A 2:2:1:6 molar ratio of Zn(ClO 4 ) 2 Á6H 2 O, tris(2-aminoethyl)amine (tren), Zn(ClO 4 ) 2 Á6H 2 O/Cu(ClO 4 ) 2 Á6H 2 O and NH 4 NCS in methanol-water solution mixtures affords homo-/heterobimetallic compounds of the type [Zn(tren)NCS] 2 [M(NCS) 4 ] (M = Zn, 1; M = Cu, 2) which have been characterized using microanalytical, spectroscopic, magnetic and other physicochemical results. The structures of the compounds are determined by X-ray diffraction measurements. Structural analyses reveal that 1 and 2 are isomorphous and consist of two discrete [Zn(tren)NCS] + cations and a [M(NCS) 4 ] 2À (M = Zn/Cu) anion. Zinc(II) centers in the [Zn(tren)NCS] + units adopt distorted trigonal bipyramidal geometry with ZnN 5 chromophores coordinated through four N atoms of tren and one N atom of terminal thiocyanate. Each metal(II) center in [M(NCS) 4 ] 2À has a distorted tetrahedral coordination environment with an MN 4 chromophore ligated by four N atoms of the terminal thiocyanates. In solid state, doubly N-H. . .S hydrogen bonded 1D chains of [Zn(tren)NCS] + cations are interconnected by tetrahedral [Zn(NCS) 4 ] 2À /[Cu(NCS) 4 ] 2À anions through cooperative N-H. . .S and N-H. . .N (in 1) and N-H. . .S and C-H. . .S (in 2) hydrogen bonds resulting in 3D network structures. Establishment of such networks seems to be aiding the crystallization.