Synthesis,Spectral, Valence‐Bond Parameters,and Single Crystal X‐ray Structural Studies on [Ni(dnpdtc)(PPh3)(NCS)] and [Ni(dnpdtc)(PPh3)(CN)]

Two new nickel complexes withplanar surrounding of Ni [Ni(dnpdtc)(PPh₃)(NCS)] (1) and [Ni(dnpdtc)(PPh₃)(CN)] (2) (dnpdtc=N, N‐dipropyldithiocarbamate) were prepared from the parent dithiocarbamate and were characterized by elemental analysis, electronic, IR and NMR spectra. The structures of both the complexes were determined by single crystal X‐ray crystallography. Thioureide stretching vibrations occur at 1528 cm^‐1 and 1521 cm^‐1 for 1 and 2 respectively. Large ³¹P chemical shifts were observed for the two compounds. A significant asymmetry in Ni—S bond distances was observed in compound 1 [2.1700(16) and 2.2251(17)Å] whereas in compound 2 the bond distances were almost similar [2.2100(14) and 2.2122(13)Å]. A marginal difference was observed with respect to the thioureide bond distances [1.340(6)Å for 1 and 1.312(5)Å for 2 ]. The observation clearly supports the less effective trans influence of SCN^— over PPh₃. However, PPh₃ and CN^— show almost similar trans influence.     

Spectroscopic Studies of a Three-dimensional, Five-coordinated Copper(Ⅱ) Complex via Hydrogen Bonds: [Cu(PDA)(H_2O)_2](H_2PDA=Pyridine-2,6-dicarboxylic Acid)

IntroductionFive- coordinated complexes with d9- configuredcations have received much attention stereochemi-cally,spectrochemically and biologically,and havebeen comprehensively discussed[1] . Usually thereare two stable configurations for the copper( )complexes with five equal coordinating atoms:anapically elongated square pyramid( SP) and a com-pressed trigonal bipyramid( TBP) ,with an obviousenergetic preference for the latter coordination.When the ligands are rigid and provide angular d…     

Crystal Structure and Electron Density Distribution in Niobium Carbide

In this paper the bonding properties, e. g. the charge distribution between the atoms and the deformation of niobium carbide densities have been studied. The crystal studied had the composition NbC_0.98. Careful and redundant data collection (74 unique reflections out of 2087 reflections measured) gave the basis for a detailed study. IAM models (independent atom model), high order and multipole refinements were made resulting in R values of R = 0.4% and R = 0.07%. In the corresponding deformation density maps electron accumulations between the niobium atoms were detected, but no bonding to the carbon atoms.     

一维链状[Mn(9-AC)2(4,4'-bpy)(H2O)2]n配位聚合物的合成及晶体结构

在水热条件下(120 ℃), 将醋酸锰、4,4'-联吡啶(4,4'-bpy)与9-蒽酸(9-HAC)反应, 得到了配位聚合物[Mn(9-AC)2(4,4'-bpy)(H2O)2]n, 通过元素分析、红外光谱、X射线单晶衍射对其进行了表征, 并用TGA研究了该配位聚合物的热稳定性. 结构解析结果表明, 该晶体属于正交晶系, Fdd2空间群, a=1.66772(12) nm, b=3.36471(16) nm, c=1.1687(4) nm, V=6.558(2) nm3, Z=8, Mr=689.60, Dc=1.397 Mg/m3, R=0.0356, wR2 = 0.0604. 在该配位聚合物中, 中心锰原子采取略微变形的八面体构型, 与两种配体共同构筑了一维直线形链结构, 链与链之间通过氢键相互作用构筑成三维超分子网络.     

Synthesis and Crystal Structure of a New Complex （H3IDC）（Prz）0.5（H2O）

The compound （H3IDC）（Prz）0.5（H2O） （H3IDC = imidazole-4,5-dicarboxylate, Prz = piperazine） has been prepared from a hydrothermal approach and was characterized by IR analysis and X-ray diffraction. Its crystal structure consists of discrete 4,5-imidazole-dicarboxylate, H2O and piperazine molecules. The whole structural motif was assembled by three different non-covalent interactions of O-H…O, N-H…O and π-π stacking, which play an important role in packing the molecules. Interestingly, the connections between imidazole-4,5-dicarboxylate molecule and water molecule result in a helical polymeric chain. Crystal data for compound 1： monoclinic system, space group P21/c, a = 6.4600（13）, b = 19.910（4）, c = 6.9123（14） A^°, β = 94.26（3）°, V= 886.6（3） A^°^3, Z= 4, C7H10O5N3, Mr = 216.18.     

[Gd(OH)(H2O)(b18c6)]I(I3)(CH3CN), a New Cationic In‐cavity Complex with Iodide and Triiodide as Anions

Single crystals of [Gd(OH)(H₂O)(b18c6)]I(I₃)(CH₃CN) were obtained from an acetonitrile solution of GdI₃, I₂ and benzo‐18‐crown‐6. The crystal structure (monoclinic, P2₁/a (no. 14), Z = 4, a = 1233.8(1) pm, b = 1925.0(2) pm, c = 1252.3(1) pm, β = 104.375(7)°) contains hydroxide bridged cationic dimers and iodide as well as triiodide as anions.     

镧系四元混合阴离子配合物[Ln(CCl3COO)2(CH3COO)(Phen)(H2O)]2的合成与晶体结构

在水乙醇溶液中合成了３ 种四元混合阴离子配合物， 用元素分析、ＩＲ、ＵＶ 及单晶Ｘ射线衍射进行了表征。［Ｌａ（ＣＣｌ３ＣＯＯ）２（ＣＨ３ＣＯＯ）（Ｐｈｅｎ）（Ｈ２Ｏ）］２·２ＤＭＦ 晶体属三斜晶系， Ｐ１ 空间群， 晶胞参数：ａ＝ １－２５１０（４） ｎｍ ， ｂ＝ １－３４６０（５） ｎｍ ， ｃ ＝ １－０３４３（３） ｎｍ ， α＝ １０２－４７（３）°， β＝ １０２－３４（２）°， γ＝ １１３－８２（２）°， μ（ＭｏＫα） ＝ ２０．４７ ｃｍ －１ ， Ｚ＝ １， Ｄｃ＝ １－８００ ｇ·ｃｍ － ３ ， Ｆ（０００） ＝ ７８０－００。稀土配合物中醋酸根以桥联方式配位， 三氯醋酸根则有２ 种配位方式， 在二者共同参与配位的体系中呈现出丰富的配位模式。     

一维链状[Mn(9-AC)_2(4,4′-bpy)(H_2O)_2]_n配位聚合物的合成及晶体结构

在水热条件下(120℃),将醋酸锰、4,4′-联吡啶(4,4′-bpy)与9-蒽酸(9-HAC)反应,得到了配位聚合物[Mn(9-AC)2(4,4′-bpy)(H2O)2]n,通过元素分析、红外光谱、X射线单晶衍射对其进行了表征,并用TGA研究了该配位聚合物的热稳定性.结构解析结果表明,该晶体属于正交晶系,Fdd2空间群,a=1.66772(12)nm,b=3.36471(16)nm,c=1.1687(4)nm,V=6.558(2)nm3,Z=8,Mr=689.60,Dc=1.397Mg/m3,R=0.0356,wR2=0.0604.在该配位聚合物中,中心锰原子采取略微变形的八面体构型,与两种配体共同构筑了一维直线形链结构,链与链之间通过氢键相互作用构筑成三维超分子网络.     

La[B5O8(OH)(H2O)]NO3•2H2O的合成与结构

采用熔融硼酸法合成了一种具有层状结构的新型水合稀土多硼酸盐, La[B₅O₈(OH)(H₂O)]NO₃•2H₂O, 并利用单晶X射线衍射技术确定了它的结构. 它属于单斜晶系, P21/n空间群. 其基本构建单元 (fundamental building block, 简称FBB)是由三个BO4和两个BO3基团所构成的一个双三元环[B5O12]基团. 结构中每一个FBB通过共顶点氧原子与周围四个同样的单元连接成具有九元环窗口的二维[B5O10]层, La³⁺位于九元环中心附近. [B5O10]层沿着b方向进行堆积, 硝酸根离子和结构中部分结晶水分子位于相邻的[B5O10]层之间.     

新颖的[CuI(dpq)2]+配合物阳离子修饰的砷钒酸盐[Cu(dpq)2]4[As8V14O42(H2O)]·2H2O的水热合成与结构表征

采用水热方法制备了一个新颖的[CuI(dpq)2]+配合物阳离子修饰的砷钒酸盐[Cu(dpq)2]4[As8V14O42(H2O)]·2H2O, X射线单晶衍射结果表明, 该化合物的结构是由4个[CuI(dpq)2]+阳离子和1个[As8V14O42(H2O)]4-簇阴离子以及2个结晶水组成的, 簇阴离子内部包含一个孤立的水分子.     

二维聚合物[MnNa(Salicylate)2(CH3OH)(H2O)]n·0.5nH2O的合成、晶体结构与活性研究

含锰的过渡金属配合物以其独特的分子结构 ,在功能材料方面显示出潜在的应用价值 [1～ 4 ] .此外 ,锰在许多生物体系中扮演着重要活性反应中心的角色 .例如在光合作用光系统 ( PS )中水氧化中心( WOC)的锰簇合物、含锰过氧化氢酶 ( Mn Catalase)、含锰超氧化物歧化酶 ( Mn SOD     

Synthesis and Crystal Structure of Neodymium Complex with Glycine [Nd(Gly)(H_2O)_7]Cl_3

ＩｎｔｒｏｄｕｃｔｉｏｎＡｐｐｌｉｃａｔｉｏｎｏｆｔｈｅｒａｒｅｅａｒｔｈｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｆｏｕｎｄｉｎｍｅｄｉｃｉｎｅａｎｄａｇｒｉｃｕｌｔｕｒｅ．Ｓｏｔｈｅｒｅｍａｙｂｅｒａｒｅｅａｒｔｈｃｏｍｐｏｕｎｄｓｉｎｐｅｐｔｉｄｅａｎｄｐｒｏｔｅｉｎｃｏｍｐｌｅｘｅｓ．Ｉｔｉｓｉｍｐｏｒｔａｎｔｔｏｕｎｄｅｒｓｔａｎｄｍｏｒｅｃｌｅａｒｌｙｔｈｅｂｏｎｄｉｎｇｏｆｔｈｅｌａｎｔｈａｎｉｄｅｉｏｎｓｉｎｔｈｅｃｏｏｒｄｉｎａｔｉｏｎｃｏｍｐｏｕｎｄｓｗｉｔｈａｍｉｎｏａｃｉｄｓ．Ｓ…     

镧系四元混合配体配合物[Ce(CH2ClCOO)2(NO3)(phen)(H2O)]2的晶体结构、芳环堆积效应和2D氢键网络

The quaternary complex, ［Ce(CH2ClCOO)2(NO3)(phen)(H2O)］2, was synthesized. Interestedly, the title compound is a dimer comparing with the 1D polymer ［La(CH2ClCOO)2(NO3)(phen)*(H2O)］n and powder compound ［Nd(CH2ClCOO)2(NO3)(phen)］. In the title compound there is a monodentate NO-3, which is a first example in the all synthesized quaternary mixed anion complexes, and the NO-3 extended the complex into a 2D network with water from other molecules by inter-molecular hydrogen bonds. The intermolecular hydrogen bonds lead to the weaker Ce—O(COO), Ce—O(NO3) and Ce—N bonds comparing with other quaternary mixed anion complexes of cerium. Also the stacking effect, which makes the compound more stable in the situation of weaker Ce—O and Ce—N bonds, was first found in the series compounds.     

锌配合物Zn(phen)(H2O)(3-mba)2的合成、结构表征及荧光性质

常温下,溶液法合成了一个单核结构的锌配合物Zn (phen)(H2O)(3-mba)2(phen:邻菲咯啉;3-Hmba∶3-甲基苯甲酸),并用红外光谱、元素分析、热重分析以及X射线单晶衍射表征了其结构.结果表明,配合物属于三斜晶系,空间群P1,晶胞参数:a=10.893(2)(A),b=11.461(2)(A),c=11.505(2)(A),α=95.54(3)°,β=115.80(3)°,γ =100.25(3)°,V=1247.9(4) (A)3,C28H24N2O5Zn,Mr=533.86,Z =2,Dc=1.421 g·cm-3,F(000) =552,最终偏离因子[I≥2σ(I)]R1=0.0471,wR2 =0.0954.在配位物分子中,中心锌离子是五配位模式,双分子间先通过O—H…O氢键形成二聚体,继而二聚体间通过相邻分子中的邻菲咯啉芳环的π-π堆积作用沿着a方向形成了一维超分子链.对配合物的荧光性能进行了测试.CCDC 1023439.     

氯代亚乙烯基双噁唑的合成、晶体结构及其电子光谱

由氯代丁烯二酰氯和α－氨基苯乙酮的盐酸盐经缩合、关环反应合成了标题化合物Ⅰ、Ⅱ．用元素分析、紫外光谱、红外光谱、质谱鉴定了其结构，并用Ｘ射线衍射法测定了Ⅰ的晶体结构，其空间群为Ｐ２１，晶胞参数α＝０．８４５０（２）ｎｍ，ｂ＝０．６９９４（１）ｎｍ，ｃ＝１．５４３２（５）ｎｍ，β＝１０２．３８（２）°，Ｚ＝２．由于在烯键碳原子上引入体积较大的氯原子，使Ⅰ和Ⅱ分子的平面性变差，其电子光谱相对于反式－１，２－双［２－５－苯基唑基）］乙烯（ＰＯＥＯＰ）有蓝移，且荧光量子产率明显下降。     

Synthesis and Structural Studies of New (Triphenylphosphine)(trialkoxysilanethiolato)gold(I) Complexes

Compounds of general formula Au{SSi(OR)₃}(PPh₃), R = Prⁱ ( 1 ), Bu^s ( 2 ) or Bu^t ( 3 ), have been obtained by reaction of AuCl(PPh₃) with triethylammonium salts of respective silanethiols, (RO)₃SiSH. Molecular and crystal structures of 1 , 2 , and 3 have been determined by the single crystal X‐ray structural analysis. Compounds 1 and 2 are the first structurally characterized metal derivatives of hydrolytically unstable trialkoxysilanethiols (PrⁱO)₃SiSH and (Bu^sO)₃SiSH.     

Synthesis and crystal structure of a new lapacholate complex with nickel(II), [Ni(Lap)2(DMF)(H2O)]

The crystal and molecular structure of dilapacholateaqua(dimethylformamide)nickel(II) was determined by X-ray diffraction. It crystallizes in the triclinic space group P 1 with a = 9.8671(9) Å, b = 10.654(1) Å, c = 15.289(2) Å, α = 86.98(1)°, β = 79.32(1)°, γ = 87.031(8)°, and Z = two molecules per unit cell. The structure was solved from 5094 reflections with I>2σ(I) and refined by full matrix least-square to an agreement R ₁-factor of 0.0564. The nickel(II) is in a NiO₆ octahedral environment, cis coordinated to two lapacholate anions through their adjacent carbonyl [Ni–O distances of 2.075(2) and 2.066(2) Å], and phenyl oxygens [Ni–O lengths of 2.011(2) and 2.021(2) Å], and to a water [d(Ni–Ow) = 2.073(2) Å] and a DMF [d(Ni–O) = 2.076(2) Å] at axial positions. Some physicochemical and spectroscopic properties of the complex are also reported.     

A New Polymer of Mixed‐Anions Complex [Pb(phen)(O2CCH3)(O2NO)]n (phen = 1,10‐phenanthroline)

The single crystal X‐ray data of a mixed anions complex of Pb^II with 1,10‐Phenantroline, [Pb(phen)(O₂CCH₃)‐ (O₂NO)], shows the complex to be polymeric as a result of acetate ligand bridging. The Pb atom has an asymmetrical eightfold coordination of two nitrogen atoms of the 1,10‐phenanthroline ligand and six oxygen atoms of the nitrate and acetate anions. The arrangement of the 1,10‐phenantroline ligand, acetate and nitrate anions suggest a gap in the coordination around the Pb^II ion, occupied possibly by a stereoactive lone pair of electrons on lead(II) where the coordination around the lead atoms is hemidirected. There is a π‐π stacking interaction between the parallel aromatic rings of an adjacent chain in the compound which might help to increase the ‘gap' in the coordination around the Pb^II ion.