Structural variations in self-assembled coordination polymers constructed by some carboxylate bridged di-copper(II) nodes and hexamethylenetetramine spacers

Four new copper(II)-hexamethylenetetramine (hmt) complexes [Cu3(2-nbz)6(μ2-hmt)]n (1), [Cu3(pa)6(μ3-hmt)]n (2), [Cu3(4-nbz)6(μ3-hmt)]n (3) and [Cu(3-nbz)2(μ4-hmt)·H2O]n (4) with three isomeric nitrobenzoates, [2-nbz = 2-nitrobenzoate, 3-nbz = 3-nitrobenzoate, 4-nbz = 4-nitrobenzoate] and phenylacetate (pa) have been synthesized and structurally characterized by X-ray crystallography. Their identities have also been established by elemental analysis and IR studies. In all four complexes, the respective [Cu2(carboxylato)4] unit with four bridging carboxylate ligands in the familiar η1:η1:μ coordination mode acts as a linear node whereas the spacer hmt coordinates in different ways which result in the observed structural variations. Complex 1 is a 1D zigzag polymer where hmt acts as angular spacer. In complexes 2 and 3, μ3-hmt is pyramidal and the resulting structures are 2D polymers with fused hexagonal rings. Complex 4 is a very rare example of a 3D diamondoid polymer with μ4-hmt acting as a tetrahedral spacer. Various weak forces, i.e. lone pair–π, π–π and CH–π interactions, play a key role in stabilizing the observed structures.

Synthesis and structural characterization of four new copper(II)-hexamethylenetetramine (hmt) complexes with isomeric 2-, 3-, 4-nitrobenzoates and phenylacetate reveal that one of them is a 1D zigzag chain, two are 2D polymers with fused hexagonal rings and the remaining one is a very rare example of a self-assembled diamondoid 3D coordination polymer.Figure optionsDownload as PowerPoint slide