Synthesis and crystal structure of bis{(μ-chloro)-chloro-[N-benzoyl-N′-(2-hydroxyethyl)thiourea] mercury(II)}

The complex bis{(µ-chloro)-chloro-[N-benzoyl-N′-(2-hydroxyethyl)thiourea] mercury(II)} was prepared by reaction of HgCl₂ with N-benzoyl-N′-(2-hydroxyethyl) thiourea(HL). The compound was characterized by IR and ¹H?NMR spectroscopy and its structure was determined by single crystal X-ray diffraction. The complex is binuclear with two Hg(II) ions tetrahedrally coordinated by a terminal chloride, two bridging chlorides and a HL molecule. The Hg(II) ion is coordinated with HL via S(1).     

Crystal and molecular structure of [N N′-(3,3′-dipropylamine)-bis(salicylideneaminato)monoacetate]cobalt(III) complex

The crystal and molecular structure of [N,N′-(3,3′-dipropylamine)bis(salicyclideneaminato)-monoacetate]cobalt(III) complex has been determined by a three-dimensional X-ray diffraction study. In the complex, the cobalt ion has an octahedral coordination environment with cis-geometry for the two salicyclideneaminato moieties. An oxygen atom of the acetate ion is coordinated to cobalt ion and another oxygen atom is hydrogen-bonded to the secondary amine nitrogen atom.     

Synthesis of cobalt(II), nickel(II) and copper(II) complexes with 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene and crystal structures of {bis(methanol)[2-(2′-N-tosylaminophenyl)iminomethyl]phenolato}nickel(II) and {bis(2,2′-bipyridine)[2-(2′-N-tosylaminophenyl)iminomethyl]phenolato}copper(II)

Electrochemical oxidation of metal anodes (cobalt, copper and nickel) in acetonitrile solutions of 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene (H₂L) gave [CoL], [CuL] and [NiL] complexes. When 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) was added to the electrolytic cell, the mixed complexes [MLL′] (M=Co, Cu, L′=bipy or M=Ni, L′=phen) were obtained. A binuclear compound of composition [Ni₂L₂(MeOH)₄] (1) was synthesized by reaction of the ligand H₂L and nickel(II) acetate in methanol. X-ray structure determination showed the compound to be binuclear, with each nickel atom coordinated to two nitrogen and two bridging phenol oxygen atoms of two dianionic ligands and two methanol molecules, in an octahedral environment. The crystal structure of [CuLbipy] (2) was determined by X-ray diffraction; with the copper atom in a distorted bipyramidal environment defined by the two bipyridine nitrogen atoms and by the phenolic oxygen and the nitrogen atoms of the dianionic ligand. The electronic and vibrational spectral data of the complexes are discussed and related to the structure.     

A novel one-dimensional copper(II) imino nitroxide polymer

A copper(II) complex [Cu(im2-py)(4,4′-bipy)(NO₃)](NO₃)·1.5H₂O (im2-py?=?2-(2′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl; 4,4′-bipy?=?4,4′-bipyridyl) has been synthesized by reaction of Cu(NO₃)·3H₂O with im2py and 4,4-bipyridyl in methanol solution. Its crystal structure has been determined by X-ray diffraction. The structure shows that each copper ion is coordinated by a bidentate imino nitroxide radical, two 4,4′-bipyridyl ligands and a nitrate group to form a distorted square pyramidal environment. The crystal structure consists of chains of copper ions linked by 4,4′-bipyridyl.     

Kristall- und Molekülstruktur von Bis[N-(diethylaminothiocarbonyl)-N′-phenylbenzamidinato]kupfer(II)

Crystal and Molecular Structure of Bis[N-(diethylaminothiocarbonyl)-N′-phenyl-benzamidinato]copper(II) The structure of bis[N-(diethylaminothiocarbonyl)-N′-phenyl-benzamidinato]-copper(II) has been determined by X-ray structure analysis. The compound crystallizes in the orthorhombic space group Pbca with a = 27.792, b = 19.197, c = 12.325 Å and 8 formula units per unit cell. The structure was solved by heavy atom technique. The final R value was R = 0.06 for 1589 observed symmetry independent reflections. The coordination polyhedron is a distorted tetrahedron. In spite of the bulky phenyl groups the ligator atoms are arranged in cis position. The chelate rings deviate clearly from planarity. The phenyl rings are appreciably twisted against the chelate rings.     

草酸根桥联一维多聚铜配合物的合成及晶体结构

合成了草酸根（ox）桥联[Cu（tmen）]^2＋单元（tmen为N,N,N’,N’-四甲基乙二胺）的一维多聚铜配合物．X-ray单晶衍射表明,该配合物由Cu（Ⅱ）和四个ox氧原子、tmen的两个氮原子配位形成畸变的八面体构型．Cu…Cu间距为0．56095（34）nm和0．56594（40）nm．水分子和草酸根间氢键可以使该配合物形成三维超分子结构．     

Metal-(phenylthio)acetic acid interactions—VI. The crystal and molecular structures of diaquabis[(phenylsulfinyl) acetato[bis(pyridine)copper(II) and bis[(benzylthio) acetato]bis(pyridine)copper(II)

The crystal structures of diaquabis[(phenylsulfinyl) acetato]bis(pyridine)-copper(II), (1), and bis[(benzylthio) acetato]bis(pyridine)copper(II) (2) have been determined using X-ray diffraction. In (1), the copper atom is at the centre of a distorted octahedron with the equatorial sites occupied in a trans configuration by two unidentate (phenylsulfinyl)acetate oxygens [Cu-O, 1.97(2),2.01(2)Å] and two pyridine nitrogens [Cu-N, 1.99(2),2.05(2) Å] with water molecules completing the polyhedron [Cu-O, 2.51(2),2.58(2) Å]. The copper atom in (2) is at the inversion centre of a distorted octahedron having in the equatorial sites, trans-related pyridine nitrogens [Cu-N, 1.993(3) Å] and four oxygens from two asymmetric bidentate (benzylthio)acetate ligands [Cu-O, 2.012(3), 2.510(5) Å].     

Synthesis, crystal, and molecular structure of the solvated complex [MoO2(L)] · DMF (L2− = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol anion)

A new dioxomolybdenum(VI) complex, [MoO₂(L)] · DMF, where L^2? = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol, has been synthesized. Its structure has been determined by X-ray diffraction analysis. The Mo atom is octahedrally coordinated by two oxo ligands that are in cis-positions with respect to each other, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) ligand L, and the DMF oxygen atom.     

Synthesis,Crystal Structure,and Biological Activity of a New Cu(I) Complex of the N-Phenyl-N′-(2-nitrobenzoyl)-thiourea

The complex bis(μ-sulfur)-sulfur-[N-phenyl-N′-(2-nitrobenzoyl)-thiourea]copper (I) was obtained from the reaction between the N-phenyl-N′-(2-nitrobenzoyl)-thiourea(HL) and copper(II). The compound was characterized by IR and ¹H NMR, ¹³C NMR spectroscopy and its structure was determined by single crystal X-ray diffraction. The complex is binuclear with two copper(I) ions coordinated by a terminal sulfur, two bridging sulfurs, and a HL molecule. In addition, the compound is also a considerable plant-growth regulator.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis, structural characterization and antibacterial activity of 2,6-diacetylpyridine bis(benzenesulfonohydrazide) Schiff bases and their copper(II) complexes

2,6-Diacetylpyridine bis(benzenesulfonohydrazide) Schiff bases (L¹, L² and L³) and their Cu(II) complexes of the general formula [CuL·H₂O] were synthesized and characterized by various spectroscopic techniques. The crystal structure of [CuL³·(py)]·py was investigated by single crystal X-ray structure analysis. The Cu(II) cation has near square pyramidal, penta-coordinate geometry. The binegatively charged tetradentate Schiff base is asymmetrically coordinated to the Cu(II) ion via the pyridine N atom, the azomethine N atom, the sulfonyl O atom and the deprotonated hydrazine N atom. There is a pyridine molecule apically coordinated to the Cu(II) ion. All the Schiff bases and their copper(II) complexes were screened by the disc diffusion method against multi-drug resistant (MDR) gram-negative and gram-positive bacteria. The minimum inhibitory concentration (MIC) values were also determined. These results show that the antibacterial activity of the Schiff bases against Methicillin-resistant Staphylococcus aureus (MRSA) is enhanced when they are chelated with the copper(II) ion.     

Two Coordination Compounds Bearing Bis(2-dimethylaminoethyl) Ether: Syntheses,Crystal Structures and Catalytic Application to the Henry Reaction

Two novel coordination compounds, namely [Cu₂(BDMAEE)(CH₃COO)₄]_n(1) and[Ni(BDMAEE)Cl₂](2)[BDMAEE=bis(2-dimethylaminoethyl) ether], have been synthesized and characterized by IR, elemental analysis, PXRD and X-ray single crystal diffraction. In compound 1, the central Cu(Ⅱ) ion is coordinated with four oxygen atoms and one nitrogen atom, forming a distorted square pyramidal geometry. The asymmetric units composed of one Cu(Ⅱ) ion, two acetates and a half of BDMAEE are connected to form an infinite 1D chain structure by the bridging acetate and the BDMAEE. In compound 2, the central Ni(Ⅱ) ion is coordinated with one oxygen atom, two chlorine anions and two nitrogen atoms, forming a distorted square pyramidal geometry. The compounds exhibited excellent catalytic properties in the Henry reaction of nitromethane with some aromatic aldehydes, and the optimized reaction conditions were obtained.     

配合物[Eu(Ⅲ)(TFPB)3bpy]的晶体结构和发光性质(英)

The crystal structure of Eu(TFPB)₃bpy [TFPB: 4,4,4-trifluoro-1-phenyl-1,3- butanedione, bpy: 2,2′-bipyridyl] has been determined by single crystal X-ray diffraction and the coordination geometry of Eu atom is a square antiprism. The complex can give the characteristic luminescence of Eu³⁺ upon UV excitation. CCDC: 224879.     

One-pot synthesis of bis-1,5,3-dithiazepanes from ethane-1,2-dithiol, formaldehyde, and ammonium salts

An efficient one-pot procedure has been developed for the synthesis of bis-1,5,3-dithiazepanes by reaction of ethane-1,2-dithiol with formaldehyde and ammonium salts. According to the X-ray diffraction data, the heterorings in 3,3′-[ethane-1,2-diylbis(sulfanediylmethanediyl)]bis(1,5,3-dithiazepane) in crystal adopt a chair conformation with axial orientation of the substituent on the nitrogen atom.     

Chiral Tetraamines Based on (S)-2-(Aminomethyl)pyrrolidine: Template synthesis and properties of copper(II) complexes

The template reaction of {bis[(S)-2-(aminomethyl)pyrrolidine]}copper(II) with formaldehyde, nitroethane, and base in MeOH yields optically pure {1,7-bis[(S)-pyrrolidin-2-yl]-4-methyl-4-nitro-2,6-diazaheptane}- copper(II) ([Cu((S,S)-mnppm)]²⁺) in high yield. The same reaction with rac-2-(aminomethyl)pyrrolidine is also described. Preparative details and spectroscopic and electrochemical properties of the Cu^II complexes and of the free ligands are reported and compared with structural, spectroscopic and electrochemical data of the Cu^II complex of the unsubstituted parent ligand 1,7-bis[(S)-pyrrolidin-2-yl]-2,6-diazaheptane (ppm). The crystal structure of [Cu(ppm)]Cl ClO₄ has been determined by X-ray diffraction methods.     

The synthesis and structure of a novel 1D copper(II) weak coordination polymer with 2,6-pyridinedicarboxylic acid

A novel copper complex, [Cu(dipic)(H₂O)₂] _n (H₂dipic?=?2,6-pyridinedicarboxylic acid), was synthesized and its crystal structure determined by X-ray diffraction. The complex has a polymeric structure of infinite one-dimensional (1D) zigzag chains, consisting of six-coordinate Cu(II) units. Each copper(II) ion is in a distorted octahedral environment with a CuNO₅ core: two oxygen atoms and one nitrogen atom from one dipic anion, one oxygen atom from an adjacent dipic ligand and two oxygen atoms from coordinated water. Each dipic anion connects two copper ions via a μ₂-oxygen atom. The zigzag 1D-chains are linked by extensive hydrogen bonds to form 2D infinite sheets.     

Bis[bis{(diphenylphosphinyl)methyl}ethyl phosphinate](ethanol) copper(II) perchlorate: synthesis, crystal and molecular structure

Bis[bis{(diphenylphosphinyl)methyl}ethyl phoshinate]bis(ethanol) metal(II) perchlorate complexes, where METAL = Co, Ni or Cu, have been prepared by the reaction of metal perchlorates and bis[(diphenylphosphinyl)methyl]ethyl phosphinate, (RPOEt), in absolute ethanol. The crystal structure of the copper complex is triclinic, space group P , a = 13.688(7) Å, b = 14.424(10) Å, c = 9.865(2) Å, = 110.43(4)°, β = 90.13(2)°, γ = 115.54(4)°, V = 1619.8 ų, Z = 1 and refined to R = 0.048 (R_w = 0.057). The structure consists of complex cations surrounded by perchlorate anions. Two RPOEt ligands and two ethanols are coordinated to the copper atom situated at the centre of symmetry 0, 0, 0. The RPOEt ligand is bidentate [Cu---O distances 1.969(4) Å, 2.312(4) Å], but the third oxygen atom from phosphoryl bonds is hydrogen bonded [2.669(6) Å], to the oxygen atom of ethanol molecule coordinated to the copper at 1.988(4) Å. The conformations of the ligand and chelate rings, magnetic data, molar conductance values, infrared and electronic spectra are given.     

1-Ethoxycarbonyl-3-ferrocenyl-propan-1,3-dion und Ferrocen-1,1'bis(2,4-dioxobutansäureethylester) als Liganden für Übergangsmetallionen. Kristallstruktur von Bis(1-ethoxycarbonyl-3-ferrocenyl-propan-1,3dionato)kupfer(II)

1-Ethoxycarbonyl-3-ferrocenyl-propane-1,3-dion and Ferrocene-1,1′bis(2,4-dioxobutanoic acid ethylester) as Ligands for Transition Metal Ions. Crystal Structure of Bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3dionato)copper(II) The ligands 1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dion and ferrocene-1,1′-bis(2,4-dioxo-butanoic acid ethylester) have been prepared by reaction of acetylferrocene or 1,1′-diacetylferrocene and diethyl oxalate. They yield neutral chelates with Cu^II, Ni^II, Zn^II, Co^II, and Mn^II. The acid dissociation constants of the ligands and the stability constants of their metal complexes including Fe^II complexes are reported. The structure of bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dionato)copper(II) was determined by X-ray structure analysis. A cis arrangement with a nearly square planar coordination sphere at the Cu atom is found.     

Coordination chemistry of amine bis(phenolate) cobalt(II), nickel(II), and copper(II) complexes

Cobalt(II), nickel(II), and copper(II) (1, 2, and 3) complexes of the dianionic form of the bis(phenolate) ligand N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-N',N'-dimethylethylenediamine (H2L) have been synthesized by electrochemical oxidation of the appropriate metal in an acetonitrile solution of the ligand. When copper is used as the anode, the addition of 1,10-phenanthroline to the electrolytic phase gave rise to a different compound [CuL]2.2CH3CN (4). The compounds [CoL]2.2CH3CN (1), [Ni2L2(H2O)].H2O (2), [CuL]2.3H2O (3), and [CuL]2.2CH3CN (4) were characterized by microanalysis, IR, electronic spectroscopy, FAB mass spectrometry, magnetic measurements and by single-crystal X-ray diffraction. The crystal structures show that the complexes have a dinuclear structure. In compounds 1, 3, and 4, two metal ions are coordinated by the two amine nitrogens and the two phenol oxygen atoms of a deprotonated pendant phenol ligand, with one phenolic oxygen atom from ligand acting as a bridge. In compounds 1 and 3, each metal center has a geometry that is closest to trigonal bipyramidal. Magnetic susceptibility data for both compounds show an antiferromagnetic coupling with 2J = -15 cm(-1) for the cobalt(II) complex and a strong antiferromagnetic coupling with 2J = -654 cm(-1) for the copper(II) complex. However, in 4 the geometry around the metal is closer to square pyramidal and the compound shows a lower antiferromagnetic coupling (2J = -90 cm(-1)) than in 3. The nickel atoms in the dimeric compound 2 are hexacoordinate. The NiN2O4 chromophore has a highly distorted octahedral geometry. In this structure, a dianionic ligand binds to one nickel through the two amine nitrogen atoms and the two oxygen atoms and to an adjacent nickel via one of these oxygen atoms. The nickel atoms are linked through a triple oxygen bridge involving two phenolic oxygens, each from a different ligand, and an oxygen atom from a water molecule. The two nickel ions in 2 are ferromagnetically coupled with 2J = 19.8 cm(-1).     

以四氟苯甲酸根及联吡啶为配体的铜配合物的合成、晶体结构及量子化学研究

水热条件下,合成了一个新的单核铜(Ⅱ)配合物[Cu(TFBA)(2,2′-bipy)(H2O)2](TFBA)(HTFBA=2,3,4,5-四氟苯甲酸,2,2′-bipy=2,2′-联吡啶),并通过元素分析、红外光谱,热重分析和X-射线单晶衍射对其进行了表征。铜(Ⅱ)分别与来自1个2,2′-bipy的2个氮原子、1个2,3,4,5-四氟苯甲酸根的1个氧原子和2个水分子中的2个氧原子配位,形成变形的四方锥的配位构型。配合物通过强的O-H…O氢键作用形成了二聚体结构,该二聚体又通过分子间弱的C-H…O氢键和C-H…π作用形成了一维链状结构。对配合物中[Cu(TFBA)(2,2′-bipy)(H2O)2]+进行了量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。     

Electrochemical synthesis of Co,Ni, and Zn complexes with 2-Pyrrole-[N-(o-hydroxyphenyl)methylimines]: The crystal structure of 2,2′-Bipyridine bis{2-[(2-pyrrole)methylimino]5-methylphenolato}nickel(II)

The electrochemical oxidation of anodic cobalt, nickel, and zinc in acetonitrile containing both 2-pyrrole-[N-(o-hydroxyphenyl)methylimines] (H₂L) and a bidentate ligand (1, 10-phenanthroline(phen) or 2,2′-bipyridine(bipy)) yielded compounds of general formula M(HL)₂ · phen and M(HL)₂ · bipy (M = Co, Ni, Zn). The crystal structure of 2,2′-bipyridine bis{2-[(2-pyrrole)methylimino]5-methylphenolato}nickel(II) was determined by X-ray diffraction. This compound crystallizes in the orthorhombic space group Pccn with a = 19.430(2), b = 28.488(2), c = 17.567(1) Å. The nickel atom has a distorted octahedral geometry, and the pyrrole nitrogen is not coordinated. The IR, ¹H-NMR and UV-visible spectra of the complexes are discussed and related to the structure.