Complexes catena-[di(4-amino-pyridine)di(μ-S,N-thiocyanato)cadmium(II)], ∞ 1 [Cd(μ-SCN) 2(L 1) 2] (1), catena-[{(1-pyridine-2-yl-ethylene)-hydrazine}di(μ-S,N- thiocyanato)cadmium(II)], ∞ 1[Cd(μ-SCN) 2(L 2)] (2), and di-μ-S,N-thiocyanatobis{(N,N-diethyl- N′-(1-pyridine-2-yl-ethylidene)-ethane-1,2-diamine)(N-thiocyanato) cadmium(II)}, [Cd(NCS)(μ-SCN)(L 3)] 2 (3) have been synthesized by reacting cadmium acetate/NH 4SCN with 4-amino-pyridine (L 1), C 5H 4N-C(CH 3)=NNH 2 (L 2), and C 5H 4N-C(CH 3)=N-CH 2-CH 2-N(C 2H 5) 2 (L 3), respectively, in methanol. Characterization by single-crystal X-ray crystallography shows that in compounds 1 and 2 the cadmium atoms have a 4N2S-hexa-coordination sphere, exhibiting pseudo-octahedral geometry. The cadmium atoms are bridged by two thiocyanate ions generating 1-D polymeric chains. Compound 3 is a centrosymmetric dimeric complex, with the cadmium atom pseudo octahedrally surrounded by a 5N1S coordination sphere. In compound 1 the crystal packing is controlled mainly by interchain N-H⋯N and C-H⋯π interactions between the aminopyridine moieties, whereas in complexes 2 and 3 π-stacking interactions between the pyridyl planes stabilize the interchain or intermolecular packing, respectively. Thiocyanate and pyridylimine chelation to metal center is also scrutinized with EHMO analysis. © 2004 Elsevier B.V. All rights reserved.