Abstract: | A cadmium–thiocyanate complex, poly(1‐cyanomethyl‐4‐aza‐1‐azoniabicyclo2.2.2]octane‐κ4N)octakis‐μ2‐thiocyanato‐κ8N:S;κ8S:N‐tricadmium(II)], Cd3(C8H14N3)2(NCS)8]n, was synthesized by the reaction of 1‐cyanomethyl‐4‐aza‐1‐azoniabicyclo2.2.2]octane chloride, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, there are two independent types of CdII cation (one on a centre of inversion and one in a general position) and both are in distorted octahedral coordination environments, coordinated by N and S atoms from different ligands. Neighbouring CdII cations are linked together by thiocyanate bridges to form a two‐dimensional network. Hydrogen‐bonding interactions are involved in the formation of a three‐dimensional supramolecular network. |