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)).     

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.      

Synthesis, Structure and Characterization of [Cu(2,2'-bpy)2][{Cu(2,2'-bpy)2}2W12O40(H2)]·4H2O

An organic-inorganic compound [Cu(2,2'-bpy)2][{Cu(2,2'-bpy)2}2W12O4o(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O,2,2'-bipyridine (2,2'-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9)(A), β=96.992(3)°, V= 8365.0(6) (A)3, Dc= 3.214 g/cm3, Z = 4,μ(MoKα) = 17.269 mm-1 and F(000) = 7324.Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR =0.0770 for 11142 observed reflections with I ＞ 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2'-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2'-bpy)2]2 cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2'-bpy)2}2 groups through bridging oxygen atoms.     

A 2D organic-inorganic hybrid [Cu(En)2(H2O)]2[Cu(En)2]4[Si2Cu2W22O78]·7H2O assembled from monocopper(II)-substituted Keggin silicotungstate dimers

The reaction of Na₁₀[A-α-SiW₉O₃₄] · 18H₂O with CuCl₂ · 2H₂O in the participation of ethylenediamine (En) under hydrothermal conditions resulted in a 2D organic-inorganic hybrid monocopper(II)-substituted Keggin silicotungstate [Cu(En)₂(H₂O)]₂[Cu(En)₂]₄[Si₂Cu₂W₂₂O₇₈] · 7H₂O (I), which was structurally characterized by elemental analyses, IR spectrum, UV spectrum, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Single crystal structural analysis shows that adjacent monocopper(II)-substituted Keggin silicotungstate [Si₂Cu₂W₂₂O₇₈]^12? dimeric subunits are interconnected by sharing terminal oxygen atoms to make the 1D polymeric linear chain and neighboring chains are combined with each other through [Cu(En)₂]²⁺ connectors giving rise to an interesting 2D organic-inorganic hybrid sheet architecture with a 4-connected topology. To our knowledge, I is the rare organic-inorganic hybrid 2D polyoxometate constructed by mono-transition-metal substituted Keggin silicotungstate dimeric subunits. The photocatalytic measurement illustrates that I can to some extent inhibit the photodegradation of rhodamine-B.     

[Cu(en)2]2+修饰的二维仲钨酸化合物:[{Na3(H2O)10}2H2{Cu(en)2(H2W12O42)}]·16H2O

利用水热合成法制备了一种基于[Cu(en)2]2+修饰的仲钨酸化合物:[{Na3(H2O)10}2H2{Cu(en)2(H2W12O42)}].16H2O(en=乙二胺)(1),借助元素分析、X射线单晶衍射分析I、R、UV、热分析和X射线光电子能谱对这种化合物进行了结构和性质研究.化合物(1)属于三斜晶系,P-1空间群.晶胞参数为:a=1.183 2(5)nm,b=1.296 0(6)nm,c=1.416 9(6)nm,α=63.348 0(10)°,β=82.844 0(10)°,γ=68.907 0(10)°,V=1.810 0(14)nm3,Z=1,R1[I2σ(I)]=0.024 7,wR2[I2σ(I)]=0.058 2.化合物(1)通过仲钨酸阴离子,铜离子和[Na3(H2O)10]3+三核簇形成了新型的二维层状结构.     

Crystal structure of the coordination polymer [Cu2(S-mal)2(bpy)2(H2O)]·2.5H2O

Journal of Structural Chemistry - In the interaction of basic copper carbonate with optically pure malic acid and 4,4′-bipyridine [Cu2(S-mal)2(bpy)2(H2O)]·2.5H2O (1) is obtained. The...     

Synthesis and crystal structures of supramolecular compounds: [Cu(mpca)2(H2O)] · 3H2O and [Cu2(mpca)2(pyr)4]

A new chelate ligand, 5-methyl-1H-pyrazole-3-carboxylic acid (mpca), has been synthesized. This ligand reacts with cupric sulfate to give two supramolecular compounds [Cu(mpca)₂(H₂O)] · 3H₂O (1) and [Cu₂(mpca)₂(pyr)₄] (Pyr = pyridine) (2), which were characterized by elemental analysis and X-ray crystal diffraction. Helical water chain and strong π–π interaction are important for the stability of the 3-D structure of these supramolecules.     

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.     

Crystal structure of [{Cu(H2O)(en)2}{Cu(en)2}Re6Te8(CN)6]·3H2O

The reaction of Cs₄[Re₆Te₈(CN)₆]·2H₂O with Cu(en)₂Cl₂ in water affords crystals of a cluster complex [{Cu(H₂O)(en)₂}{Cu(en)₂}Re₆Te₈(CN)₆]·3H₂O. The structure of the compound is determined by single crystal X-ray diffraction (a = 10.8082(4) Å, b = 16.5404(6) Å, c = 24.6480(7) Å, β = 92.696(1)°, V = 4401.5(3) ų, Z = 4, space group P2₁/n, R ₁ = 0.0331, wR ₂ (all data) = 0.0652). In the complex, cluster [Re₆Te₈(CN)₆]^4? anions are linked by Cu²⁺ cations into zigzag chains through cyanide bridges. The coordination environment of the copper cations is complemented by ethylenediamine molecules. Each of the cluster anions is additionally coordinated by a terminal fragment {Cu(H₂O)(en)₂}.     

The thermal dehydration and decomposition of Ba[Cu(C2O4)2(H2O)]·5H2O

The thermal behaviour of Ba[Cu(C₂O₄)₂(H₂O)]·5H₂O in N₂ and in O₂ has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (about 80°C), but continues until the onset of the decomposition (about 280°C). The decomposition takes place in two major stages (onsets 280 and 390°C). The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311±30 kJ mol^–1 (or 52±5 kJ (mol of H₂O)^–1). The overall enthalpy change for the decomposition of Ba[Cu(C₂O₄)₂] in N₂ was estimated from the combined area of the peaks of the DSC curve as –347 kJ mol^–1. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the -time curves could be described by the three dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125±4 kJ mol^–1 and (1.38±0.08)×10¹⁵ min^–1, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model withn=5. The other process was slow and could also be described by the contracting-geometry model, but withn=2.The values ofE _a andA were 206±23 kJ mol^–1 and (2.2±0.5)×10¹⁹ min^–1, respectively, for the fast process, and 259±37 kJ mol^–1 and (6.3±1.8)×10²³ min^–1, respectively, for the slow process.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthday     

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.     

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).     

Hydrothermal Synthesis and Characterization of [V16O38(Cl)][Cu(enMe)2]3.5·2H2O Containing {V16O38} Cluster

Compound [V16O38(Cl)][Cu(enMe)2]3.5*2H2O(1) has been hydrothermally synthesized and characterized by means of single-crystal X-ray diffraction, elemental analysis, IR, EPR and TGA analysis. The X-ray crystallography shows that compound 1 contains a new {V16O38} cluster shell, which is connected by [Cu(enMe)2]2 coordination fragments into a 3-D framework. The compound crystallized in a monoclinic system with space group P2(1)/n, M=2235.82, a=1.26076(3) nm, b=2.55802(6) nm, c=2.14742(4) nm, β=90.7380(10)°, V=6.9250(3) nm3, Z=4, F(000)=4418, Dc=2.145 g*cm-3, μ=3.227 mm-1,(Δ/σ)=0.000, S=1.066.     

Synthesis and crystal structure of a 1D chain polyoxometalate-based complex {[CuI(en)2(H2O)]2{GeW12O40[CuII(en)2]} · 2.5H2O} n

A 1-D infinite chain organic–inorganic hybrid compound, [Cu^I(en)₂(H₂O)]₂{GeW₁₂O₄₀[Cu^II(en)₂]}·2.5H₂O, was synthesized hydrothermally and characterized by IR, UV spectroscopy, TG analyses, and single-crystal X-ray diffraction. Structural analysis indicates that neighboring [GeW₁₂O₄₀]^4? polyanions are interconnected by [Cu(3)(en)₂]²⁺ subunits via W–O_t–Cu(3) bridges, generating a 1D infinite chain structure. Furthermore, the compound shows photoluminescence in the solid state at room temperature.     

Copper(II) malonate coordination frameworks with amino-1,2,4-triazole: Crystal structures and magnetic properties of [Cu2(mal)2(datz)2(H2O)]·5H2O and [Cu2(mal)2(atz)2(H2O)]·3H2O

Two new malonato-bridged copper(II) complexes of the composition [Cu₂(mal)₂(datz)₂(H₂O)]·5H₂O (1) and [Cu₂(mal)₂(atz)₂(H₂O)]·3H₂O (2) (mal = malonate, atz = 4-amino-1,2,4-triazole, datz = 3,5-diamino-1,2,4-triazole) are prepared and characterized by X-ray crystal structure determination and magnetic studies. The environment of each copper atom in 1 and 2 has distorted square pyramidal and octahedral geometries. The intrachain copper-copper separation is 6.305 Å and 3.640 Å across the carboxylates and trizolates bridges respectively for complexes 1 and 2. The magnetic properties of 1 and 2 are investigated in the temperature range 2–300 K. The overall antiferromagnetic behavior is observed in both cases.     

Studies on the non-isothermal kinetics of the thermal decomposition of [Cu(NBOCTB)][Cu(NO3)4]· H2O

The thermal decomposition process of the complex [Cu(NBOCTB)][Cu(NO₃)₄] H₂O has been studied by TG and DTG technique, and possible intermediates of the thermal decomposition have also been conjectured from the TG and DTG curves. The results suggest that the decomposition of the complex involves five steps: The non-isothermal kinetics of steps 1, 2 and 3 have been studied by means of the Achar and Coats-Redfern method based on TG and DTG curves. Step 1 is a Coring and Growth mechanism (n= 1), its kinetic equation may be expressed as: d/dt=Ae^–E/RT(1–). Steps 2 and 3 are both two order chemical reaction mechanisms, their kinetic equations can be expressed as: d/dt=Ae^–E/RT(1–)².This project was supported by the National Natural Science Youth Fundation of China.     

Synthesis and Crystal Structure of a Macrocycle [Cu(dadm)(mal)(H2O)]2·2H2O

The reaction of 4,4′-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]2(2H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2)A,Z= 106.75(3)o, V = 1693.5(6)A3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, λ(MoK() = 0.71073A, μ = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and Wr = 0.1244 for 3421 observed reflections with I > 2σ(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3A× 5.9A.     

具夹心结构(Bu4N)7H3［Ru2O(H2O)2(γ-SiW10O36)2］的合成及表征

以γ-［SiW10O36］8-及桥联的K4Ru2OCl10为原料,合成了(Bu4N)7H3［Ru2O(H2O)2(γ-SiW10O36)2］,经红外光谱、电子光谱、顺磁共振、磁化率、循环伏安和核磁共振等的表征,证明标题化合物为两聚夹心结构. 其中,γ-［SiW10O36］8-结构保持不变,填入的Ru—O—Ru为直线型,均保持了原料的基本构型.