Crystal structure and spectral characteristics of {[(C6H5)NH]2C=NH(C6H5)}[B(C6H5)4]·C2H5OH

A novel compound of {[(C₆H₅)NH]₂C=NH(C₆H₅)}[B(C₆H₅)₄]·C₂H₅OH is prepared and examined by single crystal X-ray diffraction. Crystal data: C₄₅H₄₄BN₃O, M = 653.64, monoclinic, space group P2₁/c, unit cell parameters: a = 24.375(2) Å, b = 17.5829(15) Å, c = 18.090(1) Å, β = 105.277(2)°, V = 7479.0(11) ų, Z = 8, d _calc = 1.161 g/cm³, T = 293 K, R ₁ = 0.064. The structure contains two crystallographically independent cations, two anions, and two solvate ethanol molecules. Three types of interactions occur between them: interionic N-H(N)⋯π and N(H)⋯π⋯H(C), π-delocalized system of Ph rings of the anions, and interaction of ions with ethanol molecules N-H⋯O-H(O)⋯π. The compound is characterized by IR and luminescence spectra. At room temperature, the emission intensity grows with time of exposure to UV irradiation. Original Russian Text Copyright ? 2008 by T. M. Polyanskaya, E. A. Il’inchik, V. V. Volkov, M. K. Drozdova, O. P. Yur’eva, and G. V. Romanenko __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 3, pp. 512–521, May–June, 2008.     

金属配位聚合物[Mn2（C8H3NO6）2(C12H8N2)2]n的合成及其催化氧化性能

以5-硝基间苯二甲酸,1,10-邻菲啰啉,硫酸锰(MnSO4.H2O)为原料合成了一种结构新颖的金属配位聚合物——[Mn2(C8H3NO6)2(C12H8N2)2]n(1),其结构经IR,XRD,TG-DTG和元素分析表征。X-射线单晶衍射测试结果表明,1属三斜晶系,空间群Pī,晶胞参数a=10.060 2(1),b=14.343 5(2),c=14.663 7(2),α=104.052(1)°,β=102.633(1)°,γ=110.460(1)°,Mr=888.52,V=1 812.69(4)3,Z=2,Dc=1.628 g.cm-3,F(000)=900。以30%H2O2为氧化剂,初步研究了1在苯乙烯氧化反应中的催化氧化性能。     

配合物[Mn(C13H8N2OBr)2(C5H5N)2]·3C5H5N的结构与磁性研究

The complex [Mn(C₁₃H₈N₂OBr)₂(C₅H₅N)₂]·3C₅H₅N has been synthesized and characterized by X-Ray diffraction, IR and variable temperature (～10 to ～278K) magnetic susceptibility. X-Ray diffraction result for the single crystal shows that the crystal belongs to monoclinic, space group P2₁/c, a=1.0969(3)nm, b=2.0903(5)nm, c=2.0481(6)nm, β=97.366(6), V=4.657(2)nm³, Z=4, D_c=1.47g·cm^-3。     

{Na2[μ2-(C6H4O2)2](C6H4OOH)2}4-的结构及其在固态合溶液中的NMR比较

The new compound （NH3CH2CH2NH3）2{Na2[μ2-（C6H4O2）2]（C6H4OOH）2} has been synthesized and characterized by elemental analysis, IR, UV, NMR and single crystal X-ray diffraction. The yellow crystals crystallized in the triclinic system with space group P-1 and a=0.6091（2） nm, b= 1.0274（3） nm, c= 1.2466（4） nm, α=89.073（6）°, β=89.376（6）°, γ=78.873（5）°, V=0.7653（4） nm^3, Z= 1, R1=0.0568, wR2=0.1198. Every sodium ion coordinates in trigonal prismatic fashion with two O atoms from a terminal chelating catecholato ligand and four O atoms from bridging P2 catecholato ligands, Two neighboring NaO6 trigonal prisms are face-shared and centrosymmetric with regard to the inversion center consisting of four tri-bridging O atoms to form a binuclear cluster {Na2[μ2-（C6H4O2）2]}^2- anion. The comparison of ^13C NMR spectrum of tlie complex in solid state with that in solution indicated that the rapid exchange between the bridging [μ2-（C6H4O2]^2- and terminal [C6H4OOH]^- ligands was present in solution.     

[Mo(C9H6NO)2O2]的合成和晶体结构

合成了标题化合物[Mo(C9H6NO)2(O)2](C9H6NO=8-羟基喹啉),测定了化合物的晶体结构.晶体属单斜晶系,空间群Cc,a=13.372(3),b=9.421(2),c=13.554(3)A,β=109.71(3)°,V=1607.6(8)A3.结构由直接法解出,最后可靠性因子R=0.0473,Rw=0.062.Mo原子为6配位,位于八面体的中心.两个配体氧相互处于邻位,分别与8-羟基喹啉中的N原子处于对位.     

Functionalised tetraarylstannanes Sn[C6H4-R]4 (R=-CH(CH2O)2, -CHO, -COOH, -CHN-NH-C6H3-2,4-(NO2)2, -CH2OH, -CO-NH-CH2-COO-CH3, -CH[N(C2H4)2O]2)

Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C₆H₄-CH(OCH₂)₂]₄ (2), which was transformed to Sn[C₆H₄-CHO]₄ (3) and its hydrazido and amino derivatives Sn[C₆H₄-CHN-NH-C₆H₃-2,4-(NO₂)₂]₄ (5) and Sn{C₆H₄-CH[N(C₂H₄)₂O]₂}₄ (8). Oxidation of (3) produced Sn[C₆H₄-COOH]₄ (4) while reduction of (3) gave Sn[C₆H₄-CH₂-OH]₄ (6). From the acid 4, an amino acid Sn[C₆H₄-CO-NH-CH₂-CO-OCH₃]₄ (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).     

[Ni(C6H4N2)(CHC6H4O)2]配合物晶体结构及性质

The complex has been synthesized and characterized by spectroscopic techniques and single-crystal X-ray analysis. The crystal is orthorhombic ， space group P2₁2₁2₁ with a=1.6620(3)nm， b=1.7300(4)nm， c=0.5450(1)nm and Z=4. In the crystal lattice， the molecules create a two-dimensional network structure through hydrogen bonds. The C-H…O intermolecular hydrogen bonds connect the title complex to form layer super-molecular plane structure perpendicular to the axis b， with the layers stacked by the Van der Waals interaction. CCDC： 195309.     

Synthesis and crystal structures of [UO2(C6H4NO2)2(C6H5NO2)] and [UO2SO4(C6H5NO2)(H2O)] · H2O

The complexes [UO₂(C₆H₄NO₂)₂(C₆H₅NO₂) (I) and [UO₂SO₄(C₆H₅NO₂)(H₂O)] · H₂O (II) were synthesized and studied by X-ray diffraction analysis. Crystals I are monoclinic: a = 7.0081(3), b = 14.9624(7), c = 9.1837(5) ?, β = 96.594(2)°, Z = 2, space group P2₁/m. Crystals II are triclinic: a = 6.8097(6), b = 9.3837(8), c = 10.4556(10) ?, α = 85.279(3), β = 75.434(3), γ = 69.180(3)°, Z = 2, space group . The main structural unit of crystal I is a mononuclear fragment, which belongs to the crystal chemical group AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ are ions of pyridine-2-carboxylic (picolinic) acid, M¹ are molecules of picolinic acid) of the uranyl complexes. The main structural unit of crystal II is a chain, which belongs to the crystal chemical group AT³M ₂ ¹ (where T³-SO ₄ ²⁻ , M¹ are water and picolinic acid molecules) of the uranyl complexes. Picolinic acid in complexes I, II was found to have a zwitterion structure. Original Russian Text ? E.V. Grechishnikova, E.V. Peresypkina, A.V. Virovets, Yu.N. Mikhailov, L.B. Serezhkina, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 6, pp. 468–475.     

Synthesis, structure and spectroscopic characterization of a new organic cation diphosphate: [2,6-(C2H5)2C6H3NH3]2H2P2O7?·?2H2O

The chemical preparation, crystal structure and spectroscopic characterization of [2,6-(C₂H₅)₂C₆H₃NH₃]₂H₂P₂O₇ · 2H₂O have been reported. The compound crystallizes in the monoclinic system in space group P2₁/c and cell parameters a = 14.323(2), b = 11.158(3), c = 16.387(2) ? and β = 96.34(3)°; V = 2602.8(9) ?³ and Z = 4. Crystal structure has been determined and refined to R = 0.044, using 3528 independent reflections. The atomic arrangement of the title compound shows anionic layer of formulae [H₂P₂O₇(H₂O)₂] _n ²ⁿ⁻ stacked along the c-axis. The 2,6-diethylanilinium cations establish on both sides of these inorganic layer hydrogen bonds so as to contribute to the intralayer cohesion in the network. The different building species are held together by means of O–H···O and N–H···O intermolecular hydrogen bonds in addition to electrostatic and van der Waals interactions.     

含双蝶状[2Fe2S]骨架的新型[FeFe]氢化酶模型物{（μ-FcS2）[Fe2（CO）6]2（μ-SMe）2}的合成及其晶体结构

利用1,1’-双锂二茂铁与(μ-S2)Fe2(CO)6和MeI反应,合成了一种新型的含二茂铁基[FeFe]氢化酶活性中心模型化合物——(μ-FcS2)[Fe2(CO)6]2(μ-SMe)2(1),其结构经1H NMR,IR和X-射线单晶衍射表征。1属于斜方晶系,Pbca空间群,晶胞参数a=10.705 8(13),b=21.721 0(3),c=21.721 0(3),V=6 533.2(14)3,Z=8,Dc=1.834 g·cm-3,μ=2.480 mm-1,F(000)=3 584,R1=0.038 8,wR2=0.085 6。     

一种二帽pseudo-Keggin结构簇合物[HN(C2H5)3]3[N(C2H5)3]2[MoⅣ8MoⅤ4VⅣ2O38(PO4)]的水热合成、结构和性质研究

The novel polyoxometalate, [HN(C₂H₅)₃]₃[N(C₂H₅)₃]₂[Mo^Ⅳ₈Mo^Ⅴ₄V^Ⅳ₂O₃₈(PO₄)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X-ray diffraction. The compound crystallizes in triclinic system, space group P1 with a= 1.41999(2)nm, b=1.43467(2)nm, c=1.694610(10)nm, α=95.7250(10)°, β=92.2110(10)°, γ=92.6060(10)°, V=3.42829(7)nm³, Z=2, D_c=2.388g·cm^-3, M_r=2465.10g·mol^-1, μ=2.489mm^-1, F(000)=2388, R₁=0.0584, wR₂=0.1461, S=1.164. The het-eropolyanion is a bi-capped pseudo-Keggin complex. CCDC： 186645.     

Double complex salts with [Ru(NH3)5Cl]2+ cation and [OsCl6]2? anion: Synthesis and properties. Crystal structure of [Ru(NH3)5Cl]2[OsCl6]Cl2

Double complex salts [Ru(NH₃)₅Cl][OsCl₆] and [Ru(NH₃)₅Cl]₂[OsCl₆]Cl₂ were prepared and characterized. An X-ray diffraction study showed that [Ru(NH₃)₅Cl][OsCl₆] is isostructural to the previously synthesized [Rh(NH₃)₅Cl][OsCl₆]. The structure of [Ru(NH₃)₅Cl]₂[OsCl₆]Cl₂ was solved by X-ray diffraction (a = 11.1849(8) ?, b = 7.9528(6) ?, c = 13.4122(9) ?; β = 99.765(2)°; V= 1175.75 ?³; space group C2/m; Z = 2). Thermolysis of the compounds under hydrogen and helium was studied. According to X-ray diffraction, nanosized metallic powders of the corresponding alloys are formed as the final products of thermolysis. The compositions of the obtained solid solutions are consistent with the phase diagram of the Ru-Os system.     

无机-有机杂化硫属化合物[Mn（1，2-dap）2（H2O）]2（μ-Sn2Q6）（Q=S、Se）和[Mn（tren）]2（μ-Sn2S6）的合成、晶体结构与性能

采用溶剂热方法合成了3个多元硫属化合物[Mn（1,2-dap）₂（H₂O）]₂（μ-Sn₂Q₆）（Q=S（1）和Se（2））和[Mn（tren）]₂（μ-Sn₂S₆）（3）,用X-射线单晶衍射测定了化合物的结构,并通过红外光谱、紫外-可见漫反射光谱对其进行了表征。单晶结构解析表明,化合物1和2都属于正交晶系,Pccn空间群（No.56）,晶体结构是由[Mn（1,2-dap）₂（H₂O）]²⁺配合物阳离子和[Sn₂Q₆]^4-二聚体通过Mn-Q键连接而成的[Mn（1,2-dap）₂（H₂O）]₂（μ-Sn₂Q₆）低聚体,相邻的低聚体之间通过氢键相连形成三维结构。化合物3属于三斜晶系,晶体结构是由[Mn（tren）]₂（μ-Sn₂S₆）单元通过氢键连接而成的二维结构。紫外-可见漫反射光谱结果显示化合物1,2和3的带隙分别为2.5,2.1,2.4eV,属于半导体材料。     

Synthesis and structure of gold and copper complexes: [Ph3PhCH2P]+[AuCl4]?, [NH(C2H4OH)3]+[AuCl4]? · H2O, and [Ph3EtP] 2+ [Cu2Cl6]2?

Triphenylbenzylphosphonium tetrachloroaurate (I) and triethanolammonium tetrachloroaurate hydrate (II) were prepared by reacting tetrachloroauric acid in acetone with triphenylbenzylphosphonium and triethanolammonium, respectively. Triphenylethylphosphonium hexachlorodicuprate (III) was synthesized from triphenylethylphosphonium chloride and copper chloride in acetone. The crystal structures of complexes I to III were determined by single-crystal X-ray diffraction. The phosphorus atoms in complex I have a nearly undistorted tetrahedral coordination (CPC, 108.3°–110.6°; P-C, 1.788–1.793 ?). The coordination of nitrogen atoms in the cations of complex II is a distorted tetrahedron (CNC, 111.7°–112.4°). The square coordination of aurum in I and II is only slightly distorted: the ClAuCl angles are 89.6°–90.3° (I) and 89.5°–90.6° (II) and the Au-Cl distances are 2.256–2.278 ? I) and 2.280–2.285 ? (II). The phosphorus atoms in complex III are tetracoordinated (CPC, 106.34°–111.73°; P-C, 1.790–1.795 ?). The copper atoms in III have a distorted tetrahedral coordination (ClCuCl, 98.48°–144.85°; Cu-Cl, 2.1999–2.3263 ?). The central fragment Cu₂Cl₂ in the anion of complex III is bent relative to the Cu₂ axis (the chlorine atom deviates from the Cu₂Cl plane by 0.27 ?).     

单茂钪催化剂（C5H5）Sc（CH2C6H4NMe2-o）2合成高顺式窄分布聚丁二烯

合成了6种单茂稀土催化剂Cp’LnR2(THF)n(其中,Cp’=C5H5,C5Me4SiMe3;R=CH2C6H4NMe2-o,CH2SiMe3;Ln=Sc,Y,Lu;n=0或1),并以[Ph3C][B(C6F5)4]为助催化剂,甲苯为溶剂,考察催化剂结构对丁二烯聚合活性,立体选择性,催化剂利用率以及聚合物分子量和分子量分布的影响.通过1H-NMR,13C-NMR,FTIR,GPC以及DSC对聚丁二烯进行表征,结果表明,当Cp’=C5H5,R=CH2C6H4NMe2-o,Ln=Sc,n=0时,催化剂(C5H5)Sc(CH2C6H4NMe2-o)2对丁二烯聚合活性最高,可达9600 kg-polymer/mol-Sc·h,催化剂利用率为45%,聚丁二烯顺-1,4结构含量在96%~98%之间,分子量分布窄,指数在1.3左右;以甲苯或氯苯作为聚合溶剂时,聚合活性最高,聚丁二烯分子量保持窄分布,在所有溶剂中聚丁二烯顺-1,4结构含量均达到96%以上;催化剂聚合活性随温度下降而降低,而聚合物分子量分布有变窄的趋势,温度对聚丁二烯立体选择性无明显影响;当[Bd]/[Sc]摩尔比从500增加到3000时,聚合反应1 min转化率均达到100%,聚丁二烯分子量呈可控线性增大,最高达44.6×104,且均保持聚合物窄分布.DSC谱图表明聚丁二烯Tg为-107℃,当升降温速率为10 K/min时,在-63℃和-8℃附近呈现出明显的冷结晶峰和熔融峰.     

Synthesis, Crystal Structure and Cubic Order NLO Property of Square Compound [PPh4]2[Ni（CN）4Cu（PPh3）2]2·2CH3OH

A new tetranuclear cyanide-bridged complex [PPh4]2[NiⅡ(CN)4CuⅠ(PPh3)2]2·2CH3OH ([PPh4]+ = tetraphenylphosphine cation, PPh3 = triphenylphosphine) 1 has been synthesized and characterized by IR spectroscopy, elemental analysis, electronic absorption spectra and single-crystal X-ray diffraction. This complex crystallizes in triclinic, space group Pí with a = 10.910(5), b = 15.777(7), c = 18.275(8), α = 68.752(12), β = 79.776(13), γ = 81.400(14)°, NiCuC65H50N4OP3, Mr = 1122.25, V = 2873(2)3 , Z = 2, Dc = 1.293 g/cm3, F(000) = 1156, μ = 0.826 mm-1, the final R = 0.0755 and wR = 0.2155 for 7324 observed reflections (I > 2σ(I)). The title compound exhibits a discrete square tetranuclear structure and a cubic order NLO property.     

[Os（PH3）2（CN）2（N^N）]配合物的溶剂化显色效应

采用HF/DFT的混合泛函PBE0和UPBE0优化了配合物[Os(PH3)2(CN)2(N^N)](其中N^N=2,2′-吡啶)的基态和激发态结构.在基态和激发态结构的基础上,利用含时密度泛函理论(TD-DFT)方法,结合极化连续介质(PCM)模型分别计算了它在二氯甲烷(1)、甲醇(2)、气态(3)和乙腈(4)溶液中的吸收和发射光谱.研究结果表明:优化得到的几何结构参数和相应的实验值符合得非常好.在极性较大的溶剂(2和4)中Os—P(1)和Os—C(1)键较长,Os—N(3)键较短,溶剂的极性会影响配合物的电子云分布.配合物在1-4溶剂中的最低能吸收和发射均来自分子轨道68→71的激发,该激发被指认为[d(Os)+π(CN)+π(N^N)→π*(N^N)]的跃迁具有混合的MLCT/LLCT特征.配合物在1-4溶剂中的最低能吸收和发射分别在471,410,488和445nm以及598,536,634和545nm,表明随着溶剂极性的逐渐增大(3<1<4<2),最低能吸收和发射发生明显的蓝移.这显示出通过改变溶剂极性可以调节配合物的发光颜色.     

新型一维链状配位聚合物[Cd2(C23H14O6)2(C10H9N3)2(H2O)]n的研究

配位超分子聚合物的设计合成与应用研究一直是配位化学、超分子化学、生物无机化学及材料科学等领域的热点研究课题之一,具有微孔结构的配位聚合物吸引了许多科学家的目光,这不仅因为该类配合物具有新颖的结构,展现出多种诱人的拓扑结构,更主要的 是因为它们在离子交换、催化、磁性材料、光学材料及气体贮存领域的应用潜力[1～3].     

Synthesis, thermogravimetric analysis, IR spectrum, and the crystal structure of sodium hexatunstomanganate [Na2(H2O)10][Na(H2O)3]2[MnW6O18(OH)6] · 6H2O

The complex [Na₂(H₂O)₁₀][Na(H₂O)₃]₂[MnW₆O₁₈(OH)₆] · 6H₂O was synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, X-ray diffraction. The crystals are monoclinic, space group P2₁/n, a = 11.698(2), b = 11.670(2), c = 14.652(3) ?, β = 102.52(3)°, V = 1952.7(7) ?³, ρ(calcd.)= 3.45 g/cm³, Z = 2.     

Low-temperature X-ray diffraction study of [CuII(1,10-C12H8N2)3]2+{CoIII[η5-(3)-1,2-C2B9H11]2} 2? ·CH3CN

Single crystal XRD is used to study the crystal structure of a new compound containing the dicarbollyl cluster anion Co(III) with the composition [CuPhen₃][Co(C₂B₉H₁₁)₂]₂·CH₃CN, where Phen is 1,10-phenanthroline. The crystallographic data: C₄₆H₇₁B₃₆N₇Co₂Cu, M = 1292.66, monoclinic system, P2₁/c space group, unit cell parameters a = 14.7178(2) ?, b = 19.5640(4) ?, c = 22.8663(5) ?, β = 106.6601(7)°, V = 6307.75(33) ?³, Z = 4, d _x = 1.361 g/cm³, T = 100 K, μ = 0.90 mm⁻¹. The structure is solved by the direct method and refined by the full-matrix LSM in an anisotropic-isotropic (for H atoms) approximation up to the final agreement factors R ₁ = 0.0370, wR ₂ = 0.0869 for 13,807 I _hkl ≥ 2 σ _I out of 18,295 measured I _hkl . The structure consists of [CuPhen₃] cations, Co(C₂B₉H₁₁)₂ anions, and acetonitrile molecules MeCN. The central Cu atom in the cation in the general position, and its coordination geometry is a distorted extended octahedron formed by six nitrogen atoms of the three bidentate Phen ligands. The coordination of Cu(II) in the cation is (2+2+2) with two long axial and four shorter equatorial Cu-N bonds, whose average lengths are 2.239(2) ? and 2.077(1) ? respectively. Each anion has its own position of the -C₂-groups; for Co(1), it is a quasi-gauche-configuration; for Co(2), a quasi-trans-configuration.