二羟基萘二磺酸根构筑的一维链状镉配位聚合物的合成与晶体结构

采用常规溶液挥发法,3,6-二羟基-2,7-萘二磺酸二钠盐(Na2H2dhns)、咪唑(imdz)与Cd(NO3)2·4H2O在甲醇-水溶液中反应合成了一种一维镉配位聚合物{[Cd2(dhns)(imdz)4]·H2O}n(1),并用元素分析、IR、UV、PL和TG等方法进行了表征。经X-射线单晶衍射分析确定了其晶体结构,晶体属单斜晶系,空间群C2/m,晶胞参数a=1.245 97(6)nm,b=1.558 33(9)nm,c=1.629 99(10)nm,β=90.258(6)°,V=3.164 8(3)nm3,Z=4,Mr=831.39,Dc=1.745 g·cm-3,μ=1.534 mm-1,F(000)=1 640,R=0.056 4,wR2=0.140 5,S=1.09。每个Cd髤处于畸变的八面体配位环境,2个八面体共同形成双核金属簇,金属簇经dhns4-四重桥联形成一维配位聚合物。     

基于二羟基萘二磺酸根的配合物Na3[Na5(dhns)2]·(phen)4·2H2O的合成、晶体结构和热稳定性

2,7-二羟基萘-3, 6-二磺酸二钠盐(Na₂H₂dhns)与邻菲罗啉在乙醇/水溶液中自组装得到一新的配合物Na₃[Na₅(dhns)₂]·(phen)₄ ·2H₂O (1),并用CHN元素分析、IR、TGA和X-射线单晶衍射分析进行了表征。晶体属正交晶系, Pna2₁空间群, a=2.829 85(12) nm,b=1.038 99(14) nm, c=2.259 23(13) nm, V=6.642 6(10) nm³, Z=4, D_c=1.573 g·cm^-3, R₁=0.050 6, wR₂=0.124 0, S=1.05。     

一个新的Tutton盐Na2[Co(H2O)6](SO4)2的结构与性能研究

采用溶液法合成了一个新的Tutton盐Na2[Co(H2O)6](SO4)2通过红外光谱和X-射线单晶衍射对其进行了表征.晶体结构分析表明该化合物晶体属单斜晶系,P21/c空间群,晶胞参数:a=0.6185(2)nm,b=1.2334(3)um,c=0.9137(1)nm,β=105.775(1)°,V=0.67078(2)nm3,Z=2.固体粉末紫外可见透射光谱是不连续的,具有较高的透过率和较窄的带宽(300～450 nm).用循环伏安法研究了化合物的电化学性质,发现Na2[Co(H2O)6](SO4)2掺杂氢氧化镍电极片的氧化还原峰电流均有较大提高,电极反应活性明显增加.     

{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.     

吡啶配位的夹心型杂多阴离子{[Na(H2O)2]3[Ni(C5H5N)]3(AsW9O33)2}9-的结构及磁学性质

The pyridine coordinated sandwich-type heteropolytungstate Na7[Ni（H2O）6] { [Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}·28H2O was obtained by the reaction of Na2WO4·2H2O, NaAsO2 and pyridine with NiCl2·6H2O at pH =7.0 and characterized by elemental analysis, IR, UV-Vis,^1H NMR spectra and magnetic measurement. The structure of this heteropolytungstate was determined by X-ray diffraction analysis, which crystallized in triclinic system, space group P1 with a= 1.3153（9） nm, b= 1.7228（12） nm, c=2.6866（19） nm, a=74.130（11）°,β=78.032（12）°, γ = 73.179（12）° and Z= 2, R1 = 0.0604, wR2 = 0.0915 [I〉 2σ（I）]. Polyanion {[Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}^9- has approximately C3 symmetry, and three pyridine coordinated Ni（C5H5N）^2＋ and three Na（H2O）2^＋ are encapsulated between two AsW9O33^9- . Magnetic measurements show that central Ni3 unit in the polyanion exhibits ferromagnetic Ni-Ni exchange interactions （J=6.17 cm^-1）.     

新型大环双核铜配合物[Cu2（H2L）2（SO4）2（H2O）6]·CH3OH·6H2O的合成及其晶体结构与催化性能

H2L[N,N’-二(3-吡啶基)-2,6-吡啶羧酸二酰胺]与CuSO4.5H2O反应合成了新型大环双核铜配合物——[Cu2(H2L)2(SO4)2(H2O)6]·CH3OH·6H2O(1),其结构经IR,XRD和元素分析表征。1属单斜晶系,空间群P21/C,晶胞参数a=26.870(5),b=7.563 7(15),c=28.316(6),α=90°,β=114.91(3)°,γ=90°。1在催化2,6-二甲基苯酚氧化偶联反应时表现出较好的选择性及催化活性。     

双核银配合物[Ag2(μ-(4-MeC6H4O)2PS2)2(Phen)2]的光谱性质和晶体结构

合成了双核银配合物[Ag2(μ-(4-MeC6H4O)2PS2)2(Phen)2](phen为1,10-邻菲咯啉),用元素分析、红外光谱、紫外-可见光谱和热重分析进行了表征,并用X-射线衍射法测定了晶体结构。该晶体属于正交晶系,Pbca空间群,晶胞参数为:a=1.2035(2)nm,b=1.638 3(3)nm,c=2.517 1(5)nm,V=4.963 1(17)nm 3,Dc=1.599 g.m-3,Z=4,F(000)=2 416,μ(Mo Kα)=1.072 mm-1,S=1.066,(Δ/σ)max=0.001,R1=0.037 6,wR2=0.088 8(I>2σ(I))。晶体结构研究表明每个Ag原子与不同配体(4-MeC6H4O)2PS2-的2个S原子和1个phen配体的2个N原子配位形成了具有椅式构型的八元环Ag2S4P2,Ag原子为畸变四面体AgS2N2构型,配合物通过phen的π-π堆积形成了一维结构,分子间的弱氢键C-H…O和C-H…π作用使分子进一步形成了三维网络结构。     

双核Cd(Ⅱ)配合物[Cd2(C22H14N4)2Cl2(N3)2]2·H2O的合成与晶体结构

A dinuclear Cd(Ⅱ) complex [Cdz (N3)2LzCl2]2·H2O (1) [L=4'-(4-eyanophenyl)-2,2':6',2"-terpyridine]was synthesized by reaction of ligand L with CdCl2 and NaN3 using solvothermal method and its structure was determined by X-ray crystal structure analysis. The structure indicates that the complex crystallizes in monoclinic, space group C2/c with a=1.644 5(16) nm, b=1.441 9(12) nm, c=1.9181(18) nm,β=100.349(11)°. V=4474(7) nm3, Z=2, Dc=1.570Mg·m-3,μ=1.120 mm-l, F(000)=2 100, and final R1=0.039 3, wR2=0.0811. The result shows a Cd(Ⅱ) ion was sixcoordinated by a tridentate 4'-(4-cyanophenyl)-2,2' :6',2"-terpyridine ligand and one bridging nitrogen atom of the azide group in the basal position and an chloride atom and the other bridging nitrogen atom of the azide group in the axialone, to form a distorted octahedral-pyramidal geometry. CCDC: 673291.     

以哌嗪为模板剂的二维层状硫酸铈[C4N2H12]3[Ce2(SO4)6(H2O)2]·H2O的水热合成与晶体结构表征

以哌嗪为模板剂, 在水热条件下合成了一个新的具有二维拓展骨架结构的稀土硫酸盐[C4N2H12]3[Ce2(SO4)6(H2O)2]·H2O, 并对其进行了结构表征和热分析. 单晶结构解析结果表明, 该化合物晶体属于单斜晶系, P21/c空间群, 晶体学参数a=0.66335(10) nm, b=2.8088(4) nm, c=1.02212(15) nm, β=96.160(2)°, V=1.8935(5) nm3, R1=0.0466, wR2=0.1226. 该化合物由[—Ce—S3—Ce—S1—Ce— S3—Ce—S1—]八元环连接形成二维层状结构, 无机层间通过氢键连接成三维无限结构.     

低温下Na //Cl-,SO42-,NO3-,H2O体系相平衡研究

采用等温溶解平衡法研究了四元体系Na+//Cl-,SO42-,NO-3-H2O在5、0、-5与-15℃下的相平衡关系。结果表明,4个温度下体系无复盐形成,平衡相图的构型基本一致;平衡相图均由3个结晶区(Na2SO4·10H2O、Na Cl和Na NO3)、3条单变量曲线(Na Cl-Na2SO4·10H2O、Na Cl-Na NO3、Na NO3-Na2SO4·10H2O)及1个共饱点(Na Cl-Na NO3-Na2SO4·10H2O)组成;4个温度下的平衡相图相比,随着温度的下降Na2SO4·10H2O结晶区不断扩大,Na Cl和Na NO3结晶区相对缩小;与该体系常温下的平衡相图相比,由于无复盐形成,低温下的相图大为简化。     

Synthesis, structural characterization and properties of a 3D infinitely extended structural rare earth coordination compound of K3{[Sm(H2O)7]2Na[α-SiW11O39Sm(H2O)4]2} · 14 H2O· 14 H2O

A 3D infinitely extended structural rare earth coordination compound with a formula of K₃{[Sm(H₂O)₇]₂Na[α-SiW₁₁O₃₉Sm(H₂O)₄]₂}·14H₂O has been synthesized by reaction of Sm₂O₃, HClO₄, NaOH with α-K₈SiW₁₁O39·nH₂O, and characterized by IR, UV spectra, ICP, TG-DTA, cyclic voltammetry, variable-temperature magnetic susceptibility and X-ray single-crystal diffraction. X-ray single-crystal diffraction indicates that the title compound crystallizes in a triclinic lattice, Pī space group, with a = 1.2462(3) nm, b = 1.2652(3) nm, c = 1.8420(4) nm, α = 87.45(3)°, β = 79.91(3)°, γ= 82.57(3)°, Z = 1, R₁ = 0.0778, wR₂ = 0.1610. Structural analysis reveals that Sm³⁺(1) coordination cation has incorporated into the vacant site of [α-SiW11O₃₉]⁸⁻ entity, forming the [α- SiW₁₁O₃₉Sm(H₂O)₄]⁵⁻ subunit. The two adjacent [α-SiW₁₁O₃9Sm(H₂O)4]⁵⁻ subunits are combined with each other through two Sm(1)-O-W bridges accompanying the formation of dimmer structural unit [α-SiW₁₁O₃₉Sm(H₂O)₄]₂ ¹⁰⁻ of the title compound. The neighboring dimmer structural units [α-SiW₁₁O₃₉Sm(H₂O)₄]₂ ¹⁰⁻ are linked to form the 1D chainlike structure by means of two Sm³⁺(2) and a Na⁺(1) coordination cations. The K⁺(1) cations connect the 1D packing chains constructing the 2D netlike structure, and adjacent netlike layers are also grafted by K⁺(2) cations to build the novel 3D infinitely extended structure. The result of TG-DTA curves manifests that the decomposition temperature of the title polyanionic framework is 554°C. The cyclic voltammetry measurements show that the title polyanion has the two-step redox processes in aqueous solution with pH = 3.1. Variable temperature magnetic susceptibility indicates the title compound obeys the Cruie-Weiss Law in the higher temperature range from 110 to 300 K, while in the lower temperature range from 2 to 110 K the comparatively strong antiferromagnetism interactions can be observed.     

Synthesis, crystal structure and photoluminescence of a novel tetra-nuclear calcium complex [(Ca(C15H8O7S)-(H2O)(DMSO))3(Ca(C15H8O7S) (DMSO)2]·4DMSO

The sulfonate derivate of chrysin coordinates with Ca²⁺ to form a novel tetra-nuclear calcium complex [(Ca(C₁₅H₈O₇S)(H₂O)(DMSO)₃(Ca(C₁₅H₈O₇S)(DMSO)₂]·4DMSO. The structure of the complex is characterized by IR,¹H NMR and X-ray single-crystal diffraction analysis. The results show that the complex crystallizes in triclinic, space group PĪ, cell parametera = 1.4725(6) nm,b = 1.6480(7) nm,c = 2.1006(8) nm, α = 83.928(7)°, β= 85.938(7)°, γ= 85.212(7)°,V = 5.041(3) nm³,Dc = 1.476 g/cm³,Z = 2, μ=0.568 nm⁻¹,F(000) = 2324,R = 0.0778,wR = 0.1821. In the complex, four Ca²⁺ which are bridged by four 5-hydroxyanion-7-dihydro-xyfla-vone-6-sulfonate ligands with their carbonyl and 5-hydroxyanion group build an approximate square. The coordination number of Ca²⁺ is 7 and the coordinated atoms are all oxygen from the carbonyl, hydroxyl and suflo-group of 5-hydroxyanion-7-hydroxyflavone-6-sulfonate, H₂O and DMSO. Four ligands locate on two sides of the square. Two of them on the same side are almost paralleled and aromatic п-п stacking exists between them. Ligands on the opposite side are nearly perpendicular to each other. Meanwhile, the solid of title compound has the photoluminescent phenomenon. The title compound emits green fluorescence (λ_em = 520 nm) when it is excited at the wavelength of 410 nm and its photoluminescent mechanism is discussed.     

Synthesis and structural characterization of 2-pyrazinecarboxylate zinc compound {[Zn2(Pyz)2(H2O)4] · SO4}n (Pyz = 2-pyrazinic acid)

A solvothermal reaction of 2-pyrazinic acid with Zn(SO₄)₂ · 7H₂O yielded the title complex of the formula {[Zn₂(Pyz)₂(H₂O)₄] · SO₄} _n (I). X-ray diffraction study shows that the complex I crystallizes in mono-clinic system, space group P2₁/c, with lattice parameters a = 11.2687(6), b = 7.3511(4), c = 11.8506(7) ?, β = 95.070(2)°, V = 977.83(9) ?³, Z = 4, and ρ_calcd = 2.184 mg m⁻³.     

NASICON型Na4FeV(PO4)3的合成、晶体结构和电化学性能

采用高温熔盐法制备了NASICON型Na_4Fe V(PO_4)_3单晶。单晶X射线衍射数据分析表明,Na_4Fe V(PO_4)_3属于六方R3c空间群,单胞参数为a=b=0.878 17(4) nm,c=2.170 1(2) nm,Z=6,V=1.449 31(18) nm~3。该磷酸盐属于典型的NASICON结构,由PO_4四面体和Fe/VO_6八面体共顶点组成三维框架结构,提供多维的Na~+传输通道,2种不同类型Na~+位于框架的间隙。以Na_4Fe V(PO_4)_3/C粉末样品作为钠电池正极材料并以金属钠为对电极制备电池时,电化学测试结果表明其具有较高的容量。     

Structure of [RuNO(NH3)3(H2O)Cl](NO3)2, product of interaction between hydroxonitrotriamminenitrosoruthenium(II) chloride and nitric acid

The structure of the product formed on boiling [RuNO(NH₃)₃(NO₂)(OH)]Cl·0.5H₂O in 3 M HNO₃ is determined by XRD. The crystals belong to monoclinic symmetry. Crystallographic data for H₁₁ClN₆O₈Ru are: a = 13.7924(4) ?, b = 6.9114(2) ?, c = 12.3577(4) ?, β = 111.863(1)°, V = 1093.27(6) ?³, Z = 4, d _calc = 2.185 g/cm³, space group Cc. The structure is built of complex [RuNO(NH₃)₃(H₂O)Cl]²⁺ cations and NO₃⁻ anions. The compound is studied by IR spectroscopy and X-ray phase analysis. Original Russian Text Copyright ? 2009 by V. A. Emel’yanov, E. V. Kabin, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 598–601, May–June, 2009.     

Synthesis and characterization of [Zn(2,2′-bipy)]2(H2PO3)4: A neutral zinc phosphite cluster containing ZnO3N2 and H2PO3 units

The hydrothermal synthesis, crystal structure and some properties of a zinc phosphite with a neutral cluster, [Zn(2,2′-bipy)]₂(H₂PO₃)₄, are reported. This compound crystallizes in the triclinic system of space group P-1 (No. 2), a=8.3067(5) Å, b=8.9545(4) Å, c=10.0893(6) Å, α=95.448(2)°, β=99.7530(10)°, γ=103.461(2)°, V=712.23(7) ų, Z=1. The cluster consists of 4-membered rings formed by alternating ZnO₃N₂ square pyramids and H₂PO₃ pseudo pyramids, with two “hanging” H₂PO₃ groups attached to each of the Zn centers. The clusters are linked together by extensive multipoint hydrogen bonding involving the phosphite units to form a sheet-like structure. This compound represents the first example of zinc phosphite with P---OH bonds. An intense photoluminescence was observed from this compound upon photoexcitation at 388 nm.     

Hydrothermal synthesis and characterization of layered vanadium phosphite: [HN(C2H4)3N][(VO)2(HPO3)2(OH)(H2O)]·H2O

A novel compound, [HN(C₂H₄)₃N][(VO)₂(HPO₃)₂(OH)(H₂O)]·H₂O, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. This compound crystallizes in the monoclinic system with the space group C2/c and cell parameters a=11.0753(3) Å, b=17.8265(6) Å, c=16.5229(5) Å, and β=92.362(2)°. The structure of the compound consists of vanadium phosphite layers which are built up from the infinite one-dimensional chains of [(VO)(H₂O)(HPO₃)₂]²⁻ of octahedral VO₅(H₂O) and pseudo pyramidal [HPO₃], and bridging binuclear fragments of [VO(OH)]₂. Thermogravimetric analysis and magnetic susceptibility data for this compound are given.     

The Thermal Dehydration of Magnesium Aluminum Pentafluoride Dihydrate: Crystal Structures of MgAlF5(H2O)2 and MgAlF5

 Small plate-like single crystals of MgAlF₅(H₂O)₂ have been obtained during hydrothermal treatment (270°C) of microcrystalline material prepared by precipitation of stoichiometric solutions of Al₂(SO₄)₃ ·  18H₂O and Mg(NO₃)₂ · 6H₂O with diluted hydrofluoric acid. The crystal structure of MgAlF₅(H₂O)₂ has been refined from single crystal data (Imma (# 74), Z = 4, a = 7.0637(7), b = 10.1308(10), c = 6.7745(7) ?, 398 structure factors, 33 parameters, R(F² > σ(F ²)) = 0.0245, wR(F² all) = 0.0525). Main features of the inverse weberite type structure are infinite chains of trans-bridged [AlF₆] octahedra which are connected via common fluorine atoms by isolated [MgF₄(H₂O)₂] octahedra. MgAlF₅(H₂O)₂ dehydrates at temperatures above 300°C to give MgAlF₅. XRPD analysis of this phase has revealed isotypism with FeAlF₅. The crystal structure of MgAlF₅ (Immm (# 71), Z = 2, a = 7.268(1), b = 6.123(2), c = 3.543(1) ?) is built of infinite chains of edge-sharing [MgF₆] octahedra and chains of corner-sharing [AlF₆] octahedra along [001]. Upon further heating to temperatures above 500°C, MgAlF₅ decomposes to MgF₂ and α − AlF₃.     

Heteropoly Complexes Na0.5Cs2 ? x[H0.5 ? xM

Crystals of novel heterepoly complexes (HPC) Na_0.5Cs_{2 − x} [H_{0.5 − x} M _x ^II X^III(OH)₆Mo₆O₁₈] · 7−8H₂O (M^II = Fe, Mn; X^III = Cr, Al) are synthesized. Crystal structures of the complexes Na_0.5Cs_{2 − x} [H_{0.5 − x} Fe_xCr(OH)₆Mo₆O₁₈] · 7H₂O (I) (x = 0.19) and Na_0.5Cs_{2 − x} [H_{0.5 − x} Mn_xAl(OH)₆Mo₆O₁₈] · 8H₂O (II) (x = 0.22) are determined (space group Pbcn, Z = 8, a = 23.023(4) Å, b = 22.064(4) Å, c = 11.606(3) Å, V = 5895.66 ų for I and a = 22.972(9) Å, b = 22.002(8) Å, c = 11.543(5) Å, V = 5834.18 ų for II, respectively). The [X^III(OH)₆Mo₆O₁₈]³⁻ ligands were found to be coordinated in monodentate fashion to M atoms due to the participation of a terminal O atom of the cis-MoO₂ group in coordination with the Fe and Mn atoms, which was confirmed by IR data. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 9, 2005, pp. 663–676. Original Russian Text Copyright ? 2005 by Gavrilova, Molchanov.