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1.
Mixed-ligand complexes [Ni(4-NH2Py) (i-Bu2PS2)2] (I) and Ni(4-NH2Py)2(i-Bu2PS2)2 (II) have been synthesized. Single crystals were grown and X-ray diffraction data (CAD-4 diffractometer, MoK α radiation, 1477 F hkl , R = 0.0320) were used to determine the structure of I. The crystals are orthorhombic: a = 10.675(1) Å; b = 21.681(2) Å; c = 26.302(4) Å, V = 6087.5(12) Å3, Z = 8, ρ(calc) = 1.247 g/cm3, space group Pbca. Complex I possesses a mononuclear molecular structure. The coordination polyhedron of the Ni atom is a tetragonal pyramid NS4 whose base is formed by four S atoms of two cyclic bidentate ligands i-Bu2PS 2 and the axial position is occupied by the N atom of the 4-NH2Py cycle. According to electron spectroscopy data, complex II has an octahedral N2S4 environment of the Ni atom.Original Russian Text Copyright © 2004 by T. E. Kokina, L. A. Glinskaya, E. A. Novoselova, R. F. Klevtsova, and S. V. Larionov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 899–904, September–October, 2004.  相似文献   

2.
The [Ni(DDM)2(NO3)2(H2O)2] complex (DDM is 4,4-diaminodiphenylmethane [CH2(C6H4NH2)2]) is synthesized, and its structure is determined. The crystals are triclinic, space group P , a = 5.846(1) ?, b = 9.450(2) ?, c = 13.390(3) ?, α = 105.63(3)°, β = 98.13(3)°, γ = 105.84(3)°, V = 666.6(2) ?3, ρcalcd = 1.553 g/cm3, Z = 2. The Ni(II) ion (in the inversion center) is bound to a distorted octahedral array formed by the nitrogen atoms of the primary amino groups of the DDM molecules and the oxygen atoms of the monodentate nitrato groups and water molecules (Ni(1)-N(3) 2.119(2) ?, Ni(1)-O(1) 2.122(2) ?, Ni(1)-O(w) 2.047(2) ?, angles at the Ni atoms vary in the 85.08(9)°–94.92(9)° interval). The structure contains supramolecular metallacycles formed by the O(w)-H…N(2) hydrogen bonds between the coordinated H2O molecules and the terminal amino groups of DDM. The metallacycles are joined by the Ni2+ ions into infinite chains running in the [111] direction. Original Russian Text ? Yu.V. Kokunov, V.V. Kovalev, Yu.E. Gorbunova, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 11, pp. 1838–1843.  相似文献   

3.
稀土配合物[Nd(o-NO2-C6H4COO)3(DMF)2]2的合成及其晶体结构   总被引:2,自引:0,他引:2  
赵丽芳  陈亚芍 《化学学报》2007,65(8):667-672
合成了一种新的双核倒反中心的稀土钕配合物[Nd(o-NO2-C6H4COO)3(DMF)2]2. 通过元素分析, 核磁共振谱和红外光谱对配合物的组成和结构进行了表征, 用热重分析研究了该配合物的热稳定性, 用X射线单晶衍射法测定了其晶体的结构. 钕配合物[Nd(o- NO2-C6H4COO)3(DMF)2]2晶体属三斜晶系, 空间群P-1, 晶胞参数a=1.18652(12) nm, b=1.24784(13) nm, c=1.29958(13) nm, α=64.220 (1)°, β=66.306 (1)°, γ=71.825 (1)°, V=1.5645 (3) nm3, Dc=2.167 mg/m3, Z=2, μ=3.415 mm-1, F(000)=986. 配合物中每个Nd(Ш)被4个邻硝基苯甲酸根桥联, Nd(Ш)的配位数为8, 配位原子分别来自于5个邻硝基苯甲酸羧酸根的6个氧原子和2个DMF的羰基氧原子. 配合物中的氢键和ππ 堆积作用使其成为三维立体结构. 同时发现了标题配合物固体具有光致发光现象, 发光性能测试表明该配合物具有很好的荧光性质.  相似文献   

4.
武望婷  胡怀明  王尧宇  史启祯 《化学学报》2005,63(22):2032-2036
在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C10H10N2O4)、2,2-联吡啶(C10H8N2, 简写bipy)与Eu(NO3)3•4H2O反应, 首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a=0.93392(16) nm, b=1.3100(2) nm, c=1.3895(2) nm, α=97.205(3)°, β=105.411(2)°, γ=106.364(2)°, V=15.35(2) nm3, Z=2, μ=2.118 mm-1, Dc=1.686 Mg/m3, F(000)=786, R=0.0116, wR=0.0507, GOF=0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu3+配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.  相似文献   

5.
A double complex salt [Co(N2C2H8)3][AuBr4]2Br is obtained and characterized using single crystal X-ray diffraction analysis. The crystallographic data of C6H24Au2Br9CoN6 are as follows: a = 21.6479(17) ?, b = 14.9085(12) ?, c = 8.2676(7) ?, β = 110.820(2)°, V = 1538.92(12) ?3, C2/c space group, Z = 4, d x = 3.602 g/cm3. Square planar coordination of the gold atom in the complex anion is completed to a tetragonal pyramid by an additional bromine atom of the adjacent complex anion at the Au... Br distance of 3.677 ?.  相似文献   

6.
Protonation equilibrium has been studied for the acyclic gold(III) tetraaza metallocomplex [AuB]2+ [B = N, N′-bis(2-aminoethyl)-2,4-pentanediiminato(1−)] in aqueous solution. The synthetic procedure is described. The crystal and molecular structure of the protonated form of the [AuHB](H5O2)(ClO4)4 complex has been determined. Monoclinic crystals with unit cell dimensions a = 11.964(2) Å, b = 13.789(3) Å, c = 15.496(3) Å, β = 109.00(3)°, V = 2417.1(8) Å3, Z = 4, ρcalc = 2.243 g/cm3, space group P21/n. The structure is built of nearly planar [Au(C9H20N4)]3+ complex cations, (H5O2)+ cations, and [ClO4] anions. The gold atom coordinates four nitrogen atoms of the ligand, forming a square plane. The six-membered chelate ring of the ligand is protonated at the central β-carbon atom and contains imine C=N bonds. The oxygen atoms of the perchlorate ions are hydrogen bonded to the (H5O2)+ dihydroxonium ion and to the nitrogen atoms of the NH2 groups of the [AuHB]3+ cation. Original Russian Text Copyright ? 2005 by V. A. Afanasieva, L. A. Glinskaya, R. F. Klevtsova, and I. V. Mironov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 5, pp. 909–915, September–October, 2005.  相似文献   

7.
The reaction of cis-[Pt(15NH3)2(H2O) 2] 2+ (3) with N-acetylcysteine [H3accys] was investigated in aqueous solution. In this reaction, the ammine in the platinum complex formed was liberated. A mono-dentate sulfur-boundplatinum(II) product cis-[Pt(15NH3)2(H2O)(H2accys-S)]+ (7) and six-membered che-late ring complex cis-[Pt(15NH3)2 (Haccys-S,O)] (8) were formed in solution. The dinuclear sulfur-bridged complex 9, giving a broad peak in 15N NMR, was also observed, but only present in very tiny amounts. The mass spectrometry (ES-MS) was undertaken from this re action, and the product detected was only the dinuclear sulfur bridged platinum species and species related to it by ammine loss.  相似文献   

8.
The intracomplex conversion of (2-diphenylphosphanoethyl)cyclopentadienyl zirconium and titanium complexes into the corresponding 2-phosphinothioyl and 2-phosphinoyl derivatives, viz., (η5-C5H5)[η 5-C5H4CH2CH2P(S)Ph2]ZrCl2, [η5-C5H4CH2CH2P(S)Ph2]ZrCl3, [η51C5H4CH2CH2P(O)Ph2]ZrCl3·THF, and [η51-C5H4CH2CH2P(O)Ph2]TiCl3 (7), was performed. The NMR spectroscopy data revealed the following order of the coordination ability of the functional groups with respect to the Zr center: Ph2P=O > Ph2P > Ph2P=S. An analogous order was found for the monodentate ligands (Ph3P=O > Ph3P > Ph3P=S) with respect to (η5-C5H5)ZrCl3. The molecular structure of complex 7 was established by X-ray diffraction analysis. Coordination of the Ph2P=O group to the titanium atom was found retained both in the crystalline state and solution.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116–122, January, 2005.  相似文献   

9.
The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2- anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(Ⅱ) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.  相似文献   

10.
Various routes to NiII aminoalkoxides have been investigated. A nickel isopropoxide derivative 1 was prepared by anodic dissolution of the metal in the presence of LiCl as electrolyte. Alcoholysis reactions of 1 with 1-dimethylamino-2-propanol afforded the homoleptic nickel(II) aminoalkoxide 2 together with a NiLi species 3. 2 was also obtained by metathesis reactions between sodium alkoxide and the nickel hexammine complex whereas the reaction between the latter and the aminoalcohol led to an halide solvate, cis-NiCl2(η2-ROH)2, 4. The various compounds were characterized by elemental analysis, FT-IR and UV-vis spectroscopies as well as by X-ray diffraction for 3 and 4. 3 corresponds to [Li(PriOH)Ni(η2-OCHMeCH2NMe2)Cl]2 and the overall structure can be seen as two [Ni(η2-OCHMeCH2NMe2)2Cl] moieties assembled by Li(PriOH)+. The lithium atom is 4-coordinate due to its interaction with the oxygen atoms of the aminoalkoxide ligands. Nickel is 5-coordinate with a distorted tetragonal pyramidal stereochemistry, one nitrogen being in the apical position. The metal displays a distorted octahedral surrounding for the NiCl2 adduct 4. The bond distances vary in the order NiOR < NiN ≈ NiO(H)R < NiCl for 3 and 4. The various compounds (except 1) are soluble in organic media.  相似文献   

11.
A novel heterohexanuclear complex [Ni2Ag4(μ-dppm)4(pymt)6](SbF 6)2 · 2DMF · H2O (1), was synthesized by self-assembly with [Ag2(μ-dppm)2(MeCN)2](SbF6) 2 and [Et4N][Ni(pymt)3] (dppm = bis(diphenylphosphino)methane, pymt = pyrimidine-2-thiolate) as components and characterized by IR spectra, elemental analysis, 1H-NMR spectrum, 31P-NMR spectrum and Visible-Ultraviolet spectrum. Structure of the complex was determined by X-ray analysis.  相似文献   

12.
葛红光   范广  陈三平  高胜利 《化学学报》2006,64(24):2501-2504
在水溶液中合成了离子型配合物[Ni(phen)2(H2O)2][Ni(PDC)2]•7H2O (H2PDC=吡啶-2,6-二甲酸, phen=1,10-菲啰啉). 通过元素分析、红外光谱、单晶X射线衍射以及热重分析对配合物进行了表征. 晶体数据解析表明, 化合物属于三斜晶系, 空间群为P1, a=1.0092(4) nm, b=1.4599(6) nm, c=1.4933(5) nm, α=73.982(2)°, β=78.652(2)°, γ=75.184(3)°, V=2.0256(13) nm3, Z=2, F(000)=1004, μ=1.014 mm-1, R1=0.0538, wR2=0.1493. 配合物中的结晶水分子形成一个(H2O)12水簇, (H2O)12水簇通过氢键连接为二维水网, 最终构成三维超分子网络.  相似文献   

13.
Crystals of the rhenium cluster complex (H3O)4[(C2H5)4N]6[Th2Cl4(H2O)12O]3[Re4Se4(CN)12]4 are obtained in an acidic (HCl) aqueous solution by the reaction of cluster salt K4[Re4Se4(CN)12]·6H2O with ThCl4 and (C2H5)4NCl. Single crystal X-ray analysis shows that the title compound is ionic and crystallizes in the cubic crystal system (a = 22.7322(3) ?, V = 11746.93(27) ?3, Z = 2, I4 3m space group, R = 0.0350). It contains [Th2Cl4(H2O)12O]2+ cations with two thorium atoms bonded to each other through the bridging oxygen atom forming an angle of 180° in the structure.  相似文献   

14.
New heteroleptic oxovanadium(V) chloro oximato complexes of the type [VO{Cl}3-n {ON=C(CH3)(Ar)} n ] (where Ar = C4H3O-2, C4H3S-2, C5H4N-2 and n = 1 or 2) have been synthesized in excellent yields by the reaction of VOCl3 with the sodium salts of corresponding internally functionallized oximes in refluxing anhydrous benzene. The complexes are characterized by elemental analyses and spectroscopic techniques (FT-IR, 1H-, 13C{1H}- and 51V-NMR). FAB mass spectral analysis of one of the derivatives, [VOCl{ON=C(CH3)C4H3S}2] indicates the monomeric nature of the complex. 51V-NMR spectral studies of these complexes suggest tetra-coordination around the vanadium atom in solution. However, the single crystal X-ray diffraction study of a redistribution product [VOCl{ON=C(CH3)(C4H3S-2)}2] · CH3OH obtained on recrystallization of [VOCl2{ON=C(CH3)(C4H3S-2)}] from a methanol-hexane mixture shows the vanadium(V) atom is hepta-coordinated with distorted pentagonal bipyramidal geometry. The oxo-atom occupies the axial position while the weakly coordinated CH3OH group is trans to the V=O atom. The two oximato ligands in the approximate pentagonal plane are bonded to the central vanadium atom in dihapto (η2-N, O) manner with the formation of three-membered rings. The V–Cl bond occupies the fifth position in the approximate plane.  相似文献   

15.
ZnO, 丙二酸及4,4'-bipy按物质的量之比1∶3∶0.3溶于H2O和DMF混合溶剂中(体积比4∶1), 形成的无色溶液在50 ℃反应 3 d, 得到了标题化合物{[Zn2(mal)2(4,4'-bipy)(H2O)2]•2(H2O)0.25} (mal=丙二酸根), 对其进行了元素分析、红外光谱和X射线衍射表征, 测定了晶体结构. 该聚合物属单斜晶系, P21/n空间群, a=0.71215(16) nm, b=1.8685(4) nm, c=0.73890(17) nm, β=91.486(5)°, V=0.9829(4) nm3, Z=4, Dc=1.811 g/cm3, Mr=268.03, F(000)=542, μ=25.02 cm-1. 最终偏离因子R1=0.0499, wR2=0.1374. 该化合物中Zn原子和三个丙二酸根中的4个O原子、一个水分子和4,4'-bipy的一个N原子配位, 形成的ZnNO5八面体通过4,4'-bipy和丙二酸根桥联, 组成一种新颖的三维多孔结构, 其孔道中充填游离水分子. 此外还研究了该聚合物的热性质.  相似文献   

16.
The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W2(μ-H)(μ-Cl)(Cl4(μ-dppm)2 · (THF)3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W2(μ-H)2(μ-O2CC6H5)2Cl2(P(C6H5)3)2] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2 · (THF)3] (II), has been synthesized and the value of −2J determined from variable-temperature 31P NMR spectroscopy.  相似文献   

17.
Crystal structures of chelate compounds Ni[(iso-C4H9)2PS2]2 (I) and Pd[(iso-C4H9)2PS2]2 (II) have been determined by X-ray diffraction: diffractometer X8-APEX, MoK α∔ -radiation, 1048 F hkl , R = 0.0544 for I and CAD-4 diffractometer, MoK α∔ -radiation, 1283 F hkl , R = 0.0347 for II. The crystals are rhombic: a = 12.921(5) Å, b = 17.094(5) Å, c = 22.971(5) Å; V = 5074(3) Å3, Z = 8, calc = 1.250 g/cm3, space group Pbca for I and a = 13.312(3) Å, b = 16.130(7) Å, c = 23.171(5) Å; V = 4975(3) Å3, Z = 8, ρcalc = 1. 208 g/cm3, space group Pbca for II. The structures of I and II are formed by discrete mononuclear molecules. Coordination cores MS4 (M = Ni, Pd) approach planar square configurations. Original Russian Text Copyright ? 2005 by L. A. Glinskaya, T. G. Leonova, T. E. Kokina, R. F. Klevtsova, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp. 715–720, July–August, 2005.  相似文献   

18.
In this investigation, the crystal structures of the thio-ligands 3-formylpyridine 4-phenylthiosemicarbazone (C13H12N4S, 1 ) and 4-benzoylpyridine 4-ethylthiosemicarbazone (C15H16N4S, 2 ), and of two new coordination compounds, chlorido(3-formylpyridine 4-phenylthiosemicarbazone-κS)bis(triphenylphosphane-κP)copper(I) acetonitrile monosolvate, [CuCl(C13H12N4S)(C18H15P)2]·CH3CN, 3 , and bis(3-formylpyridine 4-ethylthiosemicarbazonato-κ2N1,S)nickel(II), [Ni(C9H11N4S)2], 4 , are reported. In complex 3 , the thio-ligand coordinates in a neutral form to the Cu atom through its S-donor atom, and in complex 4 , the anionic thio-ligand chelates to the Ni atom through N- and S-donor atoms. The geometry of complex 3 is distorted tetrahedral [bond angles 99.70 (5)–123.23 (5)°], with the P—Cu—P bond angle being the largest, while that of complex 4 is square planar, with trans-S—Ni—S and N—Ni—N bond angles of 180°.  相似文献   

19.
Electronic state d6 Ni(IV) in the complex [NiH2Cl2(PH3)2] was studied by means ofab initio MO/MP4 calculations.  相似文献   

20.
Cyclometallation occurs when a solution of the complex Rh(oq)(CO)(PCBr), (PCBr = 2-bromo-3,4,5,6-tetrafluorophenyldiphenylphosphine; OQ = 8-hydroxyquinolinate) in toluene is refluxed, giving ) (PC = P(C6F4)(C6H5)2) and a dimeric compound, not yet completely characterized, formulated as Rh2Br(oq)(PCBr)2. ) was characterized by elemental analysis, by conductance measurements, and by 19F, 31P NMR and infrared spectroscopy. Its molecular structure was determined by single-crystal X-ray methods and refined by standard procedures to final agreement factors R and Rw of 0.067 and 0.060 for 5346 observed data. Lattice constants are 15.8494(6), 14.7188(5), 14.6675(5) Å and β 96.933(3)°, with monoclinic symmetry. The complex has a distorted octahedral geometry with a four atom metallocycle-ring (Rh---P---C---C) showing distorted angles of 69.8(2) and 84.8(2)° at Rh and P atoms, respectively. The analogous compound ), (5-moq = 5-methyl-8-hydroxyquinolinate), can be obtained by heating Rh(5-moq)(CO)(PCBr).  相似文献   

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