Abstract: | A new cadmium–thiocyanate complex, poly[4‐(dimethylamino)pyridin‐1‐ium [di‐μ‐thiocyanato‐κ2N:S;κ2S:N‐thiocyanato‐κN‐cadmium(II)]], {(C7H11N2)[Cd(NCS)3]}n, was synthesized by the reaction of cadmium thiocyanate and 4‐(dimethylamino)pyridine hydrochloride in aqueous solution. In the crystal structure, each CdII ion is square‐pyramidally coordinated by three N and two S atoms from five different thiocyanate ligands, four of which are bridging. The thiocyanate ligands play different roles in the build up of the structure; one role results in the formation of [Cd2(NCS)2] building blocks, while the other links the building blocks and cations via N—H...S hydrogen bonds. The N—H...S hydrogen bonds and weak π–π stacking interactions are involved in the formation of both a two‐dimensional network structure and the supramolecular network. |