Hydrothermal Synthesis and Crystal Structure of One Rare Earth Substituted Keggin-Type Germanotungstate [Cu(en)2]2[Cu(en)2(H2O)]2H3{[Cu(en)2]2[Na2(H2O)1.75][K(H2O)3][Dy2(H2O)2 (GeW11O39)3]} · 6H2O

A novel germanotungstate derivative based on the dysprosium cation and monovacant Keggin anion, [Cu(en)₂]₂[Cu(en)₂(H₂O)]₂H₃{[Cu(en)₂]₂[Na₂(H₂O)_1.75][K(H₂O)₃][Dy₂(H₂O)₂(GeW₁₁O₃₉)₃]} · 6H₂O(en = ethylenediamine) 1, has been synthesized by hydrothermal method and characterized by elemental analysis, IR-UV spectroscopy, thermal analysis and single-crystal X-ray diffraction. In the compound, one kind of clusters with the Dy³⁺/[GeW₁₁O₃₉]^8? ratio of 2:3 was observed. Especially, the 2:3 type displays the novel cluster based on the rare earth and monolacunary Keggin polyoxometalate.     

pH-dependent assembly of saturated to dilacunary Keggin-based silicotungstate: [Cu(en)2(H2O)][H2en]{γ-SiW10O36[Cu(en)2(H2O)]2}·7.5H2O

By controlling the pH of the reaction system, a dilacunary γ-Keggin silicotungstate [Cu(en)₂(H₂O)][H₂en]{γ-SiW₁₀O₃₆[Cu(en)₂(H₂O)]₂}·7.5H₂O (1) (en?=?ethylenediamine) has been hydrothermally synthesized by the reaction of CuCl₂ with α-H₄SiW₁₂O₄₀ and characterized by IR spectra, thermogravimetric analysis, and single-crystal X-ray diffraction. The product is prepared in the pH range 7.9–8.2, which reveals that pH plays a key role in the assembly of saturated α-H₄SiW₁₂O₄₀ to dilacunary [γ-SiW₁₀O₃₆]^8? polyoxometalate. The polyoxoanion {γ-SiW₁₀O₃₆[Cu(en)₂(H₂O)]₂]}^4? of 1 presents a rare [γ-SiW₁₀O₃₆]^8?-retaining structure, in which two lacunary sites of [γ-SiW₁₀O₃₆]^8? are unoccupied, meanwhile, two [Cu(en)₂(H₂O)]²⁺ groups are grafted on either side of the [γ-SiW₁₀O₃₆]^8? unit by Cu–O–W bond.     

Hydrothermal Synthesis and Crystal Structure of [Cu(en)2(H2O)]2{PW11.5Cu0.5O40[Cu(en)2]}·2H2O

A transition metal substituted polyoxotungstate,[Cu(en)2(H2O)]2{PW11.5Cu0.5O40 [Cu(en)2]}·2H2O1 based on Keggin frameworks ,has been hydrothermally synthesized and charac-terized by IR,TGA and single-crystal X-ray structural analysis.It is interesting to find that the structure unit contains two different valence cations,namely,one[Cu(1)(en)2(H2O)] and one [Cu(2)(en)2(H2O)]2 .Data for the crystal:orthorhombic system,space group Pbca,a=21.585(2),b=20.695(2),c=26.137(3)(A),V=11675(2)(A)3,Z=8,Mr=3428.23,Dc=3.901 g/cm3,F(000)=12156,μ(MoKα)=23.932mm-1,the final R=0.0468 and wR=0.0969 for 6927 observed reflections(Ⅰ＞2σ(Ⅰ)).     

A polyoxoniobate based on dimeric hexanionbate: [Cu(en)2]4{[Nb6O19H2]K(H2O)5}2 · (H2en) · 17H2O

A polyoxoniobate, [Cu(en)₂]₄{[Nb₆O₁₉H₂]K(H₂O)₅}₂ ? (H₂en) ? 17H₂O (en = ethylenediamine) (1), has been synthesized and characterized by elemental analysis, IR, XPS, TGA, and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a = 12.3533(16) Å, b = 12.7188(16) Å, c = 29.626(4) Å, α = 93.235(2)°, β = 96.094(1)°, γ = 106.098(2)°, V = 4429.0(10) ų, Z = 2. The polyoxoanion is composed of a Lindqvist-type [Nb₆O₁₉H₂]^6? dimer bi-bridged via two K⁺. K⁺ is 10-coordinate with 10 oxygens, three from one [Nb₆O₁₉H₂]^6?, one from a terminal oxygen of another [Nb₆O₁₉H₂]^6? moiety, and the other six from water molecule. Adjacent dimeric polyoxoanions are linked to form an infinite 1-D chain via O–H ··· O hydrogen-bonding interactions which exist between the two water trimers and the dimeric polyoxoanions.     

Hydrothermal Synthesis and Structure of A Novel Organic–Inorganic Hybrid Polyoxotungstate: H5[Cu(en)2H2O]{Cu(en)2[P2W19O69(H2O)]} · 2.5H2en · 8H2O

Abstract  A novel polyoxotungstate H₅[Cu(en)₂H₂O]{Cu(en)₂[P₂W₁₉O₆₉(H₂O)]} · 2.5H₂en · 8H₂O (1) has been synthesized under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. Crystal data for 1: Triclinic, P-1, a = 12.673(6) ?, b = 20.147(10) ?, c = 20.514(11) ?, α = 110.432(7)°, β = 90.171(5)°, γ = 97.502(6)°, V = 4859(4) ?³, Z = 2. Compound 1 exhibits a 1D linear structure, in which the [Cu(en)₂]²⁺ ions act as the linkages of {P ₂ W ₁₉ } lacunary units. Graphical Abstract  A novel polyoxotungstate H₅[Cu(en)₂H₂O]{Cu(en)₂[P₂W₁₉O₆₉(H₂O)]} · 2.5H₂en · 8H₂O has been made under hydrothermal conditions. Compound 1 exhibits a 1D linear structure based on the {P ₂ W ₁₉ } lacunary units linked by the [Cu(en)₂]²⁺ bridging groups.      

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

混合价配位聚合物{[Cu(en)2]2HPW9ⅥW2ⅤWⅣO40}2-[Cu(en)2H2O]2·8H2O的水热合成与晶体结构

在水热条件下合成了一个新的混合价配位聚合物{[Cu(en)2]2HPW9ⅥW2ⅤWⅣO40}2-[Cu(en)2H2O]2·8H2O,并对其进行了元素分析,IR,UV,TG-DSC等表征.X射线单晶衍射结果表明,化合物属于单斜晶系,P21/c空间群,晶胞参数a=1.88678(12)nm,b=2.30383(14)nm,c=2.61234(16)am,α=90°,β=95.844(1)°,γ=90°,V=11.2964(12)nm3,Z=4,Dc=3.954 g/cm3,R1=0.0975,wR2=0.2041.结构测定结果表明,聚合物中杂多阴离子骨架通过氧桥相连并形成一维无限链.热性质研究表明,形成标题化合物后杂多阴离子骨架分解温度大约在600.4℃,热稳定性较母体杂多酸明显增强.     

[Cu(bpp)2(bpdc)(H2O)2]×2H2O and [Cu(bpp)2](tdc)×7.5H2O的合成、晶体结构和热稳定性

在室温下, 由Cu(NO3)2 、1,3 -二（4 -吡啶基）丙烷(bpp)、4,4 ’ -联苯二甲酸(H2bpdc)和2,5-噻吩二甲酸(H2tdc)制备出两种新型铜( II)配位聚合物[Cu(bpp)2(bpdc)(H2O)2]n·2nH2O, 1 和[Cu(bpp)2]n·n(tdc) 7.5nH2O, 2。两个配位聚合物均为一维线型结构,铜原子均采取变形的八面体结构,在轴线方向上的两个水分子与铜原子存在较弱的配位作用。在配合物1中,两个bpdc羧酸根离子与铜原子配位,而2中的tdc羧酸离子没有与铜原子键合,只是作为反离子平衡电荷。在两个产物中, 配体bpp具有不同的构象。热重分析表明配合物1与2分别在110°C和160°C以下是稳定的。     

[Ni(en)2]6H2[(VO)12O6B18O42]·15H2O的水热合成和晶体结构

在水热的条件下合成了1个多聚钒硼酸盐[Ni(en)2]6H2[(VO)12O6B18O42]15H2O,化学式为C24H128B18N24Ni6O75V12(Mr=3111.62),用单晶X射线衍射方法测定了它的结构,该晶体属三方晶系,R-3空间群,晶胞参数为a=13.942(2)?=96.476(2),V=2653.9(5)?,Z=1,Dc=1.947g/cm3,=21.55cm-1,F(000)=1574,2108个可观察衍射点(I>2(I)),最终结构精修到偏离因子R=0.0594,wR=0.1398,S=1.009。在该化合物的结构中,18员环的B18O42通过18个B(3-O)V键被2个V6O15簇夹在中间,6个[Ni(en)2]基团分别通过2个Ni(3-O)B与B18O42环相连。     

Crystal structure of [Cu2(Edta)(Py)2(H2O)2] · 2H2O and [Cu(Im)6]{;Cu(Im)4[Cu(Edta)(Im)]2} · 6H2O, Products of the interaction of (Ethylenediaminetetraacetato)diaquadicopper(II) with pyridine and imidazole

The crystals of [Cu₂(Edta)(Py)₂(H₂O)₂] · 2H₂O (I) and [Cu(Im)₆]{;Cu(Im)₄[Cu(Edta)(Im)]₂} · 6H₂O (II) were isolated as a result of the reaction of an aqueous solutions of Cu₂(Edta) · 4H₂O with pyridine or imidazole, respectively. The crystals were studied by X-ray diffraction. The crystals of I are monoclinic, a = 12.682 Å, b = 6.788 Å, c = 14.834 Å, β = 91.44°, Z = 2, space group P2₁/n. The crystals of II are triclinic, a = 9.118 Å, b = 14.889 Å, c = 15.130 Å, α = 72.59°, β = 72.94°, γ = 82.54°, Z = 1, space group P{ie241-1}. In the centrosymmetric binuclear complex molecule of I, an N atom and two O atoms of the Edta ligand are coordinated to each Cu atom (Cu-N, 2.046 Å; Cu-O, 1.941 and 1.954 Å). The N atom of the pyridine molecule (Cu-N, 1.993 Å) completes the base of an elongated tetragonal pyramid (4 + 1) with the O atom of the H₂O molecule in the apex (Cu-O(w), 2.244 Å). The crystals of II are built of centrosymmetric complex cations [Cu(Im)₆]²⁺ (Cu(1)-N, 2.469, 2.021, and 2.056 Å), centrosymmetric trinuclear complex anions {;Cu(Im)₄[Cu(Edta)(Im)]₂}^2?, and crystal water molecules. In the anion, the central fragment [Cu(Im)₄]²⁺ (Cu(2)-N, 1.985 and 2.023 Å) is bonded to two peripheral complexes [Cu(Edta)(Im)]^2? through atoms O of the Edta ligand (Cu(2)-O, 2.615 Å). In the [Cu(Edta)(Im)]^2? fragment of the complex anion, the Cu(3) atom is bonded to the Edta ligand through the two N atoms and three O atoms (Cu(3)-N, 1.970 and 2.071 Å; Cu(3)-O, 1.966, 1.969, and 2.238 Å) and with the imidazole molecule, through an N atom (Cu(3)-N, 2.397 Å). The coordination polyhedra of the three copper atoms (Cu(1)-Cu(3)) in the structure of II are elongated tetragonal bipyramids (4 + 2). In the structures studied, Edta^4? is a hexadentate chelating/bridging ligand. However, the coordination mode of the ligand in these structures is different: in the binuclear complex I, the Edta ligand is coordinated to each Cu atom through an N atom and two O atoms with the formation of two chelate rings (symmetric (trans) coordination mode), whereas, in the trinuclear complex II, the Edta ligand is coordinated to the Cu(2) atom through an O atom and to the Cu(3) atom through the two N atoms and three O atoms with the formation of three chelate rings (asymmetric (cis) coordination mode).     

Synthesis of calcium titanate from [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O as a cheap single-source precursor

Calcium titanate (CaTiO₃) was conveniently synthesized by thermal decomposition of a single-source precursor [Ca(H₂O)₃]₂[Ti₂(O₂)₂O(NC₆H₆O₆)₂]·2H₂O at low temperature. This single-source precursor was characterized by elemental analysis, IR spectrum, thermal gravimetric analysis and X-ray single crystal diffraction. The calcined products at different temperature were further characterized by powder X-ray diffractions and IR spectra. The morphology, microstructure, and crystallinity of the resulting CaTiO₃ materials have been characterized by SEM and TEM. The BET measurement revealed that the CaTiO₃ powders had a surface area of 14.0 m²/g. In addition, the microwave dielectric properties of the resulting CaTiO₃ material have been measured.     

新型氨基酸-钨砷多金属氧酸盐K6［Cu(Ala)2*(H2O)2］2［Cu4(H2O)2(AsW9O34)2］*16H2O的合成与晶体结构

The novel amino-acid-containing polyoxometalate K6［Cu(Ala)2(H2O)2］2［Cu4(H2O)2\5(AsW9O34)2］*16H2O was synthesized from the rea ction of K10［Cu4(H2O)2(AsW9O34)2］*20H2O with β-alanine. Its structure has been determined by single crystal X-ray diffraction. It crystallizes in the triclinic space group P1, with a=1.196 3(2) nm, b=1.536 5(3) nm, c=1.591 4(3) nm, α=93.97(3)°, β=110.88(3)°, γ=101.07(3)°, V=2.651 8(9) nm3 and Z=1. Least-squares refinement of the structure leads to R and Rw factors of 0.067 3 and 0.162 8, respectively. An unusual structural feature of the compound is that the polyanion ［Cu4(H2O)2(AsW9O34)2］10- is linked with the amino-acid complex of Cu2+ by a μ-oxygen atom.     

CRYSTAL STRUCTURES OF Cd(H2O)2Cu(CN)3·2H2O,K[Cd(H2O)2Cu2(CN)5]·2H2O AND K2[Cd(H2O)Cu4(CN)8]·1.5H2O. STRUCTURES OF MULTI-DIMENSIONAL FRAMEWORKS FORMED WITH CADMIUM(II), COPPER(I) AND BRIDGING CYANO GROUPS

Abstract

In an attempt to form new multi-dimensional structures of cyano complexes including cadmium(II) and copper(I), four new complexes were obtained successively from an aqueous solution at intervals of from a few days to a few months. The complex 1 obtained first was unstable in the atmosphere. The crystal structures of the other complexes (2–4) obtained from second to fourth were determined by single crystal X-ray structure determinations. Their crystal data are as follows: 2 Cd(H₂O)₂ Cu(CN)₃·2H₂O, monoclinic, C2/m, a = 14.038(1), b = 9.944(1), c = 7.738(1) Å, β = 116.019(7)°, Z = 4; 3 K[Cd(H₂O)₂Cu₂(CN)₅]·2H₂O, triclinic, PI, a = 17.429(9), b = 16.519(7), c = 10.085(5) Å, α = 128.60(3), β = 137.44(2), γ = 45.82(2)°, Z = 4; 4 K₂[Cd(H₂O)Cu₄(CN)₈]·1.5H₂O, monoclinic, C2/c, a = 19.387(2), b = 16.056(3), c = 12.663(2)Å, β = 110.419(9)°, Z = 4. The main structural feature found in the complexes is that the whole framework consists of two networks, a Cd-Cu(I)-CN complex network that has an infinite network formed with bridging cyano groups between the metal atoms and a network formed with hydrogen bonding among water molecules. The second network is connected to Cd in the Cd-Cu(I)-CN complex network via a water ligand coordinated to Cd. In 2 a planar network of [CdCu(CN)₃] complexes are stacked along the c axis and the second network links the stacked complexes. 3 has a stacked structure of [Cd(H₂O)₂Cu(CN)₅]^2? in a bi-layered structure. The second network of 3, which includes K⁺ ions with an electrostatic interaction, spreads over the crystal, penetrating vacant spaces of the metal complex network. 4 has a double lattice structure with a pair of enantiomeric three-dimensional [Cd(H₂O)Cu₄(CN)₈]^2? complexes inter-penetrating each other. There are three structural factors for forming these framwork structures: (1) a non-planar coordination structure for Cd(II) that extends the planar structure of the Cu(I)-CN complex to a three-dimensional structure for the Cd-Cu(I)-CN complex; (2) a trigonal planar coordination structure for Cu(I) that generates vacant space in the metal complex network and makes possible hydrogen bonds to form the second network; (3) structural distortions of bridging cyano groups and a coordination structure of Cu(I) that cause variations of the metal complex network structure.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A POLYMERIC 1,2,4,5-BENZENETETRACARBOXYLATO COMPLEX OF Cu(II) WITH IMIDAZOLE,Cu2(C10H2O8)(C3H4N2)6(H2O)4 · 4H2O

Abstract

The title complex, Cu₂(C₁₀H₂O₈)(C₃H₄O₂)₆(H₂O)₄ · 4H₂O, consists of polymeric copper(II) complex anions and discrete copper(II) complex cations. Benzenetetracarboxyl anions bridge copper(II) atoms coordinated to water and imidazole groups to form the anionic polymeric chains along the a axis, while discrete copper(II) complex cations involving four imidazole and two water ligands are packed between parallel polymeric anionic chains, an extensive H-bonding network linking complex cations and anions.     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

三维超分子配合物Cu2(C6H4O7)·2H2O的合成及其晶体结构

通过Cu(NO3)2·6H2O与柠檬酸自装配合成了新颖的三维超分子配合物Cu2L·2H2O(1,L=C6H4O4),其结构经IR,元素分析和X-射线单晶衍射(XRD)表征.XRD研究表明,1含有奇妙的结构,2个Cu与6个L形成变形的八面体,而每个L又与6个不同的Cu配位,整个几何构架为扭曲三角双锥.1属单斜晶系,P21/c空间群,晶胞参数:a=6.920(4)A,b=9.727(5)A,c=14.487(8)A,β=91.308(10)°,V=974.82(9)A3.Z=4,R1=0.042 5,wR2=0.135 4.     

Synthesis and characterization of hybrid organic-inorganic, dimeric tungstoantimonate, {[Cu(En)2(H2O)]2[Cu4Na2(H2O)2(OH)2](α-SbW9O33)2}6?1

The copper-substituted tungstoantimonate(III) [Cu(En)₂(H₂O)₂]₂[Cu(En)₂(H₂O)]{[Cu(En)₂ (H₂O)]₂[Cu₄Na₂(H₂O)₂(OH)₂][(??-SbW₉O₃₃)₂]} · 3H₂O (I) (En = ethylenediamine) has been synthesized and characterized by IR spectrum, elemental analysis, and XPS. X-ray single-crystal analyses were carried out on I, which crystallizes in the triclinic system, space group P-1, with a = 13.071(2) ?, b = 14.434(2) ?, c = 15.729(2) ?, ?? = 83.004(3)°, ?? = 71.237(2)°, ?? = 74.787(2)°, and Z = 1. The title polyanion consists of two [??-SbW₉O₃₃]^9? trivacant moieties joined together by an annular [Cu₄Na₂(H₂O)₂(OH)₂]^8? unit leading to a sandwich-type structural framework. The central belt of I contains two crystallography unique Cu²⁺ and four disordered Cu²⁺/Na⁺ ions which reduce the symmetry of the polyanion to C _2??.     

一维链状配位聚合物[Cu(en)2]2[Cu(en)2α-AsⅢ8VⅣ14O42(HPO4)]·8H2O的合成与晶体结构

钒氧化合物由于其有趣的阴离子结构和在催化反应、药物化学以及材料科学等领域中的应用而受到人们的关注[1,2].