Synthesis,X-ray crystal structure and electrochemical properties of (dithiolato)(diimine)copper(II) complexes: [Cu(mnt)(phen)] n and [Cu(dmit)(phen)] 2

Copper (II) complexes [Cu(dmit)(phen)]₂ (1) and [Cu(mnt)(phen)] _n (2) (mnt^2??=?maleonitriledithiolate, dmit^2??=?1,3-dithiole-2-thione-4,5-dithiolate, phen?=?1,10-phenanthroline) have been prepared by ligand-exchange between phen and [N(Bu)₄]₂[Cu(dmit)₂] or [N(Bu)₄]₂[Cu(mnt)₂]. Both complexes have been characterized by spectroscopic, electrochemical, and single-crystal X-ray analysis. In complex 1, dimers are extended into a two-dimensional array by weak S5–Cu contacts. In complex 2, monomers are extended into chains in a head-to-tail arrangement by weak Cu–S coordination bonds and π–π stacking interactions.     

Synthesis and crystal structures of two azido-bridged copper(II) complexes with schiff bases

Two new end-on azido-bridged dinuclear copper(II) complexes with the formula [Cu(μ_1,1-N₃)₂(IEP)₂] (I) and [Cu(μ_1,1-N₃)₂(EMP)₂] (II), where IEP and EMP are the deprotonated forms of 2-[1-(2-isopropylaminoethylimino)ethyl]phenol and 2-ethoxy-6-[(2-methylaminoeth-ylimino)methyl]phenol, respectively, were synthesized. Both complexes were characterized by elemental analyses and IR spectra. The crystal structures were determined by the X-ray diffraction. The crystal of I is monoclinic: space group P2₁/c, a = 9.662(2), b = 15.282(3), c = 10.639(2) Å, β = 115.418(10)°, V = 1418.9(5) ų, Z = 2. The crystal of II is monoclinic: space group P2₁/n, a = 12.588(2), b = 7.705(1), c = 14.481(2), β = 91.736(5)°, V = 1403.9(2) ų, Z = 2. The two Cu atoms in each complex are bridged by two end-on azide groups. Each Cu atom is in a square pyramidal coordination. The Cu…Cu distances are 3.230(2) Å in I and 3.150(2) Å in II.     

Coordination geometry in bis(di-2-pyridylamine)copper(II) complexes. Crystal structures and spectroscopic properties of [Cu(L)2(NCS)2][Cu(L)2(NCS)]X,X= , I−

The crystal structures of [Cu(dpyam)₂(NCS)₂][Cu(dpyam)₂(NCS)](BF₄) (1) and [Cu(dpyam)₂(NCS)_1.14I_0.86][Cu(dpyam)₂(NCS)_0.77I_0.23]I (2) (dpyam?=?di-2-pyridylamine) have been determined by single-crystal X-ray methods. Species 1 and 2 consist of two crystallographically independent Cu-bearing complexes, one being centrosymmetric and octahedrally elongated, and the other close to square pyramidal. The structures of both complexes and their EPR and electronic reflectance spectra are discussed and compared with those of related complexes.     

Mixed pseudohalide complexes of copper(II). Crystal and molecular structure of [Cu(N3)(NCS)(tmen)] n and of [Cu(N3)(NCO)(tmen)]2 (tmen = N,N,N′,N′-tetramethylethylenediamine)

The compounds [Cu(N₃)(NSC)(tmen)]_n (1), [Cu(N₃)(NCO)(tmen)]_n (2) and [Cu(N₃)(NCO)(tmen)]₂ (3) (tmen=N,N,N′,N′-tetramethylethylenediamine) were synthesized and studied by i.r. spectroscopy. Single crystals of compounds (1) and (3) were obtained and characterized by X-ray diffraction. The structure of compound (1) consists of neutral chains of copper(II) ions bridged by a single azido ligand showing the asymmetric end-to-end coordination fashion. Each copper ion is also surrounded by the other three nitrogen atoms; two from one N,N,N′,N′-tetramethylethylenediamine and one from a terminal bonded thiocyanate group. Compound (2) decomposes slowly in acetone and the product formed [Cu(N₃)(NCO)(tmen)]₂ (3) crystallizes in the monoclinic system (P2₁). The structure of (3) consists of dimeric units in which the Cu atoms are penta-coordinated and connected by μ(1,3) bridging azido and cyanate ligands. In both cases the five coordinated atoms give rise to a slightly distorted square-based pyramid coordination geometry at each copper ion. The thermal behavior of [Cu(N₃)(NSC)(tmen)]_n (1) and [Cu(N₃)(NCO)(tmen)]_n (2) were investigated and the final decomposition products were identified by X-ray powder diagrams.     

1D Polymeric copper(II) azido complexes. Synthesis,spectral and structural studies of [Cu(ethyl isonicotinate)2(N3)2]n and [Cu(methyl isonicotinate)2(NO3)(N3)]n complexes

Two new 1:2 polymeric complexes of copper(II) azide with ethyl isonicotinate (1) and methyl isonicotinate (2) have been synthesized and characterized by spectroscopic and crystallographic methods. The polymeric structure of complex (1) features six coordinated copper centers, a pair of trans-coordinated ligand molecules, and asymmetric ₂-1,1 and ₂-1,3-azido bridges resulting in a 1D chain structure. In complex (2), each copper atom which is located at an inversion center, is coordinated to a pair of trans ligand molecules, to the nitrogen atom of two -1,1-azido ligand and to an oxygen atom of a bridging (-O,O) nitrogen group. The i.r., electronic and e.s.r. spectra of the complexes are reported.     

Complex [MoO2(L)(CH3OH)] (L2- = 3-methoxysalicylidenemonoethanolimine anion): Synthesis,crystal and molecular structures

The complex [MoO₂(L)(CH₃OH)] (where L^2- is 3-methoxysalicylidenemonoethanolimine anion) has been prepared and structurally characterized by X-ray diffraction. The molybdenum atom has an octahedral coordination to two ligands in cis-positions to each other, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) L^2- ligand, and also the oxygen atom of methanol. Strong O-H?O hydrogen bonds (O?O, 2.598 Å) link pairs of molecules into centrosymmetric pseudo-dimers.     

Synthesis and characterization of [Cu(Phca2en)(PPh3)X] (X=Cl, Br, I, NCS, N3) complexes: crystal structures of [Cu(Phca2en)(PPh3)Br] and [Cu(Phca2en)(PPh3)I]

New mixed-ligand copper(I) complexes, [Cu(Phca₂en)(PPh₃)X], [Phca₂en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N₃ (5)] have been synthesized and characterized by various techniques. ¹H and ¹³C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca₂en)(PPh₃)Br] (2) and [Cu(Phca₂en)(PPh₃)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh₃ moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported.     

Synthesis and crystal structures of dimeric schiff base oxovanadium(V) complexes with antimicrobial activity

Two new dimeric oxovanadium(V) complexes, [VO₂L₁]₂ · 2H₂O (I) and [VO₂L₂]₂ (II), where L¹ and L² are the monoanionic form of 5-methoxy-2-[(2-methylaminoethylimino)methyl]phenol (HL¹) and 5-diethylamino-2-[(2-methylaminoethylimino)methyl]phenol (HL²), respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination. The crystal of I is monoclinic: space group P2₁, a = 6.858(2), b = 16.630(3), c = 12.306(2) Å, β = 103.985(2)°, V = 1361.9(5) ų, Z = 2. The crystal of II is triclinic: space group $P\bar 1$ , a = 7.378(2), b = 8.838(2), c = 13.312(3) Å, α = 102.576(2)°, β = 92.044(2)°, γ = 113.017(2)°, V = 772.7(3) ų, Z = 2. The V...V distances are 3.140(1) Å in I and 3.254(1) Å in II. The V atoms in the complexes are in octahedral coordination. The effect of the complexes on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.     

Direct synthesis of a dimeric mixed-anion lead(II) complex,crystal structure of [Pb(phen)(2OCCH3)(NCS)]2

A lead(II) complex with 1,10-phenanthroline (phen) containing two different anions has been synthesized using a direct synthetic method and characterized by IR and CHN elemental analysis. The structure of [Pb(phen)(₂OCCH₃)(NCS)]₂ was confirmed by X-ray crystallography. The single crystal X-ray data of this compound shows the complex to be dimeric as a result of acetate ligand bridging. The Pb atom has an unsymmetrical six-coordinate geometry, being coordinated by three nitrogen atoms of 1,10-phenanhroline and the thiocyanate ligand and three oxygen atoms of the acetate ligand. The arrangement of the 1,10-phenanhroline, acetate and thiocyanate ligands exhibits a coordination gap around the Pb(II) ion, occupied possibly by a stereoactive lone pair of electrons on lead(II), with the coordination around lead atoms being hemidirected. There is a π–π stacking interaction between the parallel aromatic rings that may help to increase the ‘gap’ in the coordination geometry around the Pb(II) ion.     

Synthesis,crystal structures and properties of two copper(II) 2-aminomethylbenzimidazole complexes

Two new Cu^II complexes, [Cu(Hambi)₂(ClO₄)₂] and [Cu(Hambi)₂(dca)₂] (Hambi = 2-aminomethylbenzimidazole) have been prepared and characterized by X-ray diffraction, electronic paramagnetic resonance (e.p.r.) and i.r. analyses. Both complexes exhibit an elongated octahedral coordination environment with two Hambi ligands situated at the equatorial positions in a trans fashion [Cu—N bond distances range from 1.940(9) to 2.031(9) Å]. In the second complex, a new coordination mode, in which dicyanamide coordinates to copper(II) as a monodentate ligand with the amide nitrogen atom, was observed.     

Synthesis, characterization, and X-ray crystal structures of copper(II) and nickel(II) complexes with Schiff base

New copper(II) complexes, [Cu₂L¹L²] · ClO₄ (I) and [Ni(L³)₂] (II), where L¹ is the monoanionic form of 2-[1-(2-emthylaminoethylimino)ethyl]phenol, L² is the dianionic form of N,N′-ethylene-bis(2-hydroxyacetophenonylideneimine), L³ is the mono-anionic form of 2-(1-iminoethyl)phenol, were prepared and characterized using elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction. In complex I, the Cu(1) atom is coordinated by the NNO tridentate ligand L¹ and the two phenolate O atoms of L², forming a square pyramidal geometry. The Cu(2) atom in complex I is coordinated by the NNOO tetradenate ligand L², forming a square planar geometry. The Ni atom in complex II is coordinated by two phenolate O and two imine N atoms from two ligands L³, forming a square planar geometry. In the crystal structure of I, the perchlorate anions are linked to the dinuclear copper(II) complex cations through intermolecular N-H...O hydrogen bonds. In the crystal structure of II, the mononuclear nickel complex molecules are linked through intermolecular N-H...O hydrogen bonds, forming a trimer.     

Three transition‐metal complexes with the macrocyclic ligand meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane (L): [Cu(ClO4)2(L)], [Zn(NO3)2(L)] and [CuCl(L)(H2O)]Cl

The three transition‐metal complexes, (meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane‐κ⁴N)bis(perchlorato‐κO)copper(II), [Cu(ClO₄)₂(C₁₈H₄₀N₄)], (I), (meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane‐κ⁴N)bis(nitrato‐κO)zinc(II), [Zn(NO₃)₂(C₁₈H₄₀N₄)], (II), and aquachlorido(meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane‐κ⁴N)copper(II) chloride, [CuCl(C₁₈H₄₀N₄)(H₂O)]Cl, (III), are described. The molecules display a very similarly distorted 4+2 octahedral environment for the cation [located at an inversion centre in (I) and (II)], defined by the macrocycle N₄ group in the equatorial sites and two further ligands in trans‐axial positions [two O–ClO₃ ligands in (I), two O–NO₂ ligands in (II) and one chloride and one aqua ligand in (III)]. The most significant difference in molecular shape resides in these axial ligands, the effect of which on the intra‐ and intermolecular hydrogen bonding is discussed. In the case of (I), all strong hydrogen‐bond donors are saturated in intramolecular interactions, while weak intermolecular C—H...O contacts result in a three‐dimensional network. In (II) and (III), instead, there are N—H and O—H donors left over for intermolecular interactions, giving rise to the formation of strongly linked but weakly interacting chains.     

Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2]

The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].     

铜配合物[Cu(AFO)2(N3)2](DMF)(H2O)的合成和晶体结构(AFO=4,5-二氮芴-9-酮)

近年来,利用晶体工程方法设计裁剪和组装具有一维、二维、三维框架结构的固体化合物材料已成为材料科学和化学学科中最活跃的研究领域之一。研究表明在这些框架内镶嵌活性组分可得到新型功能材料,如磁性材料、非线性光学材料及新型催化剂等[1]。而叠氮根是一个多功能桥联配体,它能形成一维[2],二维[3],三维[4]等配合物,有关叠氮根的磁性研究也成为分子基铁磁体研究的一个重要方面[5]。本文报道了[Cu(AFO)2(N3)2](DMF)(H2O)(DMF=N,N 二甲基甲酰胺)配合物的合成和晶体结构,并进行了元素分析和红外光谱表征。1　实验部分1 1　试剂与…