Solvothermal syntheses of high-nuclearity vanadium(III) clusters

Superheating alcohol solutions of simple trimetallic vanadium(III) precursors gives the octa- and decametallic vanadium(III) clusters [V(8)(OEt)(8)(OH)(4)(O(2)CPh)(12)] (1) and [V(10)(OMe)(20)(O(2)CMe)(10)] (2). Cluster 2 is the largest vanadium(III) cluster synthesised to date. Thus solvothermal synthetic techniques are an excellent route to high-nuclearity vanadium(III) clusters. Both 1 and 2 consist of a planar or near-planar array of V(III) ions. The metal ions in 1 are bridged by either a micro(2)-hydroxide and two micro(2)-benzoate groups or two micro(2)-ethoxides and a micro(2)-benzoate groups, the two bridging arrangements alternating around the ring. In 2 each pair of neighbouring metal ions is bridged by two micro(2)-methoxides and a micro(2)-acetate, and this molecule is the V(III) analogue of Lippard's famous "ferric wheel". Preliminary magnetic susceptibility studies show the exchange coupling in both complexes to be antiferromagnetic in nature, with the coupling stronger in 1 than in 2.     

Synthesis,characterization and antimicrobial activity of a Zn(II) complex with 1-(1H-benzoimidazol-2-yl)-ethanone thiosemicarbazone

A new Zn(II) complex with 1-(1H-benzoimidazol-2-yl)-ethanone thiosemicarbazone [Zn(NO₃)(H₂O)(C₁₀H₁₁N₅S)]NO₃ was prepared and characterized by elemental analyses, FT-IR, ¹H NMR spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and single-crystal X-ray diffraction analysis. The coordination geometry of the pentacoordinated zinc is a distorted square pyramid. The antimicrobial activity of the complex was evaluated using a broth micro-dilution method against a panel of human pathogenic Gram positive, Gram negative bacteria and the yeast Candida albicans. The best inhibitory effect was observed against Enterobacter aerogenes (MIC = 0.031 mg mL^?1).     

Solvothermal syntheses and structures of indium(III)-binaphthalenyl dicarboxylate complexes with yellow/blue luminescence

Two novel In(III) complexes, [In(bna)(Hbna)]_n (1) and [In₂(bna)₂(μ₂-OH)₂]_n·4nH₂O (2) (H₂bna=2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylate acid), have been reported. Complex 1 adopts a 2D layer structure, where each layer composed from homochiral ligands is chiral while the ligands in two neighboring layers are enantiomer. Complex 2 is constructed by individual -In-O-In- chains, which are further connected by bna²⁻ into a 3D honeycomb framework. As a derivative of H₂bna ligand, dmbna (3) was recrystallized for structurally comparison with 1-2 (dmbna=dimethyl 2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylate). X-ray powder diffractions (XRD) and thermogravimetric analyses (TGA) for 1-2 show that they are highly thermally stable in the solid state. Complexes 1 and 2 exhibit the intense yellow luminescence at 573 nm and blue luminescence at 459 nm at room temperature, respectively. And an astonishing blue shift of 105 nm is observed for complex 1 when it is measured at 10 K.     

Polynuclear Cu(II), Ni(II) and Cd(II) coordination compounds with bis(pyrimidin-2-yl)amine and dicyanamide

In this study the synthesis, crystal structure and characterization of three new transition metal polynuclear compounds with formula [Cu(dipm)(μ-dca)₂]_n(H₂O) (1), [Ni(dipm)(μ-dca)₂]_n(C₂H₆O)_1/2 (2) and [Cd(dipm)(μ-dca)₂]_n (3) (in which dipm = bis(pyrimidin-2-yl)amine and dca = dicyanamide) are reported. The isostructural compounds 1 and 2 contain a double-bridging end-to-end dca unit connecting two metal ions and a single bridging end-to-end dca unit between subsequent metals. Compound 3 exhibits only single bridging end-to-end dca units, oriented in three directions, giving rise to a 3D framework.     

Self-assembly of three Cd(II) complexes: 0-D, 1-D,and 3-D structures based on 2-(1H-imidazol-1-methyl)-1 H-benzimidazole

Three new complexes, [Cd(L)I₂]₂ (1), {[Cd(L)I₂]?·?DMF} _n (2), and [Cd₂(L)₄(μ ₂-I)I(H₂O)] _n (3), have been obtained through self-assembly of an unsymmetrical ligand 2-(1H-imidazol-1-methyl)-1H-benzimidazole (L) with Cd(II) salts. Single-crystal X-ray diffraction shows that 1 displays a dimeric structure in which two Cd(II) ions are bridged by two bidentate bridging L. Complex 2 exhibits a 1-D chain structure (···Cd–L–Cd–L···) constructed by L bridging Cd(II) ions. In 3, the Cd(II) ions are five-connected nodes and linked by L and iodide leading to the 3-D network. Complexes 2 and 3 are synthesized maintaining the same solvents and stoichiometric ratio of metal and ligand at different reaction temperature. The different structures of the complexes indicate that the temperature plays a significant role in construction of the complexes. Luminescent properties of 1–3 have been investigated in the solid state at room temperature.     

Six novel complexes based on 5-Acetoxy-1-(6-chloro-pyridin-2-yl)-1H-pyrazole-3-carboxylic acid methyl ester derivatives: Syntheses,crystal structures,and anti-cancer activity

A novel 5-Acetoxy-1-(6-chloropyridin-2-yl)-1H-pyrazole-3-carboxylic acid methyl ester derivatives Htcdodtta (1), and it’s five complexes, [Cu₂(L¹)₂]·(CH₃CN) (2), [Cu₂(L²)_1.63(L³)_0.37]·(CH₃OH)_0.5 (3), [Cu₂(L³)(L⁴)]·(C₂H₅OH)_0.5·(CH₃OH)_0.5 (4), [Cu₂(L⁴)(L⁵)]·(H₂O) (5) and [Cu₂(L¹)_1.18(L²)_0.82] (6) have been synthesized. The Htcdodtta, HL¹-HL⁵ were formed in-situ reaction. HL¹-HL⁵ are homologues which possess two chiral carbons. Compounds 1–6 were characterized using single-crystal X-ray diffraction, IR, and elemental analysis. Compounds 2–6 are dinuclear copper complexes. The in vitro cytotoxicities of compounds 1–4 against a variety of cell lines were evaluated by MTT assays. Hela cancer cell apoptosis assay of 1 and 2 were examined by flow cytometry. The cell apoptosis in NP69, A549, Capan-2, Hela, HepG2, and HUVECs cell lines induced by compound 2 was further affirmed by cellular morphology observations.     

Solvothermal syntheses and crystal structures of new Cu(II) complexes with phenylsuccinic acid

Five new Cu(II) complexes [Cu(psa)(phen)] · 3H₂O (1), [Cu(psa)(2bpy)] · 0.5H₂O (2), [Cu(psa)(2bpy)(H₂O)] · 3H₂O (3), [Cu(psa)(4bpy)] · H₂O (4), and [Cu(psa)_0.5(N₃)(2bpy)] (5) (H₂psa = phenylsuccinic acid, phen = 1,10-phenanthroline, 2bpy = 2,2′-bipyridine, and 4bpy = 4,4′-bipyridine) were obtained under solvothermal conditions and characterized by single-crystal X-ray diffraction. Complexes 2 and 3 were formed by one-pot reaction. In complex 2, Cu(II) ion is four-coordinated and locates at a slightly distorted square center. In complex 3, the coordinated water molecule occupies the axial site of Cu(II) ion forming a tetragonal pyramid geometry. Complexes 1 and 3 are of 1D chain structures, and extended into 2D supramolecular network by hydrogen bonds. Complex 2 is of zipper structure, and further assembled into 2D supramolecular network by hydrogen bonds and π–π stacking interactions. Complex 4 is a 3D CdSO₄-like structure with twofold interpenetration, while complex 5 is a dinuclear compound. The different structures of complexes 1–5 can be attributed to using the auxiliary ligands, indicating an important role of the auxiliary ligands in assembly and structure of the title complexes.     

Syntheses and structures of three manganese coordination polymers with 1,4- bis (imidazol-1-yl)butane

Three manganese coordination polymers [Mn(bimb)₂(NCS)₂] _n (1), [Mn(bimb)₂(dca)₂] _n (2) and [Mn(bimb)₂(N₃)₂] _n (3) (bimb?=?1,4-bis(imidazol-1-yl)butane, dca?=?dicyanamide) were synthesized and characterized by X-ray crystallography, IR and thermogravimetric analysis. In 1 and 2, each Mn(II) links two Mn(II) atoms by double bimb ligands and extends to form a one-dimensional double chain structure containing the Mn₂(bimb)₂ 22-member metallocycle. 3 constructs a two-dimensional (4,4) network linked by bimb bridges.     

Synthesis,Structure and Biological Activities of 2-(1H- 1,2,3-Benzotriazol-1-yl)-1-(4-methylphenyl)-2- (1H-1,2,4-triazol-1-yl)-1-ethanone

IntroductionTriazole derivatives have become the most rapidlyexpanding group of antifungal compounds with advanta-ges of lowtoxicity, high oral bioavailability and broad-spectrum antifungal activity, which can be used againstfungi including most yeasts an…     

A novel layered supramolecular compound containing 2D network of eight-member water clusters and terephthalato extended-bridged

A novel layered supramolecular compound [Ni(L)(TPHA)]·8H₂O, containing two-dimensional (2D) water clusters and terephthalato-bridged ligand, where L = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9] octadecane, TPHA = terephthalate dianion, has been synthesized and structurally characterized by spectroscopy and X-ray crystallography. The complex is neutral, in which the nickel(II) ions are bridged by the TPHA to form a one-dimensional (1D) infinite chain structure, and containing the eight-member water cluster. The presence of octameric water clusters have effectively increased the 1D coordination polymer to a three-dimensional layered structure. Every water cluster is connected strongly by a O–H···O hydrogen bond (range of the bonds between 2.724 and 3.056 Å). The complex crystallizes in monoclinic, space group P21/c with a = 9.788(3), b = 13.030(4), c = 11.646(4) Å, and β = 104.551(5)°.     

Coexistence of two halide hydrate clusters in a crystal of 1,1′-(benzene-1,3-diyldimethanediyl)-bis(3,5,7-triaza-1-azoniatricyclo[3.3.1.13,7]decane) dibromide trihydrate. X-ray structure,Hirshfeld surface and thermal analysis

The title compound, C₂₀H₃₂N₈²⁺·2Br⁻·3H₂O, was obtained by the reaction of 1,3,5,7-triazatricyclo[3.3.1.1^3,7]decane with 1,3-bis(bromomethyl)benzene in acetonitrile. The asymmetric unit contains a unique 1,1′-(benzene-1,3-diyldimethanediyl)bis(3,5,7-triaza-1-azoniatricyclo[3.3.1.1^3,7]decane)dication, two bromide anions and three water molecules. The 3,5,7-triaza-1-azoniatricyclo[3.3.1.1^3,7]decane (C₆N₄H₁₂)⁺ moieties lie on the same side of the molecule, and the pseudo torsion angle (H₁₂N₄C₆)CH₂⋯CH₂(C₆N₄H₁₂) is −5.25 (18)°. The molecular dication C₂₀H₃₂N₈⁺ is charge-balanced by a pair of crystallographically independent halide hydrate clusters, and the cation and clusters are interlinked by CH⋯O and CH⋯Br hydrogen bonds. The Hirshfeld surface analysis and fingerprint plots reveal that the packing in compound 2 is directed mainly by H⋯H (56.7%) and H⋯Br/Br⋯H (21.3%) contacts. The thermal analysis showed between 30 and 180 °C the gradual loss of three water molecules, which represents the loss of one and two crystalline water molecules from the two types of clusters, respectively. A second noticeable weight loss between 180 and 230 °C is observed, depictive of the thermal decomposition of the dication of the title compound.     

Hydrothermal syntheses, characterizations and crystal structures of three new cadmium (II) amino-diphosphonates: effects of substitute groups on the structures of metal phosphonates

Hydrothermal reactions of cadmium(II) chloride with three amino-diphosphonic acids, C₆H₅CH₂N(CH₂PO₃H₂)₂ (H₄L¹), C₆H₅CH₂CH₂N(CH₂PO₃H₂)₂ (H₄L²) and 4-CH₃-C₆H₄CH₂N (CH₂PO₃H₂)₂) (H₄L³) resulted in three new metal amino-diphosphonates, namely, Cd(H₃L¹)₂, 1 Cd(H₃L²)₂·2H₂O 2 and Cd(H₃L³)₂3. In all three complexes, the Cd(II) ion is octahedrally coordinated by six phosphonate oxygen atoms from six ligands. Complexes 1 and 3 have a similar structure in which the CdO₆ octahedra are cross-linked by bridging ligands into a double chain along the c-axis, such double chains are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form 〈100〉 and 〈200〉 layers with the phenyl groups of the ligands orientated toward the interlayer space. The structure of complex 2 features a 〈100〉 cadmium(II) diphosphonate layer. The effects of the substitute groups attached to the amine groups on the structures of the metal phosphonates are also discussed.     

Hydrothermal Synthesis,Structure and Properties of a New Phosphomolybdate Based on Novel [Co(H2O)4(HP2Mo5O23)]8- Anions and [H8(H2O)16]8+ Water Cluster Cations

A pure inorganic [P₂Mo₅O₂₃]^6- based cobalt complex [H₈(H₂O)₁₆][Co(H₂O)₄(HP₂Mo₅O₂₃)₂] with a sandglass-like shape was synthesized and characterized by means of single-crystal X-ray diffraction, powder X-ray diffraction(PXRD), infrared spectroscopy(IR), thermogravimetry/differential scanning calorimetry(TG/DSC), ultraviolet-visible spectroscopy(UV-Vis) and cyclic voltammogram(CV). Single-crystal X-ray diffraction analysis reveals that the asymmetric unit of compound 1 consists of a half cobalt ion, one [P₂Mo₅O₂₃]^6- anion, two coordinated water molecules and eight lattice water molecules. It is especially intriguing to note that two [P₂Mo₅O₂₃]^6- clusters are symmetrical about the Co ion, like a sandglass. And a chair-like water cluster with an unprecedented centrosymmetric [H₈(H₂O)₁₆]⁸⁺ can be observed in compound 1. Additionally, the electrochemical and catalytic properties of compound 1 were also investigated.     

Hydrothermal syntheses and crystal structures of two new phosphomolybdates based on an organoamine template

Two new compounds of disphosphopentamolybdate (VI), (C₆H₁₈N₂)₂[H₂P₂Mo₅O₂₃]?·?2(H₂O) (1) and (C₆H₁₈N₂)_4.5H₃[P₂Mo₅O₂₃]₂?·?6(H₂O) (2), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic space group P 1 with a?=?11.0863(9)?Å, b?=?11.9562(9)?Å, c?=?14.2291(19)?Å, α?=?103.0410(10)°, β?=?100.3530(10)°, γ?=?103.7390(10)°, V?=?1729.8(2)?ų, Z?=?2; compound 2 crystallizes in the triclinic space group P 1 with a?=?14.6440(13)?Å, b?=?15.9168(13)?Å, c?=?17.9795(13)?Å, α?=?80.4270(10)°, β?=?86.1180(10)°, γ?=?64.1890(10)°, V?=?3720.1(5)?ų, Z?=?2. Characterizations by elemental analysis, infrared analysis, and thermal analysis are also given. Formation of 1 and 2 indicates that pH of solution plays an important role during the synthesis.     

Synthesis, Structure and Biological Activities of 2-（1H- 1,2,3-Benzotriazol-1 -yl ）-1-（ 4- methylphenyl ）-2-（1H-1,2,4-triazol-l-yl）-1-ethanone

The title compound was synthesized and characterized by IR, ^1H NMR, elemental analysis and single crystal X-ray diffraction analysis. Its biological activities were also tested. The results show that the title compound reveals inhibiting activities towards wheat gibberellin, apple ringspot, tomato early blight, peanut cercospora arachidicola and stem wilt of asparagus.     

One polynuclear copper(II) complex based on salicylaldehyde phenoxyacylhydrazone: structural and magnetic studies

One new copper(II) complex with a multidentate Schiff-base ligand salicylaldehyde phenoxyacylhydrazone (H₂L), {[Cu₄(L)₄(DMF)]·DMF}_n (1) has been synthesized and structurally characterized. Complex 1 exhibits a coordination polymer with a 1-D infinite chain-like structure, resulting from the Cu(II) centers linked by N–N single bonds. Magnetic behavior of 1 shows that it is antiferromagnetic.     

链状[NH3CH2CH2NH3]AgAsS4的溶剂热合成及表征

利用溶剂热方法合成了链状[NH3CH2CH2NH3]AgAsS4,通过单晶X射线衍射技术对其进行了晶体结构分析,该化合物晶体属单斜晶系,空间群C2/c,晶胞参数a=1.35805(8)nm,b=0.65331(3)nm,c=2.27711(9)nm,β=106.42(3)°,Z=8.化合物具有有趣的梯子状双链结构,该阴离子链由AsS4与AgS3共用顶点交替连接而成,有机阳离子在阴离子链之间存在较强的N—H…S氢键.DSC和Tg分析结果表明化合物在200℃以下是稳定的.     

Two cobalt(II) complexes based on 2-propyl-4,5-imidazoledicarboxylic acid: syntheses,crystal structures,and properties

Two complexes, [Co(H₂pimdc)₂(H₂O)₂]?·?2DMF (1) and [Co(H₂pimca)₂(H₂O)₂]?·?4H₂O (2), have been designed, synthesized, and characterized (X-ray single crystal analysis, thermal analysis, electrochemical analysis, and infrared spectrum) based on the imidazole ligand [H₃pimdc?=?2-propyl-4,5-imidazoledicarboxylic acid]. Both compounds have 3-D hydrogen-bonding networks. Because of different coordination of water, 1 forms a layer-like geometry via hydrogen bonds, but 2 forms a fishingnet-like latticed geometry via hydrogen bonds.     

Syntheses and structures of three new coordination polymers with the flexible 1,2-bis(1,2,4-triazol-1-yl)ethane ligand

Three new coordination polymers {[Ni(bte)₂(NCO)₂](H₂O)} _n (1), {[Ni(bte)₂(N₃)₂](H₂O)} _n (2) and {[Ag(bte)₂](NO₃)} _n (3) (bte?=?1,2-bis(1,2,4-triazol-1-yl)ethane) were synthesized and characterized by X-ray crystallography, IR and thermogravimetric analysis. The coordination geometry of the Ni(II) atom is distorted octahedral, coordinated equatorially by four nitrogen atoms from four triazole rings of four symmetry-related bte ligands, and axially by two nitrogen atoms from two isocyanate anions in 1 and azide anions in 2, respectively. The structures of 1 and 2 are both polymeric, with 18-membered spiro-fused rings and each 18-membered ring involving two inversion-related bte molecules. The coordination geometry of the Ag(I) atom in 3 is distorted tetrahedral, formed by four nitrogen atoms from four triazole rings of four symmetry-related bte ligands. Each bte ligand links two Ag(I) atoms and forms a two-dimensional undulated (4,4) network in 3.     

Syntheses,structures, and properties of two 2-D Cd(II) complexes based on 2-(1H-imidazol-1-methyl)-1H-benzimidazole and polycarboxylate ligands

Two 2-D Cd(II) complexes, {[Cd(imb)(bdc)(H₂O)]·CH₃OH}_n (1) and {[Cd(imb)(Hbtc)(CH₃OH)]·2H₂O·CH₃OH}_n (2), have been synthesized by reactions of CdCl₂·2.5H₂O with 2-(1H-imidazol-1-methyl)-1H-benzimidazole (imb) and 1,3-benzenedicarboxylic acid (H₂bdc) or 1,3,5-benzenetricarboxylic acid (H₃btc). Single-crystal X-ray diffraction shows that 1 possesses an infinite 2-D layered structure in which all the carboxylates chelate Cd(II) and imb bridge Cd(II) ions. Complex 2 also features an infinite 2-D layered structure and imb ligands also bridge Cd(II) ions, but two carboxylates of each 1,3,5-benzenetricarboxylate coordinate to Cd(II) in monodentate or chelating mode, leaving the third one, which is not deprotonated, uncoordinated. IR spectra, fluorescent properties, and thermogravimetric analyses of both complexes have been investigated.