Reaction of Cd(OAc)(2)center dot 2H(2)O with 4,4'-biphenyldithiol (H(2)bpdt) in different alkyldiamines at 105 degrees C gave single crystals of different 2D-layered cadmium thiolates metal-organic frameworks. The alkyldiamine acts both as a solvent and as a coordination-engineering agent to control the crystal growth and the dimensionality of the cadmium thiolate networks.