Synthesis and Crystal Structure of a Novel Heterometallic Complex [Na2Cu2Gd2（pdc）4（H2O）14·2H2O]

A novel heterometallic complex [Na2Cu2Gd2（pdc）4（H2O）14·2H2O] （H3pdc = 1H- pyrazole-3,5-dicarboxylic acid） has been synthesized and characterized by 1R spectra, elemental analysis, and single-crystal X-ray analysis. The crystal belongs to the monoclinic system, space group P2 1/c with a = 7.9521（18）, b = 12.251（3）, c = 22.293（5） A, β = 110.173（5）°, V= 2038.5（8） A^3, Mr = 1388.13, Z = 2, F（000） = 1352, Dc = 2.261 g/cm^3,/2 = 4.380 mm^-1, the final R = 0.0409 and wR = 0.0622 for 2453 observed reflections with I 〉 2σ（I）. The structural analysis shows that the Na^I, Cu^II and Gd^II ions are linked together by two kinds of bridging ligands （pdc^3- and H2O） to form a main moiety [Na2Cu2Gd2（pdc）4（H2O）14], which can be regarded as a centrosymmetric dimmer of [NaCuGd（pdc）2（H2O）7]. Many hydrogen bonds exist in the complex to build a 3D supramolecular framework.     

Structural Studies and Photoluminescence of a Novel Mercury（Ⅱ） Complex Based on a Tris[4-（1-pyrazolyl）-phenyl]amine

A novel iodine-bridged mercury（Ⅱ） complex [Hg（L）（μ-I）（I）]2 was isolated by a reaction between HgI2 and the organic ligand tris[4-（1-pyrazolyl）phenyl]amine L, and the complex and ligand were both characterized by FT-IR spectroscopy, ^1H NMR and elemental analysis. The complex crystallizes in monoclinic space group P21/c with a = 9.579（5）, b = 27.331 （5）, c = 11.268（5） А, β= 105.624（5）°, Z = 2, Dc = 2.099 g·cm^-3 and μ= 7.620 mm^-1. The title complex C54H42Hg2I4N14 is a diplex bridged dinuclear complex consisting of two Hg（Ⅱ） ions, two ligands, two bridging I-anions, and two terminal I-anions. Universal hydrogen bonds in the complex with the partners of neighboring molecule have generated a supramolecular arrangement. Solid-state emission of the ligand and its complex have been investigated at room temperature.     

In Situ Hydrothermal Synthesis of a Mononuclear Copper（Ⅱ） Complex： Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-Hydroxyl-5-sulfoisophthalic Acid）

The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.     

Synthesis and Structure of a Two-dimensional Double Chain Iron（Ⅱ） L-Trp Coordination Polymer [Fe（L-trp）e（HL-trp）2]n

The title complex [Fe（L-trp）2（HL-trp）2]n （L-trp = L-tryptohan or 2-amino-3-（1H -indol-3-yl）-propanoic acid） has been formed by a hydrothermal method involving hexaaquacobaltous perchlorate and L-tryptophan. The product was characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 19.828（3）, b = 5.4233（14）, c = 9.2796（16） A, β= 97.691（2）°, V = 988.9（3） A3, Z = 2, Mr = 462.29, Dx = 1.553 g/cm3, F（000） = 480,/a = 0.802 mm^-1, the final R = 0.0399 and wR = 0.0930 for 1738 observed reflections with I 〉 2σ（/）. The structural analysis shows that the complex assumes a two-dimensional double chain plane structure.     

Synthesis,Structure and Property of a 1D Coordination Polymer [Mn{5-（NO2）sal}2（phen）]n with 5-Nitrosalicylate Ligand

A new coordination polymer [Mn{5-（NO2）sal}2（phen）]n （5-（NO2）sal = 5-nitrosalicylate, phen = 1,10-phenanthroline） was synthesized by a hydrothermal reaction and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The title complex crystallizes in orthorhombic, space group Pbcn with α = 25.747（8）, b = 13.220（4）, c = 7.009（3） A, V= 2386（1）A^3, Z = 4, R = 0.0427 and wR = 0.0890. The 5-nitrosalicylate anions doubly bridge the Mn（Ⅱ） atoms to form a one-dimensional polymeric chain with repeated eight-membered ring units （Mn-O-C-O）2. The crystal structure is stabilized by intra- and interchain hydrogen bonding interactions. The cyclic voltammetric behavior of the title complex is also reported.     

A Novel Complex of Na（I）-Nitronyl Nitroxide [Na（NIT- 1＇-MeBzIm）3]ClO4： Synthesis and Crystal Structure

A novel complex [Na（NIT-1＇-MeBzIm）3]ClO4 （NIT-1＇-MeBzIm = 2-{2＇-[（1＇- methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction methods. The title complex crystallizes in trigonal, space group P3 and Z = 2. Crystal data： C45H57ClN12NaO10, Mr = 984.47, a = 13.9411（8）, b = 13.9411（8）, c = 14.8622（16） A, γ= 120°, V= 2501.5（3） A^3, Dc = 1.307 g/cm^3, μ（MoKα） = 0.152 mm^-1, F（000） = 1038, R = 0.0637 and wR = 0.1813 for 1957 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Na（I） ion is six-coordinated with three NIT-1＇-MeBzlm radicals. As we know, three radicals coordinating to the Na（I） ion in the main group by a chelate way is the first example. The Na（I） ion resides in a distorted octahedron with a facial configuration. Meanwhile, the intermolecular weak interactions result in a 2-D double layer conformation where the uncoordinated perchlorate anions are inserted in the packing space and take part in the H-bond interactions, and each complex is connected with six neighboring complexes and three perchlorate anions.     

Synthesis, Characterization and Crystal Structure of [Ni（S2P{O}OC6H4CH3-p）（dppv）]

O-（p-tolyl）dithiophosphato nickel complex [Ni（S2P{O}OC6HaCH3-p）（dppv）] has been synthesized by the treatment of （dppv）NiCl2 （dppv = Ph2PCH=CHPPh2） with （p-CH3C6HaO）2P{S}SH＇Et2NH in THF. The new complex was fully characterized by elemental analysis, IR, 1H NMR, 31p NMR spectroscopies and thermo-gravimetric analysis. The molecular structure of the complex was established by X-ray crystallography. The crystal crystallizes in monoclinic, space group P21/c with a = 9.2739（5）, b = 17.8803（8）, c = 20.1879（12） A, fl = 93.269（5）, V = 3342.1（3） A3, Z = 4, C33H29NiO2P3S2, Mr = 673.30, Dc = 1.338 g/cm3, F（000） = 1392 and #（MoKa） = 0.877 rnm-l. The final R = 0.0578 and wR = 0.1045 for 4138 observed reflections with 1 〉 20（/） and R = 0.1050 and wR = 0.1204 for all data. The Ni centre atom adopts a NiP2S2 square-planar geometry with two phosphorus atoms from the dppv ligand and two sulfur atoms from the O-（p-tolyl）dithiophosphate ligand. The most interesting structural feature of the title complex resides in its 1D helical chain structure constructing via intermolecular C-H＇＂O secondary interactions along the b-axis. The adjacent helical chains running in opposite directions are connected into a 1D double-stranded helical chain and further linked into a 2D supramolecular network by weak C-H.--C interaction.     

Synthesis,Structure and Norbornene Polymerization Activity of a Novel Palladium（ II ） Complex with N,N＇-bis（2-benzoyl-3-oxobutane）-trans-l,2- diaminocyclohexane Ligand

The title complex N,N＇-bis（2-benzoyl-3-oxobutane）-trans-l,2-diaminocyclo- hexane-palladium （C28H28N2PdO4） has been synthesized by the reaction of N,N＇-bis（2- benzoyl-3-oxobutane）-trans-l,2-diamino-cyclohexane with PdCI2, and characterized by ele- mental analysis, IR spectrum, WAXD and TG. The spatial structures of the complex have been confirmed by single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group C2/c with a = 29.763（6）, b = 10.320（2）, c = 18.921（4） A, fl = 102.75（3）°, V = 5668（2） A3, C28H28N2PdO4·CH3OH, Mr = 594.97, Z = 8, Dc = 1.394 g/cm3, μ（MoKa） = 0.694 mm-1, F（000） = 2448, T= 293（2） K, R = 0.0572 and wR = 0.1347 （I〉 2σ（I））. The compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the palladium complex showed excellent catalytic activity up to 9.97x 106g of PNB （mol of Pd）-1 h-1 with high monomer conversion using methylaluminoxane （MAO） as a cocatalyst.     

Antitumor Metallothiosemicarbazonate： Synthesis,Crystal Structure,Spectra and Antitumor Studies of Co（Ⅲ） Complex with Thiosemicarbazone Derivative of 2-Benzoylpyridine

The title complex [Co（L）2]Cl·4H2O I has been achieved via self-assembly by incorporating cobalt into 2-benzoylpyridine thiosemicarbazonate ligand, and characterized by elemental analysis, infrared spectra, mass spectra and single-crystal X-ray diffraction study. The crystal crystallizes in monoclinic, space group P2 1/n, with a = 10.227（3）, b = 17.363（4）, c = 17.459（4） A, β= 100.408（4）°, V= 3049.2（13） A^3, Z = 4, Mr = 677.08, Dc = 1.475 g/cm^3, μ（MoKα） = 0.834 mm^-1, F（000） = 1400, the final R = 0.0747 and wR = 0.0896 for 1663 observed reflections with I 〉 2σ（I）. The complex contains one six-coordinated cobalt ion connected by two thiosemicarbazone ligands which act as a tridentate ligand to coordinate with the center metal atoms via two pyridyl nitrogen atoms, two imine nitrogen atoms and two sulfur atoms giving rise to a mononuclear structure. Hydrogen bonds existing in the complex link the different components to stabilize the crystal structure. The antiturnor activity of the title complex was tested against A549 lung cancer cell line. Complex ! exhibits antitumor activity.     

Synthesis and Crystal Structure of a Co（ Ⅱ ） Complex with Taurine-5-methyl-2-hydroxyisophthalaldehyde Schiff Bases [Co（C13H16N2O7S2）（H2O）3]2·H2O

The title complex [CoL（H20）3]2·H2O （C26H46N4O21S4CO2）, where L = taurine-5- methyl-2-hydroxyisophthalaldehydes, has been synthesized and characterized by IR and X-ray diffraction analysis. The crystal of the complex belongs to the triclinic system, space group P1, with a = 11.197（4）, b = 13.309（5）, c = 14.486（5） ]A, a = 78.827（13）,β = 70.547（11）, γ = 81.058（13）°, Mr = 996.77, S = 1.08, V= 1987.2（13） A3, Z = 2, Dc = 1.666 g/cm3, F（000） = 1032,μ = 1.131 mm^-1, R = 0.0633 and wR = 0.1293. According to the structural analysis, the Co（ Ⅱ ） ion adopts a slightly distorted six-coordinated octahedral geometry. One N atom of the Schiff base of each molecule was hydrogenated to form hydrogen bond with O atom. Two coterminous molecules packed in one crystal water molecule are linked by intermolecular hydrogen bonds, thus generating an infinite chain constructed by hydrogen bonds.     

Synthesis and crystal structure of [Ln(4-Pyta)3(H2O)2] n (Ln = Nd,Ce, Eu,Gd; 4-Pyta = 4-pyridylthioacetate)

Four new lanthanide complexes, [Nd(4-Pyta)₃(H₂O)₂] _n (1), [Ce(4-Pyta)₃(H₂O)₂] _n (2), [Eu(4-Pyta)₃(H₂O)₂] _n (3) and [Gd(4-Pyta)₃(H₂O)₂] _n (4), have been obtained from reaction of lanthanide(III) nitrate with 4-Pyta (4-pyridylthioacetate) in water. Their structures were characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The crystals belong to triclinic, space group P 1 and all complexes exhibit one-dimensional chains that arrange to form a three-dimensional supramolecular architecture by hydrogen bonds between the chains.     

Synthesis and Crystal Structure of [（ArO）2Sm（OPPh3）（μ—OH）]2（ArO=2,6—tBu—4—Me—C6H2O）

1 INTRODUCTION In recent years, the syntheses, structures and reactivities of aryloxo lanthanide complexes have attracted a great deal of attention due to their various applications as homogeneous catalysts for organic reactions and precursors for organolan- thanide syntheses[1]. However, the reactivity of divalent lanthanide aryloxides has seldom been studied[2]. We have previously reported that (ArO)2- Sm(THF)4 (ArO = OC6H2-2,6-di-tert-butyl-4-Me) can efficiently initiate the poly…     

稀土配合物Sm2(CH3COO)4(NO3)2(phen)2 的合成、 结构及非等温热分解动力学研究

在水-乙醇混合体系中, 将浓硝酸硝化的Sm2O3与1,10-邻菲啰啉反应, 用冰醋酸调节pH≈4, 形成醋酸根桥联的双核钐配合物［Sm2(CH3COO)4(NO3)2(phen)2］(phen=1,10-邻菲啰啉), 用元素分析、红外光谱和核磁共振谱等进行了表征, 并用X射线衍射测定了配合物的晶体结构, 此外, 对配合物进行了非等温热分解动力学研究. 该晶体属于三斜晶系, P1空间 群, 晶胞参数a=0.979 6(3) nm, b=0.981 3(4) nm, c=1.127 3(4) nm, α=106.666(5)°, β=113.034(5)°, γ=102.656(5)°, V=0.885 4(5) nm3, Z=1, μ=3.361 mm-1, Dc=1.915 g/cm3, F(000)=498, R1=0.059 6, wR2=0.144 8. 该配合物是双核分子, 2个Sm(Ⅲ)离子通过4个醋酸根的羧基桥联, 每个中心离子分别与周围5个来自羧基的桥氧原子、 一个硝酸根的两个氧原子和一个邻菲啰啉分子中的两个氮原子配位, 形成九配位扭曲多面体. 非等温热分解动力学研究结果表明， 配合物第一步热分解反应可能为二级反应, 其动力学方程为dα/dT=A/［βe-E/RT(1-α)2］, 分解反应的表观活化能为344.84 kJ/mol, 指前因子lnA=66.52.     

CRYSTAL STRUCTURES OF TWO DITHIOLATO-COPPER COMPLEXES (Ph_4P)Cu(BDT)_2 AND (Ph_4P)Cu(TDT)_2

<正> [(C6H5)4P]Cu(S2C6H4)2(Ⅰ),Mr = 683. 39,monoclinic,space group C2/c,a=16. 099 (4),b= 11. 913(3) ,c = 16: 715(9) A ,β=97. 13(4)°, v = 3180. 7 A3,z=4.MoKa radiation,λ= 0. 71069A ,Dc= 1. 427g/cm3,μ= 10. 1cm-1,F(000) = 1400,R=0. 061 and Rw = 0. 068 for 2189 reflections with Ⅰ>3σ(Ⅰ). [(C6H5)4P]Cu (S2C7H6)2(Ⅰ),Mr = 711. 45,monoclinic,space group C2/c,a=16. 501(6),b = 37. 461 (15),c=16. 684(4)A,β=96. 70(4)°, v= 10248. 8(46) A3,z= 12. MoKa radiation, λ= 0. 71069A,Dc=1.383g/cm3,μ=9. 45cm-1,F(000).= 4416,R= 0. 074 and Rw= 0. 078 for 2085 reflections with I>2σ(I)(1). The copper atom in the complexes is surrounded by four sulfur atoms from two dithiolato ligands in an approximate, square-plane. The average Cu-S distances of the copmplexes(Ⅰ) and (Ⅱ) are 2. 179 and 2. 178 A, respectively.     

Synthesis and Structure of a Novel Macrocyclic Complex [Cd2(phen)4(phth)2]·4H2O

A novel complex [Cd2(phen)4(phth)2]·4H2O has been synthesized by the reaction of H2phth(phthalic acid) and phen(1,10-phenanthroline) with Cd(Ⅱ) in ethanol-water solution. X-ray crystal structure analysis shows it crystallizes in triclinic, space group P1 with a = 10.619(3), b =12.560(4), c = 12.651(4) A, α = 98.775(5), β = 109.035(5), γ = 113.576(5)°, C32H24CdN4O6, Mr=672.95, V= 1381.7(7) A3, Rint = 0.0358, Z= 2, Dc= 1.618 g/cm3, μ = 0.845 mm-1, -6 ≤h≤13, -15≤k ≤13, -15≤l≤14, F(000) = 680, S = 1.038, R = 0.0480 and wR = 0.0849 for 3992 observed reflections (I ＞ 2σ(Ⅰ)). Phth bridges Cd(Ⅱ) to form a macrocyclic compound, and a 2D supramolecular motif is formed through hydrogen bonds and π-π interaction.     

Synthesis and Crystal Structure of 1＇-Methyl-4＇-（4-chlorophenyl）-1H-indole-3-spiro-2＇-pyrrolidine-3＇-spiro-4＂-（2＂-phenyloxazole）-2,5＂（3H,4＂H）-dione

The title compound （C26H20ClN3O3） has been synthesized by 1,3-dipolar cycloaddition reaction from isatin, sarcosine and （Z）-4-（4-chlorobenzylidene）-2-phenyloxazol-5（4H）-one through a one-pot procedure, and its structure was confirmed by IR, IH NMR, elemental analysis and single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group PI, with a = 9.3903（19）, b = 11.398（2）, c = 12.603（3） A, α = 83.495（3）, β = 68.988（3）, γ = 67.178（3）^o, V= 1160.1（4）A^3 Z = 2, Mr= 457.90, Dc= 1.311 g/cm^3, p = 0.198 mm ^-1, F（000） = 476, the final R = 0.0489 and wR = 0.1144 for 3109 observed reflections with I 〉 2σ（I）.     

Synthesis and Structure of a New Dinuclear Tungsten(Ⅰ) Compound with Phenylselenol Ligand, [W2(SePh)2(CO)6(MeCN)2]

The reaction of Et4NCl, C6H5SeNa and W(CO)6 in MeCN afforded a new dinuclear tungsten(Ⅰ) complex W2(SePh)2(CO)6(MeCN)2 1 (Mr = 929.98). The crystal structure has been determined by X-ray single-crystal diffraction. 1 Crystallizes in monoclinic, space group P21/n with a = 7.501(1), b = 18.387(2), c = 9.491(1) (A), β = 103.897(2)°, V = 1270.6(3) (A)3, Z = 2, Dc = 2.431g/cm3, μ = 119.50 cm-1, F(000) = 852, R = 0.0695 and wR = 0.1724 for 2220 independent reflections with I ＞ 2σ(Ⅰ). The X-ray structure analysis reveals that the W2Se2 core of 1 is planar with W-W bond length of 3.0433(13) (A) and W-Se of 2.5922(17) (A).     

Synthesis, Crystal Structure and Luminescence Property of [Co(hmz)2(H2O)4]·2H2O

A new mononuclear Co(Ⅱ) complex, [Co(hmz)2(H2O)4]·2H2O, has been synthesized by the reaction of Co(CH3COO)2·4H2O with 1-(4-hydroxyphenyl)-5-mercaptotetrazole (Hhmz). It crystallizes in the monoclinic system, space group P21/n with a = 13.502(5), b = 6.718(3), c = 13.972(6) (A), β = 117.532(4)°, V = 1123.9(8) (A)3, Z = 2, M r = 553.45, F(000) = 570, Dc = 1.635 g/cm3, μ = 1.008 mm-1, the final R = 0.0272 and wR = 0.0684 for 2194 observed reflections (Ⅰ＞ 2σ(Ⅰ)). The Co(Ⅱ) is six-coordinated by two nitrogen atoms from two hmz-1 ligands and four water molecules, forming an octahedral geometry. The intermolecular hydrogen bonding and offset-panel π-π stacking interactions between the adjacent molecules extend the compound into a three- dimensional supramolecular framework. The title compound emits strong blue fluorescent light (λem(max) = 427 nm) at room temperature and is red-shifted compared with free ligand Hhmz (λem(max) = 342 nm).     

Crystal Structure of the Samarium Chlorosilicate Sm_3 (SiO_4)_2Cl

1INTR0DUCTIONSofarthreetyPesofstructuresoftherareearthchlorosilicateshavebeenreport-ed:La,(SiO')Cl,t"belongstoorthorhombicsystem,Ln3(SiO'),Cl(Ln=La,Pr)[z'sitomonoclinicsystem,Yb,(SiO'),Cl["toorth0rhombicsystem.WerecentlypreparedthesinglecrystalofSm,(SiO'),ClbyhightemperaturesolidstatereactionandvaportransP0rtmethod.Thoughthesamariumislightrareearthelement,thestructureisisostructuralwithYb,(SiO'),Cl.2EXPERmENTALThetitlecompoundSm,(SiO'),Clwasobtainedasanunexpectedcompoundina…     

Preparation and Crystal Structures of LaCl_3（12－crown－4）（MeOH）and［LaCl_3（phen）_2（H_2O）］·MeOH

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