一维链钴配位聚合物{[Co(H2O)4(3,3′-azpy)](3,3′-azpy)3(PF6)2}n的结构和性质的研究

The complex {[Co(H₂O)₄(3,3′-azpy)](3,3′-azpy)₃(PF₆)₂}_n(3,3′-azpy=3,3′-azobispyridine) has been synthesized and characterized. The crystal (C₄₀H₄₀F₁₂CoN₁₆O₄P₂, M_r=1157.75) belongs to the triclinic system, space group P1 with the following crystallographic parameters: a=10.759(2),b=11.012(2), c=23.207(4)?; α=85.330(10), β=83.470(10),γ=69.770(10)°;V=2560.6(8)?³,D_c=1.502g·cm^-3, μ(MoKα)= 0.498mm^-1,F(000)=1178,Z=2, and final R₁=0.0469, wR₂=0.1053 for observed reflections 5549 (I> 2.00σ(I)).The X-ray analysis reveals that cobalt(Ⅱ) cation coordination environment is a distorted octahedral geometry, the Co²⁺ ion is coordinated by four oxygen atoms of water in the equatorial plane, while the two nitrogen atoms of 3,3′-azpy occupy the axial positions. The complex forms a one-dimensional chain structure via 3,3′-azpy bridging ligand. The one-dimensional chain forms three-dimensional network by hydrogen bonds and π-π inter-actions.     

Crystal structure of metal-organic coordination polymers [Cu(bpy)2(H2O)2](NO3)2·4.5C2H5OH and [Cu2(bpy)(H2O)(L-pha)2](NO3)2·H2O

Two metal-organic coordination polymers [Cu(bpy)₂(H₂O)₂](NO₃)₂·4.5C₂H₅OH (1) and [Cu₂(bpy)(H₂O)(L-pha) ₂](NO₃)₂·H₂O (2) (L-Hpha = L-phenylalanine, bpy = 4,4′-bipyridyl) are prepared by slow evaporation of an aqueous alcoholic solution of copper nitrate, L-phenylalanine, and 4,4′-bipyridyl. The structure and composition of the obtained compounds are determined by single crystal XRD. The framework of compound 1 is positively charged and forms two types of intersecting channels. Compound 2 is a homochiral metal-organic coordination polymer whose structure contains L-phenylalanine anions.     

Solubility in the CaCl2 + Mg(NO3)2 ? Ca(NO3)2 + MgCl2-H2O system

For the first time solubility at 25 and 50°C is studied in the CaCl₂ + Mg(NO₃)₂ ↔ Ca(NO₃)₂ + MgCl₂-H₂O four-component reciprocal water-salt system in order to determine the feasibility of preparing calcium nitrate and magnesium chloride. Original Russian Text ? K.R. Matveeva, O.S. Kudryashova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 7, pp. 1200–1204.     

trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O

Methods for the synthesis of trans-diammino complexes [RuNO(NH₃)₂(NO₂)₂(OH)] (I) and [RuNO(NH₃)₂(H₂O)(NO₃)₂](NO₃)·H₂O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data: space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P2₁; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air. Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009.     

Cu(NO3)2(La(NO3)3)-CO(NH2)2-H2O三元体系的等温溶度研究

本文首次报道三元体系Cu(NO₃)₂-CO(NH₂)₂-H₂O(30℃)和La(NO₃)₃-CO(NH₂)₂-H₂O(25℃)的等温溶度及饱和溶液、折光率,绘制相应的溶度图及折光率-组成图。体系中发现有组成为Cu(NO₃)₂·4CO(NH相似文献   

Synthesis and structural characterisation of the palladium N-heterocyclic carbene cluster complexes [Pd3(μ-CO)3(NHC)3] and [Pd3(μ-SO2)3(NHC)3]

The reduction of trans-[Pd(NHC)₂Cl₂] (NHC = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IⁱPr₂ = 1,3-bis-isopropylimidazol-2-ylidene) with potassium graphite under an atmosphere of CO affords the palladium NHC carbonyl clusters [Pd₃(μ-CO)₃(NHC)₃] (NHC = IMes, 1; IⁱPr₂, 3). Treatment of 1 with SO₂ at room temperature yields the bridging SO₂ complex [Pd₃(μ-SO₂)₃(IMes)₃] (4) in quantitative yield. Complexes 1, 3 and 4 have been structurally characterised by X-ray crystallography.     

Thermal behaviour of the system Fe(NO3)3?·?9H2O–Bi5O(OH)9(NO3)4?·?9H2O–glycine/urea and of their generated oxides (BiFeO3)

Activated carbons (AC), particularly those containing sulphur, are effective adsorbents for mercury (Hg) vapour at elevated temperatures. Activated carbon-based technologies are expected to become a major part of the strategy for controlling mercury emission from coal-fired power plants. Understanding the mechanism of mercury adsorption on sulphur impregnated activated carbons (SIAC) is essential to optimizing activated carbons for better mercury removal efficiency and to developing technologies for the handling of the spent AC. In this work thermal analysis before and after mercury uptake was carried out for the SIAC prepared under various conditions from oil-sand petroleum coke using a simultaneous differential thermal analyzer. Samples were heated at 20°C min⁻¹ under nitrogen in the temperature range from ambient to 1000°C. The DSC curves suggest both endothermic and exothermic changes during heating. The endothermic processes were attributed to evaporation of moisture and other volatile components. The exothermic processes existed in a wide temperature range of 150–850°C likely due to the oxidation reactions between carbon and adsorbed oxygen, oxygen-containing surface groups. The enthalpies of liquid mercury interaction with SIAC at different Hg/AC mass ratio were also measured at 30, 40 and 50°C using a differential scanning calorimeter. The combination of thermal analysis and calorimetry techniques enabled confirmation that the interaction of mercury with SIAC involves both physical and chemical processes.     

Synthesis, properties, and molecular and crystal structure of hexaaquacopper(IV) bis(diaquacuprato-μ3-trihydroxyglutarato)germanate(IV) dihydrate [Cu(H2O)6][Ge(μ3-Thgl)2{Cu(H2O)2}2] · 2H2O

A procedure for the synthesis of the heteropolymetallic germanium(IV) and copper(II) complex with trihydroxyglutaric acid (H₅Thgl) [Cu(H₂O)₆][Ge(μ₃-Thgl)₂{Cu(H₂O)₂}₂] · 2H₂O (I) was developed and the complex was isolated for the first time in the solid state. The product was characterized by elemental analysis, powder X-ray diffraction, thermogravimetry, and IR spectroscopy. Compound I was studied by X-ray crystallography. The crystals are monoclinic, a = 10.216(2)?, b = 12.272(3)?, c = 10.679(2)?, β = 93.13(3)°, V = 1336.9(5)?³, Z = 2, space group P2₁/n, R1 = 0.0261 for 3616 reflections with I > 2σ(I). Compound I is composed of bimetallic [Ge(μ₃-Thgl)₂{Cu(H₂O)₂}₂]²⁻ anions, [Cu(H₂O)₆]²⁺ cations, and water molecules of crystallization. In the centrosymmetric trinuclear complex anion, the Ge(1) atom is bound by two fully deprotonated bridging ligands to two Cu atoms. The Ge(1) atom is coordinated at distorted octahedron vertices by six hydroxyl oxygen atoms of two Thgl⁵⁻ ligands (average Ge(1)-O distance is 1.8874(13)?). The Cu coordination polyhedron in the anion is an extended square pyramid (4 + 1) formed by the bridging hydroxyl oxygen atom (Cu(1)-O(3), 2.0039(12) ?), two carboxyl oxygen atoms (average CU(1)-O distance is 1.9674(14)?) of two Thgl⁵⁻ ligands, and two water oxygen atoms in equatorial and axial positions (Cu(1)-O, 1.9761(13) and 2.3643(14)?, respectively). In the centrosymmetric cation, the Cu coordination polyhedron is an extended square bipyramid (4 + 2). The equatorial Cu-O bond length is 1.9428(14) ? (average), the axial Cu-O bond is elongated to 2.5151(14)?. The cations and anions are combined by H-bonds.     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

Crystal and Molecular Structures of Barium cis(NO2)-trans(N)-Bis(glycinato)dinitrocobaltate(III) Hydrate [Ba(H2O)4][Co(Gly)2(NO2)2]2 · 1.43H2O

Crystals of [Ba(H₂O)₄][Co(Gly)₂(NO₂)₂]₂ · 1.43H₂O (a=8.1917(6) , b=8.4440(4) , c=19.444(1) , =98.189(9)°, Z=2, space group P2/n) contain infinite strips of alternating axially symmetric [Ba(H₂O)₄]²⁺ fragments and two dinitro-bis(glycinato)cobaltate(III) ions. In addition to four oxygen atoms of water molecules, the nearest environment of Ba includes six oxygen atoms of the carboxyl groups of four anions, two of which are also coordinated by the cobalt atoms (Ba-O, 2.77–3.01 ). The nitrite ions do not interact with the Ba²⁺ ions.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 5, 2005, pp. 329–332.Original Russian Text Copyright © 2005 by Zabel, Poznyak, Pawlowski.     

一维聚合物{[Co(N3)2(dps)2]·0.5H2O}n的合成，结构和磁性质

A coordination polymer {[Co(N₃)₂(dps)₂]·0.5H₂O}_n (1) (dps=dipyridin-4-ylsulfane) with one dimensional chains has been synthesized and the structure and magnetic properties were characterized. Complex 1 crystallizes belongs to monoclinic system and has space group P2₁/c. The Co^Ⅱ ion is six-coordinated and located at a compressed octahedral environment due to the Jahn-Teller effect. The ligand of dps bridges between Co^Ⅱ ions producing the infinite chains of Co…Co along a direction and, interestingly, four pyridyl groups of dps ligands form a propeller-shaped coordination geometry around Co^Ⅱ ion with the same spiral within the chain. These 1D chains are further linked through the hydrogen bonds to generate a 3D supermolecular network. Magnetic studies indicated that complex 1 shows very weak antiferromagnetic coupling between Co^Ⅱ ions in low temperature. CCDC: 769596.     

一维梯状配位聚合物{[Cu3(H2O)8(4，4′-bipy)2(smbdc)2]·6H2O}n的合成与晶体结构

In the title complex, {[Cu₃(H₂O)₈(4,4′-bipy)₂(smbdc)₂]·6H₂O}_n, Cu1 and Cu2 have different coordination environment. The 5-sulfo-1,3-benzenedicarboxylic acid (smbdc^3-) ligands form one-dimensional zigzag chains linked by Cu atoms. The two adjacent zigzag chains extend into one-dimensional ladder frameworks bridged by a secondary building unit [Cu(H₂O)4(4,4′-bipy)₂]²⁺. The hydrogen-bond interactions between chains make the complex a three-dimensional open supramolecular network. CCDC: 670975.     

Synthesis, structure, and characterization of a silicotungstate anion-supported organic-inorganic hybrid complex [Zn(2,2′-Bipy)3]1.5[SiW12O40Zn(2,2′-Bipy)2(OH)] · 0.25H2O

A new Keggin-type silicotungstate anion-supported organic-inorganic hybrid transition metal complex, [Zn(Bipy)₃]_1.5[SiW₁₂O₄₀Zn(Bipy)₂(OH)] · 0.25H₂O (I) (Bipy = 2,2′-bipyridine), has been synthesized by the hydrothermal method and characterized by elemental analysis, IR, UV, and EPR spectra, TG-DTA analysis, and single crystal X-ray diffraction. The structural analysis indicates that each structural unit of I consists of one [SiW₁₂O₄₀Zn(Bipy)₂(OH)]³⁻ heteropolyanion, one and a half isolated [Zn(Bipy)₃]²⁺ cations, and a quarter of crystal water molecule. The [Zn(Bipy)₂(OH)]⁺ unit is covalently bonded to one Keggin polyoxoanion [SiW₁₂O₄₀]⁴⁻ in the [SiW₁₂O₄₀Zn(Bipy)₂(OH)]³⁻ cluster. The EPR spectrum indicates the existence of Zn²⁺ with the high-spin state, and TG-DTA analysis exhibits that I has two steps of weight loss and the polyoxoanion framework is collapsed at 618°C.     

配合物[Cr3(μ3-O)(Tc)6(H2O)3]·(NO3)·4H2O的水热合成及晶体结构

通过有限个过渡金属离子如Fe,Ni,Cr,Mn与O、OH、-O或-O2CR等桥联原子或基团键合形成的具有不同尺寸的环形轮状金属离子簇合物或分子簇合物是近年来的研究热点之一[1,2].它们不仅具有独特的结构,而且在催化、非线性光学、分子自组装等方面具有潜在的应用价值[3～5].特别是具有三角型结构的过渡金属-氧轮簇化合物由于可以作为单分子磁体的磁性交换和电子耦合的研究体系,引起了研究人员的极大地兴趣[6,7].研究表明,具有[M(μ3-O)(O2CR)6L3]0/+,(M=Fe3+或Mn3+,L为水或吡啶,R为烷基或芳香基团)结构的化合物具有反铁磁作用[8,9].     

穴状Schiff碱配合物［Gd(NO3)·L］(NO3)2的晶体结构

A new mononuclear gadolinium complex ［Gd(NO₃)·L］(NO₃)₂ of Schiff base cryptand was obtained by condensation of tris (2-aminoethyl)amine with 2,6-diformyl phenol in template procedure. The complex was characterized by elemental analysis, IR, and x-ray single crystal diffraction analysis. Gadolinium is nine-coordinate in trigonal tricapped prism with five oxygen atoms from three phenols and a bidentate nitrate group, and four nitrogen atoms from three imino C=N bonds and a tertiary amine in the cryptand. The complex crystallized in triclinic system space group P1, a=1.0839(2) nm, b=1.2600(4) nm, c=1.7595(4) nm, α=82.09(2)°, β=89.22(2)°, γ=84.06(2)°， V=2.367(2) nm³, Z=2.     

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.     

双核配合物[Cu2(L-Asp)(phen)3(NO3)](NO3)·4H2O的合成及晶体结构

The new complex [Cu₂(L-Asp)(phen)₃(NO₃)](NO₃)·4H₂O (L-Asp=L-aspartic acid and phen=1,10-phenanthroline) has been synthesized and its crystal structure has been determined. The complex crystallizes in the monoclinic with space group P2₁/c, The cell parameters are: a=1.261 3(2) nm, b=1.500 8(4) nm, c=2.230 7(4) nm, β=99.55(1)°, and V=4.164 1(16) nm³，D_c=1.587 g·cm^-3. The complex contains two six-coordinated copper ions, and these two copper ions are connected together by L-aspartate to give rise to a binuclear structure. Hydrogen bonds and π-π stacking interactions are observed in the complex. CCDC: 249250.     

Mixed-ligand complexes [Cd(DMSO)5(NCS)][Cr(NH3)2(NCS)4] · 3DMSO and [Mn(DMSO)4(H2O)2][Cr(NH3)2(NCS)4]2 · 6DMSO · 2H2O: Syntheses and crystal structures

New mixed-ligand coordination compounds[Cd(DMSO)₅(NCS)][Cr(NH₃)₂(NCS)₄] · 3DMSO (I) and [Mn(DMSO)₄(H₂O)₂][Cr(NH₃)₂(NCS)₄]₂ · 6DMSO · 2H₂O (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals of compound I are monoclinic, a = 14.5275(7), b = 23.1692(11), c = 14.6969(6) ?, β = 97.057(2)°, V = 4909.4(4) ?³, space group P2₁/c, Z = 4, ρ_calcd = 1.507 g/cm³, R = 0.0556. The crystals of compound II are triclinic, a = 11.7784(3), b = 12.1760(3), c = 13.1922(2) ?, α = 85.5420(10)°, β = 87.9000(10)°, γ = 70.3680(10)°, V = 1776.46(7) ?³, space group P , Z = 1, ρ_calcd = 1.444 g/cm³, R = 0.0350. Original Russian Text ? E.A. Gerasimova, T.V. Utkina, E.V. Peresypkina, A.V. Virovets, T.G. Cherkasova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 751–755.     

三维多孔配位聚合物{[Zn2(mal)2(4,4'-bipy)(H2O)2]•2(H2O)0.25}∞ (mal＝丙二酸根)的合成、结构及性质研究

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, D_c＝1.811 g/cm³, M_r＝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.     

三维多孔配位聚合物{[Zn2(mal)2(4,4'-bipy)(H2O)2]•2(H2O)0.25}∞ (mal＝丙二酸根)的合成、结构及性质研究

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, D_c＝1.811 g/cm³, M_r＝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.