Coordination polymers of 2,5-dihydroxybenzoquinone and chloranilic acid with the (10,3)- A topology

Abrahams, Brendan F., Hudson, Timothy A., McCormick, Laura J. and Robson, Richard (2011) Coordination polymers of 2,5-dihydroxybenzoquinone and chloranilic acid with the (10,3)- A topology. Crystal Growth and Design, 11 (7), 2717-2720. (doi:10.1021/cg2005908).

Abstract

Crystalline compounds of general composition (NBu₄) ₂[M^II₂(dhbq)₃] (where M = Mn, Fe, Co, Ni, Zn, and Cd and dhbq^2- is the dianion of 2,5- dihydroxybenzoquinone) are obtained by reaction of the divalent metal acetate (or the sulfate in the case of Fe) with 2,5-diaminobenzoquinone and an excess of NBu₄Br in aqueous solution at 115 °C in sealed tubes. The dhbq^2- ligand is generated in situ by hydrolysis of the 2,5-diaminobenzoquinone. We have been unable to obtain these compounds in a crystalline form suitable for single crystal X-ray diffraction studies directly from H₂dhbq itself. A structural feature common to this series is the presence of two interpenetrating [M^II₂(dhbq) ₃]^2- coordination networks, each with the chiral (10,3)-a topology, with the two independent nets being of opposite hand - unprecedented circumstances for dhbq-based coordination polymers. Crystals of the same zinc compound as that obtained above from 2,5-diaminobenzoquinone can alternatively be obtained by in situ aerial oxidation of 1,2,4,5-tetrahydroxybenzene in the presence of Zn(OAc)₂ and NBu₄Br in aqueous methanol at room temperature. Analogous in situ aerial oxidation of 1,2,4,5-tetrahydroxy-3, 6-dichlorobenzene in the presence of Mn(OAc)₂ and NBu₄Br affords crystalline samples of the chloranilate (NBu₄) ₂[Mn^II₂(can)₃], which contains two interpenetrating (10,3)-a [Mn^II₂(can)₃] ^2- networks of opposite hand.

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Contributors

Author: Laura J. McCormick

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