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Chalcogen S∙∙∙S Bonding in Supramolecular Assemblies of Cadmium(II) Coordination Polymers with Pyridine-Based Ligands

Two cadmium(II) coordination polymers, with thiocyanate and pyridine-based ligands e.g., 3- acetamidopyridine (3-Acpy) and niazid (nicotinic acid hydrazide, nia), namely one- dimensional {; ; ; [Cd(SCN)2(3-Acpy)]}; ; ; n (1) and two- dimensional {; ; ; [Cd(SCN)2(nia)]}; ; ; n (2), are prepared in the mixture of water and ethanol. The adjacent cadmium(II) ions in 1 are bridged by two N, S-thiocyanate ions and an N, O-bridging 3-Acpy molecule, forming infinite one- dimensional polymeric chains, which are assembled by the intermolecular N–H∙∙∙S hydrogen bonds in one direction and by the intermolecular S∙∙∙S chalcogen bonds in another direction. Within the coordination network of 2, the adjacent cadmium(II) ions are bridged by N, S-thiocyanate ions in one direction and by N, O, N’-chelating and bridging nia molecules in another direction. The coordination networks of 2 are assembled by the intermolecular N–H∙∙∙S and N–H∙∙∙N hydrogen bonds and S∙∙∙S chalcogen bonds. Being the only supramolecular interactions responsible for assembling the polymer chains of 1 in the particular direction, the chalcogen S∙∙∙S bonds are more significant in the structure of 1, whilst the chalcogen S∙∙∙S bonds which act in cooperation with the N–H∙∙∙S and N–H∙∙∙N hydrogen bonds are of less significance in the structure of 2.

coordination networks ; cadmium(II) ; thiocyanate ; 3-acetamidopyridine ; nicotinic acid hydrazide ; chalcogen bonds ; hydrogen-bond motifs

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