A Novel Hybrid Solid Constructed from Tetramolybdate and Copper Complexes with Mixed Ligands: [{(Cu·phen)_2(tp)}{(Cu·phen·H_2O)_2(tp)}{Mo_4O_(14)}]

A novel copper molybdate with mixed ligands, [{(Cu·phen)2(tp)}{(Cu·phen·H2O)2(tp)}{Mo4O14}] (phen = 1,10-phenanthroline, tp = terephthalate) 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P21/c with a = 13.1711(7), b = 19.6132(10), c = 13.6910(7) , β = 117.6870(10)°, V = 3131.8(3) 3, Z = 2, C64H44Cu4Mo4N8O24, Mr = 1946.99, Dc = 2.065 g/cm3, F(000) = 1920, μ(MoKα) = 2.198 mm-1, R = 0.0810 and wR = 0.2012 for 4233 observed reflections (I > 2σ(I)). The structural analysis indicates that the title compound contains a discrete tetramolybdate cluster decorated with copper complex fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bond- ing between adjacent layers further extends the compound into a 3-D framework.     

A Novel Copper Ammonium Diphosphate--Dimorphic Cu 3 (NH 4 ) 2 (P 2 O 7 ) 2 ·3H 2 O

This article deals with the insoluble compounds, formed in CuSO 4 -(NH 4 ) 4 P 2 O 7 -H 2 O system. The solutions were analyzed by means of chemical analysis, the precipitate--by means of x-ray diffraction, chemical and thermal analysis, and FTIR spectroscopy. We have established that at least three poorly soluble compounds can form in the system CuSO 4 -(NH 4 ) 4 P 2 O 7 -H 2 O. Their chemical formulae are Cu 2 P 2 O 7 ;5H 2 O and polymorphic Cu 3 (NH 4 ) 2 (P 2 O 7 ) 2 ;3H 2 O. The first modification is most stable when |Cu + P 2 O 7 | = 0.25 M ( n = 1.0), and, in a matter of days, Dimorph A transforms to Dimorph B, which has not been described in any publications.     

{[Cu(phen)2][Cu(phen)(H2O)]2P2Mo5O23}·6H2O:一个基于Strandberg型的多金属氧酸盐

在水热条件下合成了一种新型无机-有机杂化物{[Cu(phen)2][Cu(phen)(H2O)]2P2Mo5O23}.6H2O,通过元素分析、红外光谱、热重分析和X射线单晶衍射方法确定了其晶体结构.结构分析表明:该晶体属于三斜晶系,P1-空间群,晶胞参数a=1.224 54(12)nm,b=1.435 86(14)nm,c=2.009 3(2)nm,α=80.192(2)°,β=74.585(2)°,γ=67.025(2)°,V=3.126 7(5)nm3,Z=2.     

A new cation induced chain-like complex [Cu(H2tea)(H2O)(imi)][Cu(H3tea)(imi)][Na{Mo8O26}] · 4H2O

A new complex [Cu(H₂tea)(H₂O)(imi)][Cu(H₃tea)(imi)][Na{Mo₈O₂₆}] · 4H₂O (H₃tea =triethanolamine, imi = imidazole) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction reveals that β-[Mo₈O₂₆]^4? polyanions are linked by sodium ions to form a chain. The coppers are five- and six-coordinate for [Cu(H₃tea)(imi)]²⁺ and [Cu(H₂O)(H₂tea)(imi)]⁺, respectively. Crystal packing is due to hydrogen bonds and π ··· π stacking interactions, giving a 3-D polymeric network. The magnetic properties of the title compound are also presented.     

Synthesis,structure and property of a new inorganic–organic hybrid compound [Cu(phen)2][Cu(phen)H2O]2[Mo5P2O23]·3.5H2O

A new polyoxomolybdophosphate 1, formulated as [Cu(phen)₂][Cu(phen)H₂O]₂[Mo₅P₂O₂₃]·3.5H₂O (phen = 1,10-phenanthroline) has been synthesized under hydrothermal conditions. Compound 1 crystallizes in the triclinic space group P-1 with a = 12.2429(5) Å, b = 14.3543(5) Å, c = 20.0814(8) Å, α = 80.023 (1)°, β = 74.283 (1)°, γ = 66.452(1)°, V = 3105.8(2) Å³, R₁ = 0.0375, wR₂ = 0.0885, Z = 2 and GOF = 1.009. Compound 1 is constructed from diphosphopentamolybdate clusters coordinated to Cu(II)-phen units, and free water molecules, which are connected to a three-dimensional framework via π–π stacking interactions from the phen ligands. The single-crystal X-ray diffraction, FT-IR, TG-DTA, XPS, EPR and fluorescent spectra for this compound were determined. The electrochemical properties of compound 1 are studied using cyclic voltammogram, the results indicated that the compound 1 shows good electrocatalytic activity to NO₂^?.     

A metal-oxo cluster-supported transition metal complex: synthesis,structure and properties of [Cu(phen)2]2[{Cu(phen)}2Mo8O26]·H2O

[Cu(phen)₂]₂[{Cu(phen)}₂Mo₈O₂₆]·H₂O has been synthesized from MoO₃, H₂MoO₄, Cu(Ac)₂·H₂O and 1,10-phenanthroline in aqueous solution using the hydrothermal method and characterized by single-crystal X-ray structure analysis. The title compound consists of a centrometric β-octamolybdate-supported complex anion [{Cu(phen)}₂Mo₈O₂₆]²⁻, two bis-phenanthroline Cu(I) cations, and one water molecule of crystallization.     

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.     

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 and Magnetic Properties of Copper (Ⅱ) Complexes with Pyridine N-Oxide-2-ylmethy-lidenedithiocarbazate as Ligands

A series of copper (Ⅱ) complexes with pyridine N- oxide- 2- ylmethylidened-ithiocarbazates as ligands were synthesized and characterized by IR spectra, electronic spectra and magnetic moments measurement at room temperature. Variable temperature magnetic susceptibilites (3-300K) of four complexs were measured and fitted with the Bleaney-Bowers dimer equation by considering the magnetic interaction between molecules. The fitting results show the existence of intramolecular ferromagnetic interactions and intermolecu-lar anti-ferromagnetic interactions in these copper( Ⅱ) complexes.     

Hydrothermal Synthesis and Characterization of a Novel Two-dimensional Framework Materials Constructed from Polyoxometalate and Coordination Groups:[H2Mo5.5V10.5O40(PO4)][Cu(en)2]4·7H2O

A novel compound [H2Mo5.5V10.5O40(PO4)][Cu(en)2]4*7H2O(1) was synthesized from V2O5, MoO3, CuCl2*2H2O, en, H3PO4 and H2O in an aqueous solution via the hydrothermal method and characterized by means of single-crystal X-ray diffraction, elemental analyses, IR, EPR spectra and thermal analyses. C16H80Cu4Mo5.5N16O51PV10.5 crystallized in a triclinic system, the space group is P1 with M=2660.63, a=1.283590(10) nm, b=1.289910(10) nm, c=1.387870(10) nm, V=1.80942(2) nm3, Z=2, Dx=4.883 g/cm3, F(000)=2599, μ=6.956 mm-1, (Δ/σ)=0.000, S=1.089. The crystal structure was solved by the direct methods with the final R=0.0752 and wR=0.1988 for 6311 observed reflections with I≥2σ(I). The X-ray crystallography reveals that compound 1 is a novel two-dimensional framework material constructed from the mixed Mo/V polyoxometalate and coordination groups.     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of the Copper(Ⅱ) Complex [Cu4O4(phen)4(ClC6H4COO)2(H2O)2]·(H2O)3

The title complex of copper(Ⅱ) with m-chlorobenzoic acid, 1,10-phenanthroline (phen) and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex: triclinic, space group P, a = 1.06853(12), b = 1.30740(16), c = 1.49546(17) nm, α = 101.791(2), β = 103.413(2), γ = 105.815(2)o, V = 1.8736(4) nm3, Mr = 904.67, Dc = 1.604 g/cm3, Z = 2, F(000) = 924, μ = 1.34 mm-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three water molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.     

Hydrothermal Synthesis of a 1D Paddle-wheel Cu(Ⅱ)Coordination Polymer {[Cu2(NBDOA)2·(H2O)2]·2(H2O)}n Constructed by Flexible Carboxylic Acid

A 1-D paddle-wheel copper (Ⅱ) coordination polymer constructed by 2-nitrobenzene-1,4-di(oxyacetic) acid has been synthesized by hydrothermal reaction, and its crystal structure was determined by X-ray diffraction. The crystal is of triclinic, space group P-1 with a=7.7257(12), b=8.3648(13), c=11.5516(18)(A), α=76.654(2), β=82.088(2), γ=63.636(2)°,C20H22Cu2N2O20, Mr=737.48, V=650.27(18)(A)3, Dc=1.883 g/cm3, F(000)=374, μ=1.737 cm-1 and Z=1. The final refinement gave R=0.0345 and wR=0.0995 for 1996 observed reflections with I ＞ 2σ(Ⅰ). The coordination polymer demonstrates a 1-D microporous structure, and the channel is formed by two NBDOA2- and two Cu2 ions. The ligand NBDOAH2 displays a good flexible characteristic. The 1-D chains are connected to a 3-D supramolecular network by hydrogen bonds.     

Synthesis and X-Ray Crystal Structure of Two Novel Complexes: [M II(phen)3]2V4O12·phen·22H2O(M II=Co, Ni; phen=phenanthroline)

Summary. Two novel compounds, [Co(phen)₃]₂V₄O₁₂·phen·22H₂O (1) and [Ni(phen)₃]₂ V₄O₁₂·phen·22H₂O (2), were prepared from KVO₃–1,10-phenanthroline (phen)–Co(NO₃)₂, resp. NiCl₂–H₂O reaction systems. The compounds 1 and 2 are isomorphous and crystallize in triclinic system, space group P-1. Their crystal structures are formed by two types of layers parallel to 001: a cationic one consisting of [M^II(phen)₃]²⁺ ions and an anionic one containing the cyclic V₄O₁₂ ^4– anions. The solvate phenanthroline and crystal water molecules are located in the cationic and anionic layers, respectively. The IR spectra of 1 and 2 are consistent with the presence of the cyclic V₄O₁₂ ^4– anions in the complexes.Received November 13, 2002; accepted (revised) February 3, 2003 Published online June 2, 2003     

Synthesis and Structure of a Novel Compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O

A novel compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O was synthesized by the reaction of CuSO4(5H2O with H4EDTA in pyridine/water (V/V = 1/4) solvent, and characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 1.26974(6), b = 0.67949(3), c = 1.48548(3) nm, β = 91.454(2)o, V = 1.28122(9) nm3, Z = 2, Dc = 1.673 g/cm3, Mr = 645.56, F(000) = 664, μ(MoKα) = 1.729 mm-1, the final R = 0.0353 and wR = 0.0832 for 1920 observed reflections (I > 2((I)). The compound is a centrosymmetric binuclear molecule with bridged EDTA group. Each Cu(II) atom is linked to two oxygen atoms and one nitrogen atom of EDTA, one oxygen atom of water and one nitrogen atom of pyridine to form a distorted square pyramidal environment. There exist face-to-face π-π stacking interactions between pyridine rings from neighboring molecule with the interplanar distance of 0.3670 nm and hydrogen bonding between EDTA and water molecules.     

Synthesis and Crystal Structure of [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O

The title compound, [Cu(phen)2(SO4)(H2O)]·0.5C4H4O4·7H2O (phen = 1,10-phe-nanthroline and C4H4O4 = fumaric acid), has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P with a = 11.4827(2), b = 11.9086(2), c = 13.77350(10)(A), α = 80.6830(10), β = 66.6480(10), γ = 64.0480(10)o, V = 1554.63(4) (A)3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm3, μ = 0.845 mm-1, F(000) = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections (I > 2σ(I)). The compound contains a six-coordinated copper(II) center, which is surround by four N atoms of two phen ligands (Cu-N distances in the range of 1.997(2)～2.225(2)(A)), one sulfate O atom (Cu-O = 2.0037(17) (A)) and one water O atom (Cu-O(5w) = 2.719(2) (A)) in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.     

Non-isothermal Decomposition Kinetics of Complexes [ Sm(m-MBA)3 phen]2 and [ Sm(o-MOBA)3 phen] 2·2H2O

Introduction In recent years, there has been considerable interest in complexes formed by lanthanide cations and various benzoate derivatives[1-4], due to their potential application in areas, such as extraction, separation,germicide preparation, catalysis, luminescence, and functional material preparation[5].     

Hydrothermal Synthesis and Crystal Structure of a Novel Isophthalate-bridged Copper(Ⅱ) Polymer with Two-dimensional Network Structure: [Cu2(phen)(ipt)2]2n·nH2O (ipt = isophthalate, phen = 1,10-phenanthroline)

A novel metal-organic coordination polymer [Cu2(phen)(ipt)2]2n·nH2O 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 12.338(3), b = 12.167(3), c = 18.167(4)(A), β = 111.686(14)o, V = 2534.1(10) A)3, C28H18Cu2N2O9, Mr = 653.52, Dc = 1.713 g/cm3, μ(MoKα) = 1.740 mm-1, F(000) = 1320, Z = 4, the final R = 0.0443 and wR = 0.0853 for 3543 observed reflections (I > 2σ(I)). It exhibits a novel two-dimensional network with tetra- Cu-ipt- as building units.