Crystal structure and catalytic studies of heterodinuclear complex [CuZn(μ-OAc)(μ-OH)(μ-OH2)(bpy)2](ClO4)2

The heterodinuclear copper–zinc complex [CuZn(μ-OAc)(μ-OH)(μ-OH₂)(bpy)₂](ClO₄)₂ has been synthesized from solid state reaction and its crystal structure was established. The heterobimetallic complex is quite efficient catalyst for hydrogen peroxide mediated oxidation of alcohols into corresponding carbonyl compounds.     

Synthesis,crystal structure and magnetic properties of one-dimensional cyano-bridged bimetallic complex of [Mn(Me2-bipy)2]3[W(CN)8]2·9H2O

An octacyanotungstate(V)-manganese(II) bimetallic assembly [Mn(Me₂-bipy)₂]₃[W(CN)₈]₂·9H₂O (1) (Me₂-bipy = 4,4′-dimethyl-2,2′-bipyridine) was synthesized in methanol and characterized by X-ray crystallography. X-ray analysis shows that complex 1 is a neutral, one-dimensional (1D) infinite chain polymer. Magnetic data analysis demonstrates a long-range magnetic interaction and two different antiferromagnetic coupling constants obtained by fitting between Mn and W ions in 1.     

Synthesis and crystal structure characterization of Cu ( Ⅰ ) coordinational polymer {Cu(4,4'-bipy)Br}n

利用溶剂热法合成了标题化合物,其结构经元素分析和X-射线单晶衍射表征.标题化合物属于四方晶系,I41/acd空间群,晶胞参数:a=1.4443(4)、b=1.444 3(4)、c=3.855 0(15) nm、V=8.042(4) nm3、Z =32、Mr=299.63 g/mol、Dc=1.980 g·cm-3、μ =6.10 mm-1、F(000) =4 672、R1 =0.029、wR2=0.079、S=1.05.标题化合物中Cu+分别与两个4,4'-联吡啶上一个N原子配位以及两个端基溴原子配位,形成了四面体配位几何构型.分子内Cu…Cu之间的距离为0.282 95 (13) nm.在a+c轴方向,通过4,4’-联吡啶桥联作用形成二维层状网格,层与层通过互穿插形成三维结构.     

Cyano-Bridged Heteropolynuclear Ni(II), Cu(II) and Cd(II) Complexes, [M(deten)2Ni(μ-CN)2(CN)2] n

Three new complexes [M(deten)₂Ni(μ-CN)₂(CN)₂] _n (M = Ni, Cu and Cd, deten = N,N-diethylethylenediamine) have been synthesized and characterized by chemical, thermal analysis, FT-IR and Raman spectroscopies. The crystal structure of the Cd complex has been determined by X-ray single crystal diffraction. Structural study reveals that the Ni²⁺ and Cd²⁺ ions are located on inversion centers, and adopt slightly distorted square-planar and octahedral geometries, respectively. In the crystal structure, the intermolecular N–H⋯N hydrogen bonds link the polymeric chains into a two dimensional network. Vibrational spectral data indicate the presence of two ν(C≡N) for complexes can be assigned to the terminal and bridging cyanides. The decomposition reaction take places in the temperature range 30–1000 °C in the static air atmosphere.     

Synthesis,structure and properties of a new copper (II) complex, [Cu2(4,4′-bpy)5(H2O)4](ClO4)4(4,4′-bpy)(DMF)2(H2O)2

A new copper (II) complex with formula [Cu₂(4,4′-bpy)₅(H₂O)₄](ClO₄)₄(4,4′-bpy)(DMF)₂(H₂O)₂ has been synthesized by reaction of 4,4′-bpyridine (4,4′-bpy) with Cu(ClO₄)₂. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, anion?π and C–H?π interactions are also evident in the structure. The preliminary investigation on the thermal property of the complex is presented.     

Synthesis,crystal structure and magnetic properties of a new 2D cyanide-bridged heterobimetallic Cr(I)–Mn(III) complex

A new two-dimensional cyanide-bridged Cr(I)–Mn(III) coordination polymer {K[Mn(L)]₂[Cr(CN)₅NO]}·CH₃CN (1) (L = N,N-ethylene-bis(3-methoxysalicylideneiminate)) has been successfully synthesized by the reaction of K₃[Cr(CN)₅NO] with [Mn(L)(H₂O)₂]ClO₄ and characterized by elemental analysis, FT-IR and X-ray structure determination. Investigation systematic over magnetic susceptibility of the complex reveals the overall antiferromagnetic interaction between the cyanide-bridged Cr(I) ion and Mn(III) ion and its 3D antiferromagnetic ordering behavior with typical metamagnetic character below 12.5 K.     

First macrocyclic oxamide Cu(II)–Co(II) complex: synthesis,crystal structure and magnetic properties

A oxamido-bridged binuclear complex, [Cu(L)Co(bpy)₂](ClO₄)₂·0.5C₂H₅OH·H₂O has been synthesized, and structurally and magnetically characterized, where L = 1,4,8,11- tetraazacyclotradecanne-2,3-dione and bpy = 2,2^′-bipyridine. In the complex, the copper atom from the macrocyclic oxamido-copper(II) precursor in a square-planar and cobalt atoms in a distorted octahedral environment is bridged by the oxamidate group, Cu⋯Co separation of 5.359 Å. The metal–metal separations are consistent with the sequence of decrease of the ion radius of the metal ion. The magnetic properties of the complex have been investigated. The χ_MT versus T plots is typical of antiferromagnetically coupled Cu(II)–Co(II).     

Synthesis,structure, and properties of two novel copper(II) complexes, [Cu(phen)(L)2]·6H2O and [Cu(phen)3]·(ClO4)2

Two novel copper(II) complexes, namely [Cu(phen)(L)₂]·6H₂O (1) and [Cu(phen)₃]·(ClO₄)₂ (2) have been synthesized under mild condition (HL = 5-methyl-1H-pyrazole-3-carboxylic acid, phen = 1,10-phenanthroline). We report the structural evidence of discrete water decamer conformation in the solid state. These units are found to act as supramolecular glue in the aggregation of mononuclear copper(II) complex to give a three-dimensional network through hydrogen-bonding. The preliminary investigation on the thermal behavior and the anion exchange property of the complexes are presented.     

Synthesis and structure of the pentanuclear mixed-metal cluster [Co4MoCp(μ3-SBut)(μ3-S)(μ3-CO)(μ-CO)2(CO)6]

The pentanuclear mixed-metal cluster [Co₄MoCp(μ₃-SBu^t)(μ₃-S)(μ₃-CO)(μ-CO)₂(CO)₆] (1) has been synthesised by reaction of [CoMoCp(CO)₇] with Bu^tSSBu^t. X-ray structural analysis identified an asymmetric unit with three cobalt atoms and one molybdenum forming an irregular tetrahedron while one cobalt–molybdenum edge is bridged by a cobalt atom. Crystal data: space group P2(1)/n, a=10.162(2), b=13.722(3), c=17.69(5) Å, β=91.44(2)°, Z=4.     

A predesigned 1D chain of alternating di-μ1,1-azido bridged dinuclear Ni(II) and pyrazine: Synthesis,structure and magnetic properties

A new Ni(II) complex, [Ni₂(L)₂(μ_1,1-N₃)₂(pyz)]_n (1) (where pyz = pyrazine) has been synthesized using a dinuclear di-μ_1,1-azido bridged Ni₂ molecular building block derived from a tridentate NNO donor Schiff base ligand, HL (2-[(3-methylamino-propylimino)-methyl]-phenol) along with pyrazine as spacer. Single crystal X-ray analysis shows that complex 1 is a 1D chain in which dimeric Ni₂ units [Ni₂L₂(N₃)₂] are linked to each other by the bridging pyrazine ligand. Variable-temperature magnetic susceptibility studies indicate the presence of moderate ferromagnetic exchange coupling in complex 1 with J value of 53.54 cm^− 1.     

1D zigzag coordination polymer [Cu(tacn)(4,4′-bipy)]n·(ClO4)2n (tacn=1,4,7-triazacyclononane): structure,spectroscopic, and magnetic properties

A new one-dimensional coordination polymer, [Cu(tacn)(4,4^′-bipy)]_n ·(ClO₄)_2n (tacn = 1,4,7-triazacyclononane, 4,4^′-bipy = 4,4^′-bipyridine), has been synthesized and characterized by X-ray crystallography, elemental analysis, IR, electronic spectra, ESR and variable-temperature magnetic susceptibility (4–300 K). The Cu(II) ion is five-coordinated in a distorted square-pyramidal environment to three nitrogens of tacn and two nitrogens from two 4,4^′-bipy ligands. Each 4,4^′-bipy, in which two pyridine rings are slightly twisted, links two [Cu(tacn)]²⁺ units to form 1D zigzag chain. The magnetic behavior shows very weak interaction between metal ions.     

Synthesis and X-ray characterization of the new pentanickel cluster cation [Ni5(μ5-S)(μ3-S)2(μ2-S)(μ-CH3COO)(PPh3)5]+

By reacting Ni(CH₃COO)₂·6H₂O with H₂S in the presence of PPh₃, the new Ni/S cluster of formula [Ni₅(μ₅-S)(μ₃-S)₂(μ₂-S)(μ-CH₃COO)(PPh₃)₅]PF₆·C₇H₈·0.5CH₂Cl₂ has been isolated and characterized by X-ray diffraction analysis. Crystal data: space group P2₁/c, a=15.774(4), b=21.235(7), c=29.288(7) Å, β=95.66(4)°. The inner core consists of a square pyramid of five nickel atoms, linked together by a bridging acetate and four variously bridging sulfur ligands. The ³¹P{¹H} NMR spectra in dichloromethane solution are consistent with the above geometry.     

Synthesis and crystal structure of [Ni{bis(2,5-dihydroxysalicylidene)ethylenediaminato}]: a hydrogen bonded assembly of Ni(II)–salen complex

The hydrogen bonded assembly of salen type complexes was studied. The nickel(II) complex with N,N^′-bis(2,5-dihydroxysalicylidene)ethylenediaminato was synthesized, and structurally characterized. The compound has two hydroxy groups at the both terminals of the tetradentate ligand. One of the two hydroxy groups of the nickel(II) complex forms a hydrogen bond with a coordinating oxygen donor of the adjacent molecule to yield a hydrogen bonded one-dimensional chain. These chains are also associated by π–π interactions with interlocking fashion to produce a two-dimensional structure. The guest ethanol molecules are incorporated between the two-dimensional layers.     

Two novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu2Ln2(ox)(SiW11)2} dimers and [Cu(en)(ox)]/[Cu(en)2] linkers

Two novel 2-D organic–inorganic hybrid silicotungstates [H₂en][Cu(en)₂(H₂O)]₂{[Cu(en)₂]₃[Cu(en)(ox)]₂[Ln₂(ox)(α-SiW₁₁O₃₉)₂]}·nH₂O (Ln = Er^III, n = 10 for 1, Ln = Sm^III, n = 8 for 2) with mixed organic ligands of ox and en (ox = oxalate, en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis (TGA), power X-ray diffraction (PXRD) and X-ray single-crystal diffraction, respectively. Notably, 1 and 2 are isomorphic and exhibit the first novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu₂Ln₂(ox)(SiW₁₁)₂} dimers and [Cu(en)(ox)]/[Cu(en)₂] linkers. Furthermore, the TG curve of 1 and 2 display three steps of weight loss in the range of 25–1000 °C.     

A 2-D polymer constructed through bridging acetate,hydroxo, aqua and bipyridine ligands: crystal structure of {[Cu2(μ-CH3COO)(μ-OH)(μ-H2O)(4,4′-bipy)](2H2O)(SiF6)}n

A novel 2-D coordination polymer constructed by μ₂-acetate-O,O^′, μ₂-hydroxo, μ₂-aqua and 4,4^′-bipyridine (bipy) ligands has been synthesized and structurally characterized. Linear 1-D chain built by bridged μ₂-acetate-O,O^′, μ₂-hydroxo and μ₂-aqua units is composed of Cu₂O₂ motifs and syn-anti bridged acetate ligands. The copper atom with a five-coordination has a distorted square-pyramidal geometry completed by two nitrogen atoms from 4,4^′-bipyridine and three oxygen atoms from acetate, hydroxo and water ligands. The strong stacking effect is observed between 4,4^′-bipyridine ligands.     

Preparation,characterization and X-ray structure of {[(3,2,3-tet)Ni(μ-CO3)Ni(3,2,3-tet)][(3,2,3-tet)Cu]}(ClO4)4: a heteronuclear trimetallic complex containing hydrogen bonds

A heteronuclear trimetallic complex {[(3,2,3-tet)Ni(μ-CO₃)Ni(3,2,3-tet)][(3,2,3-tet)Cu]}⁴⁺ (3,2,3-tet=N,N′-bis(3-aminopropyl)ethylenediamine) has been prepared by the reaction of Ni(II), 3,2,3-tet, Na₂CO₃ and Cu(3,2,3-tet)(ClO₄)₂ in situ. The complex is composed of two units, [(3,2,3-tet)Ni(μ-CO₃)Ni(3,2,3-tet)]²⁺ and [Cu(3,2,3-tet)]²⁺, which are linked by hydrogen bonding. The carbonate ion in the former unit acts as a bis-μ-bidentate ligand and adopts cis arrangement, and the resulting dinuclear complex has cis-β configuration for both Ni(II) ions.     

New dinuclear Pd(II) complex with pyrazolate bridges. Synthesis and crystal structure of [Pd(μ-pz)(pzH)2]2(BF4)2 (pzH=pyrazole)

Dinuclear pyrazolate-bridged Pd(II) complex [Pd(μ-pz)(pzH)₂]₂(BF₄)₂ has been prepared by treatment of pyrazole (pzH), sodium ethoxide, and [Pd(CH₃CN)₄](BF₄)₂. The new complex has been characterised by elemental analyses, IR, ¹H NMR, ¹³C{¹H} NMR, and single crystal X-ray diffraction methods. This structure shows two palladium atoms bridged by two pyrazolate ligands. The square-planar geometry of each Pd atom is completed by two pyrazole ligands. The six-membered dipalladacycle formed by the two Pd atoms and the two bridging pyrazolate ligands adopt a distorted boat-like conformation. This compound is the first example of a dinuclear Pd(II)–pyrazolate homoleptic complex.     

Synthesis,characterization and catalytic properties of a copper complex containing decavanadate nanocluster,Na2[Cu(H2O)6]2{V10O28}·4H2O

A copper complex containing decavanadate nanocluster, Na₂[Cu(H₂O)₆]₂{V₁₀O₂₈}·4H₂O, was prepared by reaction of Cu(NO₃)₂·4H₂O and NH₄VO₃ in an aqueous solution at pH = 4 and its structure was characterized using IR, CV and X-ray crystallography. It was found to be a highly efficient and effective catalyst for the azide alkyne cycloaddition and one-pot three-component (A³) coupling of aldehydes, amines, and alkynes to produce 1,2,3-triazoles and propargylamines respectively in high yields without any co-catalyst or activator.