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This paper describes four novel hydrogen-bonded copper(I) supramolecules with channel structures. The reactions of copper(I) salt with 3-cyano-6-methyl-2(1H)-pyridinone (Hcmp) in acetone have isolated four polymeric coordination products Cu(Hcmp)4X, where X = ClO4- (1), BF4- (2), PF6- (3), and CF3SO3- (4). All four compounds crystallized in the tetragonal system. Each structure contains a three-dimensional framework of tetrahedral CuN4 centers linked by intermolecular hydrogen bonds through pyridone N and O atoms in a head-to-tail mode. The very special structural features of the four compounds are related to the two types of hydrogen-bonding. Complexes 1 and 2 with smaller counteranions involve each Hcmp group hydrogen-bonded to two adjacent others (type A), which generates an open square channel filled with aligned ClO4- or BF4- ions, whereas 3 and 4 involve 1:1 pairwise hydrogen-bonding of Hcmp (type B) which results in four independent interpenetrating diamond-like frameworks with big cavities to accommodate larger anions of PF6- and CF3SO3-. Novel insight into the unique role played by the hydrogen-bonding mode and distances on the architecture of the network is discussed. The study indicates that the metal complex supramolecular structures can be rationally designed via hydrogen-bonding interactions.
Munakata et al. (Mon,) studied this question.