Synthesis and Crystal Structure of [VO2（C17H11N3O2） ] [VO （C4H13N3）（C6H5N3O） ]（C2H5OH）

The reaction of VO（acac）2 with 2-hydroxyl-1-naphthaldehyde isonicotinyl hydrazone and amines （ethylenediamine or diethylenetriamine） in CH3OH yields crystals of novel vanadium compounds characterized by IR, NMR spectroscopic methods and X-ray single-crystal structure determination. Two different vanadium units exist in the crystal cell of [VO2（C17H11N3O2）][VO- （C4H13N3）（C6H5N3O）]（C2H5OH） which crystallizes in the triclinic system, space group P1 with a = 8.0104（17）, b = 13.898（3）, c = 14.955（3）A, α = 89.103（4）, β = 79.551（4）, γ = 78.352（4）°, V = 1603.3（6）A^3, Mr = 723.54, Dc = 1.499 g/cm^3, Z = 2, λ（MoKα） = 0.71073 ]A,μ= 0.644 mm^-1, F（000） = 748, the final R = 0.0547 and wR = 0.0997 for 8920 observed reflections with I 〉 2σ（I）. According to structure analysis, two different molecules are arranged in the lattice and the two vanadium atoms adopt octahedral and square pyramidal coordination geometries, respectively. The interactions between DNA and vanadium complexes have been investigated by UV-Vis absorption spectro- photometry.     

[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O的 合成、晶体结构及磁性质

Mn(O2CMe)2·4H2O、咪唑、苯甲酸和N(n-Bu)4MnO4在无水乙醇溶剂中反应,制备得到锰的三核μ3-O桥联配位化合物[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O.该配位化合物的X射线单晶衍射表明,其属于单斜晶系,空间群P21/C,晶胞参数：a=1.52832(19)nm,b=1.9722(2)nm,c=2.1023(3)nm,β=92.597(3)°,Z=4.变温磁化率(5～280K)研究表明,该配位化合物中3个锰离子在低温下存在弱的反铁磁性耦合,交换积分J=-2.34cm^-1。     

4[CuCl(C5H5N)4]·[W10O32]·2(C5H5N)·3H2O的合成及晶体结构

标题化合物是通过(NH_4)_2WS_4, CuCl_2·2H_2O在吡咤溶液中反应制得。晶体呈蓝色, 属三斜晶系, 空间群P1, 晶胞参数为:a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)。V=2.907(3) nm, Z=1, D_m=2.56 g cm~(-3)。结构由Patterson法和Fourier法测出。对5692个收集到的独立衍射数据进行计算, 最后R=0.046。结构测定表明, 晶体由W_(10)O_(32)~(4-), [CuCl(C_5H_5N)_4]~+, C_5H_5N和H_2O所组成。W_(10)O_(32)~(4-)的结构见图1, W原子处在O原子的八面体配位中, 彼此共边和共顶点相连。[CuCl(C_5H_5N)_4]~+的结构见图2, Cu原子由1个Cl和4个N原子配位, 呈略有变形的四方锥形, 这种离子是首次报导。C_5H_5N和H_2O填入正负离子堆积的空隙中。     

Synthesis and structure of bismuth-containing complexes [Ph3PMe] 2 + [BiI5]2− and [Ph3PMe] 2 + [BiI5 · C5H5N]2− · C5H5N

The complexes [Ph₃PMe] ₂ ⁺ [BiI₅]^2? (I) and [Ph₃PMe] ₂ ⁺ [BiI₅ · C ₅H₅N]^2? · C ₅H₅N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-C_Ph 1.779(2), P-C_Me 1.793(1) Å. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-I_eq 3.0031(4), Bi-I_eq 3.0485(5) Å). The crystal of complex II consists of the anions [BiI₅ · C ₅H₅N]^2?, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-C_Ph 1.785(3)–1.792(3), P-C_Me 1.793(3), 1.786(3) Å). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) Å).     

Synthesis and physicochemical study of diazabicycloundecene hexamolybdochromate [C9H16N2]H3[CrMo6O18(OH)6] · 2H2O

Quinazoline hexamolybdochromate [C₉H₁₆N₂]H₃[CrMo₆O₁₈(OH)₆] · 2H₂O has been synthesized and studied by mass spectroscopy, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The compound crystallizes in triclinic system with the unit cell parameters a = 15.06 Å, b = 13.08 Å, c = 8.17 Å, α = 59.85°, β = 123.15°, γ = 107.01°, V = 1165.62 ų, ρ_pycn = 3.58 g/cm³, and Z = 2.     

Synthesis and Structural Characterization of Pd[CH3O（O）C6H3CHNNC（S）NH2]（C5H5N）

1 INTRODUCTION Palladium (Ⅱ) coordination and organometallic compounds usually show square planar environments at the metal center[1], and have experienced an im- portant development in the past years due to their acting as intermediates in different types of catalytic reactions and numerous applications in organic synthesis[2]. Although palladium plays an increase- ingly recognized role as a biometal[3], little is known about the structure and function of palladium compounds in living …     

电荷转移盐[C5H10NO]3[PW12O40]·C5H9NO·3H2O的合成和晶体结构

由N-甲基吡咯烷酮和H3PW12O40·nH2O反应得到了标题化合物,并以元素分析,红外光谱,质谱和X射线单晶衍射对其结构进行了表征．结构解析表明,该化合物属于三斜晶系,Pi空间群,晶胞参数为：α=1．335（2）nm,b=1．374（2）nm,c=1．826（2）nm,α=98．92（2）°,β=107．7（2）°,γ=109．9（2）°,V=2．873（1）nm^3,Z=2,Dc=3．840Mg/m^3,μ=24．05mm^-1,F（000）=2926,R1=0．0632,wR2=0．1403．在该化合物中,杂多阴离子仍保持其Keggin结构,通过静电引力与阳离子作用．     

[（C6n5NO2）Pr（H2O）4]（CrMo6O24H6）·（C6H5NO2）·2．5H2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[（C6n5NO2）Pr（H2O）4]（CrMo6O24H6）·（C6H5NO2）·2．5H2O,通过红外光谱和X射线单晶衍射对其进行了表征．结果表明,该化合物属于单斜晶系,C2/c空间群．a=2．3442（9）nm,b=1．3291（5）nm,c=2．458（1）nm,β=103．08（1）°,V=7．460（5）nm^3,R1=0．0727,wR2=0．1903．结构分析表明,[CrMo6O24H6]^3-阴离子通过端氧担载一个配位的Pr^3＋离子形成中性的（C6H5NO2）Pr（H2O）4（CrMo6O24H6）基团,相邻的中性基团在O1-Pr-O1桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构．     

配合物[Sm（C7H5O3）2（C4H6NO2S）]·2H2O的热化学研究

将六水氯化钐,水杨酸与硫代脯氨酸3种物质一起反应,制得了一种新的稀土三元固体配合物[Sm（C7H5O3）2（C4H6NO2S）].2H2O（s）。通过红外光谱、热重差热分析、元素分析等手段确定了其结构与组成。在常压、298.15 K下,分别测定了六水氯化钐、水杨酸、硫代脯氨酸和该配合物在混合溶剂（二甲亚砜∶乙醇∶3 mol.L-1HCl=1∶1∶1）中的溶解焓,并根据热化学原理得出了298.15 K时配合物[Sm（C7H5O3）2（C4H6NO2S）].2H2O（s）的标准摩尔生成焓ΔfHmΘ=（-2913.73±3.10）kJ.mol^-1。     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

(C5H7N2)3(AsMo12O40)·3C5H6N2·2H2O的水热合成、晶体结构及催化性能

采用水热法合成了一种新的3-氨基吡啶砷钼多金属氧酸盐配合物(C5H7N2)3(AsMo12O40)·3C5H6N2·2H2O。 通过单晶X射线衍射、红外光谱、紫外光谱和差热-热重对其进行了表征。 用催化消除丙酮的反应为模式反应,测试了配合物的催化性能。 研究结果表明,标题配合物是由Keggin结构[AsMo12O40]3-杂多阴离子、[C5H7N2]+阳离子、[C5H6N2]分子和结晶水分子组成。 配合物属于单斜晶系,P21/n空间群;晶胞参数a=1.33820(12) nm,b=2.2542(2) nm,c=1.9848(2) nm,β=100.27(3)°,V=5.8912(10) nm3,Z=4,Rgt(F)=0.0590,wRref(F2)=0.1882。 配合物对催化消除丙酮具有较好的的活性,催化实验结果表明,160 ℃下,0.20 g的催化剂可将初始浓度均为1.3 g/m3,流速为4.5 mL/min的丙酮完全消除。     

Copper complexes with N-allylisoquinolinium halides: Synthesis and crystal structures of [C9H7N(C3H5)]2CuIICl2.86Br1.14, [C9H7N(C3H5)CuIBr2] · H2O, and [C9H7N(C3H5)CuIBr2]

Crystals of the copper bromide complexes with N-allylisoquinolinium halides of the composition [C₉H₇N(C₃H₅)]₂Cu^IICl_2.86Br_1.14 (I), [C₉H₇N(C₃H₅)]Cu^IBr₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^IBr₂ (III) are prepared by ac electrochemical synthesis, and their structures are studied by X-ray diffraction analysis (DARCh-1 (for I) and KUMA/CCD (for II and III) diffractometers). The crystals of compound I are monoclinic: space group P2₁/n, a = 15.053(5) Å, b = 10.486(4) Å, c = 17.179(10) Å, γ = 109.77(3)°, V = 2552(4) ų, Z = 4. The crystals of complex II are triclinic: space group P $\overline 1 $ , a = 7.040(1) Å, b = 7.610(2) Å, c = 12.460(2) Å, α = 79.54(3)°, β = 86.73(3)°, γ = 89.51(1)°, V = 655.4(2) ų, Z = 2. The crystals of complex III are monoclinic: space group P2₁/n, a = 12.799(1) Å, b = 7.692(1) Å, c = 13.491(1) Å, β = 111.08(1)°, V = 1239.3(2) ų, Z = 4. The structure of compound I is built of the Cu^IIX ₄ ^2? tetrahedra and N-allylisoquinolinium cations united by the C-H···X contacts into corrugated layers. The crystal structure of π-complex II is formed of dimers of the composition [C₉H₇(C₃H₅)]₂ Cu ₂ ^I Br₄ forming layers in the direction of the z axis due to the C-H···X contacts. An important role in structure formation belongs to water molecules that cross-link the organometallic layers through the O-H···X contacts into a three-dimensional framework. When kept in the mother liquor for 6 months, the crystals of compound II transformed into crystals of compound III, whose structure consists of {[C₉H₇(C₃H₅)]₂Cu ₂ ^I Br₄} _n columns united through the C-H···Br contacts (H···Br 2.84(3)?2.92(4) Å) into a three-dimensional framework.     

Crystal structure and properties of H3[PMo12O40] · 3C2H6O

The title compound H₃[PMo₁₂O₄₀]· 3C₂H₆O was prepared and characterized by X-ray crystallography, its i.r. spectrum, cyclic voltammetry and e.s.r. spectra. The anion of the title compound is a Keggin-type heteropoly structure based upon a central PO₄ tetrahedron surrounded by 12 MoO₆ octahedra arranged in four groups of three edge-shared octahedra Mo₃O₁₃. Weak hydrogen bonds exist between the organic solvent molecules and the heteropoly anion. The catalytic activity of the title compound was determined by the synthesis of butyl acetate. The conversion of n-BuOH reached 93.3% and the yield of MeCO₂Bu-n was 92.0% when the ratio of MeCO₂H to n-BuOH, catalyst amount, reaction time, reaction temperature were 2:1, 0.24% of the reactants (50 mg), 2.0 h and 115 120 °C, respectively.     

Two Light-Metal Dihydrogenisocyanurate Hydrates Linked by Diagonal Relationship: Syntheses,Crystal Structures,and Vibrational Spectra of Li[H2N3C3O3]·1.75 H2O and Mg[H2N3C3O3]2·8 H2O

Single-crystalline materials of Li[H₂N₃C₃O₃] · 1.75 H₂O and Mg[H₂N₃C₃O₃]₂ · 8 H₂O were obtained by dissolving stoichiometric amounts of the respective carbonates with cyanuric acid in boiling water followed by gentle evaporation of excess water after cooling to room temperature. Even though both of these compounds crystallize in the triclinic space group P1 according to X-ray structure analyses of their colorless and transparent single crystals, they adopt two new different structure types. Li[H₂N₃C₃O₃] · 1.75 H₂O exhibits the unit-cell parameters a = 884.71(6) pm, b = 905.12(7) pm, c = 964.38(7) pm, α = 67.847(2)°, β = 62.904(2)° and γ = 68.565(2)° (Z = 4), whereas the lattice parameters for Mg[H₂N₃C₃O₃]₂ · 8 H₂O are a = 691.95(5) pm, b = 1055.06(8) pm, c = 1183.87(9) pm, α = 85.652(2)°, β = 83.439(2)° and γ = 79.814(2)° (Z = 2). In both cases, the singly deprotonated isocyanuric acid forms monovalent anions consisting of cyclic [H₂N₃C₃O₃]^– units, which are arranged in ribbons typical for most hitherto known monobasic isocyanurate hydrates. The structures are governed by the oxophilic strength of the respective cation which means that they fulfil their oxophilic coordination requirements either solely with water molecules ([Mg(OH₂)₆]²⁺ for Mg²⁺) or with crystal water and one or two direct coordinative contacts to carbonyl oxygen atoms (O_(cy)) of [H₂N₃C₃O₃]^– anions ([(Li(OH₂)_2–3(O_(cy)1–2]⁺ for Li⁺). In both structures occur dominant hydrogen bonds N–H ··· O within the anionic [H₂N₃C₃O₃]^– ribbons as well as hydrogen bonds O–H ··· O between these ribbons and the hydrated Li⁺ and Mg²⁺ cations.     

[（C6n5NO2）Pr（H2O）4]（CrMo6O24H6）·（C6H5NO2）·2．5H2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[（C6n5NO2）Pr（H2O）4]（CrMo6O24H6）·（C6H5NO2）·2．5H2O,通过红外光谱和X射线单晶衍射对其进行了表征．结果表明,该化合物属于单斜晶系,C2/c空间群．a=2．3442（9）nm,b=1．3291（5）nm,c=2．458（1）nm,β=103．08（1）°,V=7．460（5）nm^3,R1=0．0727,wR2=0．1903．结构分析表明,[CrMo6O24H6]^3-阴离子通过端氧担载一个配位的Pr^3＋离子形成中性的（C6H5NO2）Pr（H2O）4（CrMo6O24H6）基团,相邻的中性基团在O1-Pr-O1桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构．     

Syntheses,Crystal Structures and Properties of Three New Complexes [Ni（C9N2O2H7）2（CH3OH）2],[Zn（C9N2O2H7）2（H2O）2] and [Cd（C9N2O2H7）2（CH3OH）2]

Three novel metal-organic complexes with formulas [Ni(C9N2O2H7)2(CH3OH)2](1),[Zn(C9N2O2H7)2(H2O)2](2) and [Cd(C9N2O2H7)2(CH3OH)2](3) were synthesized by the reactions of Ni,Zn and Cd salts with ethyl 2-benzimidazolylacetate under hydrothermal conditions or layering technique,and characterized by single-crystal X-ray diffraction analysis,IR spec-troscopy,solid-state luminescent properties and thermogravimetric(TG) analysis.The crystal data for these three complexes are as follows:for 1,monoclinic,space group P21/c,a = 9.384(3),b = 9.634(3),c = 11.292(3) ,β = 95.787(5)°,V = 1015.7(5) 3,Z = 2,F(000) = 492,Dc = 1.547 Kg/m3,μ = 1.002 mm-1,the final R = 0.0451 and wR = 0.0900 for 1833 observed reflections with Ⅰ 2σ(Ⅰ);for 2,orthorhombic,space group Pbca,a = 10.031(4),b = 10.379(4),c = 17.525(7),V = 1824.6(12) 3,Z = 4,F(000) = 928,Dc = 1.645 Kg/m3,μ = 1.392 mm-1,the final R = 0.0452 and wR = 0.0996 for 1661 observed reflections with Ⅰ 2σ(Ⅰ);for 3,monoclinic,space group P21/c,a = 9.9114(13),b =10.4852(15),c = 10.4120(14) ,β = 108.453(5)°,V = 1026.4(2) 3,Z = 2,F(000) = 532,Dc = 1.705 Kg/m3,μ = 1.110 mm-1,the final R = 0.0322 and wR = 0.0805 for 1822 observed reflections with Ⅰ 2σ(Ⅰ).In the three complexes,the ethyl 2-benzimidazolylacetate shows the same chelating mode,and the adjacent units are interlinked into a two-dimensional layer through hydrogen-bonds(O-H···O,N-H···O).     

[（n-C16）H33）N（CH3）3]2[TiF6]·2H2O的合成、结构和热稳定性

利用水热法在150℃合成了新的化合物六氟钛酸十六烷基三甲基胺二水合物（[（n-C16H33）N（CH3）32[TiF6]·2H2O）,并利用单晶X射线衍射技术解析了其结构,同时利用傅立叶变换红外光谱、元素分析及热分析技术加以佐证.该化合物由六氟钛酸根离子（TiF26-）、水分子及十六烷基三甲基胺离子（[（n-C16H33）N（CH3）3]＋）组成,属于单斜晶系,其空间群为C2/c.氢键在其构筑三维结构时起着重要的作用.     

双电荷离子[C12H12N2O]2+和[C12H12N2S]2+的气相单分子分解反应研究

The unimolecular dissociation reactions of doubly charged ions were reported,which resulted from a tandem mass spectrometer and a reversed geometry double focusing mass spectrometer by electron impact.Mass analyzed ion kinetic energy spectrometry(MIKES) was used to obtain the kinetic energy releases in charge separation reactions of doubly charged ions.The intercharge distances between the two charges at transition states can be calculated from the kinetic energy releases.Transition structures of unimolecular dissociation reactions were infered from MIKES and MS/MS.     

同多化合物[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O的合成与晶体结构

以MoO3和C6H5CH2N(CH3)2为原料,制得[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O,并通过扩散法得到无色透明晶体.X射线单晶衍射表明,晶体属三斜晶系,空间群为P墿,晶胞参数a=1.0685(2)nm,b=1.4050(3)nm,c=1.0643(2)nm,α=93.12(3)°,β=110.26(3)°,γ=71.41(3)°,V=1.4179(5)nm3,R=0.0383.