一个二维Honeycomb-like聚合簇合物 (Et4N)3{[MoS4Cu2(m-CN)]2(m’-CN)}·2MeCN的合成和晶体结构

采用一个预制的簇合物(Et₄N)₂[MoS₄(CuCN)₂]·H₂O(1)和HAc在MeCN中混合反应，生成了一个有趣的二维聚合簇合物(Et₄N)₃{[MoS₄Cu₂(m-CN)]₂(m’-CN)}·2MeCN (2)。通过元素分析，红外光谱及单晶X-射线衍射分析对簇合物2进行了表征。在2的结构中，前驱体1中的MoS₄Cu₂簇核得到了保留，并且此簇核作为三重连接点通过单一氰桥和其他相同的簇核相连，形成一个阴离子型的2D (6,3)（蜂窝状）网络。由预制的簇合物1通过醋酸诱导形成的超分子2表明这种简单的合成方法有可能应用到许多其他相关的体系。     

Synthesis and X-ray crystal structure of the dinuclear copper(I) complex [Cu2((Me-Pk)2En)(PPh3)4](ClO4)2 · 2CHCl3

The new dinuclear copper(I) complex, [Cu₂((Me-Pk)₂En)(PPh₃)₄](ClO₄)₂ · 2CHCl₃ (I), where (Me-Pk)₂En = N,N′-bis(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine), has been synthesized and characterized by elemental analyses, FT-IR, and single-crystal X-ray diffraction method. In this complex, two Cu(PPh₃)₂ units are connected by one (Me-Pk)₂En bridging ligand. The coordination geometry around each copper(I) atom is a distorted tetrahedron formed by two N atoms from (Me-Pk)₂En and two P atoms from the PPh₃ ligands. The distance between two copper atoms is 7.06(1) ?.     

一维链状钴配位聚合物{[Co(4，4′-bipy)(C9H8O3N)2](H2O)4}n的溶剂热合成、晶体结构及热稳定性

One novel coordination polymer {[Co(4,4′-bipy)(C₉H₈O₃N)₂](H₂O)₄}_n with p-acetamidobenzoic acid and 4,4′-bipy has been synthesized. It was characterized as crystallizing in the triclinic space group P1, with: a=1.138 1(2) nm, b=1.165 2(2) nm, c=1.223 3(2) nm, α=88.47(3)°, β=88.00(3)°, γ=65.78(3)°, V=1.478 4(4) nm³, D_c=1.446 g·cm^-3, Z=1, F(000)=670. Final GooF=1.106, R₁=0.041 5, wR₂=0.110 4. The crystal structure shows that the cobalt(Ⅱ) ion is lined with one 4,4′-bipy molecule, forming a one-dimension chain with Z-type structure, which coordinated with two nitrogen atoms of two 4,4′-bipy molecules and four oxygen atoms from two p-acetamidobenzoic acid molecules, giving a distorted octahedral coordination geometry. The result of TG analysis shows that the title complex was stable under 230.0 ℃. CCDC: 741932.     

Synthesis and structure of bismuth complex [n-Bu4N] 2+ [Bi2I8 · 2 Me2S=O]2?

Bismuth complex [Bu₄N]₂⁺[Bi₂I₈ · 2Me₂S=O]²⁻(I) was synthesized by reacting tetrabutylammonium iodide with bismuth iodide. In the cations, an N atom has a distorted tetrahedral coordination (CNC angles change in the range from 107.9(5)° to 111.9(5)°). In the centrosymmetric binuclear anion, octahedral bismuth atoms are bound to each other through the bridging (br) iodine atoms (Bi-I_br, 3.2779(7) ? and 3.3156(9) ?), which are coplanar with four terminal (t) iodine atoms (Bi-I_t, 2.9392(7) ? and 2.9534(8) ?). Two remaining positions near the bismuth atom are occupied by an iodine atom (Bi-I, 3.0079(8) dimethyl sulfoxide (DMSO) molecule (Bi-O, 2.456(5) ?).     

Zr 5Ir 2In 4 – A Superstructure of the Lu 5Ni 2In 4 Type

Zr₅Ir₂In₄ was synthesized by reaction of the elements in a glassy carbon crucible in a water-cooled sample chamber of an induction furnace. The sample was characterized by X-ray diffraction on both powder and single crystals. Zr₅Ir₂In₄ crystallizes with a pronounced Lu₅Ni₂In₄ type subcell, space group Pbam, a=1739.5(6), b=766.3(2), c=338.9(2) pm. Weak additional reflections force a doubling of the subcell c axis. The superstructure of Zr₅Ir₂In₄ is of a new type: Pnma, a=1739.5(6), b=677.8(2), c=766.3(2) pm, wR2=0.0529, 1592 F² values, and 60 variable parameters. The group-subgroup scheme for the klassengleiche symmetry reduction is presented. The formation of the superstructure is most likely due to a puckering effect (size of the iridium atoms). The crystal chemistry of Zr₅Ir₂In₄ is briefly discussed.     

A novel rhenium-aqua structure: the synthesis and structural characterization of (PPh4)4[ReN(H2O)(CN)3-μ-CN-ReN(CN)4]?·?5H2O

A novel cyano bridged rhenium nitrido complex, [ReN(H₂O)(CN)₄-μ-CN-ReN(CN)₄]⁴⁻ (I) was isolated during a kinetic study of the reaction of ReN(H₂O)(CN)₄]²⁻ with pyridine-2,3-dicarboxylic acid. Yellow crystals of (I), suitable for X-ray structure determination were isolated and the structural data showed an unsymmetrical binuclear rhenium complex with a cyano ligand acting as a bridge between two metal atoms, Re(1) and Re(2). The nitrogen of the bridged cyano ligand coordinates trans to the nitrido ligand of Re(1). The rhenium-nitrido bond distances are 1.657(4) and 1.656(5) ? for Re(1)–N(9) and Re(2)–N(10) respectively. Re(1) and Re(2) are displaced from the planes formed by the four carbon atoms of the cyano ligands towards the nitrido ligands by 0.348(2) and 0.3403(2) ?, respectively.     

{[Co(4，4′-bipy)(ambdc)(H2O)2](4，4′-bipy)(DMF)}n合成与晶体结构

A novel coordination polymer of {[Co(4,4′-bipy)(ambdc)(H₂O)₂](4,4′-bipy)(DMF)}_n has been synthesized using 5-aminoisophthalic acid (H₂ambdc), 4,4′-bipyridine(4,4′-bipy) and metal salts. The ambdc ligand in title compound has a μ₂-monodentate coordination mode and the structure of the title compound is a two-dimensional network. CCDC: 279054.     

七配位二聚体配合物{(PhCH2)2Sn·[2,6-(O2C)2C5H3N](CH3OH)}2的合成及结构

在三乙胺存在下利用三苄基氯化锡和2,6-吡啶二甲酸,以1:1摩尔比反应,合成了七配位二聚体{(PhCH2)2Sn[2,6-(O2C)2C5H3N](CH3OH)}2.通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征.用X射线单晶衍射法测定了该化合物的晶体结构.化合物为三斜晶系,P1空间群,晶胞参数a=0.9625(6)nm,b=1.0947(9)nm,c=1.996(3)nm,α=90.00(2)°,β=87.69(3)°,γ=90.00(3)°,Z=2,V=2.102(6)nm3,μ=1.248mm-1,F(000)=1000,R1=0.0476,wR2=0.0782.化合物中2个锡原子呈七配位畸变五角双锥构型.生物活性测试结果表明,该化合物具有较强的体外抗肿瘤活性.     

超分子三维氢键网络：{[Cu(phen)3](SO4)(H3PCA)2(8H2O)}的晶体结构

A new complex， {[Cu(phen)₃](SO₄)(H₃PCA)₂(8H₂O)}， was synthesized and structurally characterized by single-crystal X-ray analysis. The complex is composed of copper cations， sulfate anions， 1，10-phenanthroline， protocatechuic acid and lattice water molecules. The structure of H₃PCA， SO₄^2- and waters comprises packing of anionic three-dimensional network by hydrogen bonds with cavities. The complex can be considered as a model of host/guest supramolecule. The three-dimensional hydrogen-bonding network is the host species. The Cu(phen)₃²⁺ cations， guest species， occupied the cavities of the host. And the results demonstrate that the form of protocatechuic acid at pH< 1 should be free ligand. CCDC： 191733.     

二个新颖的一维聚合物{(PyH)3[Cu3Br6]}∞和{(γ-MePyH)2[Cu2Br4]}∞的合成和晶体结构

Reactions of CuBr with equimolar PyHBr or γ-MePyHBr afforded two novel one-dimensional bromocuprate(Ⅰ)polymers {(PyH)₃[Cu₃Br₆]}_∞ (1) and {(γ-MePyH)₂[Cu₂Br₄]}_∞(2)， respectively. Both 1 and 2 were charac-terized by IR， elemental analysis， and X-ray crystallography. Crystal data for 1: monoclinic， space group P2₁/n， a=0.93262(12)nm， b=1.3497(2)nm， c=1.9149(2)nm， β=93.465(7)°， V=2.4060(5)nm³， Z=4. Crystal data for 2: orthorhombic， space group Pbcm， a=0.8659(4)nm， b=1.5669(6)nm， c=1.2849(5)nm， V=1.7432(2)nm³， Z=4. The structure of 1 has a unique helical chain composed of [Cu₃Br₅] units and μ-bromide anions while that of 2 shows a linear chain consisted of [Cu₂(μ-Br)₂] units bridged by pairs of μ-Br atoms. CCDC: 1， 208412; 2， 208413.     

Crystal structure of [(C5Me4Et)3Rh3(μ3-Se)2](PF6)2CH3CN and [(C5Me4Et)2Rh2(μ2-Cl)3]PF6

The crystal structure of [(C₅Me₄Et)₃Rh₃(μ₃-Se)₂](PF₆)₂ and [(C₅Me₄Et)₂Rh₂(μ₂-Cl)₃]PF₆, obtained in the reaction of [(C₅Me₄Et)Rh(C₆H₆)](PF₆)₂ with ZnSe in 4M HCl under hydrothermal conditions, is determined. In agreement with the 18VE rule, the triangular cluster contains single metal-metal bonds (Rh-Rh 2.864(1) ?), whereas they are absent in the binuclear complex (Rh ...Rh 3,216(1) ?). Original Russian Text Copyright ? 2009 by P. A. Abramov, M. N. Sokolov, A. V. Virovets, and V. P. Fedin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 1, pp. 169–172, January–February, 2009.     

Synthesis of [MoOS3Cu3I(3, 5-diMePy)4]·CH3CN and (Et4>N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] from Solid State Product [Et<

Treatment of iodide bridged dimer [NEt₄]₄[Mo₂O₂S₆Cu₆I₄Br₂] 1 with 3,5-bimethylpyridine or with Kin CH₃CN afforded the tetranuclear cluster [MoOS₃Cu₃I(3,5-diMePy)₄]·CH₃CN 2 and dodecanuclear cluster (Et₄N)₄[Mo₄Cu₈O₄S₁₂{(Ph₂PS)₂N}₄] 3. Monomeric 2 possess a nest shaped skeleton. The structure of oligomeric 3 can be regarded as a tetramer of nest shaped MoCu₃OS₃ groups co polymerized by sharing the limbic Cu atoms.     

Syntheses,structures, and optical properties of heteroselenometallic W–Se–Ag polymer compounds {[Et4N][(μ-WSe4)Ag]}n and {[Ln(Me2SO)8][(μ3-WSe4)3Ag3]}n (Ln = Pr,Er)

The one-dimensional linear polymer W–Se–Ag compound {[Et₄N][(μ-WSe₄)Ag]}_n (1) was obtained from the reaction of [Et₄N]₂[WSe₄] and AgNO₃ in a mixed solvent, MeCN/DMF (1:10). Treatment of a solution of 1 in Me₂SO with Ln(NO₃)₃ · 6H₂O resulted in the formation of a helical chain polymer compound {[Ln(Me₂SO)₈][(μ₃-WSe₄)₃Ag₃]}_n (Ln = Pr 2, Er 3). The solid-state structures of the three polymer compounds 1, 2, and 3 have been established by X-ray crystallography. The third-order non-linear optical properties of the linear polymer compound 1 were determined by z-scan techniques with 7 ns pulses at 532 nm.     

[{Pt4(en)4(NHCOtBu)4}{Tl(18-crown-6)}2](PF6)6的合成与晶体结构

The compound [{Pt₄(en)₄(NHCO^tBu)₄}{Tl(18-crown-6)}₂](PF₆)₆ has been synthesized by a simple one-pot multicomponent reaction. Its structure was determined by X-ray single crystal diffraction analysis. The cation of the compound consists of one linearly arranged [Pt₄(en)₄(NHCO^tBu)₄]⁴⁺ chain and two [Tl(18-crown-6)]⁺ ions located at the two ends of the platinum chain. The complex crystallizes in a triclinic P1 with a=1.060 5(1), b=1.252 3(1), c=2.015(2) nm, α=107.430(2)°, β=91.032(2)°, γ=101.910(2)°, V=2.489 6(4) nm³, Z=2, R₁=0.074 4, wR₂(I>2σ(I))=0.222 5, S=1.062. CCDC: 294083.     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

Investigations on the thermal behaviour of [Ni(NH3)6](NO3)2 and [Ni(en)3](NO3)2 using TG–MS and TR-XRD under inert condition

Thermal behaviour of hexaamminenickel(II) nitrate and tris(ethylenediamine)nickel(II) nitrate have been investigated by means of simultaneous thermogravimetry/DTA coupled online with mass spectral (MS) studies and temperature resolved X-ray diffraction (TR-XRD) techniques under inert atmospheric condition. Both the complexes produce highly exothermic reactions during heating due to the oxidation of the evolved ammonia or ethylenediamine by the decomposition products of Ni(NO₃)₂. Evolved gas analysis by MS studies detected fragments like NH₂ and NH ions with weak intensity. The decomposition of nitrate group generates N, N₂, NO, O₂ and N₂O species. Ethylenediamine (m/z 60) is fragmented to H₂ (m/z 2), N (m/z 14), NH₃ (m/z 17) and CH₂=CH₂/N₂ (m/z 28) species. The formation of the intermediates was monitored by in situ TR-XRD. The residue of thermal decomposition for both the complexes was found to be crystalline NiO in the nano range.     

[Bi2Cl10(H2-Norf)4(H2O)8](H-Norf是诺氟沙星)(英)

The crystal structure of [Bi2Cl10(H2-Norf)4(H2O)8] (1) comprises [H2-Norf]^ cations and [Bi2Cl10]4^- anions, that are loosely associated via H-bonding interactions, as well as water molecules that also participate in H-bonding interactions. Strong blue-fluorescent emission of 1 at solid state is observed at the room temperature. CCDC:238237.     

Synthesis,X-ray crystal structure and thermal decomposition of two peroxovanadium complexes with coordinated ammonia molecules: [{VO(O2)2(NH3)}2{μ-Cu(NH3)4}] and [Zn(NH3)4][VO(O2)2(NH3)]2

The compounds [{VO(O₂)₂(NH₃)}₂{μ-Cu(NH₃)₄}] (1) and [Zn(NH₃)₄][VO(O₂)₂(NH₃)]₂ (2) were prepared and characterized by elemental analysis and infrared spectra. The single crystal X-ray study revealed that the structure of 1 consists of trinuclear complex molecules [(NH₃)OV(O₂)₂{μ-Cu(NH₃)₄}(O₂)₂VO(NH₃)] with a rare heterobimetalic peroxo bridge: copper(II)–peroxo ligand–vanadium(V). The structure of 2 is composed of tetraamminezinc(II) cations and ammineoxodiperoxovanadate(V) anions. In course of thermal decomposition of 1 performed up to 620 °C, the following intermediate products: [Cu(NH₃)₂(VO₃)₂], and subsequently a mixture of V₂O₅ with monoclinic β-Cu₂V₂O₇, were gradually formed. The final product of decomposition is Cu(VO₃)₂. The thermal decomposition of 2 is a two-step process. In the first stage, [Zn(NH₃)₃(VO₃)₂] as supposed intermediate was formed, which transformed at higher temperatures by release of ammonia molecules to the monoclinic modification of Zn(VO₃)₂.     

Synthesis and crystal structure of [Mo3S4(Dppen)3Cl3]PF6 · 1.5CH2Cl2 and [W3S4(Dppe)3Br3]2ZnBr4 · 5.5CH3CN

New cluster complexes [Mo₃S₄(Dppen)₃Cl₃]PF₆ · 1.5CH₂Cl₂ (Dppen = cis-Ph₂PCH=CHPPh₂) (I) and [W₃S₄(Dppe)₃Br₃]₂(ZnBr₄)₂ · 5.5CH₃CN (Dppe = Ph₂PCH₂CH₂PPh₂) (II) were synthesized. Their molecular and crystal structures were determined by X-ray diffraction. Diphoshine ligands in the complexes I and II are coordinated in the bidentate mode, providing an arrangement of three chelate rings, giving rise to chirality.