Studies on Synthesis, Characterization and Antibacterial Activity of ...

November 2012 –January 2013, Vol. 3, No. 1, 109-116. e- ISSN: 2249 –1929Journal of Chemical, Biological and Physical SciencesAn International Peer Review E-3 Journal of SciencesAvailable online atwww.jcbsc.orgSection A: Chemical ScienceCODEN (USA): JCBPATResearch Article<strong>Studies</strong> on Synthesis, Characterization and AntibacterialActivity of Novel Coordination PolymersPurav Talaviya 1 and J.A.Chaudhari 21 Department of Chemistry, JJT University, Jhunjhunu, Rajasthan-India2 Shri R.K.Parikh Arts & Science College Petlad, Gujarat-IndiaReceived: 25 November 2012; Revised: 17 December 2012; Accepted: 5 January 2013Abstract: Novel bis ligand namely 5,5'-(6-phenoxy-1,3,5-triazine-2,4-diyl) bis(azanediyl) diquinolin-8-ol (PBDQ), was synthesized by condensation of 5-amino 8-hydroxy quinoline with2,4-dichloro-6-phenoxy-1,3,5-triazine in the presence of a base catalyst. This ligand wascharacterized by Elemental analysis, IR, and 1 H-NMR. Coordination polymers of this bisligand(PBDQ) were prepared with Cu (II), Ni (II), Co (II), Mn(II), and Zn(II) metal ions. Allof these coordination polymers were characterized by elemental analyses, IR spectral anddiffuse reflectance spectral studies. The thermal stability was evaluated by thermogravimetricanalyses. In addition, all of the coordination polymers have been characterized by theirmagnetic susceptibilities. The microbicidal activities of all the samples have been monitoredagainst plant pathogens.Keywords: Ligands, 8-hydroxyquinoline, antibacterial and antifungal activities, coordinationpolymers, IR, NMR, reflectance spectra and thermo gravimetric analysis (TGA).INTRODUCTIONIn recent years, the study on Co-ordination polymer has made much progress 1-3 . 8-quinolinol is well knownas an analytical reagent 4,5 . Its various derivatives are very useful in pharmaceuticals 6 . Several azo dyes basedon 8-quinolinol are also reported for dyeing of textiles as well as their chelating properties 7,8 . A promisingmethod has been reported for the formation of coordination polymers of enhanced chelating ability by usinga bidentate 8-hydroxyquinoline moiety in which two 8-hydroxyquinolinyl end groups are joined with bridge,usually at the 5,5’-position 9–11 . The 5–Amino 8-hydroxy quinolinol is the easiest preparable precursor for the109 J. Chem. Bio. Phy. Sci. Sec. A, 2012-2013, Vol.3, No.1, 109-116.

<strong>Studies</strong>...Purav Talaviya et al.preparation of bis-ligand and thus bis-ligands based on 5–Amino 8–hydroxyquinoline have been reported forcoordination polymers 11, 12 . Ion exchange resins have also been prepared from 5–amino 8–hydroxyquinolineand amino or hydroxyl functionalized polymers 13,14 . The literature survey reveals that bis-8-hydroxyquinoline ligand having 1, 3, 5-triazine ring as a bridge has not been reported so far. Hence, it wasthought to undertake such type of study. Thus the present paper deals with synthesis, characterization andchelating properties of ligand (PBDQ) and its co-ordination polymers are shown in Scheme 1.110 J. Chem. Bio. Phy. Sci. Sec. A, 2012-2013, Vol.3, No.1, 109-116.

<strong>Studies</strong>...Purav Talaviya et al.Table-1: Analysis of PBDQ ligand and its metal chelatesEmpirical Formula Mol. Cal Yield Elemental Analysis (%) Found(Calcd)g/mol % C H N MC 27 H 19 N 7 O 3 489 68 66.25 (66.21) 3.91(3.87) 20.03(19.99) ---C 27 H 17 N 7 O 3 Cu .2H 2 O 586 70 55.24(55.19) 3.61(3.56) 16.70(16.65) 10.82(10.78)C 27 H 17 N 7 O 3 Ni .2H 2 O 582 67 55.6 8(55.64) 3.63(3.58) 16.83(16.79) 10.12(10.07)C 27 H 17 N 7 O 3 Co .2H 2 O 581 67 55.70(55.65) 3.64(3.59) 16.84(15.80) 10.08(10.04)C 27 H 17 N 7 O 3 Mn .2H 2 O 578 66 56.06(56.12) 3.66(3.62) 16.95(16.91) 09.50(09.45)C 27 H 17 N 7 O 3 Zn .2H 2 O 587 68 55.07(55.02) 3.59(3.55) 16.65(16.61) 11.11(11.06Table-2: Spectral features and magnetic moment of metal chelatesMetalChelatesµ effBMElectronic Transitions IR spectral feacturesData cm -1SpectralCommon for all cm -1PBDQ -Cu +2PBDQ -Ni +2 1.933.84226901586522988146958100C.TEg → 2 T 2 gA 2 g→ 3 T 1 g(P)A 2 g→ 3 T 1 g(F)A 2 g→ 3 T 2 g3300 Quinoline Moiety2200160015001090 C-O-M &PBDQ -Co +2 4.53 2072019880119904 T 1 g(F)→ 4 A 2 gT 1 g(F)→ 4 T 1 g(P)T 1 g(F)→ 4 T 2 g1420 O-M750 N-M660PBDQ -Mn +2 5.11 2296517655153796 A 1 g→ 6 A 1 g ( 4 Eg)A 1 g→ 4 T 2 g( 4 G)A 1 g→ 4 T 1 g( 4 G)PBDQ -Zn +2 Diamagnetic -----IR Analysis: The important infrared spectral bands and their tentative assignments for the synthesizedligand H 2 L and its coordination polymers were recorded as KBr disks and are shown in Table-2.IR spectrum of ligand of PBDQ show a broad band extended from 3300 to 2200 cm -1 that might beresponsible to phenolic -OH group bonded to N atom of 8-hydroxyquinoline moieties 20 .Several bands appeared between 1500 and 1600 cm -1 region may arised from aromatic breathing and 3400cm -1 for –NH group. The IR band at 1580 cm -1 (C=N of 8-quinolinol system) of PBDQ ligand shifted tohigher frequency side 1600 cm -1 in the spectra of the metal complexes indicating involvement of nitrogen in112 J. Chem. Bio. Phy. Sci. Sec. A, 2012-2013, Vol.3, No.1, 109-116.

<strong>Studies</strong>...Purav Talaviya et al.the complexes formation 21 , whereas the band at 1420 cm -1 in the IR spectrum of PBDQ assigned to in-plane–OH deformation was shifted towards higher frequency in the spectra of the coordination polymer due to theformation of the M–O bond 22 . This was further confirmed by a weak band at 1090 cm -1 corresponding to C–O–M stretching, while bands around 750 and 660 cm -1 correspond to the N →M vibration 2 3.1 H NMR Analysis: The structural analysis of the ligand (PBDQ) was determined by 1 H NMR spectrum.NMR(DMSO) 6.9 – 8.2 ppm (15H) Multiplet Aromatic5.3 ppm (1H) Singlet (OH)4.0 ppm (1H) Singlet (NH)Magnetic Measurements: Magnetic moments of coordination polymers are given in Table-2. The diffuseelectronic spectrum of Cu +2 complex shows two broad bands, 15865 and 22690 cm -1 . The first band may bedue to a 2 Eg → 2 T 2 g transition, while the second band may be due to charge transfer. The first band showsstructures suggesting a distorted octahedral structure for the Cu +2 metal complex 24,25 . The Co +2 metalcomplex gives rise to two absorption bands at 20720 cm -1 , 19880 cm -1 and 11990 cm -1 which can beassigned 4 T 1 g(F)→ 4 A 2 g, 4 T 1 g(F)→ 4 T 1 g(P) and 4 T 1 g(F)→ 4 T 2 g transitions, respectively. These absorptionbands and the µ eff value indicate octahedral configuration of the Co +2 metal complex 26,27 . The spectrum ofMn +2 polymeric complex comprised three bands at 22965 cm -1 ,17655 cm -1 and 15379 cm -1 . These bandsmay be assigned to 6 A 1 g→ 6 A 1 g( 4 Eg), 6 A 1 g→ 4 T 2 g( 4 G) and 6 A 1 g→ 4 T 1 g( 4 G) transitions, respectively. The highintensity of the bands also suggests that they may have some charge transfer character. The magneticmoment is found to be lower than normal range. In the absence of low temperature measurement ofmagnetic moment, it is difficult to attach any significance to this. As the spectrum of the metal complex ofNi +2 show three distinct bands at 22988 cm -1 ,14695 cm -1 and 8100 cm -1 are assigned as 3 A 2 g→ 3 T 1 g(P),3 A 2 g→ 3 T 1 g(F) and 3 A 2 g→ 3 T 2 g transition, respectively, suggesting the octahedral environment for Ni +2 ion.The observed µ eff values in the range 1.93–5.11 B.M are consistent with the above moiety 28,29 .Thermal <strong>Studies</strong>: The TGA data for the Co-ordination polymers samples at different temperatures indicatethat the degradation of the co-ordination polymers is noticeable beyond 300 0 C. The rate of degradationbecomes a maximum at a temperature between 400 and 500 0 C. This may be due to acceleration by metaloxides, which form in situ. Each polymer lost about 60% of its weight when heated up to 690 0 C. Inspectionof the thermograms of all coordinated polymer samples revealed that all samples suffered appreciableweight loss in the range of 150 to 280 0 C. This may be due to the presence of a coordinated water molecule.Antimicrobial Activities: The antibacterial and antifungal data obtained from analysis are shown inTable-3 and Table-4, respectively. The increase in antimicrobial activity may be considered in light ofOvertone’s concept 30 and Tweedy’s chelation theory 31 . According to Overtone’s concept of cellpermeability, the lipid membrane that surrounds the cell favors the passage only of lipid-soluble materialsdue to which liposolubility is an important factor controlling the antimicrobial activity. On complexation,the polarity of the metal ion will be reduced largely due to the overlap of the ligand orbital and partialsharing of the positive charge of the metal ion with donor groups. Further, it increases the delocalization of -electrons over the whole chelate ring and enhances the lipophilicity of the coordination polymers. Thisincreased lipophilicity enhances the penetration of the coordination polymer into lipid membranes andblocks the metal binding sites in the enzymes of microorganisms. These coordination polymers also disturbthe respiration process of the cell and thus block the synthesis of proteins, which restricts further growth ofthe organisms.113 J. Chem. Bio. Phy. Sci. Sec. A, 2012-2013, Vol.3, No.1, 109-116.

<strong>Studies</strong>...Purav Talaviya et al.Table-3: Antibacterial activity of coordination PolymersCompounds Gram +ve Gram –veBacillus Staphylococcus klebsiella Salmonella E.coliSubtilis Aureuspromioe TyphiPBDQ 20 19 22 22 23(Cu BDQ(H 2 O) 2 ) n 34 36 31 32 29(Co BDQ(H 2 O) 2 ) n 32 30 24 23 23(Ni PBDQ(H 2 O) 2 ) n 30 26 26 25 26(Mn PBDQ(H 2 O) 2 ) n 31 33 24 24 22(Zn PBDQ(H 2 O) 2 ) n 30 32 29 32 23Table-4: Antifungal activity of coordination PolymersCompounds Zone of Inhibition at 1000 ppm (%)AspergillusNigerCandidaalbicansTrichodermaharsianumMucormucedoPBDQ 29 24 24 20 21(Cu PBDQ(H 2 O) 2 ) n 40 30 38 34 40(Co PBDQ(H 2 O) 2 ) n 32 29 30 28 30(Ni PBDQ(H 2 O) 2 ) n 31 26 32 25 26(Mn PBDQ(H 2 O) 2 ) n 31 26 32 25 32(Zn PBDQ(H 2 O) 2 ) n 35 26 30 24 28Botrytis cinereaCoordination polymers exhibit higher biocidal activity as compared with the free ligands; from thecomparative analysis shown in Table-3 and Table-4, respectively, it is observed that all the coordinationpolymer are more potent biocidals than the free ligands. From the data obtained, it is clear that Cu (II) ishighly active among the coordination polymer of the respective metal.CONCLUSIONThe results at present work show the following conclusions. The design synthesis of new bis-ligand has beenperformed successfully, and analysed by normaly spectral study. A series of some novel coordinationpolymer from bis-ligands with transition metals have been prepared and characterized for their spectral andmagnetic properties. All the synthesized coordination polymer compounds were screened for theirantimicrobial activity. The coordination polymers exhibited behave toxic for gram-negative bacteria (E.coli,samonella typhi and klebsiella promioe) and gram-positive bacteria (Bacillus subtilis and staphylococcusaureus), and plant pathogenic organisms (fungi) used were Aspergillus niger, Candida albicans,Trichoderma harsianum, Mucor mucedo, and Botrytis cinerea microorganisms. In comparison with theligand, coordination polymers were more active against one or more bacterial strains, thus introducing anovel class of metal-based bactericidal agents. The information regarding geometry of the coordinationpolymer was obtained from their electronic and magnetic moment values. The magnetic moment values ofcoordination polymer indicate an octahedral geometry.114 J. Chem. Bio. Phy. Sci. Sec. A, 2012-2013, Vol.3, No.1, 109-116.

<strong>Studies</strong>...Purav Talaviya et al.ACKNOWLEDGEMENTWe are grateful to the Principal, Shri R.K.Parikh Arts and Science College Petlad for providing thenecessary research facilities.REFERENCES1. S.Sherman, J. Ganon, G. Buchi, K. O.Howell and W. R. Eneyel, (1980). Chem.Tech.(Vol. 9), Epoxy Resins, John Wiley Inc., New York, 267.2. H.S. Freeman and J. F. Esancy (1991). Colour Chemistry, Elsever, London and NewYork.3. E. M Smolin and L.Rapopret, (1954). S-Triazine and Derivatives, Interscience, NewYork.4. A.I.Vogel, A Textbook of Quantitative Chemical Analysis, 5th ed.; revised by J.Besselt,R.C Denny, Jeffery, J.H.; Mendham, J. ELBS: London, 1996.5. V.M. Ivanor; T.F Metkina,. Zh. Anal. Khim 1978, 33, 2426.6. J.H. Burckhalter, V.C.Stephars, H.C.Searberough, W.S.Briniger, W.E Edergton, J. Am.Chem. Soc. 1954, 76, 4902.7. C.Vogel; Heinz, W. Brazil Pat., 78, 05,009, 1977; Ger.Pat. 2,832,758, 1977.8. J.H Burckhalter; R. Leib, Eswaran. J. Org. Chem. 1961, 26, 4078.9. H.Horowitz,; J.P. Perros, J. Inorg. Nucl. Chem. 1964, 26, 139.10. Bailer, Jr., C.J.; Judd, M.L.; McLean, M.J. Coordination Polymers (WADC TechnicalReports), 1959, 116, 58–51 lpar;Part II).11. R.D.Patel, S.R.Patel, H.S. Patel, Eur. Polym. J. 1987, 23, 229.12. T.B.Shah, H.S. Patel, R.B. Dixit, B.C. Dixit, Int. J. Polym. Anal. and Charact. 2003, 8,369.13. C.Xian Ren, F. Yuqi, I. Hisanori, H.Kazuhisa, O.Kousaburo, Analytical Sci. 1995, 11,313. Bis Bidentate Ligand 527 Downloaded By [INFLIBNET India Order] At: 03:55 18June 2011.14. W.Abraham, D. Abraham, R. Guy, and Abraham, P. Reactive Polymers, Ion Exchangers,Sorbents. 1984, 2, 301.15. K.D. Patel, S.C.Pachani, R.B. Dixit, Int. J. Inorganic and Orgeno Metallic Polymers2003.16. H.S. Patel, V.K. Patel, Indian J. Hetrocycl Chem. 2003, 12, 253.17. A.I. Vogel, Textbook of Quantitative Chemical Analysis, 4th ed.; ELBS: London, 1978.18. P.R. Murrey, E.J.Baran, M.A. Pfuller, F.C.Tenovov, Yolken, R.H. An AntimicrobialAgent and Susceptibility Testing; Americal Soc. Microbiology:Washington, DC, 1995,p. 1327.19. J. P, Phillips, R L Elbinger and Merritt L L, J Am Chem Soc., 1949, 71, 3984.20. L. J. Bellamy Infrared Spectra of Coordination polymer Molecules, Chapman and Hall,London, 1957.21. H.M. Parekh, P.K. Panchal, M.N. Patel, J. Therm. Anal. Cal. 2006, 86, 803.22. M.S.Masoud, M.F. Amira, A.M.Ramadan, El-Ashry, G.M. Spectrochim. Acta, Part A2008, 69, 30.23. K.C. Satpathy, A.K. Pande, R.Mishra, I.Panda, Synth. React. Inorg. Met. Org. Chem.1991, 21, 531.24. B.J. Hathway, A.A. Tomilson,G. Coord Chem. Rev. 1980, 5, 1.25. H.B. Pancholi, M.M. Patel, J. Polym. Mater. 1996, 13, 261–267.26. R. Papplardo, J. Chem. Phys. 1960, 33, 613.27. J. Lewis, R.S. Wilkins, Modern Coordination Chemistry; New York, 1960, p. 290.115 J. Chem. Bio. Phy. Sci. Sec. A, 2012-2013, Vol.3, No.1, 109-116.

<strong>Studies</strong>...Purav Talaviya et al.28. B. N. Figgis and J.Lewis The Magneto Chemistry of Coordination polymer in ModernCoordination Chemistry, Interscience, New York, 1960.29. J. O. Williams Adv Phys Org Chem., 1979, 15, 159..30. I .J. Patel and I.M. Vohra, E Journal of Chemistry, 2006, 3(2), 110-116.31. B.G. Tweedy, Phytopathology 1964, 55, 910. 528 H. S. Patel and K. D. PatelDownloaded By: [INFLIBNET India Order] At: 03:55 18 June 2011.Corresponding Author: Purav Talaviya; Department of Chemistry,JJT University, Rajasthan-, India116 J. Chem. Bio. Phy. Sci. Sec. A, 2012-2013, Vol.3, No.1, 109-116.