Copper(II) complexes of N(4)-substituted thiosemicarbazones derived from pyridine-2-carbaldehyde: Crystal structure of a binuclear complex

Ten copper(II) complexes {[CuL¹Cl] (1), [CuL¹NO₃]₂ (2), [CuL¹N₃]₂ · 2/3H₂O (3), [CuL¹]₂(ClO₄)₂ · 2H₂O (4), [CuL²Cl]₂ (5), [CuL²N₃] (6), [Cu(HL²)SO₄]₂ · 4H₂O (7), [Cu(HL²)₂] (ClO₄)₂ · 1/2EtOH (8), [CuL³Cl]₂ (9), [CuL³NCS] · 1/2H₂O (10)} of three NNS donor thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL¹], pyridine-2-carbaldehyde-N(4)-2-phenethyl thiosemicarbazone [HL²] and pyridine-2-carbaldehyde N(4)-(methyl), N(4)-(phenyl) thiosemicarbazone [HL³]} were synthesized and physico-chemically characterized. The crystal structure of compound 9 has been determined by X-ray diffraction studies and is found that the dimer consists of two square pyramidal Cu(II) centers linked by two chlorine atoms.     

Crystal structures and voltammetric behavior of three copper(II) complexes derived from bulky Schiff bases

Three Schiff base copper(II) complexes have been prepared and characterized by elemental analysis, mass spectra, i.r., electronic spectra, _eff and X-ray crystal structures. Cyclic voltammetry studies on the complexes indicate a dependence of the cathodic potentials upon electronic effects, but independence on the solid state structure.     

Synthesis and antibacterial activities of metal(II) complexes with Schiff bases derived from 3,5-diiodosalicylaldehyde

Two new Schiff bases (2,4-diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol and 2,4-diiodo-6-[(3-morpholin-4-yl-propylimino)-methyl]-phenol), condensed from 3,5-diiodosalicylaldehyde with 2-morpholinoethylamine and 3-morpholinopropylamine, have been designed and synthesized. Reaction of the Schiff bases with Zn(OAc)₂ · 2H₂O, Cu(OAc)₂ · H₂O, Ni(OAc)₂ · 4H₂O, Co(OAc)₂ · 4H₂O, Cd(OAc)₂ · 2H₂O, Mn(OAc)₂ · 4H₂O, Fe(SO4)₂ · 7H₂O, and Hg(OAc)₂ led to the formation of 16 new mononuclear complexes. The complexes were characterized by UV, Infrared, ESI-MS, and elemental analyses, and 3,5-diiodosalicylalidene-2-morpholinoethylaminozinc(II) (1) and 3,5-diiodosalicylalidene-2-morpholinoethylaminocopper(II) (2) were characterized by single crystal X-ray diffraction. Based on crystal structural analysis of 1 and 2, coupled with their spectral similarity with 3–16, it can be concluded that 3–16 have structures similar to 1 and 2. All the complexes were assayed for antibacterial activities against three Gram positive bacterial strains (Bacillus subtilis, Staphylococcus aureus, and Streptococcus faecalis) and three Gram negative bacterial strains (Escherichia coli, Pseudomonas aeruginosa, and Enterobacter cloacae) by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide method. Among the complexes tested, 8 and 16 showed the most favorable antibacterial activity with minimum inhibitory concentration of 0.781, 12.5, 6.25, 3.125, 3.125, 6.25 and 1.562, 6.25, 1.562, 3.125, 3.125, 1.562 µg mL^?1 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli, and E. cloacae, respectively.     

Synthesis,characterization, and antibacterial activity of two zinc(II) complexes with Schiff bases derived from rimantadine

The reactions of zinc(II) chloride and two Schiff base ligands derived from rimantadine and 5-chlorosalicylaldehyde/4-methoxysalicylaldehydes, generated two novel complexes [Zn(L¹)₂Cl₂] (I) and [Zn(L²)₂Cl₂] (II), where L¹ = 2-((1-(1-adamantan-1-yl)ethyl)-iminomethyl)-4-chlorophenol, L² = 2-((1-(1-adamantan-1-yl)ethyl)iminomethyl)-5-methoxyphenol. The complexes were characterized by the means of IR, ¹H NMR, elemental analysis, molar conductance and thermal analysis. A single-crystal X-ray diffraction analysis reveals that both complexes crystallize in orthorhombic system, space group Fdd2 for I and Pbcn for II. In two complexes crystals, each asymmetric unit consists of one zinc(II) ion, two corresponding Schiff base ligands and two chlorine atoms; the central zinc atom lies on a twofold rotation axis and is four-coordinate via two chlorine atoms and two oxygen atoms from the Schiff base ligands, forming a distorted tetrahedral geometry.     

Diphenyltin(IV) complexes of the 2-quinolinecarboxaldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate (Hqaldsme and Hqaldsbz): X-ray crystal structures of Hqaldsme and two conformers of its diphenyltin(IV) complex

New organometallic tin(IV) complexes of the empirical formula Sn(NNS)Ph₂Cl (NNS = anionic forms of the 2-quinolinecarboxaldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate) have been prepared and characterized by IR, electronic, ¹H NMR and ES mass spectroscopic techniques. The molecular structures of the 2-quinolinecarboxaldehyde Schiff base of S-methyldithiocarbazate (Hqaldsme) and its diphenyltin(IV) complex, Sn(qaldsme)Ph₂Cl, have been determined by X-ray diffraction. In the solid state, the ligand remains as the thione tautomer in which the dithiocarbazate chain adopts an E,E configuration and is almost coplanar with the quinoline ring. The Sn(qaldsme)Ph₂Cl complex crystallizes in two distinctly different conformationally isomeric forms, each having the same space group but different lattice parameters. X-ray analysis shows that in each polymorph, the tin atom adopts a distorted octahedral geometry with the Schiff base coordinated to it as a uninegatively charged tridentate chelating agent via the quinoline nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom. The two phenyl groups occupy axial positions and the chloride ligand occupies the sixth coordination position of the tin atom. The deprotonated ligand adopts an E,E,Z configuration in the complex.     

Preparation,characterization and biological evaluation of copper(II) and zinc(II) complexes with Schiff bases derived from amoxicillin and cephalexin

Copper(II) and zinc(II) complexes of Schiff bases obtained by condensation of amoxicillin and cephalexin with salicylaldehyde/pyridoxal were prepared and characterized by microanalytical, thermogravimetric, magnetic and spectroscopic data. All the complexes were found to be six‐coordinate and containing two water molecules. The electron paramagnetic resonance spectral lines exhibited rhombic distortion from axial symmetry, with g_|| > g_? > g_e, in the copper(II) complexes. The geometry of the zinc(II) complexes appears to be octahedral. All the compounds under investigation showed antibacterial activity. The antibacterial activity showed the following trend: copper(II) complexes > zinc(II) complexes > Schiff base ligands > parent drugs. The copper(II) complexes with the Schiff bases derived from cephalexin showed substantially enhanced activity against Pseudomonas aeruginosa compared with the parent drug. All the copper complexes were also found to be active against kaolin paw oedema, whereas the parent drugs were inactive. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis, structures, and antimicrobial activity of nickel(II) and zinc(II) complexes with Schiff bases derived from 3-bromosalicylaldehyde

The Schiff bases 2-bromo-6-[(3-cyclohexylaminopropylimino)methyl]phenol (HCMP) and 2-bromo-6-[(3-dimethylaminopropylimino)methyl]phenol (HDMP) derived from 3-bromosalicylaldehyde with N-cyclohexylpropane-1,3-diamine and N,N-dimethylpropane-1,3-diamine, respectively, and their nickel(II) and zinc(II) complexes [Ni(CMP)₂] (I) and [ZnCl₂(HDMP)] (II) have been prepared and characterized by elemental analyses, IR, and single crystal X-ray crystallographic determination. The crystal of I is monoclinic: space group P2₁/c, a = 12.0304(6), b = 13.1594(6), c = 10.2445(5) Å, β = 101.019(1)°, V = 1591.9(1) ų, Z = 2. The crystal of II is monoclinic: space group C2/c, a = 22.286(5), b = 12.210(3), c = 14.513(3) Å, β = 124.118(3)°, V = 3269.5(13) ų, Z = 8. The Schiff base HCMP coordinates to the Ni atom through the phenolate O, imine N, and amine N atoms, while the Schiff base HDMP coordinates to the Zn atom through the phenolate O and imine N atoms. The effect of these complexes on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans were studied.     

DNA-binding,antioxidant activity and solid-state fluorescence studies of copper(II), zinc(II) and nickel(II) complexes with a Schiff base derived from 2-oxo-quinoline-3-carbaldehyde

A Schiff base derived from 2-oxo-quinoline-3-carbaldehyde-4-aminophenazone and its Cu(II), Zn(II) and Ni(II) complexes were synthesized. The molecular structures of the Zn(II) and Ni(II) complexes were determined by X-ray crystal diffraction. The DNA-binding modes of the compounds were investigated by spectroscopic methods, viscosity measurements and ethidium bromide-DNA displacement experiments. The experimental evidence indicated the compounds interact with calf thymus DNA through intercalation. Additionally, the compounds exhibited potential antioxidant properties in in vitro studies, and the Cu(II) complex was the most effective. The solid-state fluorescence properties of the Zn(II) complex were studied.     

Zinc(II) and cadmium(II) complexes of Schiff bases derived from amino acids and pyridine-3-carboxaldehyde: synthesis,crystal structures,and fluorescence

Two d¹⁰ Schiff-base complexes, Zn₂(L₁)₂(H₂O)₆ ? SO₄ (1) and Cd(L₂)₂(H₂O)₄ (2) [HL₁ = 3-((pyrid-3-yl)-methylene)aminobenzoic acid; HL₂ = 4-((pyrid-3-yl)-methylene)aminobenzoic acid], have been synthesized and structurally characterized by elemental analyses, FT-IR spectra, and thermal studies, as well as single crystal X-ray diffraction. Complex 1 is a dinuclear macrocyclic structure with 22-membered rings and is assembled into a 3-D sandwich supramolecular network motif through H-bonding interactions; 2 is a mononuclear structure and is interlinked through H-bonding and π ··· π stacking contacts to generate another 3-D supramolecular network. Furthermore, fluorescent properties of the two complexes are also reported.     

Antibacterial evaluation of some Schiff bases derived from 2-acetylpyridine and their metal complexes

A series of Schiff bases derived from 2-acetylpyridne and their metal complexes were characterized by elemental analysis, NMR, FT-IR and UV-Vis spectral studies. The complexes were screened for anti-bacterial activity against Methicillin-resistant Staphylococcus aureus (MRSA), Acinetobacter baumanni (AC), Klebsiella pneumonie (KB) and Pseudomonas aeruginosa (PA) using the disc diffusion and micro broth dilution assays. Based on the overall results, the complexes showed the highest activities against MRSA while a weak antibacterial activity was observed against A. baumanii and P. aeruginosa.     

Biological activity of Co(III) and Ni(II) complexes of pyridine-2-carbaldehyde N(4)-methylthiosemicarbazone: Synthesis, characterization, crystal structure of Co(III) complex of pyridine-2-carbaldehyde N(4)-methylthiosemicarbazone1

Transition metal complexes formulated as [Co(L)₂]ClO₄ (I) and [Ni(L)₂] · H₂O (II), where HL = pyridine-2-carbaldehyde N(4)-methylthiosemicarbazone, have been synthesized. Complex I was characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction studies. In complex I, the ligand is N₂S tridentate, coordinating to the metal center through pyridine nitrogen, imine nitrogen and sulfur atoms. Hydrogen bonds link the different components to stabilize the crystal structure. Preliminary in vitro screening indicated that the free ligand was active against various bacteria and fungi and all the tested compounds showed significant antitumor activity against K562 leukaemia cell line, and can therefore be candidates for further stages of screening in vitro and/or in vivo.     

Synthesis and characterization of azo-linked Schiff bases and their nickel(II), copper(II), and zinc(II) complexes

Azo compounds were prepared by coupling of benzenediazonium chloride ions with 1-amino-2-hydroxy-4-naphthalene sulfonic acid under alkaline conditions, and Schiff bases, L_1–3 were then obtained by the condensation of 1-amino-2-hydroxy-3-(phenylazo)-4-naphthalene sulfonic acid, 1-amino-2-hydroxy-3-(4-ethylphenylazo)-4-naphthalene sulfonic acid, and 1-amino-2-hydroxy-3-(4-nitrophenylazo)-4-naphthalene sulfonic acid with salicylaldehyde. New copper(II), nickel(II), and zinc(II) complexes of the Schiff base ligands were also prepared and characterized by spectroscopic methods, magnetic measurements, elemental, and thermogravimetric analysis.     

Synthesis and mesogenic properties of binuclear copper(II) complexes derived from salicylaldimine Schiff bases

The synthesis and mesomorphic (liquid crystal) properties of new binuclear dihalocopper(II) complexes derived from N- and ring-substituted salicylaldimine Schiff bases are reported, together with the mesomorphic properties of their monomeric precursor complexes. With just N-substituents both the dichlorodicopper(II) binuclear complexes and their mononuclear analogues are waxy solids with melting points that increase with their N-chain length. However, with both N- and ring-substituents in the 4-positions, the mononuclear and binuclear complexes are each liquid crystalline or mesogenic, except in case of the mononuclear complexes where the N-substituent is straight chain alkyl. The other mononuclear complexes exhibit a variety of liquid crystal phases: smectic A, C, and E (SA, SC, and SE, respectively). The liquid crystal phase SA is observed in the binuclears with shorter chain N-substituents p-R-O-C6H4- and shorter chain ring-substituents. The chain lengths were increased until the phase behavior expanded to a further form SC in the case of an N-substituent p-C14H29O-C6H4- and a -OC12H25 ring substituent. This points the way toward achieving multiphase behavior with these binuclear systems. The Cu-Br analogues of the binuclear complexes behave similarly but with significant qualitative differences, specifically lower mesophase stability and higher melting temperatures. The structures of the nonmesogenic binuclears ([Cu(N-dodecylSal)X]2, X=Cl, Br) were determined with the aid of X-ray crystallography. These are prototypes for the structures of the binuclear complexes and especially for the shape of the central Cu2O2 X2 core in the binuclears: distorted planar coordination about the copper with distortion toward tetrahedral measured by a characteristic twist angle tau (0 degrees planar; 90 degrees tetrahedral). The binuclear complexes also show magnetic coupling which can be used to estimate the geometry. For [Cu(N-dodecylSal)X]2 tau>36 degrees, which corresponds to weaker coupling than observed in the mesogenic binuclears where a stronger magnetic coupling indicates a geometry closer to planar (tau=25 degrees). The mesophases were characterized by differential scanning calorimetry (DSC) analysis and optical polarized microscopy.     

Synthesis,structural characterization and biological activities of metal(II) complexes with Schiff bases derived from 5-bromosalicylaldehyde: Ru(II) complexes transfer hydrogenation

In this study, two novel Schiff base ligands (L¹ and L²) derived from condensation of methyl 2-amino-6-methyl-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate and methyl 2-amino-6-phenyl-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate, both starting matter with 5-bromo-salicylaldehyde, and their Zn(II) and Ni(II) metal complexes have been prepared using a molar ratio of ligand:metal as 1:1 except the Ru(II) complexes 1:0.5. The structures of the obtained ligands and their metal complexes were characterized by elemental analysis, FT-IR, ¹H NMR, ¹³C NMR, UV–vis, thermal analysis methods, mass spectrometry, and magnetic susceptibility measurements. Antioxidant and antiradical activity of Schiff base ligands and their metal complexes were been evaluated in vitro tests. Antioxidant activities of metal complexes generally were more effectives than free Schiff bases. 1c and 2c were used as catalysts for the transfer hydrogenation (TH) of ketones. 1c, 2c complexes were found to be efficient catalyst for transfer hydrogenation reactions.     

Nickel(II) complexes with Schiff bases derived from salicylaldehyde or pentanedione and 3-aminopropanethiol

Template reactions of salicylaldehyde or pentanedione with 3-aminopropanethiol (Hapt) in the presence of Ni(II) ions are described. When salicylaldehyde was used, a dinuclear Ni(II) complex [Ni(bit′)]₂ (2) (H₂bit′?=?2-(3′-mercaptopropyliminomethyl)phenol) was obtained instead of the reported trinuclear one [Ni(bit)]₃ (1) (H₂bit?=?2-(2′-mercaptoethyliminomethyl)phenol) containing 2-aminoethanethiol (Haet). Starting from pentanedione, the expected dinuclear complex [Ni(pit′)]₂ (H₂pit′?=?2-(3′-mercaptopropylimino)pentanol) was not obtained, nor was [Ni(pit)]₂ (3) (H₂pit?=?2-(2′-mercaptoethylimino)pentanol). The complex was found to be a trinuclear Ni(II) complex [Ni{Ni(apt)₂}₂]²⁺ (4), as confirmed by elemental analysis, electronic and NMR spectra. Complexes 1 and 3 were also synthesized and their ¹³C, ¹H–¹H and ¹³C–¹H?NMR spectra are discussed in detail. The X-ray crystal structure of 2 shows that two Ni(II) ions are connected by the thiolate donor atom from each ligand, resulting in a four-membered ring. Differences in reactivity and properties is due to the presence of an additional methylene group in the aminoalkane arm of the ligand.     

Crystal structures of copper(II) and zinc(II) complexes derived from 3-(2-pyridyl)pyrazole

Two dinuclear complexes [Zn(μ-L)(NO₃)(H₂O)]₂ (1) and [Cu₂(μ-L)₂(HL)₂](NO₃)₂(C₁₂H₈Br₂)_0.5·H₂O (2), (HL = 3-(2-pyridyl)pyrazole, C₁₂H₈Br₂ = 4,4′-dibromobiphenyl) are synthesized under hydrothermal conditions and characterized by elemental analysis and X-ray single crystal diffraction. Crystal data for 1: triclinic, \(P\bar 1\), a = 8.8478(7) Å, b = 15.0550(11) Å, c = 16.4310(12) Å, α = 107.588(4)°, β = 112.498(3)°, γ = 115.595(3)°, V = 2099.8(9) ų, Z = 2; for 2: triclinic, \(P\bar 1\), a = 7.2870(15) Å, b = 8.6840(17) Å, c = 9.3290(19) Å, α = 107.588(4)°, β = 112.498(3)°, γ = 115.595(3)°, V = 528.77(18) ų, Z = 1. Complex 1 and 2 are both dinuclear structures which are further packed into a 1D supramolecular chain and a 3D supramolecular framework via weak C–H…O hydrogen bond interactions respectively.     

Synthesis,characterization and crystal structure of some new Mn(II) and Zn(II) macroacyclic Schiff base complexes derived from two new asymmetrical (N5) branched amines and pyridine-2-carbaldehyde or O-vaniline and their antibacterial properties

Two new branched pentadentate amines (N₅), 3,6-bis(2-pyridylmethyl)-5 methyl-3,6-diazaheptane diazahexane-1-amine (1) and 4,7-bis(2-pyridylmethyl)-6-methyl-4,7-diazaheptane-1-amine (2) have been prepared. These have been used for the synthesis for the eight new macroacyclic Schiff base complexes, by template [1 + 1] condensation of pyridine-2-carbaldehyde or O-vaniline and amines (1 and 2) in the presence of Mn(II) and Zn(II) metal ions in methanol. The isolated complexes were characterized by a combination of microanalysis, IR and Mass spectroscopy. The structure of MnL¹(ClO₄)₂ indicates that in the solid state the Mn(II) ion adopts a slightly distorted octahedral geometry. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Enterococcus faecalis, Bacillus cereus and Staphylococcus epidermidis and also against the three Gram-negative bacteria: Citrobacter freundii, Enterobacter aerogenes and Salmonella typhi. The structure of the complexes derived from pyridine-2-carbaldehyde and metal–ligand interactions in these complexes were also theoretically studied. It was indicated that the structure of complexes is similar to each other and metal–ligand interactions depend mainly on the nature of metal ion and is similar for this series of ligands.     

Transition metal complexes of furfural and benzil schiff bases derived from S-benzyldithiocarbazate

New nickel(II), copper(II), cobalt(III) and rohdium(III) complexes of two Schiff base ligands formed by condensation of furfural and benzil with S-benzyldithiocarbazate have been synthesized and characterized by elemental analysis and magnetic and spectroscopic measurements. The nickel(II) complexes, Ni(NS)₂ and Ni(ONS)₂ (NS and ONS stand for the uninegatively charged furfural and benzil Schiff bases, respectively) are square-planar and octahedral, respectively. The Cu(NS)Cl complex is paramagnetic with a magnetic moment fo 1.73 B.M. A halogen-bridged dimeric structure is proposed for this complex. The copper(II) complex, Cu(ONS)Cl is diamagnetic, suggesting strong antiferromagnetic interactions between a pair of copper(II) ions in a thiolo sulphur-bridged dimeric or polymeric structure. Cobalt(II) ions are oxidized in the presence of the Schiff bases with the concomitant formation of cobalt(III) complexes of empirical formulae, Co(NS)₃, Co(ONS)₂ClO₄ and Co(ONS)₂Cl, respectively, which are spin-paired and octahedral. The rhodium(III) complex of the furfural Schiff base, Rh(NS)₂Cl is tentatively assigned a halogen-bridged dimeric structre.