Thermal, Spectral, Fluorescence, and Antimicrobial Studies of Cobalt, Nickel, Copper, and Zinc Complexes Derived from 4-[(5-Bromo-thiophen-2-ylmethylene)-amino]-3-mercapto-6-methyl-5-oxo-[1,2,4]triazine
A new series of cobalt, nickel, copper, and zinc complexes of bidentate Schiff base derived from the condensation of 5-bromothiophene-2-carboxaldehyde with 4-amino-3-mercapto-6-methyl-5-oxo-[1,2,4]triazine were synthesized. Physical (magnetic measurements, molar conductance, TG), spectral (UV-Vis, IR, 1HNMR, fluorescence, ESR), and analytical data have established the structures of synthesized Schiff base and its metal complexes. The presence of coordinated water in metal complexes was confirmed by IR and TG studies. The Schiff base exhibits a strong fluorescence emission, contrast to this partial fluorescence quenching phenomena is observed in its metal complexes. A square planar geometry for Cu(II) and octahedral geometry for Co(II), Ni(II) and Zn(II) complexes have been proposed. The Schiff base and its metal complexes have been screened for antibacterial (Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, A. flavus). 1. Introduction Triazine chemistry has attracted attention due to the utility of melamine derivatives as starting material for a variety of polymers [1], as scavenging resins in organic manipulations [2] and in medicinal chemistry [3]. They provide a wide range of applications in the field of optics [4], herbicides [5], and pharmaceuticals [6]. These are valuable bases for estrogen receptor modulators and are also used as bridging agents to synthesize herbicides and in the production of drugs or polymers [7, 8]. Many derivatives of 1,2,4-triazine form colored complexes with different metal ions and can be used as analytical reagent for their determination [9]. A range of polymer-supported triazines and their metal-bound analogues were screened for use in catalysis and organic synthesis [10, 11]. Goodman et al. reported that triazine-derived copper complexes have superoxide radical scavenging activity in pathological processes [12]. In our last publication, we have reported that Schiff base derived from 4-amino-3-mercapto-6-methyl-5-oxo triazine shows antibacterial and antifungal activity and enhanced antimicrobial activity is observed, when the Schiff base is combined to transition metal ions [13]. Encouraged by above-mentioned finding, we found it is to investigate the thermal, spectral, fluorescence, and antimicrobial studies of cobalt, nickel, copper, and zinc complexes derived from 4-[(5-bromo-thiophen-2-ylmethylene)-amino]-3-mercapto-6-methyl-5-oxo triazine. 2. Experimental 2.1. Materials All the chemicals used in the present study were of analytical
References
[1]
J. H. K. K. Hirschberg, A. Ramzi, R. P. Sijbesma, and E. W. Meijer, “Ureidotriazine-based supramolecular copolymers,” Macromolecules, vol. 36, no. 5, pp. 1429–1432, 2003.
[2]
M. Yanase, M. Matsuoka, Y. Tatsumi et al., “Thermodynamic study on supramolecular complex formation of fullerene with calix[5]arenes in organic solvents,” Tetrahedron Letters, vol. 41, no. 4, pp. 493–497, 2000.
[3]
M. Pattarawarapan, S. Reyes, Z. Xia, M. C. Zaccaro, H. U. Saragovi, and K. Burgess, “Selective formation of homo- and heterobivalent peptidomimetics,” Journal of Medicinal Chemistry, vol. 46, no. 17, pp. 3565–3567, 2003.
[4]
J. R. Galán-Mascarós, J. M. Clemente, and K. R. Dunbar, “Synthesis, structure and magnetic properties of the one-dimensional chain compound {K[Fe(1,3,5-triazine-2,4,6-tricarboxylate) ] }∞,” Journal of the Chemical Society, Dalton Transactions, no. 13, pp. 2710–2713, 2002.
[5]
H. O. Esser, G. Dupllis, C. Vogel, G. J. Marco, P. C. Kearney, and D. D. Kaufman, Herbicides Chemistry, Degradation and Mode of Action, Marcel Dekker, New York, 2nd edition, 1976.
[6]
C. Courme, N. Gresh, M. Vidal et al., “Synthesis of aryl phosphates based on pyrimidine and triazine scaffolds,” European Journal of Medicinal Chemistry, vol. 45, no. 1, pp. 244–255, 2010.
[7]
P. De Hoog, P. Gamez, W. L. Driessen, and J. Reedijk, “New polydentate and polynucleating N-donor ligands from amines and 2,4,6-trichloro-1,3,5-triazine,” Tetrahedron Letters, vol. 43, no. 38, pp. 6783–6786, 2002.
[8]
H. S. Patel and V. C. Patel, “Polyimides containing s-triazine ring,” European Polymer Journal, vol. 37, no. 11, pp. 2263–2271, 2001.
[9]
N. R. El-Brollosy, “Synthesis and reactions of some new 1,2,4-triazine derivatives of biological interest,” Phosphorus, Sulfur and Silicon and Related Elements, vol. 163, pp. 77–89, 2000.
[10]
S. Br？se, S. Dahmen, F. Lauterwasser, N. E. Leadbeater, and E. L. Sharp, “Polymer-bound 1-aryl-3-alkyltriazenes as modular ligands for catalysis. Part 2: screening immobilized metal complexes for catalytic activity,” Bioorganic and Medicinal Chemistry Letters, vol. 12, no. 14, pp. 1849–1851, 2002.
[11]
B. Erb, J. P. Kucma, S. Mourey, and F. Struber, “Polymer-supported triazenes as smart reagents for the alkylation of carboxylic acids,” Chemistry-A European Journal, vol. 9, no. 11, pp. 2582–2588, 2003.
[12]
B. A. Goodman, C. G. Palivan, H. Palivan, and S. Tomas, “Local structure is critical for superoxide dismutase activity in copper complexes: relationship between EPR parameters, structure and activity in some sterically hindered copper(II) bis(hydrazono-triazine) complexes,” Applied Magnetic Resonance, vol. 25, no. 1, pp. 13–28, 2003.
[13]
K. Singh, Y. Kumar, P. Puri, C. Sharma, and K. R. Aneja, “Synthesis, spectroscopic, thermal and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with Schiff base derived from 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine,” Medicinal Chemistry Research, vol. 21, no. 8, pp. 1708–1716, 2012.
[14]
A. Dornow, H. Mengel, and P. Marx, “Uber 1, 2, 4-triazine, I darstellung einiger neuer s-triazolo[3.2-c-]-as-triazine,” Chemische Berichte, vol. 97, pp. 2173–2178, 1964.
[15]
A. I. Vogel, Book of Quantitative Chemical Analysis, Addison-Wesley/Longman, London, UK, 5th edition, 1999.
[16]
K. R. Aneja, C. Sharma, and R. Joshi, “Fungal infection of the ear: a common problem in the north eastern part of Haryana,” International Journal of Pediatric Otorhinolaryngology, vol. 74, no. 6, pp. 604–607, 2010.
[17]
K. R. Aneja, C. Sharma, and R. Joshi, “In vitro efficacy of amaltas (Cassia fistula L.) against the pathogens causing otitis externa,” Jundishapur Journal of Microbiology, vol. 4, no. 3, pp. 175–183, 2011.
[18]
N. Gopalakrishna Bhat and B. Narayana, “Complexes of Ag(I), Tl(I), Zn(II), Hg(II), Cd(II), Pd(II), Co(II) and Ni(II) with 4-[(4-Dimethylamino-benzylidene)-amino]-5-ethyl-2,4-dihydro-[1,2,4] triazole-3-thione (HDEDT) and 4-[(Benzylidene)amino]-6-(t-butyl)-4H-[1,2,4]- triazine-3-thione-5-one (HBBTT),” Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, vol. 35, no. 3, pp. 253–262, 2005.
[19]
K. Singh, D. P. Singh, M. Singh Barwa, P. Tyagi, and Y. Mirza, “Some bivalent metal complexes of Schiff bases containing N and S donor atoms,” Journal of Enzyme Inhibition and Medicinal Chemistry, vol. 21, no. 6, pp. 749–755, 2006.
[20]
K. Singh, Y. Kumar, and M. S. Barwa, “Synthesis, characterization and thermal studies of Co(II), Ni(II), Cu(II) and Zn(II) Complexes of some Schiff bases derived from 4-amino-3-mercapto-6- methyl-5-oxo-1,2,4 triazine,” South African Journal of Chemistry, vol. 63, pp. 169–174, 2010.
[21]
G. B. Bagihalli, P. G. Avaji, S. A. Patil, and P. S. Badami, “Synthesis, spectral characterization, in vitro antibacterial, antifungal and cytotoxic activities of Co(II), Ni(II) and Cu(II) complexes with 1,2,4-triazole Schiff bases,” European Journal of Medicinal Chemistry, vol. 43, no. 12, pp. 2639–2649, 2008.
[22]
K. Singh, M. S. Barwa, and P. Tyagi, “Synthesis, characterization and biological studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with bidentate Schiff bases derived by heterocyclic ketone,” European Journal of Medicinal Chemistry, vol. 41, no. 1, pp. 147–153, 2006.
[23]
A. J. Atkins, D. Black, R. L. Finn et al., “Synthesis and structure of mononuclear and binuclear zinc(II) compartmental macrocyclic complexes,” Dalton Transactions, no. 9, pp. 1730–1737, 2003.
[24]
A. K. Singh, O. P. Pandey, and S. K. Sengupta, “Synthesis, spectral characterization and biological activity of zinc(II) complexes with 3-substituted phenyl-4-amino-5-hydrazino-1, 2, 4-triazole Schiff bases,” Spectrochimica Acta—Part A, vol. 85, no. 1, pp. 1–6, 2012.
[25]
M. A. Phaniband, S. D. Dhumwad, and S. R. Pattan, “Synthesis, characterization, antimicrobial, and DNA cleavage studies of metal complexes of coumarin Schiff bases,” Medicinal Chemistry Research, vol. 25, pp. 493–502, 2010.
[26]
A. B. P. Lever, Inorganic Spectroscopy, Elsevier, Amsterdam, The Netherlands, 1968.
[27]
V. P. Singh and P. Gupta, “Synthesis and spectral studies of metal(II) complexes with succinic acid dihydrazones and their biological activity,” Pharmaceutical Chemistry Journal, vol. 42, no. 4, pp. 196–202, 2008.
[28]
N. Raman, K. Pothiraj, and T. Baskaran, “DNA interaction, antimicrobial, electrochemical and spectroscopic studies of metal(II) complexes with tridentate heterocyclic Schiff base derived from 2′-methylacetoacetanilide,” Journal of Molecular Structure, vol. 1000, no. 1–3, pp. 135–144, 2011.
[29]
S. A. Patil, S. N. Unki, A. D. Kulkarni, V. H. Naik, and P. S. Badami, “Co(II), Ni(II) and Cu(II) complexes with coumarin-8-yl Schiff-bases: spectroscopic, in vitro antimicrobial, DNA cleavage and fluorescence studies,” Spectrochimica Acta—Part A, vol. 79, no. 5, pp. 1128–1136, 2011.
[30]
G. G. Mohamed, M. M. Omar, and A. A. Ibrahim, “Biological activity studies on metal complexes of novel tridentate Schiff base ligand. Spectroscopic and thermal characterization,” European Journal of Medicinal Chemistry, vol. 44, no. 12, pp. 4801–4812, 2009.
[31]
T. Rosu, M. Negoiu, S. Pasculescu, E. Pahontu, D. Poirier, and A. Gulea, “Metal-based biologically active agents: synthesis, characterization, antibacterial and antileukemia activity evaluation of Cu(II), V(IV) and Ni(II) complexes with antipyrine-derived compounds,” European Journal of Medicinal Chemistry, vol. 45, no. 2, pp. 774–781, 2010.
[32]
B. A. Yamgar, V. A. Sawant, S. K. Sawant, and S. S. Chavan, “Copper(II) complexes of thiazolylazo dye with triphenylphosphine and or NCS- as coligands: synthesis, spectral characterization, electrochemistry and luminescence properties,” Journal of Coordination Chemistry, vol. 62, no. 14, pp. 2367–2374, 2009.
[33]
Q. H. Wang, W. Weng, J. M. Liu, L. Z. Cai, and G. C. Guo, “Synthesis, crystal structure, and fluorescence properties of several schiff-base compounds,” Journal of Coordination Chemistry, vol. 59, no. 5, pp. 485–492, 2006.
[34]
P. B. Maravalli, K. B. Gudasi, and T. R. Goudar, “Thermal studies of cobalt(II), nickel(II) and copper(II) 3-substituted-4-salicylideneamino-5-mercapto-l ,2,4-triazole complexes,” Transition Metal Chemistry, vol. 25, no. 4, pp. 411–414, 2000.
[35]
K. Kumar Narang, J. Prasad Pandey, and V. Prasad Singh, “Synthesis, characterization and physicochemical studies of some Copper(II) tetrathiocyanato dithallate(I) complexes with hydrazides and hydrazones,” Polyhedron, vol. 13, no. 4, pp. 529–538, 1994.
[36]
A. H. Osman, “Synthesis and characterization of cobalt(II) and nickel(II) complexes of some schiff bases derived from 3-hydrazino-6-methyl[1,2,4] triazin-5(4H)one,” Transition Metal Chemistry, vol. 31, no. 1, pp. 35–41, 2006.
[37]
Y. Anjaneyulu and R. P. Rao, “Preparation, characterization and antimicrobial activity studies on some ternary complexes of Cu(II) with acetyl acetone and various salicylic acids,” Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, vol. 16, no. 3, pp. 257–272, 1986.
[38]
N. Dharmaraj, P. Viswanathamurthi, and K. Natarajan, “Ruthenium(II) complexes containing bidentate Schiff bases and their antifungal activity,” Transition Metal Chemistry, vol. 26, no. 1-2, pp. 105–109, 2001.
