Hydrothermal Synthesis and Crystal Structure of a New Sandwich-type Molybdenum Phosphate

The crystal structure of the title compound, [enH2][Fe{MoⅤ6O12(OH)3(HPO4)- (H2PO4)3}2]6en6H2O (en = H2NCH2CH2NH2), hydrothermally synthesized from a mixture of Na2MoO42H2O, Fe2(SO4)3, H3PO4, H2N(CH2)2NH2 and water, has been determined by single- crystal X-ray diffraction. The crystal is of triclinic, space group P?with a = 11.9014(1), b = 13.4246(2), c = 13.8719(2) , a = 87.465(1), b = 69.981(1), g = 64.960(1)? V = 1873.46(4) 3, Z = 1, Mr = 2997.89, F(000) = 1466, m = 2.427 mm-1 and Dc = 2.657 g/cm3. The final R = 0.0404 for 5570 observed reflections (I > 2s(I)). The structural analysis reveals that each cluster anion contains two coplanar {Mo6} rings of six edge-sharing Mo(O5OH) octahedra, and the two {Mo6} rings are linked together through one octahedral FeⅡ ion to generate a sandwich-type cluster with rigorous () symmetry. Moreover, these clusters are further linked into a three-dimensional frame- work by hydrogen bonds.

A Layered Vanadium Oxide with Cobalt(Ⅱ) Coordination Complex: Hydrothermal Synthesis and Crystal Structure of (py)_5Co_2(H_2O)_3[V_4O_(12)]

A novel layered mixed metal vanadium-cobadt complex, （py）5Co2（H2O）3[V4O12] 1 （py = pyridine）, was hydro（solvo）thermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in orthorhombic, space group Pca21 with a = 17.473（4）, b = 11.447（2）, c = 17.509（4）A^°, V = 5005.3（7）A^°3, Z = 4, Mr = 3502.1（12）, Z = 4, Dc = 1.827 g/cm^3,μ（MoKα） = 2.023 mm^-1, F（000） = 1928, S = 1.020, the final R = 0.0400 and wR= 0.1063 for 6035 observed reflections with I 〉 2σ（I） and 460 variables. Complex 1 consists of tetrahedral VO4 groups to form the large layers which are alternately bonded by two cobalt complex species Co（py）2（H2O）2 and Co（py）3（H2O）.

Synthesis and Crystal Structure of Cubane-type Molybdenum Cluster Complex Mo_4S_4(DTP)_4[μ-SOP(OEt)_2]_2

A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure has been determined by X-ray crystallography and the data for the title compound: Mo4S14P6O14C24H60, triclinic P , Mr = 1591.14, a = 12.5596(5), b = 14.3441(5), c = 18.0005(6) ? = 85.318(1), = 70.495(1), = 78.415(2)? V = 2994.2(2) ?, Z = 2, Dc = 1.765 g/cm3, (MoK? = 1.515 mm-1, F(000) = 1596, R = 0.0918 and wR = 0.1908 for 3546 reflections (I > 2(I)). X-ray analysis reveals that two weak CH贩稯 hydrogen bonds exist in the packing diagram with C贩稯 distance 3.22(5) ? The structure of A is similar to that of -Mo4S4(DTP)6 except that one sulfur of each bridging DTPs has been replaced by oxygen during the reaction, resulting in two bridging [SOP(OEt2)2] - ligands.

Mild Hydrothermal Synthesis,Crystal Structure and Magnetic Behavior of AgCu(IO_3)_3:a Quasi-one-dimensional S=1/2 Chain Compound

A new complex AgCu（IO3）3 is synthesized by mild hydrothermal method and characterized by single-crystal X-ray diffraction and magnetization measurement.AgCu（IO3）3 is triclinic,space group P1,with a = 7.3081（1）,b = 7.8089（1）,c = 8.2447（1）A,α = 67.159（1）,β = 74.982（1）,γ = 80.982（1）°,and Z = 2.AgCu（IO3）3 is isostructral with Ag Pb（IO3）3.The structure of Ag Cu（IO3）3 consists of CuO6 chain columns parallel to the c axis,formed by corner-sharing Cu（1） and Cu（2） octahedra and flanked by corner-sharing IO3 groups; these CuO6 columns are cross-linked into a three-dimensional framework through I–O and Ag–O bonds.I（1）,I（2） and I（3） are coordinated respectively with 3 oxygens on the same side to form trigonal pyramids confirming the presence of a stereochemically active lone pair of each I^5＋ cation.In the CuO6 chain columns,Cu（1）O6 and Cu（2）O6 octahedra are tetragonally distorted with four shorter bonds in the square planes and two longer apical bonds.Cu（1）O6 octahedra were corner sharing with Cu（2）O6 octahedra with a shorter Cu（1）–O（1） bond in the square planes and a longer apical Cu（2）–O（1） bond,which forms a Cu（1）–Cu（2） magnetic chain along the c direaction.Magnetization measurement shows weak antiferromagnetic property in low temperature range.Ag Cu（IO3）3 provides a new example of a quasi-one-dimensional magnetic system.

Synthesis and Crystal Structure of a Molybdenum Carbonyl Compound with Thiolate and Dithiocarbamate Ligands, [Bu_4N][(OC)_4Mo(μ-SC_6H_5)_2Mo(C_5H_(10)CNS_2)(CO)_2]

A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate ligands, [Bu4N][（CO）4Mo（μ-SC6H5）2Mo（C5H10dtc）（CO）2] 1 （CsH10dtc = S2CNC5H10）, has been prepared by reaction of [Mo2（SC6H5）2（CO）8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162（3）, b = 17.466（2）, c = 20.453（4） A,β= 100.77（1）°, Z = 4, V= 4619（2）A^3, C40H56Mo2N2O6S4, Mr = 980.95, De= 1.389 g/cm^3,μ = 7.66 cm^-1, F（000） = 1988 and R = 0.0746 for 5161 observed reflections with I 〉 2σ（I）. The complex contains a [Mo2S2]^2- planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.

Hydrothermal Synthesis, Crystal Structure and Thermal Analyses of Pyrazine-2,3-dicarboxylic Acid Bridged Co(II) Coordination Polymer of _∞~2[Co(phen)(μ-L)_(3/3)]·H_2O (H_2L = Pyrazine-2,3-dicarboxylic Acid)

A novel pyrazine-2,3-dicarboxylic acid bridged Co(II) phen complex 2 ∞ [Co- (phen)(μ-L)3/3]?H2O (H2L = pyrazine-2,3-dicarboxylic acid) has been hydrothermally synthesized, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group P21/n with a = 11.480(2), b = 11.885(2), c = 12.939(3) ?, β = 110.55(3)°, V = 1653.1(6) ?3, Mr = 423.25, Dc = 0.425 g/cm3, Z = 4, R = 0.0361 and wR = 0.1011. The title complex consists of 2D 2 ∞ [Co(phen)(μ-L)3/3] layers and crystal water molecules. Each Co atom is octahedrally coordinated by three N atoms and three O atoms to form 2D 2 ∞ [Co(phen)(μ-L)3/3] polymeric layers. Furthermore, such 2D layers are stacked into 3D supramolecular frameworks via Van der Waals’ intermolecular forces, strong and weak hydrogen-bond interactions. The coordination phen and crystal water molecules are resided into cavities of the frameworks.

Hydrothermal Synthesis and Crystal Structure of a Zinc Complex:[Zn_(2.5)(phen)(BDC)_2(OH)] (phen = 1,10-Phenanthroline, BDC = Benzene-1,4-dicarboxylic Acid)

A metal-organic coordination polymer [ZnE.s（phen）（BDC）2（OH）]2 （phen = 1,10- phenanthroline, BDC = benzene-1,4-dicarboxylic acid） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The complex crystallizes in the triclinic system, space group PI with a = 11.199（2）, b = 11.593（2）, c = 11.865（3）/A, α= 99.330（1）, β = 111.506（1）, γ = 104.804（1）^o, V= 1328.4（5）A^3, Dc= 1.722 g/cm^3, Z = 1, Mr = 1377.82, F（000） = 692,μ（MoKa） = 2.306 mm^-1, S = 1.093, R= 0.0281 and wR = 0.0756 for 4179 observed reflections （I 〉 2σ（/））. The coordination polyhedron around Zn（II） can be described as a tetrahedron, trigonal bipyramid and octahedron. It is worth noting that the crystal structure of 1 is composed of tetranuclear zinc clusters linked by {ZnO6} units.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Coordination Polymer Assembled by Phthalate and 4,4′-Bipyridine

A metal-organic coordination polymer {[Zn（Pht）（4,4＇-bipy）（H2O）2]·2H2O}n （Pht = phthalate, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in the monoclinic system, space group P2/n, a = 7.6346（14）, b = 11.316（2）, c = 10.8133（19） ,A, β = 92.A.A,A.（3）°, V = 933.3（3） A^3, C18H20N2O8Zn, Mr = 457.73, Dc = 1.629 g/cm^3, F（000） = 472, Z = 2,μ（MoKa） = 1.367 mm^-1, the final R = 0.0323 and wR = 0.0821 for 1859 observed reflections （Ⅰ〉 2σ（Ⅰ））. The structure of 1 exhibits a two-dimensional bilayer framework formed by hydrogen bonding interactions. Furthermore, 1 shows yellow photoluminescent property at room temperature.

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a New Isophthalate- bridged Zinc(II) Polymer with One-dimensional Chain Structure: [Zn(ipt)(im)_2]_(2n)·3nH_2O (ipt = Isophthalate, im = Imidazole)

A new metal-organic coordination polymer [Zn（ipt）（im）2]2n·3nH2O 1 has been obtained by using hydrothermal synthesis and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P2（1/n） with a = 10.653（3）, b = 17.891（6）, c = 10.743（4）A^°,β= 117.093（5）°, V= 1822.9（10） A^°3, Mr= 413.65, Dc = 1.507 g/cm^3,/t（MoKa） = 1.390 mm^-1, F（000） = 840, Z = 4, the final R = 0.0444 and wR = 0.1066 for 2434 observed reflections （I〉 2σ（I））. Furthermore, compound 1 shows blue photoluminescent property at room temperature.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper(Ⅱ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.

Hydrothermal Synthesis and Crystal Structure of a New Three-dimensional Heterometallic Coordination Polymer

A new 3d-4fheterometallic polymer {[Sm2Cu（PDC）2（SO4）2（H20）6]·2H2O}n 1 has been synthesized by Sm2O3, Cu（SO4）2·5H2O and pyridine-3,5-dicarboxylic acid under hydrothermal conditions. The compound crystallizes in triclinic system, space group Pi, with a = 6.352（7）, b = 10.040（10）, c = 10.315（11） A, α = 94.958（14）, β = 95.556（7）, γ = 99.747（14）°, V = 641.7（12）A3, Z = 1, M, = 1030.63, Dc= 2.651 Mg/m3,μ = 5.615 mm-1, F（000） = 491, the final R = 0.0491 and wR = 0.1345 for 2098 observed reflections with I 〉 2σ（I）. The compound is a three-dimensional network structure in which infinite lanthanide-carboxylate chains are linked by [Cu（$04）2]2- metalloligands to form a mixed-metal coordination network.

Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH_2]^(2+)·[SbCl_5]^(2-)}_2

A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.

Hydrothermal Synthesis and Crystal Structure of a New Nickel(Ⅱ) Complex with 3,4-Pyridinedicarboxylic Acid and 1,4-Bis(imidazol-1-ylmethyl)-benzene Ligands

A metal-organic coordination polymer [Ni（PDB）（bix）（H20）]n （H2PDB = 3,4-pyri- dinedicarboxylic acid, bix = 1,4-bis（imidazol-l-ylmethyl）-benzene） 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. Blue crystals crystallize in the triclinic system, space group PI with a = 9.1849（8）, b = 9.2065（9）, c = 12.9308（12） °, a = 103.3070（10）, β = 104.7160（10）, y = 90.5900（10）°, V = 1026.42（16）/k3, C21H19NsNiOs, Mr = 480.12, Dc = 1.553 g/cm3, F（000） = 496, Z = 2,/l（MoKa） = 0.991 mm-1, the final R = 0.0325 and wR = 0.0799 for 3561 observed reflections （I 〉 2σ（I））. The structure of 1 exhibits a two-dimensional network structure.

Hydrothermal Synthesis and Crystal Structure of a Cobalt(II) Coordination Polymer: [Co(C_2O_4)(bix)]_n (bix = 1,4-Bis(imidazol-1-ylmethyl)-benzene)

A new two-dimensional cobalt coordination polymer has been prepared and fully characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The compound [Co（C2O4）（bix）]n 1 crystallizes in the monoclinic system, space group C2/c, with a = 11.549（3）, b = 15.700（3）, c = 9.260（2） A, β = 102.984（3）°, V = 1636.0（6） A^3, C16HIaCON4O4, Mr= 383.23, Dc = 1.556 g/cm^3, μ（MoKa） = 1.078 mm^-1, F（000） = 780, Z = 4, the final R = 0.0455 and wR = 0.1286 for 1483 observed reflections （I 〉 2σ（I））. Of the compound, the Co center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the cobalt atom and each bix serving as a bridging ligand by employing two N-donors to coordinate with the Co center. An infinite {Co2（C2O4）2}∞ chain is formed along the α axis. Furthermore, the 1D chains are held together via bix ligands to generate a two-dimensional network structure with 1D coronal-like channels （ca. 5.691A × 15.700A）.

Hydrothermal Synthesis and Crystal Structure of a Novel Isophthalate-bridged Copper(II) Polymer with Two-dimensional Network Structure: [Cu_2(phen)(ipt)_2]_(2n)·nH_2O (ipt = isophthalate, phen = 1,10-phenanthroline)

A novel metal-organic coordination polymer [Cu2（phen）（ipt）2]2n-nH2O 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 12.338（3）, b = 12.167（3）, c = 18.167（4）A, β= 111.686（14）°, V = 2534.1（10）A^3, C28H18Cu2N2O9, Mr = 653.52, Dc = 1.713 g/cm^3,μ（MoKα） = 1.740 mm^-1, F（000） = 1320, Z = 4, the final R = 0.0443 and wR = 0.0853 for 3543 observed reflections （1 〉 2σ（I））. It exhibits a novel two-dimensional network with tetra-Cu-ipt-as building units.

Hydrothermal Synthesis and Structure of a New Molybdenum Phosphate: (NH_3CH_2CH_2NH_3)_(2.5)[Mo_5O_(15)(PO_4) (HPO_4)]·7.5H_2O

The title compound (C5N5H41P2Mo5O30.5) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It belongs to triclinic system, space group P , with a=9.9645(6), b=10.8666(7), c=15.814(1)? α=71.482(3), β=88.528(2), γ=78.448(2)°, V=1589.4(2)3, Dc=2.510g/cm3, Z=2,μ=2.138mm-1,λ(MoKα) = 0.71073 ? F(000)=1180. The final R and wR were 0.0396 and 0.1052 for 6626 observed reflections with I ≥2σ(I), respectively. The result of the structure analysis indicates that the [Mo5O15(PO4) (HPO4)]5- anion in the title compound consists of five edge-sharing or corner-sharing MoO6 octahedra and two corner-sharing PO4 tetrahedra. Each MoO6 octahedron adopts distorted octahedral geometry.

Hydrothermal Synthesis and Crystal Structure of a Zinc(II) Polymer with a Two-dimensional Layer Structure: [Zn(pzdc)(phen)]_n·nH_2O

A metal-organic coordination compound formulated as [Zn（pzdc）（phen）]n·nH2O 1 （H2pzdc = pyrazine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n with a = 11.607（2）, b = 11.719（2）, c = 13.140（3）A^°, β = 110.707（3）°, V= 1671.9（6）A^°3, C18H12ZnN4O5, Mr= 429.69, De = 1.707 g/cm^3,μ（MoKa） = 1.511 mm^-1, F（000） = 872, Z = 4, the final R = 0.0356 and wR = 0.0853 for 2713 observed reflections （I 〉 2σ（I））. It exhibits an interesting two-dimensional layer structure and shows yellow photoluminescent property at room temperature.

Hydrothermal Synthesis and Crystal Structure of a Cadmium(II) Polymer with One-dimensional Chain Structure: [Cd(bpy)(BDC)]_n·nbpy

A metal-organic coordination polymer [Cd（bpy）（BDC）]n·nbpy （bpy = 2,2-bipyri-dine, H2BDC = terephthalic acid） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group C2/c with a = 15.723（5）, b = 21.695（5）, c = 7.576（5） A, β = 116.171（7）°, V = 2319.3（18）A^3, C28H20CdN4O4, Mr = 588.88, Dc = 1.686 g/cm^3, μ（MoKα） = 0.987 mm^-1, F（000） = 1184, Z = 4, the final R = 0.0464 and wR = 0.0831 for 1882 observed reflections （Ⅰ〉 2σ（Ⅰ））. It exhibits a three-dimensional network with channels constructed from one-dimensional coordination chains via C–H…O hydrogen bonds and significant aromatic π-π stacking interactions.

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Cd(Ⅱ) Complex Based on Biimidazole and Isonicotinate-N-oxide

A new complex [Cd（H2biim）2（H2O）2]·（ino）2·4H2O （H2biim = 2,2＇-biimidazole, ino = isonicotinate-N-oxide） has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380（6）, b = 8.0402（7）, c = 13.5094（11） , α = 104.269（1）, β = 93.604（1）, γ = 98.349（1）°, V = 780.93（11） 3, Mr = 765.00, Dc = 1.627 g/cm3, F（000） = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ（I） and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.