New polynuclear coordination species containing the ditopic bis(l-imidazolyl) methane (Bim) ligand have been prepared as microcrystalline powders and structurally characterized by ab initio X-ray powder diffraction methods. [Zn(CH3COO)(2)(Bim)](n) contains 1D chains with tetrahedral metal atoms bridged by Bim ligands; [CdBr2(Bim)](n) shows a dense packing with hexacoordinated Cd(II) ions and mu-Br and mu-Bim bridges; at variance, the isomorphous [ZnCl2(Bim)], and [ZnBr2(Bim)](n) species contain cyclic climers based on tetrahedral Zn(II) ions. Thermodiffractometric analysis allowed estimation of the linear thermal expansion coefficients and strain tensors derived there from. Bim-rich phases, with 2:1 ligand-to-metal ratio, were also isolated: ZnBr2(Bim)(2)(H2O)(3) and [Cd(CH3COO)(2)(Bim)(2)](n) containing cis and trans MN4O2 chromophores, respectively, show 1D polymers built upon M(2)Bim(2) cycles, hinged on the metal ions. In all species the conformation of the Bim ligands is C, (or nearly so), while in the few sparse reports of similar coordination polymers the alternative C-2 one was preferentially observed.