Construction of Three-Dimensional Supramolecular Coordination Copper(I) Compounds with Channel Structures Hosting a Variety of Anions by Changing the Hydrogen-Bonding Mode and Distances

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)4]X, 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.