The title complexes [M（ImH）4（tfbdc）（H2O）] （1： M = Co; 2： M = Ni） （ImH = imidazole, tfbdc = 2,3,5,6-tetrafluoroterephthalate） were synthesized by the reaction of M（OAc）2·4H2O, H2ffbdc and ImH in water solution. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, cyclic voltammetry and X-ray single crystal structure analysis. Structural analysis reveals that 1 and 2 possess isostructure： monoclinic, P2 1/c, Z=4. M（II） ion in complexes 1 and 2 has a distorted octahedral geometry coordinated by one oxygen atom from water, one oxygen atom from tfbdc2- and four nitrogen atoms from ImHs. They are discrete zero-dimensional molecular complexes. And the adjacent monomeric components are connected by hydrogen bonds to form a supramolecule. Electrochemical properties of the complexes 1 and 2 show that electron transfer of M（II） between M（III） in electrolysis is a quasi-reversible process.
Two new supramolecular compounds, 2C10HgN2＋CsHF4O42-C8H2F4O4/（H2tfbdc） （tfbdc）＇（Hbipy）2 （1） and C4H6NEE＋.CsHF4O427（tfbdc）（H2pz） （2）, were synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P1, with a = 8.3453（12）, b = 10.1798（15）, c = 10.6626（16） A, a = 87.591（2）, β = 74.047（2）, ）, = 69.006（2）, V= 834.53（12） A3, Dc = 1.614 g/cm3, F（000） = 400, u = 1.45 cm^-1, Z= 2, the final R = 0.0353 and wR = 0.1005 for 5882 observed reflections withI〉 2σ（I）; and compound 2 crystallizes in the monoclinic system, space group P21/c, with a = 10.471（4）, b = 5.4419（19）, c = 12.249（4） A,β = 114.909（6）°, V= 633（4） A3, Dc = 1.669 g/cm3, F（000） = 320, u = 1.63 cm-1, Z = 2, the final R = 0.0794 and wR = 0.2923 for 3213 observed reflections with I〉 2σ（I）. Both compounds 1 and 2 crystallize as charge-transfer organic salts with the dianionic or neutral acid components lying at the inversion centers. Hbipy＋ cations and anionic acid in compound I are linked to form a chain by means of C-H..-O hydrogen bonds. Adjacent chains are further extended into a two-dimensional layer network via N-H.O and O-H-N hydrogen bonds. In compound 2, the acid and base subunits are arranged alternately to generate a linear tape motif via N-H...O hydrogen bonds; these tapes are further combihed into a three-dimensional array with CdSO4 topology via C-H...O intermolecular hydrogen bonds.
