Hydrothermal Synthesis and Crystal Structure of a One-dimensional Copper（Ⅱ） Complex

A metal-organic coordination polymer [Cu(cbba)2(bix)]n(Hcbba = 2-(4'-chlorine-benzoyl)-benzoic acid,bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis,IR,TG,UV and single-crystal X-ray diffraction.Blue crystals crystallize in the monoclinic system,space group C2/c with a = 26.127(3),b = 10.6143(14),c = 14.5676(19) ,β = 111.289(2),V = 3764.3(8) 3,C42H30Cl2CuN4O6,Mr = 821.14,Dc = 1.449 g/cm3,F(000) = 1684,Z = 4,μ(MoKα) = 0.777 mm 1,the final R = 0.0528 and wR = 0.1200 for 2241 observed reflections(I > 2(I)).The structure of 1 exhibits a one-dimensional chain-like structure.     

Synthesis and Crystal Structure of a New Dimolybdenum（V） Complex Na4[Mo2O4（HNTA）2]2·19H2O

The new binuclear molybdenum（V） complex Na4[Mo2O4（HNTA）2]2·19H2O （NTA = nitrilotriacetate） has been prepared and characterized by single-crystal X-ray diffraction analysis and IR. The crystal has space group Pnma with a = 10.2239（2）,b = 23.8174（3）,c = 23.1845（4） A,V = 5645.58（16）A^3,Z = 4,C24H66Mo4N4Na4O51,Mr = 1702.50,Dc = 1.958 g/cm^3,μ = 1.027 mm^-1,F（000） = 3280,T = 293（2） K,the final R = 0.0609 and wR = 0.1449 for 5512 observed reflections （I 〉 2σ（I））. Each MoV atom has a distorted octahedral coordination geometry,and the two coordination octahedra share a common edge to form a dioxo-bridged Mo2O4 unit which is coordinated by NTA ligands. The dianionic binuclear units [Mo2O4（HNTA）2]^2- are interconnected by Na^＋ into a layered structure.     

Synthesis and Structure of a New Mixed-polyoxometalate （W/Mo） Compound： H5K{[Co（H2O）5]2（H2Mo3.24W8.76O42）}·19H2O

One new polyoxometalate compound connected via cobalt/potassium cations,namely H5K{[Co（H2O）5]2（H2Mo3.24W8.76O42）}·19H2O 1,was prepared and characterized by ele- mental analysis and IR spectroscopy. Single-crystal X-ray diffraction analysis result reveals that anions of {[Co（H2O）5]2（H2Mo3.24W8.76O42）}6- in compound 1 are linked by potassium cations to form one- dimensional chain,based on which a three-dimensional network is further constructed with the help of hydrogen bonds. Crystal data： H67Co2KMo3.24O72W8.76,Mr = 3297.87,monoclinic,C2/c,a = 19.0126（10）,b = 16.6025（5）,c = 19.1908（10）A,β = 106.713（1）°,V = 5801.8（5） A^3,Z = 4,Dc = 3.755 g/cm^3,F（000） = 5961,μ = 18.730 mm^-1,R = 0.0569 and wR = 0.1437 （I 〉 2σ（I））.     

Hydrothermal Synthesis and Structure of One New Polyoxotungsate [Ni(trien)]_4[Ni_4(H_2O)_2(HPW_9O_(34))_2]·4H_2O

One new sandwich-type tetra-nickel substituted polyoxotungsate,[Ni(trien)]4-[Ni4(H2O)2(HPW9O34)2]·4H2O(1,trien=triethylenetetramine),has been hydrothermally synthesized and characterized by IR,elemental analysis,TGA,and single-crystal X-ray diffraction analysis.Crystal data for 1:triclinic,space group P with a=13.279(3),b=13.816(3),c=14.494(4),α=95.403(1),β=113.173(4),γ=93.809(3)o,V=2418.0(10)3,Z=1 and Dc=3.861 g/cm3.X-ray crystallographic study shows that compound 1 is a relatively rare inorganic-organic hybrid polyoxo tungstate constructed from sandwich Ni-substituted polyoxo-anions and nickel complexes.     

Synthesis,Crystal Structure and Characterization of a Cobalt Coordination Polymer： [Co（bib）（L）]-0.5H2O

The title coordination polymer, [Co（bib）（L）].0.5H2O 1 （bib = 1,1＇-（1,4-butanediyl）bis（imidazole） and L = 4,4＇-oxy（bisbenzoate） has been hydrothermally synthesized and characterized by IR and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a = 8.8568（5）, b = 19.936（1）, c = 26.209（2） γ, y = 97.510（1）°, V= 4587.8（5） A3, Z = 8, CoC24H23N4O5.5, Mr = 514.39, Dc = 1.489 g/cm3, F（000） = 2128, μ（MoKa） = 0.795 mm^-1, R = 0.0419 and wR = 0.1002. Compound 1 exhibits a rare two-fold interpenetrating CdSO4 type topology. The O-H...O hydrogen bonds stabilize the structure of 1.     

Synthesis,Structure and Photoluminescence of a Binuclear Zinc（Ⅱ） Coordination Polymer Based on 2-Carboxycinnamic Acid and Dipyrido [3,2-a： 2＇,3 ＇-c]-phenazine

A binuclear zinc（Ⅱ） complex with 2-carboxycinnamic acid （2-ccm） and dipyrido- [3,2-a：2＇,3＇-c]phenazine （DPPZ）, {[Zn2（2-ccm）2（DPPZ）2]·2H2O}n, was synthesized and characterized by elemental analysis, IR, single-crystal X-ray diffraction, thermal gravimetry and fluo- rescent emission. It crystallizes in monoclinic, space group P21/c with a = 13.409（4）, b = 25.530（7）, c = 13.952（4） A, β = 99.554（3）°, V= 4710（2） A3, Z= 4, C56H36N8O10Zn2, Mr= 1111.67, Dc = 1.568 g/cm3, μ（MoKα） = 1.093 mm^-1, F（000） = 2272, R = 0.0422 and wR = 0.0895. In the crystal, the basic unit of 1 is a binuclear Zn2 entity which is linked by 2-ccm ligand to form a 1D double chain along the a axis. The O-H...O hydrogen bonding and π-π interactions lead to a 3D supramolecular motif. In addition, thermal and luminescent properties of complex 1 have also been investigated.     

A Layered Vanadium Oxide with Cobalt（Ⅱ） Coordination Complex： Hydrothermal Synthesis and Crystal Structure of （py）5Co2（H2O）3[V4O12]

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）.     

Hydrothermal Synthesis and Crystal Structure of a Zinc（Ⅱ） Polymer with a Two-dimensional Layer Structure： [Zn（pzdc）（phen）]n·nH2O

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 Novel Hexanuclear Copper（Ⅱ） Complex：[Cu_6（DPPZ）_4（btc）_4（H_2O）_8]·5H_2O

A new hexanuclear copper(Ⅱ) complex,[Cu 6 (DPPZ) 4 (btc) 4 (H 2 O) 8 ]·5H 2 O (1,DPPZ=dipyrido[3,2-a:2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid),has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489(4),b=14.234(5),c=14.484(5),α=82.848(4),β=79.399(4),γ=73.646(4)°,V=2421.2(13) 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F(000)=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I > 2σ(Ⅰ).In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Novel Water Cluster [Mn(phen)_2·H_2O·Cl]·p-FBA·3H_2O

A novel water cluster [Mn(phen)2·H2O·Cl]·p-FBA·3H2O (p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline) was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768(1),b = 11.5960(1),c = 12.9916(2) ,α = 101.816(2),β = 95.397(2),γ = 103.052(2)o,V = 1502.8(3) 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese(Ⅱ ) ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a (H2O)4 water cluster. This water pattern forms a cross-linked discrete ring. The steady (H2O)4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional (1D) structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.     

Synthesis and Crystal Structure of a New Mo/Au/S Cluster [Et4N][Mo2S4（AuPPh3）（edt）2]· 0.25Et2O·0.25MeOH （edt = Ethanedithiolate）

Reactions of the preformed cluster precursor [Et4N]2[Mo2S2（μ-S）2（edt）2] （edt = ethanedithiolate） （1） with [Au（PPh3）Cl] in MeOH/MeCN gave rise to a new heterobimetallic Mo/Au/S cluster [Et4N][Mo2S4（AuPPh3）（edt）2]·0.25Et2O·0.25MeOH （2·0.25Et2O·0.25MeOH）. It was characterized by elemental analysis, IR spectrum and X-ray analysis. 2·0.25Et2O·0.25MeOH crystallizes in the monoclinic system, space group C2/c with a = 20.117（4）, b = 9.2705（19）, c = 44.418（9） A^°, β= 93.19（3）°, V = 8271（3） A^°^3, Z = 8, Dc = 1.794 g/cm^3, T = 193 K, C31.25H43AuMo2NO0.50PS8, Mr = 1116.96, F（000） = 4380, μ（MoKa） = 4.603 mm^-1, S = 1.019, R = 0.0672 and wR = 0.1708 for 7243 observed reflections with I 〉 2σ（I）. The anion of 2 consists of a butterfly-shaped Mo2S4Au core in which one [AuPPh3]^＋ cation is coordinated by one bridging S and two terminal S atoms of the [（edt）2Mo2（S）2（μ-S）2] moiety. The Au（I） center adopts a pseudo-tetrahedral coordination geometry, and the Au-S bond lengths vary from 2.425（2） to 2.898（3）A^°.     

Synthesis and Crystal Structure of a Novel 2D Coordination Polymer [Cu_3（mal）_2（di-2-pyridlyktone）_2]

A novel coordination polymer of Cu II with flexible ligands,namely,[Cu 3 (mal) 2 (di2-pyridlyktone) 2 ] (1,H 2 mal=maleic acid),was synthesized and characterized by single-crystal X-ray diffraction,thermogravimetric analyses,elemental analysis and IR spectroscopy.The structure indicates that the complex crystallizes in monoclinic,space group P2 1 /c with a=10.268(2),b=17.737(3),c=8.038(1),β=98.275(2)°,V=1448.6(4) 3,Z=2,D c=1.883 Mg·m-3,μ=2.260 mm-1,F(000)=826,and the final R=0.0321 and wR=0.0820.In 1,three Cu II centers (Cu(1),Cu(2),Cu(1A)) are bridged by two uncommon μ 3-bridging H 2 mal ligands,furnishing a centrosymmetric trimetallic unit.Via further Cu-O COO coordination interactions,extention of these trimetallic units in two directions gives rise to an infinite corrugated 2D layer.In addition,thermal stability and electrochemistry of 1 were studied.     

Hydrothermal Synthesis and Crystal Structure of An Iron（Ⅱ） Formate [H3CO3] [Fe（HCO2）3]

An iron(Ⅱ) formate [H 3 CO 3 ][Fe(HCO 2) 3 ] (1) has been synthesized under hydro-thermal conditions and characterized by single-crystal X-ray diffraction analysis.Complex 1 crystallizes in the orthorhombic system,space group Pnna with a=8.4130(4),b=11.8306(6),c=8.9468(4),α=106.527(4),β=105.876(4),γ=103.173(4) o,M r=253.94,V=890.48(7)3,Z=4,D c=1.894 g/cm 3,μ=1.721 mm-1,F(000)=512,R int=0.0164,the final R=0.0323 and wR=0.0998 for 979 observed reflections (I > 2σ(I)).1 exhibits a 3D open microporous framework formed by formate anions bridging Fe(Ⅱ) ions.     

Synthesis,Structure, and Luminescent Property of a 3-D Strontium Complex [Sr_3(pda)_2(Hpda)_2(H2O)_2]_n·2nH_2O

The title complex [Sr3(pda)2(Hpda)2(H2O)2]n·2nH2O(H2pda = pyridine-2,6-dicar- boxylic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 10.3795(8), b = 9.2225(7), c = 18.5726(14) , β = 104.377(2)o, V = 1722.2(2) 3, C28H22N4O20Sr3, Mr = 997.36, Z = 2, Dc = 1.923 g/cm3, μ = 4.722 mm-1, F(000) = 984, the final R = 0.0269 and wR = 0.0538. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by carboxylate groups. The luminescent property of the title complex has been investigated.     

Synthesis and Crystal Structure of a New Complex {[ Co^ⅢL2]·[Co^Ⅱ（H2O）6]0.6·2.25H2O }4 （H2L = N-（2-Hydroxyphenyl）salicylidenimine）

The reaction of Co（OAc）2·4H2O with the Schiff base H2L in a methanol solution affords the red crystals of { [Co^ⅢL2]·[Co^Ⅱ（H2O）6]0.5·2.25H2O}4 1 （H2L = N-（2-hydroxyphenyl） salicylidenimine）. The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n, C104Hi14Co6NaO37, Mr = 2421.61, a = 10.625（3）, b = 16.335（4）, c = 15.265（4）A^°, β = 102.990（4）°, V= 2581.6（11）A^°^3, Z = 1, Dc= 1.558 g/cm^3,μ = 1.034 mm^-1, F（000） = 1252, R = 0.0414 and wR = 0.1167 for 5889 reflections. The Co（HI） atom is six-coordinated by two nitrogen atoms and four oxygen atoms of two tridentate L ligands. The abundant hydrogen bonding interactions extend the complex into a one-dimensional supra- molecular framework. The uncoordinated water molecules act as space-fillers and consolidate the whole architecture through the hydrogen bonding interactions.     

Synthesis, Crystal Structure and Thermal Stability of the Coordination Polymer [Co（2-mpac）_2（py）·4H_2O）]_n

A new coordination polymer with the formula of [Co(2-mpac)2(py)·4H2O)]n (1, 2-mpac = 5-methyl-2-pyrazinecarboxylic acid, py = pyrazine) has been synthesized through hydrothermal synthesis and structurally characterized by X-ray single-crystal diffraction method. 1 exhibits a 3D supramolecular network. Crystal data: monoclinic, space group C2/m, a = 15.907(9), b = 7.104(3), c = 9.793(5), β = 95.232(8)o, V = 1102.0(10)3, Z = 2, S = 0.995, the final R = 0.0509, wR = 0.1626 for 1002 observed reflections with (I > 2σ(I)) and R = 0.0530, wR = 0.1667 for all data. In addition, elemental analysis, IR and thermalgravimetric analysis are presented.     

Synthesis and Crystal Structure of [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2·3.5DMF

A new copper（H） complex [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2-3.5DMF has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 10.722（3）, b = 18.170（4）, c = 20.923（7）A,α = 105.297（9）, β = 101.701（10）, γ = 105.74（1）°, V= 3615（1）A^3, Z = 2, C58.50H64.50Cu4N1l.50O3150, Mr = 1686.90, Dc = 1.550 g/cm^3,μ= 1.255 mm^-1, F（000） = 1728.00, T = 150（2） K, the final R = 0.0640 and wR = 0.173 for 11310 observed reflections with I 〉 2σ（I）. In the crystal, each formular unit consists of two dinuclear copper（H） compounds, between which the O-H…O hydrogen bonds exist. Each Cu^Ⅱ cation is six-coordinated in an octahedral geometry. The intermolecular hydrogenbonding interaction leads to a 3-D framework of the title compound.     

Hydrothermal Synthesis,Structure and Magnetic Property of a Novel Hexa-Ni~Ⅱ Substituted Polyoxometalate

A novel hexa-NiⅡ substituted trilacunary Keggin polyoxometalate [{Ni6（μ3- OH）3（en）3（H2O）6}（B-α-PW9O34）]-6H2O 1 （en = ethylenediamine） has been hydrothermally synthesized and characterized by IR spectra, elemental analysis, thermogravimetric analysis （TGA）, single-crystal X-ray diffraction and magnetic property. Compound 1 crystallizes in the hexagonal space R3c with a = 20.4124（5）, c = 21.4427（4）A, γ = 120.000°, V = 7737.5（3）A3, Z = 6, GOF = 1.083, R （wR） = 0.0317 （0.0610）. Single-crystal X-ray diffraction indicates that 1 contains a hexa-Nin substituted trivacant Keggin [{Ni6（μ3-OH）3（en）3（H2O）6}（B-α-PW9O34）] unit. The magnetic study shows the presence of ferromagnetic coupling interactions within hexa-Nin clusters with J1 = 0.69 cm-1 and J2 = 0.92 cm^-1 for 1.