An unusual chain cadmium(II) coordination polymer: catena‐poly[[(2,2′‐bipyridyl‐κ2N,N′)cadmium(II)]‐di‐μ‐chlorido‐[(2,2′‐bipyridyl‐κ2N,N′)cadmium(II)]‐di‐μ‐thiocyanato‐κ2N:S;κ2S:N]

The title complex, [CdCl(NCS)(C₁₀H₈N₂)]_n, represents an unusual Cd^II coordination polymer constructed by two types of anionic bridges and 2,2′‐bipyridyl (bipy) terminal ligands. These two types of bridges are arranged around inversion centers. The distorted octahedral coordination of the Cd^II center is provided by two chloride ions, one N‐ and one S‐donor atom from two thiocyanate ions, and a pair of N atoms from the chelating bipy ligand. Interestingly, adjacent Cd^II ions are interconnected alternately by paired chloride [Cd...Cd = 3.916 (1) Å] and thiocyanate bridges [Cd...Cd = 5.936 (1) Å] to generate an infinite one‐dimensional coordination chain. Furthermore, weak interchain C—H...S interactions between the bipy components and thiocyanate ions lead to the formation of a layered supramolecular structure.