Synthesis, characterization and crystal structures of di-three-coordinated copper(I) macrocyclic Schiff base complexes

The air-stable di-copper(I) complexes Cu₂L(SCN)₂ (1) and Cu₂L(SCN)_1.86I_0.14 (2) of the N₄ macrocyclic Schiff base ligand L have been synthesized and characterized by IR, elemental analysis, UV-Vis and crystal structure determination. X-ray analysis of the complexes shows an approximate distorted trigonal planar geometry around each copper(I) ion that is constructed from one N-bonded thiocyanate (or iodide in 2) group and two imine nitrogen atoms. DFT calculations were used to determine the structural features of the Cu₂L(SCN)₂ complex, and these were consistent with the experimental data for the complex.     

Synthesis, X-ray crystal structures, spectroscopic and cyclic voltammetric studies of Cu(II) Schiff base complexes of pyridoxal

Two mononuclear Cu(II) complexes, [Cu(L¹H₂)](ClO₄)_1.25Cl_0.75·1.25H₂O (1) and [Cu(L²H₂)](ClO₄)₂ (2), of the pyridoxal Schiff base ligands N,N′-dipyridoxylethylenediimine (L¹H₂) and N,N′-dipyridoxyl-1,3-propanediimine (L²H₂) are reported. X-ray crystal structures of both complexes are also reported. In both complexes the pyridoxal nitrogen atoms remain protonated. In the solid state, the tetradentate Schiff base ligand is virtually planar in 1, while in 2 the ligand conformation is like an inverted umbrella. In cyclic voltammetry experiments it is found that in these complexes the Cu(III) and Cu(I) states are more easily accessible than in their salen type analogs. The pyridoxal Schiff base complexes are also found to be resistant to oxidative electro-polymerization, unlike their corresponding salicyl aldehyde Schiff base complexes.     

The crystal structures and electrochemical studies of two naphthalenic Schiff base copper(II) complexes

The Schiff base ligands, 2-hydroxy-N-cyclohexyl-l-naphthaldimine (I), and 3-hydroxy-N-cyclohexyl-2-naphthaldimine (II), and their corresponding Cu^II complexes (1–2) respectively were synthesized and characterized. The crystal and molecular structures of bis-{(cyclohexyl)[(2-oxo-1H-naphth-1-ylidene)-methyl]aminato}copper(II) (1) and bis-{(cyclohexyl)[(3-oxo-2H-naphth-2-ylidene)-methyl]aminato} copper(II) (2), were determined. The X-ray diffraction study shows that the geometry around the metal atom for (1), is stepped square planar with a step of 1.063 Å while for (2), the geometry around the metal atom for square planar with an angle between the coordination planes O(1)---Cu---N(1) and O(1a)---Cu---N(1a) of 39.9°. Electrochemical studies show a dependence of the Cu^II/Cu^I potentials on the ligand structure.     

Synthesis,characterization, and electrochemical study of two new macroacyclic Schiff bases and their copper(II) and zinc(II) complexes

Two new potentially octadentate N₂O₆ Schiff-base ligands 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)phenoxy)phenylimino)methyl)-6-methoxyphenol H₂L¹ and 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)-4-tert-butylphenoxy)phenylimino)methyl)-6-methoxyphenol H₂L² were prepared from the reaction of O-Vaniline with 1,2-bis(2′-aminophenoxy)benzene or 1,2-bis(2′-aminophenoxy)-4-t-butylbenzene, respectively. Reactions of H₂L¹ and H₂L² with copper(II) and zinc(II) salts in methanol in the presence of N(Et)₃ gave neutral [CuL¹]?·?0.5CH₂Cl₂, [CuL²], [ZnL¹]?·?0.5CH₂Cl₂, and [ZnL²] complexes. The complexes were characterized by IR spectra, elemental analysis, magnetic susceptibility, ESI–MS spectra, molar conductance (Λ_m), UV-Vis spectra and, in the case of [ZnL¹]?·?0.5CH₂Cl₂ and [ZnL²], with ¹H- and ¹³C-NMR. The crystal structure of [ZnL¹]?·?0.5CH₂Cl₂ has also been determined showing the metal ion in a highly distorted trigonal bipyramidal geometry. The electrochemical behavior of H₂L² and its Cu(II) complex, [CuL²], was studied and the formation constant of [CuL²] was evaluated using cyclic voltammetry. The logarithm value of formation constant of [CuL²] is 21.9.     

Synthesis,crystal structures and fluorescence properties of two new di- and polynuclear Cd(II) complexes with N2O donor set of a tridentate Schiff base ligand

Two new Cd(II) complexes, having one binuclear structure [Cd₂(L)₂(Cl)₂] (1) and another azido bridged one-dimensional zig-zag polynuclear network [Cd₃(μ_1,1-N₃)₄(L)₂{H₂N(CH₂)₂N(C₂H₅)₂} · H₂O]_n (2) have been synthesized from a tridentate N₂O donor Schiff base ligand LH, [LH = (OCH₃)(OH)C₆H₃CHN(CH₂)₂N(C₂H₅)₂], which is the condensation product of 2-hydroxy-4-methoxybenzaldehyde and 2-diethylaminoethylamine. Both the complexes 1 and 2 have been characterized by elemental analyses, IR & ¹H NMR spectroscopy, TGA and fluorescence studies. Finally their structures have been established by single crystal X-ray diffraction method. Structural study reveals that in the complex 1, two Cd(II) centers are held together by two μ₂-phenolato oxygen atoms and the terminal chlorine atom occupies the apical site of the square pyramidal environment of each metal center. In case of complex 2, the trinuclear asymmetric unit contains octahedral Cd(II) centers which are further held together by doubly end-on azido bridging to form a zig-zag polynuclear structure. It also displays intraligand ¹(π–π^∗) fluorescence and can potentially serve as photoactive material.     

Synthesis and characterization of three novel manganese(II) octaaza macrocyclic Schiff base complexes containing a phenanthroline and two pyridyl units as pendant arms. X-ray crystal structure determination of one manganese(II) complex

Three new branched hexadentate amines (N₆), 3,6-bis(2-pyridylmethyl)-3,6-diazaoctane-1,8-diamine (1), 3,7-bis(2-pyridylmethyl)-3,7-diazanonane-1,9-diamine (2) and 3,8-bis(2-pyridylmethyl)-3,8-diazadecane-1,10-diamine (3) have been synthesized. Subsequently, three novel Schiff base macrocyclic complexes containing a phenanthroline and two 2-pyridylmethylpendant arms have been prepared by template [1+1] cyclocondensation of 2,9-dicarboxaldehyde-1,10-phenanthroline and the branched hexadentate amines (1–3), in the presence of Mn(II) in methanol. These complexes have ligands with 18-, 19- and 20-membered hexaaza macrocycles and two 2-pyridylmethyl pendant arms (L¹, L² and L³, respectively). All the complexes have been characterized by elemental analysis and IR spectroscopy. The crystal structure of [MnL¹](ClO₄)₂ · 3CH₃CN was determined and indicates that in the solid state the complex adopts a slightly distorted hexagonal bipyramidal geometry with the Mn(II) ion located within a hexaaza macrocycle with the two 2-pyridylmethyl pendant arms coordinating in axial positions.     

Syntheses,characterization and X-ray crystal structures of Ni(II) complexes of tridentate monocondensed and tetradentate dicondensed Schiff bases

Two octahedral complexes [Ni(HL¹)₂](ClO₄)₂ (1) and [Ni(HL²)₂](ClO₄)₂ (2) and a square planar complex [Ni(HL³)]ClO₄ (3) have been prepared, where [HL¹ = 3-(2-amino-ethylimino)-butan-2-one oxime, HL² = 3-(2-amino-propylimino)butan-2-one oxime] and H₂L³ = 3-[2-(3-hydroxy-1-methyl-but-2-enylideneamino)-1-methyl-ethylimino]-butan-2-one oxime. All the complexes have been characterized by elemental analyses, spectral studies and room temperature magnetic moment measurements. The molecular structures of all three compounds were elucidated on the basis of X-ray crystallography; complexes 1 and 2 are seen to be the mer isomers.     

Synthesis,characterization and crystal structures of dinuclear macrocyclic Schiff base copper(I) complexes bearing different bridges

Utilizing a new 20-membered macrocyclic Schiff base ligand with two coordination sites formed from the [2+2] condensation of 1,3-diaminopropane and benzene-1,3-dicarboxaldehyde in the presence of CuX (X = Cl⁻, Br⁻, I⁻) salts, air-stable dicopper(I) complexes were synthesized in acetonitrile, intramolecularly linked via two halide groups, and characterized by different physico-chemical techniques. The single crystal X-ray diffraction technique indicates these complexes consist of two N₂X₂ donor sets that have distorted tetrahedral coordination environments around the copper(I) ions. In these halogen-bridged binuclear Cu₂LX₂ systems the Cu?Cu separation can be controlled, as this distance is reduced on increasing the halide size and hence the X?X repulsion, with the rigidity of the macrocycle playing a significant role.     

Spectral characterization,electrochemical, antimicrobial and cytotoxic studies on new metal(II) complexes containing N2O4 donor hexadentate Schiff base ligand

We report the biological activity of the new Schiff base ligand H₂L (H₂L = 6,6′-((1E,11E)-5,8-dioxa-2,11-diazadodeca-1,11-diene-1,12-diyl)bis(2,4-dichlorophenol)), its derived metal(II) complexes [Cu(L)] (1), [Co(L)] (2), [Ni(L)] (3) and [Zn(L)] (4), along with their structural characterizations by using various analytical and spectroscopic techniques. Electrochemical investigations showed that all of these Cu(II), Co(II) and Ni(II) complexes were reversibly reducible. Although the change of the number of unpaired electrons are different of the metal cations, they have an effect on the redox potentials of the Co(II)/(I), Ni(II)/(I) and Cu(II)/(I) couples. The ¹H NMR and FTIR data concluded that the Schiff base ligand H₂L acts as a hexadentate ligand coordinating with metal(II) ions through the oxygen atoms of the (COC), phenolic (COH) groups and nitrogen atom of the azomethine (CHN) group. UV-Visible absorption spectra studies clearly revealed the octahedral geometry of the prepared metal(II) complexes. Complexes 1 and 4 were found to be efficient in bringing about antimicrobial activities. The proposed mechanism of their antimicrobial activities has been discussed. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay showed the remarkable cytotoxicity of complex 1 (IC50 = 17 ± 1.3 μg/mL) on human breast cancer MCF-7 cells than Schiff base ligand H₂L and complexes 2–4. Moreover, AO/EB staining assay revealed cell death due to apoptosis in MCF-7 cells and the generation of ROS by the Schiff base ligand H₂L and its derived metal(II) complexes 1–4 may be a possible cause for their cytotoxic activity.     

Sodium-mediated self-assembly of two nickel(II) Schiff base complexes: crystal structure and characterizations

Sodium-assisted self-assembly of two nickel(II) Schiff base complexes under similar reaction conditions yield hetero-metallic compounds [{Ni(salpn)}₂Na(ClO₄)] (1) and [{Ni(salpr)}₃Na][Ni(salpr)]₂ClO₄·2H₂O (2) (where salpn?=?N,N′-bis-(salicylidene)-1,3-diaminopropane and salpr?=?N,N′-bis-(salicylidene)-1,2-diaminopropane). Both have been characterized by physico-chemical techniques and single-crystal X-ray diffraction. Crystal structure reveals that in the tri-metallic system of 1 sodium is sandwiched between two [Ni(salpn)] units while the hexametallic system of 2 consists of tetrametallic cluster ion [{Ni(salpr)}₃Na]⁺ with encapsulated sodium by three [Ni(salpr)] units. In both complexes, sodium adopts distorted trigonal prismatic geometry leaving nickel(II) in a distorted square-planar environment. Structural characterization also reveals that 2?:?1 (for 1) and 3?:?1 (for 2) self-assemblies of metallo-ligand and sodium were achieved with slight variation in ligand backbone.     

Synthesis,crystal structures and spectral studies of square planar nickel(II) complexes containing an ONS donor Schiff base and triphenylphosphine

Five mononuclear nickel(II) complexes, viz. [Ni(L1)(PPh₃)] (1), [Ni(L2)(PPh₃)] (2), [Ni(L3)(PPh₃)] (3), [Ni(L4)(PPh₃)] (4) and [Ni(L5)(PPh₃)] (5) (where L1, L2, L3, L4 and L5 are dianions of N-(2-mercaptophenyl)salicylideneimine, 5-methyl-N-(2-mercaptophenyl)salicylideneimine, 5-chloro-N-(2-mercaptophenyl)salicylideneimine, 5-bromo-N-(2-mercaptophenyl)salicylideneimine and N-(2-mercaptophenyl)naphthylideneimine, respectively), have been synthesized and characterized by means of elemental analysis, electronic, IR, ¹H, ¹³C and ³¹P NMR spectroscopy. Single crystal X-ray analysis of two of the complexes (1 and 5) has revealed the presence of a square planar coordination geometry (ONSP) about nickel. The crystal structures of the complexes are stabilized by intermolecular π–π stacking between the ligands (L) and by various C–H···π interactions.     

Synthesis,structure and magnetic properties of mono- and di-nuclear nickel(II) thiocyanate complexes with tridentate N3 donor Schiff bases

The 1:1 condensation of N-methyl-1,3-diaminopropane and N,N-diethyl-1,2-diminoethane with 2-acetylpyridine, respectively at high dilution gives the tridentate mono-condensed Schiff bases N-methyl-N′-(1-pyridin-2-yl-ethylidene)-propane-1,3-diamine (L¹) and N,N-diethyl-N′-(1-pyridin-2-yl-ethylidene)-ethane-1,2-diamine (L²). The tridentate ligands were allowed to react with methanol solutions of nickel(II) thiocyanate to prepare the complexes [Ni(L¹)(SCN)₂(OH₂) (1) and [{Ni(L²)(SCN)}₂] (2). Single crystal X-ray diffraction was used to confirm the structures of the complexes. The nickel(II) in complex 1 is bonded to three nitrogen donor atoms of the ligand L¹ in a mer orientation, together with two thiocyanates bonded through nitrogen and a water molecule, and it is the first Schiff base complex of nickel(II) containing both thiocyanate and coordinated water. The coordinated water initiates a hydrogen bonded 2D network. In complex 2, the nickel ion occupies a slightly distorted octahedral coordination sphere, being bonded to three nitrogen atoms from the ligand L², also in a mer orientation, and two thiocyanate anions through nitrogen. In contrast to 1, the sixth coordination site is occupied by a sulfur atom from a thiocyanate anion in an adjacent molecule, thus creating a centrosymmetric dimer. A variable temperature magnetic study of complex 2 indicates the simultaneous presence of zero-field splitting, weak intramolecular ferromagnetic coupling and intermolecular antiferromagnetic interactions between the nickel(II) centers.     

Synthesis,crystal structure,and antibacterial activity of two new mononuclear nickel(II) complexes of a NNS Schiff base

Two new mononuclear nickel(II) complexes, [Ni(L)(N₃)] (1) and [Ni(L)₂(NCS)₂] (2), where HL = 2-{[phenyl(pyridin-2-yl)methylidene]amino}benzenethiol, a tridentate Schiff base derived from 2-aminothiophenol and 2-benzoylpyridine, have been prepared and characterized. The syntheses of 1 and 2 have been achieved by the reaction of equimolar amounts of nickel perchlorate and HL in the presence of azide and thiocyanate, respectively. The complexes have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction, and other physicochemical studies. Structural studies reveal that 1 and 2 adopt two different geometries, distorted square planar in 1 and octahedral in 2. The two mononuclear complex units are held together by π…π or C–H…π weak intermolecular interactions to develop supramolecular networks in their solid states. The antibacterial activity of 1, 2 and their constituent Schiff base has been tested against some gram(+) and gram(?) bacteria.     

Synthesis and spectral characterization of mercury(II) complexes with the bidentate Schiff base ligand N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane: The crystal structures of [Hg((23-MeO-ba)2en)I2] and [Hg((23-MeO-ba)2en)Br2]

Three mercury(II) complexes, [Hg((23-MeO-ba)₂en)X₂] (X = I (1), Br (2) and Cl(3)), and the ligand (23-MeO-ba)₂en ((23-MeO-ba)₂en = N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane) have been synthesized and characterized by elemental analyses, FT-IR and ¹H NMR spectroscopy. The crystal and molecular structures of 1 and 2 were determined by X-ray crystallography from single-crystal data. The metal-to-ligand ratio was found to be 1:1. The mercury(II) center in 1 and 2 has a distorted tetrahedral geometry with HgN₂I₂ and HgN₂Br₂ chromophores, respectively. The Schiff base ligand (23-MeO-ba)₂en acts as a chelating ligand, coordinating via the two nitrogen atoms to the mercury(II) center, and it adopts an E,E conformation. The coordination sphere of the mercury(II) center in 1 and 2 is completed by the two I and Br atoms, respectively. In complex 1 an inter-molecular non-classical hydrogen bond of the type C-H?O was found, while in complex 2 inter- and intra-molecular non-classical hydrogen bonds of the type C-H?X (X = O and Br) were found. The ¹H NMR spectra of the complexes exhibit downfield as well as upfield shifts of the free ligand resonances, reflecting changes in the ligand’s geometry during its coordination.     

Synthesis,X-ray crystal structure,and electrochemistry of polynuclear azido-bridged manganese(III) and copper(II) Schiff base complexes

New azido-bridged [Mn^III(salabza)(μ-1,3-N₃)]_n (1), and [Cu^II₄(salabza)₂(μ-1,1-N₃)₂(N₃)₂(HOCH₃)₂],(2) complexes with an unsymmetrical Schiff base ligand, {H₂salabza = N,N’-bis(salicylidene)-2-aminobenzylamine}, have been synthesized, characterized by spectroscopic and electrochemical methods, and their crystal structures have been determined by X-ray diffraction. In complex 1, each manganese(III) atom is coordinated with N₂O₂ donor atoms from salabza and two adjacent Mn(III) centers are linked by an end-to-end (EE) azide bridge to form a helical polymeric chain with octahedral geometry around the Mn(III) centers. Complex 2 is a centrosymmetric tetranuclear compound containing two types of Cu(II) centers with square pyramidal geometry. Each terminal copper atom is surrounded by N₂O₂ atoms of a salabza ligand, and the oxygen atom of the methanol molecule. Each central copper(II) ion is coordinated with two phenoxo oxygen atoms from one salabza, one terminal azido, and two end-on (EO) bridging azido ligands. The central copper(II) ions are linked to each other by the two end-on (EO) azido groups.     

Preparation,spectroscopic characterization and X-ray crystal and molecular structures of nickel(II), copper(II) and zinc(II) complexes of the Schiff base formed from isatin and S-methyldithiocarbazate (Hisa-sme)

Complexes of general formula, [M(isa-sme)₂] · n(solvate) [M = Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; isa-sme = monoanionic form of the Schiff base formed by condensation of isatin with S-methyldithiocarbazate; n = 1 or 1.5; solvate = MeCN, DMSO, MeOH or H₂O] have been synthesized and characterized by a variety of physicochemical techniques. An X-ray crystallographic structure determination of the [Ni(isa-sme)₂] · MeCN complex reveals a six-coordinate, distorted octahedral geometry. The two uninegatively charged, tridentate, Schiff base ligands are coordinated to the nickel(II) ion meridionally via the amide O-atoms, the azomethine N-atoms and the thiolate S-atoms. By contrast, the crystal structure of [Zn(isa-sme)₂] · MeOH shows a four-coordinate distorted tetrahedral geometry. The two dithiocarbazate ligands are coordinated as N, S bidentate chelates with the amide O-atom not coordinated. The structure of the copper(II) complex [Cu(isa-sme)₂] · DMSO is complicated and comprises two different complexes in the asymmetric unit, one four- and the other five-coordinate. The four-coordinate copper(II) has a distorted (flattened) tetrahedral geometry as seen in the Zn(II) analogue whereas the five-coordinate copper(II) has a distorted square-pyramidal geometry with one ligand coordinated to the copper(II) ion as a tridentate (N, S, O) ligand and the other coordinated as a bidentate N, S chelate. EPR spectroscopy indicates that in solution only one form is present, that being a distorted tetrahedral complex.     

The structures and cyclic voltammetry of three copper(II) complexes derived from bulky ortho-hydroxy Schiff bases

Three copper(II) complexes derived from bulky ortho-hydroxy Schiff base ligands, (1)-(3), were synthesized and characterized by chemical analysis, UV-Vis, IR, μ_eff and mass spectrometry. The solid state structures of compounds (1)-(3) were determined. The solid state X-ray diffraction studies of these compounds show that the geometry is intermediate between square planar and tetrahedral. Moreover, EPR studies in DMF solution at 77 K suggest that the geometry of these complexes in solution is different from that observed in the solid state by X-ray crystallography. Furthermore, cyclic voltammetry studies performed for (1)-(3), indicate a dependence of the cathodic potentials upon conformational and electronic effects.