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1.
A mixture of copper(II) chloride dihydrate and ligands derived from amantadine and 5-halogenated salicylaldehyde in anhydrous methanol generated two novel complexes C34H38Cl2CuN2O2 (I) and C34H38Br2CuN2O2 (II), respectively. The complexes were characterized by melting point, elemental analysis, molar conductance, IR, UV-Vis, and single-crystal X-ray diffraction (CIF files nos. 1435429 (I), 1435430 (II)). Single-crystal X-ray diffraction analysis reveals that both complexes crystallize in monoclinic system, P21/c space group. Each asymmetric unit consists of two mononuclear copper(II) complex molecules and each complex molecule includes one copper(II) atom two corresponding deprotonated ligands. The central copper(II) atom is four-coordinated via two nitrogen atoms and two oxygen atoms from the corresponding Schiff base ligands, forming a distorted tetrahedral geometry. Electrochemical properties of the complexes were studied by cyclic voltammetry.  相似文献   

2.
Abstract

Complexes 1-3, C34H36X4CuN2O2 (X?=?Cl, Br, I), were synthesized with copper chloride dihydrate and three new Schiff base ligands derived from amantadine and 3,5-dihalosalicylaldehydes. They were characterized by IR, UV–VIS, elemental analysis, molar conductance, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that 1 and 2 crystallize in the triclinic system, Pī space group. Each asymmetric unit consists of one copper(II) ion, two corresponding deprotonated Schiff base ligands and one lattice dichloromethane molecule. 3 crystallizes in the monoclinic system, P21/n space group. Each asymmetric unit consists of one copper(II) ion and two deprotonated iodo- Schiff base ligands. The tetra-coordination of the central copper(II) ion in 1-3 is constructed by two nitrogen atoms and two oxygen atoms from the corresponding Schiff base ligands, forming a distorted tetrahedral geometry. Electrochemical properties of the complexes were determined by cyclic voltammetry.

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3.
《Journal of Coordination Chemistry》2012,65(16-18):2569-2583
Abstract

Two copper(II) coordination complexes, formulated as [Cu(tmen)(Clba)2] (1) and [Cu(tmen)(Hsal)2·H2O] (2) (where tmen?=?N,N,N′,N′-tetramethyl ethylenediamine (C6H16N2), Clba1? = 2-chlorobenzoate (C7H4ClO21?), and Hsal1? (C7H5O31? = monoanion of o-hydroxybenzoic acid (salicylic acid)), have been synthesized and characterized by elemental combustion analysis, spectroscopic techniques, thermal studies, and single crystal X-ray analyses. Complex 1 consists of two distinct monomeric units in which the coordination environment around the central copper(II) ion is a distorted octahedron with a CuN2O4 chromophore, constituted by a chelating tmen molecule, and two 2-chlorobenzoate1? anions coordinated through their carboxylate-O atoms in an asymmetrical bidentate fashion. Complex 2 is also a monomer and consists of an CuN2O3 chromophore, in which tmen is coordinated to Cu(II) through its two N atoms in a chelating bidentate fashion, and an aqua-O and the two o-hydroxybenzoate1? (HSal1?) anions are coordinated through one of their carboxylate-O atoms in a monodentate mode, forming a square pyramidal structure. Hydrogen bonding interactions especially of O–H…O, N–H…O, and C–H…Cl types interweave monomeric units and stabilize the overall crystal structures in both complexes. Thermal analysis and antibacterial activities of 1 and 2 against various bacterial strains were also investigated.  相似文献   

4.
Abstract

The title complex, Cu2(C10H2O8)(C3H4O2)6(H2O)4 · 4H2O, consists of polymeric copper(II) complex anions and discrete copper(II) complex cations. Benzenetetracarboxyl anions bridge copper(II) atoms coordinated to water and imidazole groups to form the anionic polymeric chains along the a axis, while discrete copper(II) complex cations involving four imidazole and two water ligands are packed between parallel polymeric anionic chains, an extensive H-bonding network linking complex cations and anions.  相似文献   

5.
Two new N2O2 unsymmetrical Schiff bases, H2L1 = 3-[({o-[(E)-(o-hydroxyphenyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol and H2L2 = 3-[({o-[(E)-(2-hydroxy-1-naphthyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol, and their copper(II) and nickel(II) complexes, [CuL1] (1), [CuL2] (2), [NiL1] (3), and [NiL2] (4), have been synthesized and characterized by elemental analyses and spectroscopic methods. The crystal structures of these complexes have been determined by X-ray diffraction. The coordination geometry around Cu(II) and Ni(II) centers is described as distorted square planar in all complexes with the CuN2O2 coordination more distorted than the Ni ones. The electrochemical studies of these complexes indicate a good correlation between the structural distortion and the redox potentials of the metal centers. The ligand and metal complexes were also screened for their in vitro antibacterial activity.  相似文献   

6.
Abstract

Three new Cu(II) Schiff base complexes with bidentate N-donor heterocyclic co-ligands, 2,2'-bipyridine (1), 1,10-phenanthroline (2), and 2,9-dimethyl-1,10-phenanthroline (3), were synthesized and characterized by FT-IR and UV-vis spectroscopy. Molecular structures of [C20H21CuN4O](ClO4) (1) and [C24H25CuN4O](ClO4) (3) were characterized by single-crystal X-ray crystallography. The Schiff base ligand is an N2O-type ligand, which is the mono-condensed form of the reaction between 1,3-propanediamine and salicylaldehyde. The antibacterial activities of these complexes were investigated against one gram positive and four gram negative bacteria. Considerable antibacterial activity was obtained against both gram type bacteria. Complexes 2 and 3 with 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, respectively, showed better antibacterial activity compared to 1 which has the 2,2'-bipyridine co-ligand.  相似文献   

7.
Four mononuclear copper(II) complexes, [Cu(LFQM-115)2] (1), [Cu(LFQM-116)2] (2), [Cu(LFQM-117)2] (3) and [Cu(octyloxy)2] (4) [LFQM-115 = 2-hydroxy-4-O-methylbenzophenone (C14H11O3), LFQM-116 = 2-hydroxy-4-O-butylbenzophenone (C17H18O3), LFQM-117 = 2-hydroxy-4-O-(33-dimethylallyl)benzophenone (C18H18O3) and octyloxy = 2-hydroxy-4-O-octylbenzophenone (C21H25O3)], have been prepared and investigated by infrared spectroscopy, thermal analysis, and powder and single crystal X-ray diffraction. Even though the synthesis and infrared analysis of 1, 2, and 4 have been reported previously, their crystal structures were elucidated for the first time here. In addition, the crystal structures of LFQM-116 and LFQM-117 were also determined by single crystal X-ray diffraction. The pseudo-translational symmetry found in LFQM-116 and the isomorphism between LFQM-115 and LFQM-117 are discussed. The complexes were prepared from a reaction of copper(II) nitrate trihydrate and the respective ligand in a (1:2) molar ratio in methanol (for 1 and 2) or THF (for 3 and 4) with addition of NaOH. Furthermore, crystallographic studies show that each copper(II) exhibits a square planar geometry, coordinated by four oxygens of two ligands. The nature and crystal packing of the intermolecular interactions are discussed. Compounds 2 and 3 are isomorphic crystals and all structures have the same supramolecular synthon.  相似文献   

8.
Two novel complexes, C38H48CoN2O2 (I) and C38H48N2O2Zn (II), were prepared through an analogous procedure with a corresponding metal chloride and a bulky Schiff base ligand (HL) which derived from rimantadine and salicylaldehyde in appropriate solvents, respectively. They were structurally characterized by the means of IR, UV-Vis, elemental analysis, molar conductance, PXRD and single-crystal X-ray diffraction (CIF files nos. 946735 (I), 893304 (II)). Single-crystal X-ray diffraction analysis reveals that I belongs to the triclinic system, \(P\overline 1 \) space group; each asymmetric unit consists of one cobalt(II) complex and one lattice ethanol molecule. In each complex molecule, cobalt(II) atom is four-coordinated via two oxygen atoms and two nitrogen atoms from the deprotonated Schiff base ligands, forming an approximate planar geometry. The crystal structure also involves strong O–H···O intermolecular hydrogen bonds between the solvent alcoholic and phenol O atoms of complex molecule. Complex II belongs to the monoclinic system, Cc space group. Each asymmetric unit consists of one zinc(II) ion and two deprotonated ligands. Zinc(II) atom lies on a twofold rotation axis and is four-coordinated via two nitrogen atoms and two oxygen atoms from the Schiff base ligands, forming a distorted tetrahedral geometry.  相似文献   

9.
Six secondary amine palladacycles bearing monodentate ligands (1a, 2a), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp) containing bridging and bidentate ligands (1b, 2bd), and four C,C-type phosphorus ylide complexes containing thiourea (tu) (3a), phenyl isothiocyanate (4a), and bridging and terminal azide groups (5 and 5a) have been synthesized. Resulting complexes have been characterized by elemental analyses, IR, 1H-, 13C{1H}-, and 31P{1H}-NMR spectroscopy with single crystal X-ray structure determination of 1a and 2a. The Pd in 1a and 2a occupies the center of a slightly distorted square planar environment formed by Caryl, Namine, Npyridine, and Cl. The catalytic efficiency of complexes showed that in most cases, amine palladacycles display better catalytic activities than the phosphorus ylide Pd(II) complexes. Comparison between bidentate and bridging dppe complexes showed that dppe-bridged dimer 2d has higher catalytic activity than dppe bidentate complex.  相似文献   

10.
In the two title copper(II) complexes, [CuL(C5H7O2)]n, (I), and [CuL′(C5H7O2)], (II), respectively, where HL is 4‐hydroxy‐3‐methoxybenzaldehyde picoloylhydrazone, C14H12N3O3, and HL′ is 4‐methoxybenzaldehyde picoloylhydrazone, C14H12N3O2, the CuII ions display a highly Jahn–Teller‐distorted octahedral and a square‐planar coordination geometry, respectively. In complex (I), two neighbouring CuII atoms are bridged by L and acetylacetonate, alternately, giving rise to a one‐dimensional chain of CuN2O4 octahedra interconnected by these two ligands along the a axis. In addition, the hydroxy H atom of the vanillin group connects to the carboxyl O atom of the adjacent chain via an O—H...O hydrogen bond, giving rise to a three‐dimensional supramolecular assembly. Complex (II) displays a discrete structure.  相似文献   

11.
Aluminium and zinc complexes bearing the N,O-chelating Schiff base ligand 4,6-bis-1-(2-(dimethylamino)ethylimino)ethyl)benzene-1,3-diol, (C6H2(OH)2(NCH2CH2NMe2)2) (1a), have been synthesized. Bimetallic aluminium and zinc alkyl complexes (2a4a) were prepared by treatment of the hexadentate 1a with the appropriate amount of AlMe3, ZnMe2 and ZnEt2, respectively. 2a has been characterized crystallographically, it lies on a crystallographic two-fold rotation axis and each aluminium centre adopts a five coordinate geometry. Complex 2a was tested as a catalyst in the ring-opening polymerisation of ɛ-caprolactone. We describe here the synthesis of two neutral ligands (1a and (C6H2(OH)2(C6H5NH2) (C=O(CH3)) (1b)) and demonstrate their application in the synthesis of molecular aluminium and zinc derivatives.  相似文献   

12.
The synthesis and characterisation of two cobalt(II) complexes, [CoIILBr-acrCl2] (1a) and [CoIILH-acrCl2] (1b), with acridine head-units resulting from an unexpected ligand rearrangement from a diphenylamine head-unit, and the intended cobalt(II) complex, CoIILBr-dpa(Cl)(H2O) (2), are reported. Single crystals of the two dark green acridine-based cobalt(II) complexes, 1a and 1b, form in a one-pot reaction of cobalt(II) chloride, the chosen diphenylamine-2,2′-dicarboxaldehyde (Ia 4,4-′dibromo- or Ib unsubstituted), triethylamine and two equivalents of 2,4-dimethylaniline in acetonitrile, in 23% yield. In contrast, the intended diphenylamine-based complex was isolated in two steps: first isolation of the Schiff base ligand, then complexation with cobalt(II) chloride and deprotonation with potassium tert-butoxide, in methanol/dichloromethane, giving 2 as a bright yellow solid in 67% yield. All three complexes feature cobalt(II) centres, with N2Cl2 approximately tetrahedral coordination for 1a and 1b confirmed by single crystal structure determinations. It is proposed that after one imine ‘arm’ forms, cobalt(II) coordination facilitates the other aldehyde undergoing an intramolecular cyclisation to form the new heterocyclic acridine head-unit. The structures of both of the resulting acridine-based complexes, 1a and 1b, and that of the originally intended Schiff base ligand, HLBr-dpa, were confirmed by single-crystal X-ray diffraction. These are the first examples of complexes of an acridine ligand of this type.  相似文献   

13.
Indium(III) chloride tetrahydrate and Schiff-base ligands derived from adamantaneamine and 3-/4-methoxysalicylaldehyde gave two complexes, C22H32Cl3InN2O3 (1) and C36H44Cl3InN2O4 (2), respectively. The complexes were characterized by IR, 1H NMR, elemental analysis, molar conductance, thermal analysis, and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, P21/n space group with the asymmetric unit consisting of one indium(III), one N-(3-methoxysalicylidene)-aminoadamantane (L1), three chlorides and one N,N-dimethylformamide molecule. The indium is six-coordinate with reversed triangular-prism geometry via three oxygens and three chlorides. Complex 2 crystallizes in the triclinic system, P 1 space group; the asymmetric unit consists of one indium(III), two N-(4methoxysalicylidene)-aminoadamantane (L2), and three chlorides. The indium is five-coordinate with distorted trigonal-bipyramidal geometry via two oxygens and three chlorides. Antibacterial activities of the complexes have been investigated against Escherichia coli and Staphylococcus aureus.  相似文献   

14.
《Journal of Coordination Chemistry》2012,65(16-18):2510-2525
Abstract

Two triply-bridged dinuclear copper(II) complexes of formula [LCu(μ-OH)(μ-OAc)(μ-X)CuL]X?0.5H2O where L is a bidentate ligand of N-(pyridine-2-ylmethyl)propane-2-amine and X=Cl, 1 and Br, 2 were synthesized and characterized by elemental analyses, spectroscopic techniques (IR, UV–Vis, EPR), thermal analysis, conductance measurements, and single-crystal X-ray structure determination. The structures of both complexes are similar. The complexes show a distorted square-pyramidal arrangement around each copper(II) ion with a CuN2O2X chromophore in which both copper(II) ions are connected by a hydroxo bridge and a triatomic syn-syn carboxylato bridge in equatorial positions and a halide ion bridge at the axial site. The chromotropism behavior of the complexes, including solvato-, thermo-, and halochromism, were investigated in detail. Their halochromism was investigated in the pH range of 2.0–11.0 by visible absorption spectroscopy. The reversible color variations from blue to colorless are attributable to deprotonation and protonation of the ligands. The complexes show reversible thermochromism in solution due to dissociation and recombination of ligands to copper ions.  相似文献   

15.
The Schiff bases H2La, H2Lb, and H2Lc have been prepared from the reaction of 2-amino-4-chlorophenol with acetylacetone, benzoylacetone, and dibenzoylmethane, respectively. Organotin(IV) complexes [SnPh2(La)] (1), [SnPh2(Lb)] (2), [SnPh2(Lc)] (3), and [SnMe2(Lc)] (4) have been synthesized from the reaction of SnPh2Cl2 and SnMe2Cl2 with these Schiff bases. The synthesized complexes have been characterized by elemental analysis and FT-IR, 1H, 13C, and 119Sn NMR spectroscopy. Spectroscopic data suggest the Schiff bases are completely deprotonated and coordinated tridentate to tin via imine nitrogen and phenolic and enolic oxygen atoms; the coordination number of tin is five. Thermal decomposition of the complexes has been studied by thermogravimetry. The in vitro antibacterial activities of the Schiff bases and their complexes have been evaluated against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. H2La, H2Lc, and all complexes exhibited good activities and have potential as drugs.  相似文献   

16.
Abstract

The title complex, [Mn(C3H4N2)4(H2O)2]·(C8H4O4), was prepared by reaction of terephthalato (diaqua)manganese (II) with imidazole in ethanol/water solution. The complex crystallizes in space group C2/c with cell parameters a = 22.494(5), b = 7.741(2), c = 16.287(3)Å, β = 120.94(3)°, Z = 4. The complex consists of complex Mn(II) cations and uncoordinated terephthalate anions; the latter link cations through an H-bonding network. Thermal analyses and IR spectra are discussed in terms of the formation of the complex.  相似文献   

17.
Four mononuclear copper(II) complexes of two new carboxamide derivatives formulated as [Cu(L1)2](ClO4)2 (1a), [Cu(L1)2](NO3)2 (1b), [Cu(L2)2(H2O)2](ClO4)2 (2a), and [Cu(L2)2(H2O)](NO3)2 (2b) have been isolated in pure form from the reaction of L1 and L2 [where L1 = N-(furan-2-ylmethyl)-2-pyridinecarboxamide and L2 = N-(thiophen-2-ylmethyl)-2-pyridinecarboxamide] with copper(II) salts of perchlorate and nitrate. All the complexes were characterized by physicochemical and spectroscopic tools along with single-crystal X-ray diffraction studies. The structural analyses showed that 1 is monomeric of square planar geometry with copper(II) chelated by two L1 ligands. Complex 2 differs in coordination geometry, being octahedral and distorted square pyramidal. Two L2 ligands occupy the equatorial positions of the octahedral 2a and the basal sites of the pyramidal 2b, with water molecules that complete the coordination sphere in each case. Electrochemical studies using cyclic voltammetry showed a reversible redox behavior of the copper(II) in 1 and 2. The electronic spectroscopic behavior and the trend of one electron equivalent redox potential corresponding to a CuII/CuI couple have also been confirmed by density functional theory calculations. The spectroscopic and viscosity measurement study in tris–HCl buffer suggested an intercalative interaction of 1a and 2 with calf thymus DNA likely due to the stacking between the non-coordinated furan and thiophene chromophore with the base pairs of DNA.  相似文献   

18.
The zinc(II) and nickel(II) complexes of glycine–vanillin Schiff base were synthesized by one-step solid–solid reaction at room temperature. The composition and structure of the complexes were characterized by elemental analyses, Fourier transform infrared spectra (FTIR), X-ray powder diffraction (XRD), and thermogravimetry and differential scanning calorimetry (TG–DSC). The crystal structure of the complexes belongs to monoclinic system with the lattice parameters: a = 0.6807 nm, b = 1.3818 nm, c = 1.2011 nm, β = 95.80° for [Zn(C10H9O4N)(H2O)3], and a = 0.7457 nm, b = 1.3331 nm, c = 1.2560 nm, β = 91.89° for [Ni(C10H9O4N)(H2O)3]·1.5H2O. The experimental results indicate that the zinc and nickel ions are all six-coordinated by imino nitrogen, carboxylic oxygen, and phenolic oxygen from the Schiff base ligand, and oxygen from three coordinated water molecules, respectively. The possible pyrolysis reactions in the thermal decomposition processes of the complexes and the experimental and calculated percentage mass loss are also given. The two complexes have the most intense antibacterial activities against Escherichia coli.  相似文献   

19.
Preparation of the ligands HL1 = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-ethylphenol; HL2 = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-methoxyphenol and HL3 = 2,6-[(N-phenylpiperazin-1-yl)methyl]-p-nitrophenol are described together with their Cu(II) complexes with different bridging units. The exogenous bridges incorporated into the complexes are: hydroxo [Cu2L(OH)(H2O)2](ClO4)2.H2O (L1=1a, L2 =1b, L3 =1c), acetato [Cu2L(OAc)2]ClO4.H2O (L1 =2a, L2 =2b, L3 =2c) and nitrito [Cu2L1(NO2)2(H2O)2]ClO4.H2O (L1=3a, L2 =3b, L3 =3c). Complexes1a,1b,1c and2a,2b,2c contain bridging exogenous groups, while3a,3b,3c possess only open μ-phenolate structures. Both the ligands and complexes were characterized by spectral studies. Cyclic voltammetric investigation of these complexes revealed that the reaction process involves two successive quasireversible one-electron steps at different potentials. The first reduction potential is sensitive to electronic effects of the substituents at the aromatic ring of the ligand system, shifting to positive potentials when the substituents are replaced by more electrophilic groups. EPR studies indicate very weak interaction between the two copper atoms. Various covalency parameters have been calculated.  相似文献   

20.
Tetradentate Schiff-base carboxylate-containing ligands, bis(2-pyridylmethyl)amino-5-valeric acid (Hpmva) and bis(2-pyridylmethyl)amino-6-caproic acid (Hpmca), react with copper(II) perchlorate to give rise to the carboxylated bridged chain complexes {[Cu(μ-pmva)(H2O)](ClO4)}n (1) and {[Cu(μ-pmca)(H2O)](ClO4)}n (2). These complexes have been characterized by X-ray crystallography, spectroscopic, and variable-temperature magnetic susceptibility measurements. In 1 and 2, each of the copper(II) ions exhibit CuN3O2 coordination environments with the three nitrogen atoms of the ligand and one oxygen atom belonging to the carboxylate group of an adjacent molecule occupying the basal position and a water molecule coordinated in the axial position. The electronic spectra of the complexes are significantly affected by the coordination geometry. Magnetic susceptibility measurements indicate that complexes exhibit very weak ferromagnetic interactions.  相似文献   

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