 and 2, respectively, by recrystallization from DMF and DMSO. In compound 4, as in 3, the 4,4′-dipyridyldisulfide has only been partially oxidized to 4-pyridylsulfonate and a proportion of these units remain in the structure as disulfide. However, in 5 the oxidation is complete. The structural analysis of these coordination polymers reveals that, in all cases, weak interactions such as classical and non-classical hydrogen bonds, as well as CH⋯π, S⋯π and S⋯O interactions, join the polymeric chains to generate three-dimensional networks.

Graphical abstract: From copper(II) carboxylate to copper(II) 4-pyridylsulfonate coordination polymers as a consequence of the copper(II)-assisted oxidative cleavage of the 4,4′-dipyridyldisulfide ligand

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The article was received on 24 Sep 2008, accepted on 10 Dec 2008 and first published on 27 Jan 2009


Article type: Paper
DOI: 10.1039/B816721D
Citation: CrystEngComm, 2009,11, 817-826
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    From copper(II) carboxylate to copper(II) 4-pyridylsulfonate coordination polymers as a consequence of the copper(II)-assisted oxidative cleavage of the 4,4′-dipyridyldisulfide ligand

    R. Carballo, B. Covelo, N. Fernández-Hermida, A. B. Lago and E. M. Vázquez-López, CrystEngComm, 2009, 11, 817
    DOI: 10.1039/B816721D

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