The tetrahedral cluster Ge4S104- and the rodlike ligand 4,4′-bipyridine are utilized in addition copolymerization reactions with the metal (II) ions of Mn, Fe, Co, Cu, and Zn in the preparation of 3-D open-framework solids, MxCol-xGe4S10-2(CH3)4N (x = 0.86, M = Mn; x = 1, M = Mn, Fe, Co, and Zn), 1, and Cu(4,4′-bpy)2. PF6, 2, having diamond-like structures. These structures are viewed in terms of the cubic diamond structure, where the carbon atoms have been replaced by either a cluster or a metal ion and the C-C bond by a sulfide or the 4,4′-bpy. These compounds have been fully characterized by single crystal x-ray crystallography and their composition was confirmed by elemental analysis; they contain 3-D channel systems where cations or anions reside to balance the charge on the framework.