Spectral and structural studies of copper(II) complexes of thiosemicarbazones derived from salicylaldehyde and containing ring incorporated at N(4)-position

Mononuclear and binuclear copper(II) complexes (1-8) with two ONS donor thiosemicarbazone ligands {salicylaldehyde 3-hexamethyleneiminyl thiosemicarbazone [H2L1] and salicylaldehyde 3-tetramethyleneiminyl thiosemicarbazone [H2L2]} have been prepared and physico-chemically characterized. IR, electronic and EPR spectra of the complexes have been obtained. The thiosemicarbazones bind to metal as dianionic ONS donor ligands in all the complexes except in [Cu(HL1)2] (2) and [Cu(HL2)2] (6). In compounds 2 and 6 the ligands are coordinated as monoanionic HL- ones. The magnetic susceptibility measurements indicate that all the complexes are paramagnetic. In complex [(CuL1)2] (1), the magnetic moment value is lower than the expected spin only value. In all the complexes g(||)>g( perpendicular)>2.0023 and G values within the range 2.5-3.5 are consistent with dx2-y2 ground state. The complexes were given the formula as [(CuL1)2] (1); [Cu(HL1)2] (2); [CuL1bpy] (3); [CuL1phen] (4); [CuL1gamma-pic].2H2O (5); [Cu(HL2)2] (6); [CuL2py].3H2O (7); [CuL2bipy] (8). The structure of the compound 8 have been solved by single crystal X-ray crystallography and was found to be distorted square pyramid around copper(II) ion.     

Spectroscopic evaluation of manganese(II) complexes derived from semicarbazones and thiosemicarbazones

Manganese(II) complexes having the general composition Mn(L)2X2 [where L=isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl-, 1/2SO(4)2-] have been synthesized. All the complexes were characterized by elemental analyses, molar conductance, magnetic moment susceptibility, EI-mass, 1H NMR, IR, EPR and electronic spectral studies. All the complexes show magnetic moments corresponding to five unpaired electrons. The possible geometries of the complexes were assigned on the basis of EPR, electronic and infrared spectral studies.     

Manganese(II) and copper(II) complexes of some nitrogenoxygen and nitrogensulphur donor ligands

Manganese(II) and copper(II) complexes of the type M(ligandH)₂ with some nitrogenoxygen and nitrogensulphur donor ligands (HL) viz. phenylpyruvic acid semicarbazone (ppysc), 4-methylphenylpyruvic acid semicarbazone (4-mppysc), phenylpyruvic acid thiosemicarbazone (ppytsc) and 4-methylphenyl pyruvic acid thiosemicarbazone (4-ppytsc), have been synthesised. All the complexes have been characterised by magnetic moment measurements, IR electronic and electron spin resonance special studies. All the ligands behave as tridentate.     

Spectral studies of iron(III) complexes of substituted thiosemicarbazones of 2-acetylpyridine

Summary Iron(III) complexes of four substituted thiosemicarbazones of 2-acetylpyridine of general. formula [FeL₂]ClO₄ (where L is a deprotonated ligand) have been synthesised and characterised by elemental analyses, magnetic susceptibility measurements in the polycrystalline state at room temperature, i.r. spectra, electronic spectra and e.s.r. spectra recorded in polycrystalline state, in methanol solution at room temperature and at 77 K. All the complexes are 1:1 electrolytes. The ligands coordinate via the pyridine nitrogen, imine nitrogen and thione sulphur. E.s.r. spectra and with magnetic studies suggest a spin-paired configuration for the iron(III) complexes.Author to whom all correspondence should be directed     

Cobalt(II) complexes of 4-acetamidobenzaldehyde N(4)-substituted thiosemicarbazones

Cobalt(II) complexes of five 4-acetamidobenzaldehyde N(4)-substituted thiosemicarbazones have been prepared in EtOH solution and characterized by i.r., electronic and n.m.r. spectra, and by magnetic susceptibilities and molar conductivity measurements. The thiosemicarbazones coordinate as monoanionic or neutral ligands via the thiosemicarbazone azomethine nitrogen and thione/thiolato sulfur, the latter by loss of the thioamide hydrogen, N(2)H. The resulting cobalt(II) complexes exhibit a varied stereochemistry.     

Structural, spectral and antimicrobial studies of copper(II) complexes of 2-benzoylpyridine N(4)-cyclohexyl thiosemicarbazone

Six new copper(II) complexes of 2-benzoylpyridine N(4)-cyclohexyl thiosemicarbazone (HL) have been synthesized and characterized by different physicochemical techniques like molar conductivity measurements, magnetic studies and electronic, infrared and EPR spectral studies. Five of the complexes have been found to possess the stoichiometry [CuLX], where X = Cl (1), Br (2), NO₃ (3), NCS (4), N₃ (5). The complex prepared from copper sulfate has the composition [Cu₂L₂SO₄] · (H₂O)₂ (6). In all the complexes the deprotonated ligand, L and the anion were found to be coordinated to the Cu(II) ion. The terdentate nature of the ligand is evident from the IR spectra. The metal ligand bonding parameters evaluated from the EPR spectra indicate strong in-plane σ and in-plane π bonding. The magnetic and spectroscopic data indicate a square planar geometry for complexes 1, 3, 4 and 5, while the complexes 2 and 6 are assigned a square pyramidal geometry. Crystal structure of the complex [CuLCl] reveals two molecules per asymmetric unit of a monoclinic lattice, with space group symmetry P2₁/n. The complexes [ CuLBr ₂] (2) and [CuLNCS] (4) crystallized into triclinic lattices with space group . Compound 2 exists as a thiolate bridged copper(II) dimer. The antimicrobial activity of the ligand and the copper complexes were tested against five types of bacteria isolated from clinical samples. The complexes were found to be active against Bacillus sp., Vibrio cholera O1, Staphylococcus aurus and Salmonella paratyphi.     

New iron(III) complexes with thiosemicarbazones derived from 5-methyl-3-formylpyrazole

New iron(III) complexes of 5-methyl-3-formylpyrazole thiosemicarbazone (HMPzTS) and 5-methyl-3-formylpyrazole-4-phenylthiosemicarbazone (HMPzPTS), namely [Fe(MPzTS)₂]X and [Fe(MPzPTS)₂]X respectively, where X=Cl, NO₃, SCN and ClO₄, have been synthesised and physico-chemically characterised by magnetic measurements (polycrystalline state), electronic, i.r., e.s.r. and Mössbauer spectra. All are cationic complexes containing two monoprotonic tridentate ligands with NNS donor sites and an anionic counterpart; they behave as 1:1 electrolytes in MeOH/DMF. Coordination to central iron(III) via the pyrazolyl nitrogen (²N), the azomethine nitrogen and the thiolato sulphur atom is confirmed in the complexes from i.r. data. E.s.r. data (RT & LNT) reveal the presence of a spin-paired iron(III) cation with d² _xyd² _yzd¹ _xy configuration. The ⁵⁷Fe Mössbauer spectral data (RT) are commensurate with the presence of two iron(III) spin states, the percentage of each being dependent upon the counterion of the species.     

Study in Aqueous Solutions of Bioactive 2-Pyridineformamide-Derived Thiosemicarbazones and Their Iron(II) and Iron(III) Complexes

The binary systems of iron(II) and iron(III) with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives were studied in aqueous solution by pH-potentiometry, ultraviolet–visible spectroscopy and EPR spectra. The formation constants of the iron(II) and iron(III) complexes were calculated from potentiometric and electronic absorption data at 25 °C and ionic strength μ = 0.1 mol·L^?1 using the HYPERQUAD program. The values of the formation constant of the FeL species decrease in the order Fe:H2Am4DH > Fe:H2Am4Me ≈ Fe:H2Am4Et > Fe:H2Am4Ph in the same way as the basicity of the ligands. The species distribution diagrams show that the species FeL₂ predominates at physiological pH in the Fe:H2Am4DH, Fe:H2Am4Me and Fe:H2Am4Et systems. The similar EPR spectra of these iron(III) binary systems indicate the same coordination spheres around the metallic center and the EPR g values suggests that the unpaired electron is in the d_xy orbital, indicating a d _xz ² d _yz ² d _xy ¹ ground state configuration for the complexes. For the Fe(III):H2Am4Ph system the EPR results indicated dimerization and antiferromagnetic interaction due to the presence of only one thiosemicarbazone ligand around the metallic center.     

Transition metal quinone-thiosemicarbazone complexes 3: Spectroscopic characterizations of spin-mixed iron (III) of naphthoquinone-thiosemicarbazones

An interesting series of iron (III) complexes with naphthoquinone-thiosemicarbazones are synthesized and physico-chemically characterized by elemental analysis, UV-vis, IR, EPR and magnetic susceptibility measurements. They possess a cationic octahedral [FeL2]+ species and a tetrahedral [FeCl4]- anion and exhibit unusual spin-mixed states involving high-spin and low-spin ferric centers as revealed from magnetic behavior with significant amount of exchange interactions mediated by intermolecular associations. The magnetic susceptibility data is fitted with S1=5/2 and S2=1/2 Heisengberg's exchange coupled model; H=-2JS1S2 and the magnetic exchange interactions are found to be of the order of -13.6 cm-1 indicating the moderate coupling between two paramagnetic centers present in different chemical and structural environment. The presence of spin-paired iron (III) cation having dxz2dxz2dxz1 ground state is revealed from the EPR spectra with three prominent peaks while the high-spin tetrahedral iron (III) anion exhibits characteristics g=4 signal whose intensity increases with lowering the temperature suggesting its influence on the magnetic properties of the complex molecule. FTIR measurements indicate tridentate ONS donor systems involving quinone/hydroxyl oxygen, imine/hydrazinic nitrogen and thione/thiol sulfur atoms as binding sites for naphthoquinone-thiosemicarbazones.     

Synthesis and spectroscopic studies on iron(III) complexes of 1-benzotriazol-1-yl-1-[(p-X-phenyl)hydrazono]propan-2-one

A new series of iron(III) complexes are synthesized from the reaction of the polyfunctional ligands 1-benzotriazol-1-yl-1-[p-X-phenyl]hydrazono]propan-2-one (X=H, Cl, NO(2), CH(3) or OCH(3) corresponding to HL(1),HL(2), HL(3), HL(4) or HL(5), respectively, with iron(III) chloride in the presence of LiOH by the conventional and microwave induced energy methods. The conventional method led to the formation of [FeL(3)].nH(2)O but the microwave induced energy gave [FeLCl(2)], n=1-3 and L is the anion of HL(1)-HL(5). The complexes are characterized by the elemental analysis, molar conductivity, magnetic and spectral (FT-IR, UV-vis and ESR) studies. The magnetic and spectral studies showed that [FeLCl(2)] are polymeric octahedral, [Fe(L(1))(3)].H(2)O is a low spin octahedral and (d(xz),d(yz))(4) (d(xy))(1) ground state, [FeL(3)].nH(2)O, L=anion of HL(4) or HL(5) and are octahedral with intermediate spin (S=32) with ground state (d(xy))(2)(d(xz),d(yz))(3) electronic configuration while for the anions of HL(2) and HL(3), they have (t(2g))(3)(e(g))(5) admixed with (d(xy))(2)(d(xz),d(yz))(3) configurations. From the ESR data, the contribution of the high spin (S=52) and low spin (S=32) to the quantum mechanical spin intermediate (QMS), and the crystal field parameters Delta and V are calculated and related to the electronic and steric effects of the ligands. The electronic spectral data confirm that obtained from the ESR, and the different ligand field parameters as well as the pi-->t(2g), t(2g)-->e(g), e(g)-->pi*, pi-->pi* transitions are estimated and compared with that experimentally obtained.     

First row transition metal complexes of (E)-2-(2-(2-hydroxybenzylidene) hydrazinyl)-2-oxo-N-phenylacetamide complexes

Manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and chromium(III) complexes of (E)-2-(2-(2-hydroxybenzylidene)hydrazinyl)-2-oxo-N-phenylacetamide were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment. Mononuclear complexes are obtained with 1:1 molar ratio except [Mn(HOS)(2)(H(2)O)(2)] and [Co(OS)(2)](H(2)O)(2) complexes which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a monobasic bidentate one and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the carbonyl oxygen atom, azomethine nitrogen atom and the hydroxyl oxygen. Moreover, the ligand behaves as a dibasic tridentate and coordination occurs via the enolic oxygen, azomethine nitrogen and the hydroxyl oxygen atoms. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complexes possesses a square planar geometry. From the modeling studies, the bond length, bond angle, HOMO, LUMO and dipole moment had been calculated to confirm the geometry of the ligands and their investigated complexes. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes. The protonation constant of the ligand and the stability constant of metal complexes were determined pH-metrically in 50% (v/v) dioxane-water mixture at 298 K and found to be consistent with Irving-Williams order. Moreover, the minimal inhibitory concentration (MIC) of these compounds against Staphylococcus aureus, Escherechia coli and Candida albicans were determined.     

EPR, mass, IR, electronic, and magnetic studies on copper(II) complexes of semicarbazones and thiosemicarbazones

Copper(II) complexes having the general composition Cu(L)(2)X(2) [where L = isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC), and 4-aminoacetophenone thiosemicarbazone (LLD) and X = Cl(-), 1/2SO(4)(2-)] have been synthesized. All the Cu(II) complexes reported here have been characterized by elemental analyses, molar conductance, magnetic moment susceptibility, EI mass, (1)H NMR, IR, EPR, and electronic spectral studies. All the complexes were found to have magnetic moments corresponding to one unpaired electrons. The possible geometries of the complexes were assigned on the basis of EPR, electronic, and infrared spectral studies.     

Electron paramagnetic resonance characteristics of some non-heme low-spin iron(III) complexes

We have recorded the powder EPR-spectra of some near octahedral iron(III) complexes with tridentate ligands donors and analysed their spectra with simple ligand field analysis and for some cases with the angular overlap model (AOM). We have determined the electron praramagnetic resonance (EPR) characteristic of bis 1,4,7-triazacyclonane iron(III)chloride at 4 K and found that it was similar to the characteristics of the so-called 'highly anisotropic low spin' complexes. We have recorded the powder spectra of bis (2,6-bis(benzimidazoly-2-yl)pyridine) iron(III) perchlorate and made an AOM-analyses of the structural similar complex bis-(2,6 (N-carbamoyl)-pyridine) iron(III). With a combination of ligand field analyses and AOM, we could determine the pi-donor properties of these ligands. The same approach have been used to determine the pi-donor properties of the hydroperoxo ligand. Finally we have recorded the powder EPR-spectrum of [Fe(CN)6]3- doped in K3[Co(CN)6] and [Co(NH3)6][Co(CN)6] at 4 and 100 K and in water at 4 K. The spectra are interpreted as the effect of a dynamic Jahn-Teller distortion.     

Studies on Co(II) and Co(III) complexes of di-2-pyridyl ketone N(4)-cyclohexyl and N(4)-phenyl thiosemicarbazones

Six new Co(II) and Co(III) complexes (1–6) of di-2-pyridyl ketone N(4)-cyclohexyl thiosemicarbazone (HL¹) and di-2-pyridyl ketoneN(4)-phenyl thiosemicarbazone (HL²) have been synthesized and spectrochemically characterized. HL¹ is newly synthesized and has been structurally characterized by single crystal X-ray diffraction studies, while HL² has been previously reported. HL¹ crystallizes into a monoclinic lattice with the space group P2₁. The complexes are characterized by magnetic, EPR, NMR and other spectroscopic studies. The EPR spectra of the paramagnetic complexes reveal axial features with eight hyperfine lines clearly resolved in the perpendicular region.     

Preparation,Characterization, Biological Activity and 3D Molecular Modeling of Mn(II), Co(II), Ni(II), Cu(II), Pd(II) and Ru(III) Complexes of Some Sulfadrug Schiff Bases

Mn(II), Co(II), Ni(II), Cu(II), Pd(II) and Ru(III) complexes of Schiff bases derived from the condensation of sulfaguanidine with 2,4‐dihydroxy benzaldehyde ( HL1 ), 2‐hydroxy‐1‐naphthaldehyde ( HL2 ) and salicylaldehyde ( HL3 ) have been synthesized. The structures of the prepared metal complexes were proposed based on elemental analysis, molar conductance, thermal analysis (TGA, DSC and DTG), magnetic susceptibility measurements and spectroscopic techniques (IR, UV‐Vis, and ESR). In all complexes, the ligand bonds to the metal ion through the azomethine nitrogen and α‐hydroxy oxygen atoms. The structures of Pd(II) complex 8 and Ru(III) complex 9 were found to be polynuclear. Two kinds of stereochemical geometries; distorted tetrahedral and distorted square pyramidal, have been realized for the Cu(II) complexes based on the results of UV‐Vis, magnetic susceptibility and ESR spectra whereas octahedral geometry was predicted for Co(II), Mn(II) and Ru(III) complexes. Ni(II) complexes were predicted to be square planar and tetrahedral and Pd(II) complexes were found to be square planar. The antimicrobial activity of the ligands and their metal complexes was also investigated against the gram‐positive bacteria Staphylococcus aures and Bacillus subtilis and gram‐negative bacteria, Escherichia coli and Pesudomonas aeruginosa, by using the agar dilution method. Chloramphenicol was used as standard compound. The obtained data revealed that the metal complexes are more or less, active than the parent ligand and standard. The X‐ray crystal structure of HL3 has been also reported.     

Antibacterial,DFT and molecular docking studies of Rh(III) complexes of Coumarinyl‐Thiosemicarbazone nuclei based ligands

Coumarinyl thiosemicarbazone derivatives (1E)‐1‐(1‐(2‐oxo‐2H‐chromen‐3‐yl)ethylidene)thiosemicarbazide (OCET), (1E)‐1‐(1‐(6‐bromo‐2‐ oxo‐2H‐chromen‐3‐yl)ethylidene)thiosemicarbazide (BOCET) and 1‐(1‐(3‐oxo‐3H‐benzo[f]chromen‐2‐yl)ethylidene)thiosemicarbazide (NOCET) and their Rh(III) complexes were synthesized, the characterization was carried out by elemental analysis, IR, UV–Visible, mass, magnetic measurement and molar conductance techniques. Data interpretation of the Rh(III) complexes indicates that the ligands of coumarinyl thiosemicarbazone derivatives were formed in stoichiometric ratios as 1:2 (metal: ligand). The studied ligands act as a bidentate ligand by using both azomethine nitrogen and thiol sulphur as monoanion center of donation. The theoretical conformational structure analyses were performed using density functional theory for ligands and complexes at B3LYP functional with 6‐31G(++)d,p basis set for ligands and LANL2DZ basis set for complexes. The charge distribution within the ligands and its Rh(III) complexes was calculated using Mulliken population analysis of (MPA) and natural population analysis (NPA). The antibacterial activity of the prepared compounds was tested against some types of Gram positive and negative bacteria. Molecular docking investigation proved that, the ligands and complexes had interesting interactions with active site amino acids of ribosyltransferase (code: 3GEY).     

Iron(II) and Iron(III) Perchlorate Complexes of Ciprofloxacin and Norfloxacin

The reactions of ciprofloxacin (CIP) and norfloxacin (NOR) with iron(II) and iron(III) perchlorate have been investigated. The optical spectra support the formation of four complexes for each oxidation state with 1 : 1, 1 : 2, 1 : 3 and 1 : 4 metal to ligand molar ratios. The electrical conductivity and magnetic susceptibility measurements show that the isolated complexes are high spin and the Fe(ClO 4 ) 2 and Fe(ClO 4 ) 3 complexes behave as 1 : 2 and 1 : 3 electrolytes, respectively. The IR spectra indicate that CIP and NOR bind to the iron ion as bidentate ligands through the carbonyl oxygen atom and one of the oxygen atoms of the carboxylate group.     

Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L(1)) and semicarbazone (L(2)) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L)(2)(SO(4)) and Cu(L)(2)(SO(4)) [where L=L(1) and L(2)] which are of five coordinated square pyramidal geometry.     

Chlorobis(2,2,2-trichloroethoxy)-and dichloro(2,2,2-trichloroethoxy)-iron(III): Synthesis,characterization, and coordination chemistry

Chlorobis(2,2,2-trichloroethoxy)- and dichloro(2,2,2-trichloroethoxy)iron(III) have been synthesized. They react with various oxygen and nitrogen donor ligands to yield adducts formulated as FeCl(OCH₂CCl₃)₂ · 2 L or FeCl₂(OCH₂CCl₃) · 2 L (L = ligand). The depressed magnetic moments of these compounds show the presence of strong antiferromagnetic interactions between iron atoms. The infrared and ¹H nmr spectra establish the presence of bridging and terminal alkoxy groups and ligands (L) are cis to each other. The electronic spectra of these complexes indicate that each iron atom is approximately octahedrally coordinated. Mass spectral data are in favour of dimeric structure for the title compounds.     

Cobalt(II) complexes with 2-aminoacetophenone N(4)-substituted thiosemicarbazones

Cobalt(II) complexes with 2-aminoacetophenone thiosemicarbazone and three N(4)-substituted thiosemicarbazones have been prepared in EtOH solution and characterized by physical and spectral methods. I.r. and electronic spectra of the thiosemicarbazones and their complexes, along with physical properties of the complexes, have been obtained. The 2-aminoacetophenone thiosemicarbazones coordinate both as neutral and anionic ligands via the thiosemicarbazone moiety's imine nitrogen and thione/thiolato sulfur [on loss of the N(2) hydrogen].