Abstract
Complexes of vanillin-4-methyl-4-phenyl-3-thiosemicarbazone with cobalt(II), nickel((II), copper(II) and zinc(II) metal ions were synthesized and characterized by elemental analysis, molar conductance, magnetic moment, infrared spectra, electronic spectra, 1H and 13C NMR, mass spectrum and thermal analysis. The low molar conductance values indicate that all the complexes are non-electrolytes. Spectral studies indicate that the ligand act in a tridentate manner coordinating with the metal ion through sulphur, oxygen and nitrogen atoms. Based on magnetic moment measurements, spectral studies and thermal analysis, suitable geometry was proposed for the metal complexes. Thermal stability of the complexes was ascertained on the basis of thermo gravimetric analysis and the lattice parameters, space group and grain size of the ligand and complexes were determined by using powder XRD measurements. Surface morphology of ligand and complexes were studied using SEM analysis. Antimicrobial studies were carried out against gram-positive, gram-negative bacteria and two fungal pathogens.
Graphic abstract
Vanillin-4-methyl-4-phenyl-3-thiosemicarbazone and its cobalt(II), nickel(II), copper(II) and zinc(II) complexes were synthesized and characterized and suitable geometry was proposed. All complexes except copper complex were stable up to 280 °C. The ligand and complexes belong to monoclinic crystal system with different space groups. Copper and zinc complexes of vanillin thiosemicarbazone were found to possess high antibacterial and antifungal activity.
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Ramachandran E, Raja D S, Bhuvanesh N S P and Natarajan K 2013 Synthesis, characterization and in vitro pharmacological evaluation of new water soluble Ni(II) complexes of 4N-substituted thiosemicarbazones of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde Eur. J. Med. Chem. 64 179
Kumar A V, Sarala Y, Asha S, Vanitha S, Babu S and Reddy A V 2018 Synthesis, Characterization Antimicrobial and Antioxidant Activities of 2,4-dihydroxybenzaldehyde-4-phenyl-3-thiosemicarbazone (DHBPTSC) and its Pd(II), Ni(II) mixed Ligand and Cu(II) Complex having Heterocyclic Bases J. Appl. Pharm. Sci. 84 71
Shawish H B, Maah M, Halim S N A and Shaker S A 2016 Synthesis, characterization and structural studies of binuclear nickel(II) complexes derived from dihydroxybenzaldehyde thiosemicarbazones, bridged by 1,2-bis(diphenylphosphino)ethane Arab. J. Chem. 9 1935
Kumar S M, Dhahagani K, Rajesh J, Nehru K, Annaraj J, Chakkaravarthi G and Rajagopal G 2013 Synthesis, characterization, structural analysis and DNA binding studies of nickel(II)–triphenylphosphine complex of ONS donor ligand – Multisubstituted thiosemicarbazone as highly selective sensor for fluoride ion Polyhedron 59 58
Latheef L and Kurup M R P 2008 Spectral and structural studies of nickel(II) complexes of salicylaldehyde 3-azacyclothiosemicarbazones Polyhedron 27 35
Mosa A I, Ibrahim M M and Aldhlmani S A 2013 Spectroscopic and Solution Studies of Some Transition Metal Complexes of New 4-Hydroxy Coumarin Semi- and Thiosemicarbazone Complexes J. Sol. Chem. 42 2364
Graiff C, Canossa S and Predier G 2014 coordinative properties of the pyridine-2- carbaldehyde thiosemicarbazone ligand towards Ni(ii) J. Mol. Struct. 55 493
Yousef T A, Abu El-Reash G M, O A El-Gammal and Bedier R A 2013 Synthesis, characterization, optical band gap, in vitro antimicrobial activity and DNA cleavage studies of some metal complexes of pyridyl thiosemicarbazone J. Mol. Struct. 1035 307
Ali A Q, Teoh S G, Eltayeb N E, Ahamed M K B and Abdul Majid A M S 2014 Synthesis of copper(II) complexes of isatin thiosemicarbazone derivatives: In vitro anti-cancer, DNA binding, and cleavage activities Polyhedron 74 6
Prathima B, Rao Y S, Reddy S A, Reddy Y P and Reddy A V 2010 Copper(II) and nickel(II) complexes of benzyloxybenzaldehyde-4- phenyl-3-thiosemicarbazone: Synthesis, characterization and biological activity Spectrochim. Part A: Mol. Biomol. Spectrosc. 77 248
Cao w, Qi j, Qian K, Tian L, Cheng Z and Wang Y 2019 Structure-activity relationships of 2-quinolinecarboxaldehyde thiosemicarbazone gallium(III) complexes with potent and selective anticancer activity J. Inorg. Biochem. 191 174
Alomar K, Landreau A, Allain M, Bouet G and Larcher G 2013 Synthesis, structure and antifungal activity of thiophene-2,3-dicarboxaldehyde bis(thiosemicarbazone) and nickel(II), copper(II) and cadmium(II) complexes: Unsymmetrical coordination mode of nickel complex J. Inorg. Biochem. 126 76
Mbah J A, Ayimele G A, Eyonganyoh E N and Nfor E N 2017 Synthesis, Molecular Structure and Antibacterial Activity of Benzylmethyl-4-Methyl-3-Thiosemicarbazone Int. J. Org. Chem. 7 83
Aljahdali M and EL-Sherif A A 2013 Synthesis, characterization, molecular modeling and biological activity of mixed ligand complexes of Cu(II), Ni(II) and Co(II) based on 1,10-phenanthroline and novel thiosemicarbazone Inorg. Chim. Acta 407 58
El-Sawaf A K, El-Essawy F, Nassar A A and El-Samanody E A 2018 Synthesis, spectral, thermal and antimicrobial on cobalt(II), nickel(II), copper(II), zinc(II) and palladium(II) complexes containing thiosemicarbazone ligand J. Mol. Struct. 1157 381
Piri Z, Moradi–Shoeili Z and Assoud A 2019 Ultrasonic assisted synthesis, crystallographic, spectroscopic studies and biological activity of three new Zn(II), Co(II) and Ni(II) thiosemicarbazone complexes as precursors for nano-metal oxides Inorg. Chim. Acta 484 338
Pawar A S, Mlowe S, Garje S S, Akerman M P and Revaprasadu N 2017 Zinc thiosemicarbazone complexes: single source precursors for alkylamine capped ZnS nanoparticles Inorg. Chim. Acta 7 463
Rai B K, Kumar S, Anand R and Pandey A 2013 Spectral and Antimicrobial Screening of Cu(II), Ni(II) and Co(II) Coordination Compounds with Nitrogen Oxygen and Sulphur Containing Tridentate Schiff Base Orient. J. Chem. 29 655
Nair M S and Joseyphus R S 2008 Synthesis and characterization studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes of tridentate Schiff base derived from vanillin and DL-α-aminobutyric acid Spectrochim. Acta Part A 70 749
Sharma S, Athar F, Maurya M R and Azam A 2005 Copper(II) complexes with substituted thiosemicarbazones of thiophene-2-carboxaldehyde: synthesis, characterization and antiamoebic activity against E. Histolytica Eur. J. Med. Chem. 40 1414
Muralisankar M, Sujith S, Bhuvanesh N S P and Sreekanth A 2016 Synthesis and crystal structure of new monometallic and bimetallic copper(II) complexes with N-substituted isatin thiosemicarbazone ligands: Effects of the complexes on DNA/protein-binding property, DNA cleavage study and in vitro anticancer activity Polyhedron 118 103
Aly A A, Brase S and Weis P 2019 Tridentate and bidentate copper complexes of [22] paracyclophanyl-substituted thiosemicarbazones, thiocarbazones, hydrazones and thioureas J. Mol. Struct. 1178 311
Kumar S M, Dhahagani K, Rajesh J, Nehru K, Annaraj J, Chakkaravarthi G and Rajagopal G 2013 Synthesis, characterization, structural analysis and DNA binding studies of nickel(II)–triphenylphosphine complex of ONS donor ligand – Multisubstituted thiosemicarbazone as highly selective sensor for fluoride ion Polyhedron 59 58
Mosa A I, Emara A A A, Yousef J M and Saddiq A A 2011 Novel transition metal complexes of 4-hydroxy-coumarin-3-thiocarbohydrazone: Pharmacodynamic of Co(III) on rats and antimicrobial activity Spectrochim. Part A 81 35
Guveli S, Ozdemir N, Koca A, Bal-Demirci T and Ulkuseven B 2016 Spectroscopic, electrochemical and X-ray diffraction studies on nickel(II)-complexes of acetophenone thiosemicarbazones substituted six-carbon groups Inorg. Chim. Acta 7 443
Datta S, Seth D K, Gangopadhyay S, Karmakar P and Bhattacharya S 2012 Nickel complexes of some thiosemicarbazones: Synthesis, structure, catalytic properties and cytotoxicity studies Inorg. Chim. Acta 392 118
Mishra P M, Kumar M, Chaudhary R S and Kumar C 2013 Synthesis and Characterization of Divalent Transition Metal Complexes Containing Thiosemicarbazone Ligands Orient. J. Chem. 29 1651
El-Asmy A A and Al-Hazmi G A A 2009 Synthesis and spectral feature of benzophenone-substituted thiosemicarbazones and their Ni(II) and Cu(II) complexes Spectrochim. Part A 71 1885
Wang B, Yang Z, Lü Z, Hai J, Wang Q and Chen Z 2009 Synthesis, characterization, cytotoxic activity and DNA binding Ni(II) complex with the 6-hydroxy chromone-3-carbaldehyde thiosemicarbazone J. Organomet. Chem. 694 4069
Devi J, Yadav M and Sharma S O 2018 Synthesis and Characterization of Transition Metal(II) Schiff Bases Complexes Derived from 2,5-Dihalosalicylaldehyde and 4-Methyl-3-thiosemicarbazide Asian J. Chem. 30 2445
Ferraz K O, Wardell S M S V, Wardell J L, Louro S R W and Beraldo H 2009 Copper(II) complexes with 2-pyridineformamide-derived thiosemicarbazones: Spectral studies and toxicity against Artemia Spectrochim. Part A 73 140
Kovala-Demertzi D, Alexandratos A, Papageorgiou A, Yadav P N, Panagiotis Dalezis, and Demertzis M A 2008 Synthesis, characterization, crystal structures, in vitro and in vivo antitumor activity of palladium(II) and zinc(II) complexes with 2-formyl and 2-acetyl pyridine N(4)-1-(2-pyridyl)-piperazinyl thiosemicarbazone Polyhedron 27 2731
Abou-Melha K S 2008 Octahedral Co(II) and Ni(II) complexes of Schiff bases, semicarbazone and thiosemicarbazone, synthesis, biological, spectral, and thermal Studies J. Coord. Chem. 61 2053
Sinha B, Bhattacharya M and Saha S 2019 Transition metal complexes obtained from an ionic liquid-supported Schiff base: synthesis, physiochemical characterization and exploration of antimicrobial activities J. Chem. Sci. 131 19
Matović D Z, Ristic B, Joksovic M and Trifunovic S R 2000 Square-planar copper(II) complexes with a novel tetradentate amido-carboxylate ligand. Crystal structure of [Co(H 2O)6][Cu(mda)].2H2O Trans. Met. Chem. 25 720
Nair M S, Arish D and Joseyphus R S 2012 Synthesis, characterization, antifungal, antibacterial and DNA cleavage studies of some heterocyclic Schiff base metal complexes J. Saudi Chem. Soc. 16 83
Saif M, Mashaly M M, Eid M F and Fouad R 2012 Synthesis, characterization and thermal studies of binary and/or mixed ligand complexes of Cd(II), Cu(II), Ni(II) and Co(III) based on 2-(Hydroxybenzylidene) thiosemicarbazone: DNA binding affinity of binary Cu(II) complex Spectrochim. Part A 92 347
Reddy D H K, Lee S, Seshaiah K and Babu K R 2012 Synthesis, characterization of thiosemicarbazone metal complexes and their antioxidant activity in different in vitro model systems J. Serb. Chem. Soc. 77 229
Refat M S, El-Deen I M, Anwer Z M and El-Ghol S 2009 Bivalent transition metal complexes of coumarin-3-yl thiosemicarbazone derivatives: Spectroscopic, antibacterial activity and thermogravimetric studies J. Mol. Struct. 920 149
Joseyphus S R and Nair M S 2010 Synthesis, characterization and biological studies of some Co(II), Ni(II) and Cu(II) complexes derived from indole-3-carboxaldehyde and glycylglycine as Schiff base ligand Arab. J. Chem. 3 195
Lekshmi V K and Nath G R 2018 Synthesis and Characterization Studies of Cobalt(II), Nickel(II), Copper(II) and Zinc(II) Complexes of Carboxymethyl-N-Methyl-N-Phenyl Dithiocarbamate Orient. J. Chem. 34 3064
Chandra S and Tyagi M 2009 Synthesis and antimicrobial activities of n-s donor ligand and its transition metal complexes Int. J. Chem. Sci. 7 116
Netalkar P P, Netalkar S P and Revankar V K 2014 Nickel(II) complexes of thiosemicarbazones: synthesis, characterization, X-ray crystallographic studies and in vitro antitubercular and antimicrobial studies Trans. Met. Chem. 39 519
Beckford F A and Webb K R 2017 Copper complexes containing thiosemicarbazones derived from 6- nitropiperonal: Antimicrobial and biophysical properties Spectrochim. Part A 183 158
Acknowledgements
One of the author (Lekshmi V Kumar) acknowledge the CSIR, New Delhi for the financial support through the grant no. 08/537(0004)/2014 EMR-1, dated 27/08/2014. Authors are thankful to STIC, CUSAT, Kochi for the instrumental analysis of samples, SICC, University of Kerala, Thiruvananthapuram for PXRD analysis.
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Kumar, L.V., Nath, G.R. Synthesis, characterization and biological studies of cobalt(II), nickel(II), copper(II) and zinc(II) complexes of vanillin-4-methyl-4-phenyl-3-thiosemicarbazone. J Chem Sci 131, 76 (2019). https://doi.org/10.1007/s12039-019-1658-x
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DOI: https://doi.org/10.1007/s12039-019-1658-x