The title compound [Zn(btzb)2Cl2]·2H2O (1·2H2O, btzb=1,2-bis(5-tetrazolyl)benzene) was synthesized in situ by the [2+3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions. 1·2H2O crystallizes in the monoclinic system, space group P21/c with a=9.0119(18), b=7.5566(15), c=18.076(5), β=114.67(2)o, V= 1118.6(4)3, Z=2, Dc=1.784 g/cm3, T=223(2) K, C16H16N16O2Cl2Zn, Mr=600.74, F(000)=608, μ(MoKα)=1.393 mm-1, S=1.081, R=0.0306 and wR=0.0669 for 1896 observed reflections with I > 2σ(I). The Zn2+ ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms, forming a distorted octahedral coordination geometry. A number of intermolecular hydrogen bon-ding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure. The luminescent property of 1·2H2O was also investigated.
The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)(μ-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563(3), b = 8.9547(18), c = 17.846(4) , β = 101.29(3)o, V = 2438.9(9) 3, Z = 4, Dc = 1.878 g/cm3, T = 193(2) K, C20H30ClCuMo2S4, Mr = 689.60, F(000) = 1376, μ(MoKα) = 2.335 mm–1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I > 2σ(I). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) , respectively.
The title compound, [Cu3(dmpzm)4(μ-1,3-dca)2(dca)4]·2H2O (dmpzm = 1,1'-methyle- nebis(3,5-dimethyl-1H-pyrazole), dca = dicyanamide) 1·2H2O, was synthesized via the reaction of CuCl2·2H2O with dmpzm and Na(dca), and characterized by elemental analysis and IR spectra. 1·2H2O crystallizes in the monoclinic system, space group C2/m with a = 13.578(3), b = 16.769(3), c = 14.769(3) , β = 104.10(3)o, V = 3261.4(11) 3, Z = 2, Dc = 1.466 g/cm3, T = 153(2) K, C56H68N34O2Cu3, Mr = 1440.09, F(000) = 1490, μ(MoKα) = 1.040 mm-1, S = 1.150, R = 0.0553 and wR = 0.1123 for 2744 observed reflections with I > 2σ(I). The central copper atom is chelated by two dmpzm ligands and coordinated by two bridging dca anions, forming a slightly distorted octahedral geometry. The two external copper atoms adopt a square-pyramidal coordination geometry, coor- dinated by one chelating dmpzm ligand and one bridging and two terminal dca anions. Two inter- molecular hydrogen bonding interactions result in the formation of a 2D (4,4) hydrogen-bonded network.
Reactions of NiCl2·6H2O with dmpzm and formic or acetic acid at PH = 7 pro- duced the two title compounds, [Ni(dmpzm)2(HCO2)]Cl·2H2O 1 and [Ni(dmpzm)2(OAc)]Cl·3H2O 2 (dmpzm = 1,1'-methylenebis(3,5-dimethyl-1H-pyrazole)). 1 and 2 were characterized by elemental analysis, IR spectra, and thermogravimetric analysis. 1 crystallizes in the orthorhombic system, space group Pcca with a = 18.700(2), b = 8.6843(9), c = 18.098(2) , V = 2939.1(5) 3, Z = 4, Dc = 1.319 g/cm3, T = 193 K, C23H37ClN8NiO4, Mr = 583.75, F(000) = 1232, μ(MoKα) = 0.792 cm-1, S = 1.079, R = 0.0772 and wR = 0.1958 for 2265 observed reflections with I > 2σ(I). 2 crystallizes in the orthorhombic system, space group Pcca with a = 17.011(3), b = 18.630(4), c = 19.300(4) , V = 6117(2) 3, Z = 8, Dc = 1.337 g/cm3, T = 193(2) K, C24H41ClN8NiO5, Mr = 615.79, F(000) = 2608, μ(MoKα) = 0.768 cm-1, S = 1.059, R = 0.0518 and wR = 0.1109 for 5124 observed reflections with I > 2σ(I). The Ni atoms in 1 or 2 are chelated by two dmpzm ligands and one formate or acetate anion, forming slightly distorted octahedral geometries. In the crystals of 1 or 2, intermolecular hydrogen bonding interactions result in the formation of 2D hydrogen-bonded frameworks.
