Synthesis and Structural Characterization of a New Cadmium(II) Complex with a Double Betaine

A new flexible double betaine L （L = 1,4-bis（pyridinio-4-carboxylato-N-methyl）benzene, C20H16N2O4） and its cadmium（Ⅱ） complex [Cd（H2O）aL（NO3）]NO3.H2O 1 were synthesized. Complex 1 was obtained by self-assembly reaction of [Cd（NO3）2]-4H2O and L in hot water,and its crystal structure was determined by single-crystal X-ray diffraction analysis. Crystallographic data for complex 1： C20H24CdN4O14.H2O, Mr = 674.85, monoclinic, space group P21/c, a =13.7854（3）, b = 14.2820（3）, c = 14.9188（4） ,A°, β = 116.418（1）°, V = 2630.5（1）A°^3, Z = 4, Dc= 1.704g/cm^3,/J（MoKα） = 0.911 mm^-1, F（000） = 1368, the final R = 0.0315 and wR = 0.0768 for 3637 observed reflections with I 〉 2σ（I）. In complex 1, L acts as a monodentate ligand to link a Cd（Ⅱ） ion in a novel coordination mode of double betaines. The mononuclear [Cd（H2O）aL（NO3）] units are connected through intermolecular hydrogen bonds and π-π stacking reactions to generate a 3D network.

Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

Synthesis and Crystal Structure of a New Lanthanum(III) 4-Cyanobenzoate Complex

A new dinuclear La（Ⅲ） complex [La2（4-cba）4[H（4-cba）2]2（phen）2（H2O）4] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by singlecrystal X-ray diffraction. Crystallographic data： C88H58La2N12O20, Mr = 1881.28, triclinic P1, a = 7.518（3）, b = 17.033（6）, c = 17.551（6）A, α = 115.333（4）, β = 92.9910（10）, γ = 99.366（5）°, V = 1985.3（12）A^3, Z = 1, Dc = 1.574 g/cm^3, F（000） = 944 μ = 1.145 mm^–1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with Ⅰ 〉 2σ（I）. In 1, two nine-coordinated La（Ⅲ） ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La（Ⅲ） ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.

Synthesis, Single-crystal Structure, and Optical and Magnetic Properties of CaEr_2S_4

Brown needle-like crystals of CaEr2S4 were isolated as the major product from a reaction of elements and binary sulfides by a two-step flux technique. CaEr2S4 crystallizes in the orthorhombic space group Pnma with a=12.845（4）, b=3.862（4）, c=13.001（2）（A）, V=645.0（7）（A）3,Z=4, F（000）=880,μ（MoKα）=27.794 mm^-1, the final R=0.0528 and wR=0.0562 for 1070observed reflections with I 〉 3σ（I）. The CaEr2S4 structure forms a three-dimensional framework that consists of interconnected tetra-octahedral Er4S18 fragments. Ca^2＋cations, in a monocapped trigonal prism geometry, are stuffed in two parallel rows into the one-dimensional channels along the b direction. CaEr2S4 is an infrared-transparent semiconductor with a band gap of 1.81 eV. Magnetic susceptibility measurements over 6～300 K indicate a Curie-Weiss paramagnetic behavior for the phase, with an effective magnetic moment of 9.64（1） μB per Er^3＋ ion.

Synthesis and Crystal Structure of a Hepta-nuclear V-Cu-S Cluster:[VS_4Cu_6(Py)_8Br_3]

The title compound has been synthesized by the reaction of(NH4)3VS4, CuBr and NMe4Br in pyridine and its structure was determined by singlecrystal X-ray diffraction. Crystallographic data: C40H40Br3Cu6N8S4V, M4= 1432. 95,orthorhombic space group Fdd2, a= 29. 9519 (2), b=13. 4719 (2), c= 25. 8612 (4)A, V= 10435. 2 (4), Z= 8, Dc= 1.824 g/cm3, F(000)= 5616,μ(MoKa) =50.64 cm-1, the final R =0.091 and wR =0. 206 for those 3401 unique reflectionshaving . The crystal structure determination shows that the cluster consists of a tetrahedral VS4 core encapsulated by a distorted octahedral array of six copperatoms which have two different coordination geometries, trigonal and tetrahedral.

Synthesis and Crystal Structure of an Octa-nuclear V-Cu-S Cluster:[VS_3O(CuPBu_3)_2(CuSPBu_3)]_2

The title compound has been synthesized by reaction of (NH4)3VS4,CuCl, and PBu3 in CH2Cl2 and its structure was determined by single crystal X-raydiffraction. Crystallographic data: C72 H162 Cu6O2P6S8V2, Mr= 1985. 57, monoclinicspace group C2/c, a= 17. 864(3), b= 25. 946(8), c= 24.071 (7),β= 112. 79(2)°,V = 10285. 9, Z= 4, Dc= 1. 28 g/cm3, F(000) = 4192, μ(MoKa) = 16. 7 cm-1,the final R=0.065 and Rw =0.074 for 4051 unique reflections with I> 3σ(I). Thestructure can be described as a metal-sulfur dodecahedral cage fused by two incompletecubane-like VS3Cu3 units connected by Cu - S bonds. The Cu - S bonds within theasymmetric VS3Cu3 unit are slightly shorter than those linking the two centrosymmetrically related VS3Cu3 units. The six copper and two vanadium atoms display asomewhat distorted cubane array with a μ4-S atom on each face of the metal cubane.

Structural Studies of [V_2S_6O_2(CuPPh_3)_4(CuMeCN)_2]·2CH_2Cl_2·2PrOH

The title V-Cu-S heterometallic cluster compound C84 H86Cl4Cu6N2O4P4S6V2, crystallizes in the monoclinic space group P21/n with a=16.381(5), b=17.114(3),c=16.749(6) A,β=107. 04(3)°,V=4490(2)A3, Mr=2128.84,Z=2,Dc=1. 57 g/cm3,μ= 19. 6 cm-1,F(000)=2160. Final R=0.074(Rw=0.082) for 2662 unique reflections with I≥3σ(I). The V atom in the compound retains the tetrahedral geometry of the VS3O with S-V-S or S-V-O angles of 108.6(6)～110.3 (6)°.The cluster core [V2Cu6S6O2] of the compound can be regarded as two cluster cores [VCu3S3O] bonded by bondings of the Cu-Cu'(distances of 2.774(3)～2.707(5) A) and Cu-S (distances of 2.463(7)～2.396(9) A) with centrosymmetric. Atoms of the cluster core V2Cu6 form a distorted cube with the Cu Cu'or the V-Cu distances of 2. 774(3)～2. 707(5) A.

Synthesis and Crystal Structure of a Heteropentanuclear Yb(Ⅲ)-Cu (Ⅱ) Complex:[Yb_2Cu_3(O_2CCH_2CI)_(12)(H_2O)_8]·2H_2O

The title complex [Yb2Cu3 （O2CCH2CI ）12 （H2O）8]·2H2O（Mr=1838. 73） crystallized in monoclinic space group P21/c, with a=10. 424 （6 ）, b= 17.953（4）, c=15. 193（4）A, β=100. 18（1）, V=2798（2） A3, Z=2, Dc=2.18 g/cm3, R=0. 066, Rw=0. 081 for 3653 unique reflections with I＞ 3（I）, u=50. 9cm-1, F （000）=1782, in which the Cu and Yb atoms are bridged uniquely bychloroacetate groups. The Cu atoms display two types of coordination spheres, a fourcoordinate distorted square and a five-coordinate square pyramid, and the coordinationgeometry of each Yb atom is a square antiprism.