synthesis-spectral-characterization-and-biological-activities-of-cuii-

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________________________________________ Author for correspondence E-mail: duraiuymail.com drt_maruthavananyahoo.co.in manasu2kyahoo.co.in argovindhgmail.com chemtryahoo.co.in Int. J. Chem. Sci.: 144 2016 2566-2574 ISSN 0972-768X www.sadgurupublications.com SYNTHESIS SPECTRAL CHARACTERIZATION AND BIOLOGICAL ACTIVITIES OF CuII COMPLEX WITH SCHIFF’S BASE LIGAND DERIVED FROM PHENYLACETYLUREA AND SALICYLALDEHYDE P. DURAIRAJ a T. MARUTHAVANAN b S. MANJUNATHAN c R. GOVINDHARAJU d and T. RAMACHANDRAMOORTHY e a Department of Chemistry Excel Engineering College Pallakkapalayam Sankari West P.O. KOMARPALAYAM – 637303 Dist.: Namakkal T.N. INDIA b Department of Chemistry Sona College of Technology SALEM – 636 005 T.N. INDIA c Department of Chemistry Government Arts College Ponneri CHENNAI – 601204 T.N. INDIA d Department of Chemistry Government Arts College ARIYALUR – 621713 T.N. INDIA e PG Research Department of Chemistry Bishop Heber College Autonomous TIRUCHIRAPPALLI – 620017 T.N. INDIA ABSTRACT A new copperII complex of Schiff’s base derived from phenylacetylurea condensed with salicylaldehyde SBPS and thiocyanate ion was synthesized by using microwave irradiation. Microwave synthesis gives high yield of the complex within a short time. The molecular formula and the probable geometry of the complex had been deduced from elemental analysis electrical conductivity magnetic susceptibility infra red electronic and EPR spectra. The molar conductance value indicates that the CuII complex is a non-electrolyte. The FT-IR spectra show that SBPS and thiocyanate ion are coordinated to the metal ion in a monodentate manner. The covalency character of the complex was indicated by the EPR spectrum. The geometry of the complex was found to be tetragonally distorted octahedral. The antibacterial and antifungal activities of the free ligand SBPS and their CuII complex were studied against the microorganisms viz. E. coli Klebsiella Pneumonia P. aeurginosa S. aureus Bacillus cereus. Aspergillusflavus Aspergillusniger Aspergillusoryzae Aspergillussojae and Candida albicans using agar - well diffusion method. The complex shows moderate activity against the bacteria and enhanced activity against the fungi as compared to the free ligands. Key words: CopperII complex Schiff’s base Thiocyanate ion Antibacterial and antifungal.

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Int. J. Chem. Sci.: 144 2016 2567 INTRODUCTION In recent trend there is an enhanced interest in the synthesis of transition metal containing Schiff’s base. Schiff’s base has several applications in biological clinical and analytical fields 1 owing to their enhanced biological and pharmaceutical activities. Schiff’s bases have attracted many research workers 2 . Schiff’s base complexes are used important in many important catalytic reactions 3 . They are also used in the di-oxygen uptake and oxidative catalyst 45 . In the present work the Schiff’s base derived from phenylacetylurea and Salicylaldehyde by condensation is used as primary ligand for the preparation of complex. The prepared complex is characterized by the physico-chemical and spectral studies. EXPERIMENTAL Materials and methods Phenylacetylurea potassium thiocyanate and copper nitrate were purchased from Alfa Aaser Company and used as such. The organic solvents used viz. DMSO DMF methanol ethanol were of AnalaR grade and used as such without further purification. Preparation of Schiff’s base The Schiff’s base primary ligand was prepared by refluxing an ethanolic solution of required mole ratios of phenylacetylurea with salicylaldehyde in the presence of NaOH for more than an hour. It was recrystallized in ethanol. O NH O NH 2 + O O H H Reflux NaOH O NH O NC O H H Fig. 1: Schiff’s base of phenylacetylurea with Salicylaldehyde SBPS Instrumentations CHN elemental analyses were performed using Thermo Finnegan make Flash EA1112 Series CHNSO analyzer. The electrical conductivity measurement was carried out

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P. Durairaj et al.: Synthesis Spectral Characterization and…. 2568 using 10 -3 M solution of the metal complex in acetonitrile with systronic conductivity Bridge model number-304 at 30 o C. The UV spectrum of the CuII complex was recorded on Varian Cary 5000 model UV spectrophotometer. Infrared spectra for the complex and the ligands were recorded on a Perkin Elmer spectrum RX-I FT-IR spectrometer in KBr discs at room temperature. The Far-IR spectrum of the complex was recorded by Bruker 3000 FT-IR spectrometer. JES FA 200 model Spectrometer was used to record the EPR spectrum. The antibacterial and antifungal activities of the ligands SBPS and thiocyanate using potassium thiocyanate and their complex were done by agar- well diffusion method. Synthesis of copper complex 2.27 g 8.24 mmol of SBPS in ethanol and 1.05 g 8.27 mmol of potassium thiocyanate in ethanol were added to copper nitrate 1.00 g 4.13 mmol in methanol followed by microwave irradiation for a few seconds after each addition by using IFB 25 BG-1S model microwave oven. The resulting precipitate was filtered washed with 1:1 ethanol: water mixture and dried under vacuum. A yellowish green coloured complex was obtained with the yield of 72. Pharmacology Antimicrobial activity The copper complex and the ligands were tested for in vitro antimicrobial activity by the well diffusion method 6 using agar nutrient as the medium. The antibacterial and the antifungal activities of the ligand and the copper complex were evaluated by well diffusion method against the strains cultured on potato dextrose agar as medium. The stock solution 10 -2 M was prepared by dissolving the compounds in DMSO and the solutions were serially diluted to find Minimum Inhibitory Concentration values. According to the typical procedure 7 a well was made on the agar medium inoculated with the microorganisms. The well was filled with the test solution using a micropipette and the plate was incubated for 24 hrs for bacteria and 72 hrs for fungi at 35 o C. At the end of the period the diameter of inhibition zones formed on the medium were evaluated in millimeters mm. RESULTS AND DISCUSSION Elemental analysis and metal estimation The elemental analysis and metal estimation of the complex lead to the formula MSBPS 2 SCN 2 . The percentages of carbon hydrogen nitrogen and copper in the complex were found to be 52.74 52.73 3.64 3.67 10.85 10.83 and 8.20 8.16

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Int. J. Chem. Sci.: 144 2016 2569 respectively. The experimental data are in good agreement with the theoretical values given in the parentheses. Molar conductance The molar conductance of 10 -3 M solution of CuSBPS 2 SCN 2 in acetonitrile was found to be 81.03 Ω -1 cm 2 mol -1 indicating its non electrolyte 8 nature. Electronic spectra For CuSBPS 2 SCN 2 the λ max values at 545 nm 18348 cm -1 406 nm 24630 cm -1 and 249 nm 40160 cm -1 corresponding to 2 E g ← 2 B 1g 2 B 2g ← 2 B 1g and 2 A 1g ← 2 B 1g transitions suggest the tetragonally distorted octahedral geometry 9 . The magnetic moments value 1.79 BM is consistent with the presence of one unpaired electron. This value lies above the spin-only value of 1.76 BM probably due to the mixing of ground state with excited states through spin-orbit coupling 10 . The reported μ eff values are in the range of 1.75-2.20 BM 1112 . These facts confirm the tetragonally distorted octahedral geometry for the copper complex. FT-IR spectra The IR spectrum of the pure ligand shows the characteristic frequencies as follows: the band at 3388 cm -1 indicates the νN-H stretching frequency of primary amine at 1668 cm -1 indicates symmetric stretching frequency and at 1622 cm -1 the asymmetric stretching frequency of νN-H in secondary amine. The νCO stretching frequency of the ligand is observed at 1475 cm -1 . In the CuII complex νN-H is shifted to 1656 cm -1 and the symmetry stretching frequency at 1622 cm -1 is shifted to 1605 cm -1 which confirms the entry of ligands into the coordination sphere. In addition to that the value at 2072 cm -1 indicates the presence of SCN − in the coordination sphere of the complex 1314 . Far-IR Spectra In the Far-IR spectrum of the complex the frequency at 448.5 cm -1 corresponds to Cu-N imido nitrogen bond 15 and at 342.2 cm -1 indicates the Cu-N from thiocyanate bond 16 . Thus it is confirmed. EPR spectrum The X-band EPR spectrum of DMSO solution of the CuII complex at 77 K LNT Fig. 3 provides useful information about the metal ion environment. The spin Hamiltonian parameters of the complex were calculated and summarized in Table 1.

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P. Durairaj et al.: Synthesis Spectral Characterization and…. 2570 Fig. 2: Far-IR-spectrum of CuII complex Fig. 3: EPR -spectrum of CuII complex Table 1: Spin Hamiltonian parameters of CuII complex of SBPS and SCN at 300 and 77 K Complex Spin Hamiltonian parameters CuSBPS 2 SCN 2 g || g ┴ g av G A || 10 -4 cm -1 α 2 2.3869 2.2750 0.4304 0.7220 177.62 0.4304 The spectrum shows four well resolved peaks in the low field region and one intense peak in the high field region. The g-tensor value of the copper complex can be used to derive the ground state. In octahedral complexes the unpaired electron lies in the d x2-y2 orbital 17 . For this complex the observed g-tensor values are g ║ 2.3869 g ┴ 2.2750 2.0023

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Int. J. Chem. Sci.: 144 2016 2571 which suggest that this complex has an octahedral geometry and the ground state is 2 B 1g . The EPR parameters of the complex coincide well with the related systems which confirm that the complex has an octahedral geometry and it is axially symmetric. In the EPR spectra the g-values are related with the exchange interaction coupling constant G by the expression 18 . G g || - 2:0023/g ┴ - 2.0023 According to Hathaway 19 if G value is greater than four the exchange interaction is negligible because the local tetragonal axes are aligned parallel or are slightly misaligned. If its value is less than four the exchange interaction is considerable and the local tetragonal axes are misaligned. For the present CuIIcomplex G 0.7220 indicating considerable exchange interaction in the complex. The g av and the covalent in-plane σ-bonding α 2 parameters are calculated according to the following equation 20 g av 1/3 g || + 2g ┴ α 2 Cu A /0.036 + g || -2.0023 +3/7g ┴ -2.0023 + 0.04 The α 2 value less than 1.0 indicates the presence of considerable covalent character associated with the metal-ligand bond 2122 . Biological activity Antibacterial activity The antibacterial activities of the copper complex and SBPS were evaluated against the bacteria E. coli Klebsiella Pneumonia P. aeurginosa S. aureus Bacillus cereus. Aspergillusflavus Aspergillusniger Aspergillusoryzae Aspergillussojae and Candida albicans at MIC concentration using agar-well diffusion method. The complex shows moderate activity against the tested microbes. The antibacterial activities of the free ligand and the complex are as shown in Table 2. Table 2: Antibacterial activities of CuSBPS 2 SCN 2 complex zone of inhibitionmm S. No. Ligand/Complex Zone of inhibition mm S.aureus Bacillus cereus E. coli P. aeruginonosa Kelebsiella 1 SBPS 6 10 10 6 5 2 CuSBPS 2 SCN 2 14 18 17 18 10

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P. Durairaj et al.: Synthesis Spectral Characterization and…. 2572 Antifungal activity The antifungal activities of the copper complex and SBPS were evaluated against the Aspergillusflavus Aspergillusniger Aspergillusoryzae Aspergillussojae and Candida albicans at various concentrations and compared with the antifungal activities of all the complexes which are lower than those of flukonazole standard.The complex shows enhanced activity against the tested fungus. The antifungal activities of the free ligand and the complex are as shown in Table 3. Table 3: Antifungal activities of CuSBPS 2 SCN 2 complex Diameter of zone of inhibition in mm S. No. Fungus Concentration 100 µgmL -1 200 µgmL -1 400 µgmL -1 1 Aspergillusflavus 7 12 20 2 Aspergillusniger 8 15 24 3 Aspergillusoryzae 0 9 19 4 Aspergillussojae 9 15 26 5 Candida albicans 8 17 29 Fig. 4: Zone of inhibition in mm Antifungal effects of the CuSBPS 2 SCN 2 complex CONCLUSION In the present study our efforts were to synthesize and characterize a new CuII metal complex with SBPS and thiocyanate ion as ligands. The new complex was synthesized

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Int. J. Chem. Sci.: 144 2016 2573 using microwave irradiation Green synthesis. The synthesized complex was characterized by various chemical and spectral analyses. Based on the analytical electrical conductance spectral and magnetic moment data tetragonally distorted octahedral geometry had been suggested for the CuII complex. The antibacterial and the antifungal activities of the ligand were compared with the CuII complex. The complex showed moderate activity against the bacteria and enhanced activity against the fungi. ACKNOWLEDGEMENT The authors are thankful to the Head SAIF IIT and the Director STIC Cochin for providing the spectral data collection. The authors also thank the Management and the Principals of Sona College of Technology Salem and Dr. Navalar Nedunchezhiyan College of Engineering Tholudur for permitting them to carry out this work. REFERENCES 1. A. P. Mishra and Monika Soni Metal Based Drugs 2008 1-7 2008. 2. R. K. Dubey U. K. Dubey and C. M. Mishra Indian J. Chem. 47A 1208-1212 2008. 3. K. Krishnakutty Muhammed Basheer Ummathur and Sayudevi P. Analesdela Asociacia Quimica Argentina 961-2 1-8 2008. 4. N. Elataher EltayebTaha and Taj Elsir A. Ahmed 62 0-0 2005. 5. D. M. Boghaei and M. Lashani-Zadegan J. Sci. Ir. Iran 114 301-304 2000. 6. M. J. Pelczar E. C. S. Chan and N. R. Krieg Microbiology Blackwell Science New York 5 th Edn. 1998. 7. O. N. Irobi M. Moo-Young and W. A. Anderson Int. J. Pharm. 34 87 1996. 8. W. G. Geary The Use of Conductivity Measurements in Organic Solvents for the Characterization of Coordination Compounds Coord. Chem. Rev. 7 81-122 1971. 9. B. Narayana and M. R. Ganjendragad Tr. J. Chem. 21 65 1997. 10. A. A. Sakthivel N. Raman and L. Mitu Monatshefte Fur Chemi. 1445 605-620 2013. 11. B. M. Figgis and J. Lewis Prog. Inorg. Chem. 6 37-64 1964. 12. Juman Ahmed Naser J. Al-Nahrain University 141 30-39 2011.

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P. Durairaj et al.: Synthesis Spectral Characterization and…. 2574 13. G. Mahmoudi A. Morsali Cryst. Engg. Comm. 9 1062-1072 2007. 14. A. Arunachalam T. Ramachandramoorthy S. Padmavathy and S. Amalafathima Rani Int. J. Pharm. Pharmaceut. Sci. 68 91-94 2014. 15. R. Govindharaju S. Balasubramaniyan L. Palanivelan K. Rajasekar and T. Ramachandramoorthy World J. Pharmaceut. Res. 38 788-795 2014. 16. Zahid H. Chohan Asifa Munawar and Claudiu T. Supuran Metal Based Drugs 83 137-143 2001. 17. A. L. Sharma I. O. Singh M. A. Singh H. R. Singh R. M. Kadam M. K. Bhide and M. D. Sastry Transition Met. Chem. 26 532-537 2001. 18. N. Raman T. Baskaran A. Selvan and R. Jeyamurugan J. Iran. Chem. Res. 1 129- 139 2008. 19. B. J. Hathaway and A. A. G. Tomlinson CopperII Ammonia Complexes Coord. Chem. Rev. 5 1-43 1970. 20. P. Tharmaraj D. Kodimunthiri C. D. Sheela and C. S. Shanmuga Priya J. Serb. Chem. Soc. 74 927-938 2009. 21. A. A. EiBindary and A. Z. EI Sonbati Pol. J. Chem. 74 615-620 2000. 22. N. Raman V. Muthuraj S. Ravichandran and A. Kulandaisamy Proc. Indian Acad. Sci. Chem. Sci.. 115 161-167 2003. Revised : 19.06.2016 Accepted : 21.06.2016