Ni[S_2P(OCH_2CH_2Ph)_2]_2与4-甲基吡啶加合反应及加合物的结构表征

采用紫外光谱法研究了Ni[S_2P(OCH_2CH_2Ph)_2]_2与4-甲基吡啶的加合反应,测定了反应的平衡常数:β_1=39.5(R_1=1)和β_2=2.20×10_4(R_2=0.9981).用元素分析、红外光谱、单晶X-射线衍射法对合成的加合物Ni[S_2P(OCH_2CH_2Ph)_2]_2·(4-MePy)_2进行了结构表征.加合物为单斜晶系,空间群P2_1/c,晶胞参数:a=1.2920(4)mn,b=1.7498(4)nm,c=1.0979(3)nm,α=90.00°,β=113.05(3)β,γ=90.00°.     

双核银配合物[Ag2(μ-(4-MeC6H4O)2PS2)2(Phen)2]的光谱性质和晶体结构

合成了双核银配合物[Ag2(μ-(4-MeC6H4O)2PS2)2(Phen)2](phen为1,10-邻菲咯啉),用元素分析、红外光谱、紫外-可见光谱和热重分析进行了表征,并用X-射线衍射法测定了晶体结构。该晶体属于正交晶系,Pbca空间群,晶胞参数为:a=1.2035(2)nm,b=1.638 3(3)nm,c=2.517 1(5)nm,V=4.963 1(17)nm 3,Dc=1.599 g.m-3,Z=4,F(000)=2 416,μ(Mo Kα)=1.072 mm-1,S=1.066,(Δ/σ)max=0.001,R1=0.037 6,wR2=0.088 8(I>2σ(I))。晶体结构研究表明每个Ag原子与不同配体(4-MeC6H4O)2PS2-的2个S原子和1个phen配体的2个N原子配位形成了具有椅式构型的八元环Ag2S4P2,Ag原子为畸变四面体AgS2N2构型,配合物通过phen的π-π堆积形成了一维结构,分子间的弱氢键C-H…O和C-H…π作用使分子进一步形成了三维网络结构。     

[NiCl(Ph_2PCH_2CH_2OH)_2Cl·H_2O]~+Cl~-和[Ni(Ph_2P(O)CH_2CH_2OH)_4]~(2+)[NiCl_4]~(2-)的合成及晶体结构

通过NiCl2·6H2O与双齿配体2-(二苯基膦)乙醇(Ph2PCH2CH2OH)或其氧化物2-(二苯基氧膦)乙醇[Ph2P(O)CH2CH2OH]的反应,制得两种结构新颖的阳离子型镍配合物[NiCl(Ph2PCH2CH2OH)2 (H2O)]+Cl-(1)和[Ni(Ph2P(O)CH2CH2OH)4]2+[NiCl4]2-(2).通过元素分析、31P核磁共振及X射线单晶衍射对配合物1和2的结构进行了表征.配合物1的晶体属单斜晶系,C2/c空间群,中心金属Ni具有六配位八面体几何构型.配合物2属四方晶系,I4(1)/a空间群,中心原子Ni与PO基团中的O配位形成平面四边形构型.     

SYNTHESIS AND STRUCTURE OF (Et_4N)_2[Ni_2(OSC_5H_4)_2(μ-SC_6H_4OH)_2]

<正> The synthesis and structure of cluster compound(Et4N)2[Ni2-(OSC6H4)2(u-SC6H4OH)2] are reported. Mr = 876.54,space group P21/n, a = 9.179(4), b = 17.487(6), c = 12.840(4) A;B=92.87(3)°;V=2058.6(2)A3; Z = 2; DC = 1.182g·cm-3.     

钼钒氧簇二聚体[Ni(enMe)_2]_4{[Ni(enMe)_2][Ni(enMe)_2(H_2O)]_2[Mo_8~(Ⅵ)V_6~(Ⅳ)O_(38)(V~ⅤO_4)]_2}·8H_2O的合成与结构表征(英文)

在水热条件下合成了一例新型的多金属氧酸盐二聚物,[Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe)2(H2O)]2[Mo8ⅥV6ⅣO38(VⅤO4)]2}.8H2O(1)(enMe=1,2-丙二胺),利用元素分析、红外光谱分析、粉末X射线衍射、热重分析和单晶X射线衍射表征了其结构。结果表明,化合物(1)属于单斜晶系,P2(1)/n空间群.晶胞参数为a=1.9685(4)nm,b=1.3549(3)nm,c=2.7039(5)nm,α=90°,β=93.94(3)°,γ=90°,V=7.195(2)nm3,Z=4,Dc=2.390g/cm3,Mr=2588.4,μ=3.195mm-1,F(000)=5012,最终R1=0.0743,wR2=0.1861.与此同时,(1)是第一个具有二帽-Keggin型钼钒氧簇的二聚体,它由过渡金属部分[Ni(enMe)2(H2O)]22+连接形成{[Ni(enMe)2][Ni(enMe)2(H2O)]2[Mo8ⅥV6ⅣO38(VⅤO4)]2}8-二聚阴离子.     

配合物Bi[S2P（OC6H4But-p）2]3的合成和晶体结构

合成了配合物Bi[S2P(OC6H4But-p)2]3,通过元素分析、红外光谱、紫外-可见光谱、热重分析和X-射线衍射法进行了结构表征。该晶体属于单斜晶系,C2/c空间群;晶胞参数为:a=30.907(5),b=12.7421(9),c=20.287(2),α=90.00°,β=120.925(18)°,γ=90.00°,V=6853.7(19)3,Dc=1.338g/cm3,Z=4,F(000)=2804,μ(Mo Kα)=2.869mm-1,S=1.062,(Δ/σ)max=0.001,R1=0.0621,wR2=0.1906(I>2σ(I))。晶体结构研究表明,配合物中的(p-ButC6H4O)2PS2-为双齿配体,Bi(III)原子与3个配体(p-ButC6H4O)2PS2-的6个S原子配位形成了畸变八面体构型,分子通过C3—H3…O3氢键形成了一维链状结构。     

由大环配体[As_4W_(40)O_(140)]~(28-)与Ni~Ⅱ形成的新型超大杂多化合物

在pH=4.0的水溶液中,NiCl2·6H20,NH4Cl与Na27[NaAs4W40O140].60H2O反应,得到了新的杂多砷钨酸盐(NH4)20[Na2(H2O)2Ni(H2O)5(Ni(H2O)}2As4W40O140].61H2O单晶,用X射线单晶衍射法及元素分析确定了其结构,晶体属三斜晶系,P1空间群;其晶胞参数为:a=1.33135(18),b=1.9722(3),C=3.6430(5)nm,a=78.010(2)。,β=82.145(2)。,γ=74.385(2)。,V=8.978(2)nm3,Z=2,R1=0.0512,wR2=0.0684(I>2σ).在聚阴离子[Na2(H2O)2Ni(H2O)5{Ni(H2O)}2As4W40O140]20-中,2个Ni2+和2个Na+分占大环配体[As4W40O140]28-内的4个S2空位,每个S2位提供4个Od向金属离子配位,2个Ni2+的配位数为6,两个Na+的配位数分别为5和6,另一个Ni2+处于环外,与[As4W40O140]28-的一个端基氧(Od)桥连成键,其配位数为6.     

CRYSTAL STRUCTURE OF [Ni((C)_6H_(11)O)_2PS_2)·(C_4H_9NH_2)_4]-(C_6H_(11)O)_2PS_2

<正> [Ni((C6H11O)2PS2)·(C4H9NH2)4](C6H11O)2PS2,Mr-=938. 05, triclinic,P1,a=13. 513(6),b=16. 040 (7), c= 12. 891(6) A , α= 95. 66 (4),β= 90. 23(4),γ= 75. 46(3)°,V = 2691 A3,Z=2,Dc= 1. 16 g·cm3.μ=6. 07cm-1,MoKa radiation, λ=0. 71069 A ,F(000) = 1020,R=0. 100 for 4595 reflections with I≥3σ(I). The title compound molecule consists of a complex cation [Ni((C6H11O)2PS2)(C4H9-NH2)4]+ and a complex anion (C6H11O)2PS2- . The Ni (Ⅱ) atom in the cation is octahedrally coordinated by four nitrogen atoms from four w-butylamine ligands and two sulfur atoms from one (C6H11O)2PS2 group.     

三维配合物Ni_2(BTEC)(H_2O)_4·2H_2O的合成及其晶体结构

以1,2,4,5-苯四甲酸(H4BTEC)为原料,用水热法合成了新的三维配合物Ni2(BTEC)(H2O)4·2H2O(1),其结构经IR,元素分析和X-射线单晶衍射表征.1属三斜晶系,P-1空间群,晶胞参数:a=0.691 5(3) nm, b=0.740 2(3) nm, c=1.554 2(7) nm, α=88.344(6)°, β=85.070(6)°, γ=86.594(6)°, V=0.790 9(6) nm3, Z=2, Mr=475.63 g·mol-1, Dc=1.997 g·cm-3, μ=2.457 mm-1, F(000)=484, R1=0.029 2, wR2=0.064 8, S=1.011. 1中Ni原子均处于倒反中心上,与BTEC4-配体的四个羧基上的4个O原子和两个配位水上的2个O原子配位,形成一个畸变的八面体几何构型.H4BTEC完全去质子化,并以μ6-配位方式桥联6个Ni原子,形成罕见的(4,6)-连接点的三维超分子结构,其拓扑类型为(44.62)2(44.610.8).     

超分子化合物[Ni(H2O)6]1.5·[Ni(ptc)(Hptc)]·(H2O)4的水热合成及晶体结构

以2,4,6-吡啶三甲酸(H3ptc)和六水合高氯酸镍为原料用水热方法合成了三维超分子配合物[Ni(H2O)6]1.5.[Ni(ptc)(Hptc)].(H2O)4,并经X射线衍射分析确定了其单晶结构.该晶体属三斜晶系,P墿空间群,晶胞参数为:a=1.03058(16)nm,b=1.11852(17)nm,c=1.4689(2)nm,α=74.725(2)°,β=77.777(2)°,γ=64.734(2)°,V=1.4675(4)nm3,Mr=798.20,Z=2,ρ=1.806g/cm3,F(000)=822,μ=1.701mm-1,R1=0.0373,wR2=0.0993.结果表明,在组成该超分子体系的基本结构单元[Ni(ptc)(Hptc)]3-和[Ni(H2O)6]2+中,Ni(Ⅱ)离子均处于变形八面体配位环境中.配合物单元之间通过氢键相互连接,形成了无限延伸的三维超分子网状结构.     

Thermal decomposition of (NH4)2MoS4 and (NH4)2WS4heat of formation of (NH4)2MoS4

The reactions (NH₄)₂MeS₄ = 2 NH₃ + H₂S + MeS₃ (Me = Mo, W) were investigated by measuring the decomposition vapour pressures. Thermochemical data were obtained from these measurements: ΔH = 52 kcal/mole and ΔS = 105 cal/deg.mole for the decomposition of the tetrathiomolybdate. Similarly, ΔH = 69 kcal/mole and ΔS = 106 cal/deg.mole were obtained for the decomposition of the tetrathiotungstate. The normal heat of formation of (NH₄)₂MoS₄ was found to be ΔH = ?140 kcal/mole. The kinetics of thermal decomposition of the above reactions were also measured.     

Synthesis and Characterization of Gd2[Pt2(SO4)4(HSO4)2](HSO4)2

Red single crystals of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ (triclinic, , Z = 1, a = 844.02(9), b = 908.50(9), c = 939.49(8) pm, α = 107.73(1)°, β = 112.10(1)°, γ = 103.53(1)°) were obtained by the reaction of [Gd(NO₃)(H₂O)₇][PtCl₆]·4H₂O with sulfuric acid at 320 °C in a sealed glass ampoule. In the crystal structure, Pt₂ dumbbells are coordinated by four chelating sulfate groups and two monodentate hydrogensulfate ions. Two further HSO₄^? ions are not bonded to the Pt₂ dumbbell. The Gd³⁺ ions are eightfold coordinated by oxygen atoms. The IR data of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ are typical for these type of compounds. The thermal decomposition of the compound leads to elemental platinum and Gd₂O₃.     

SYNTHESES AND CRYSTAL STRUCTURES OF (Et_4N)_2(Fe_2Se_2(SPh)_4) AND (Et_4N)_2(Fe_4Se_4Cl_4)

<正> Since the discovery of iron-sulfur proteins , a number of analogous compounds of the active sites of iron-sulfur proteins has been synthesized and characterized . Due to the similarity between sulfur and selenium, some selenoproteins with similar active site as iron-sulfur proteins were found . We have synthesized a series of iron-selenium compounds in correlative study with the iron-sulfur compounds. In this paper, we will discuss the syntheses and crystal stuctures of the title compounds. The spectroscopic properties of these compounds have been under investigation.     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .     

Kinetic and thermodynamic study of the Na4(UO2)2(OH)4(C2O4)2 complex

The synthesis, the characterization, and the thermal decomposition of the dioxouranium(VI) ternary complex of formula Na₄(UO₂)₂(OH)₄(C₂O₄)₂, has been studied. The identification of the compound was performed by chemical analysis and by infrared spectrometry. Thermal decomposition of the compound occurs in several steps due to the decomposition of the salt to Na₂O and UO₃ oxides. The stoichiometry of the steps, hypothesized by means of the thermodynamic and kinetic parameters, is confirmed by the evolved gas analysis studied by FTIR spectrometer coupled to TG/DSC apparatus. Model‐fitting and model‐free kinetic methods have been used in kinetic analysis. The latter allows determining kinetic scheme. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 661–669, 2003     

A hydrothermal investigation of the 1/2V2O5-H2C2O4/H3PO4/NH4OH system: synthesis and structures of (NH4)VOPO(4).1.5H2O, (NH4)0.5VOPO(4).1.5H2O, (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2](2).3H2O, and (NH4)2[VO(HPO4)]2(C2O4).5H2O

The 1/2V2O5-H2C2O4/H3PO4/NH4OH system was investigated using hydrothermal techniques. Four new phases, (NH4)VOPO(4).1.5H2O (1), (NH4)0.5VOPO(4).1.5H2O (2), (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O (3), and (NH4)2[VO(HPO4)]2(C2O4).H2O (4), have been prepared and structurally characterized. Compounds 1 and 2 have layered structures closely related to VOPO(4).2H2O and A0.5VOPO4.yH2O (A = mono- or divalent metals), whereas 3 has a 3D open-framework structure. Compound 4 has a layered structure and contains both oxalate and phosphate anions coordinated to vanadium cations. Crystal data: (NH4)VOPO(4).1.5H2O, tetragonal (I), space group I4/mmm (No. 139), a = 6.3160(5) A, c = 13.540(2) A, Z = 4; (NH4)0.5VOPO(4).1.5H2O, monoclinic, space group P2(1)/m (No. 11), a = 6.9669(6) A, b = 17.663(2) A, c = 8.9304(8) A, beta = 105.347(1) degrees, Z = 8; (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O, triclinic, space group P1 (No. 2), a = 10.2523(9) A, b = 12.263(1) A, c = 12.362(1) A, alpha = 69.041(2) degrees, beta = 65.653(2) degrees, gamma = 87.789(2) degrees, Z = 2; (NH4)2[VO(HPO4)]2(C2O4).5H2O, monoclinic (C), space group C2/m (No. 12), a = 17.735(2) A, b = 6.4180(6) A, c = 22.839(2) A, beta = 102.017(2) degrees, Z = 6.