Research Journal of Recent Sciences ______ ______________________________ ______ ___ __ _ ISSN 2277 - 2502 Vol. 1( ISC - 2011 ), 1 10 - 116 (201 2 ) Res.J. Recent .Sci. International Science Congress Association 110 Synthesis, characterization and Biological studies of Cu(II) and Ni(II) coplxswithNwitatShiff’sasligasas 4 - hydroxy - 3 - (1 - (arylimino )ethyl)chromen - 2 - one Girgaonkar M.V. and Shirodkar S.G. Department of Chemistry , PG Department of Chemistry and Research Centre N.S.B. College, Nanded , INDIA Available online at: www.isca.in (Received 29 th December 2011, revised 7 th January 2012 , accepted 24 th January 2012 ) Abstract NwitatShiff’sasligas,4 - hydroxy - 3 - (1 - (arylimino)ethyl )chromen - 2 - one were synthesized by condensation of primary aromatic amines with 3 - acetyl - 4 - hydroxychromen - 2 - one. These were characterized by IR, 1 HNMR, 13 CNMR and mass spectral analysis. Cu(II) and Ni(II) complexes were synthesized and characterized by the ir mass, IR, electronic and XRD spectral analysis. Magnetic moments and molar conductance properties were studied using standard methods. Octahedral geometry around these metal ions has been proposed on the basis of magnetic and spectral studies. In vitro biological screening effects of the investigated compounds were tested against the bacterial species Staphylococcus aureus, Escherichia coli, Salmonella typhi and Bacillus subtilis by Agar cup method. Fungal species Aspergillus niger, Penicillium chrysogen um, Fusarium moneliforme and Aspergillus flavus by the posion plate method. A comparative study of inhibition values of the Schiff base ligands and their complexes in dicates that the complexes exhibit higher antimicrobial activity than the free ligands. Keywords: Schiff base, s pectra, a ntibacterial, a ntifungal. Introduction There are a number of reports that natural and synthetic coumarin derivatives possessing antimicrobial activity 1 . 4 - Hydroxy - 3 - substituted coumarins, a class of fused ring heterocycles, occur widely among natural products and have importance in medicine 2 . Many natural products with the coumarinic moiety exhibit interesting biological and pharmacological properties. Th ey are antibacterial, anti - HIV active 3 and antihelimenthic 4 . The Schiff base ligands and their metal complexes find paramount applications in the field of biological studies 5 , clinical 6 , dyes industry 7 , and food industry 8 . Literature survey reveals that w ork has been carried out on lanthanide complexes of Schiff bases derived from 8 - formyl - 7 - hydroxy - 4 - methyl - 2H - chromen - 2 - one 9 . Studies on metal complexes with Schiff base derived from 3 - formyl - 4 - hydroxychromen - 2 - one and semicarbazone were reported 10 . Less w ork seems to have been carried out on the metal complexes of Schiff bases derived from 4 - hydroxy - 3 - (1 - (arylimino)ethyl)chromen - 2 - one and primary aromatic amine. In the views of above facts, we report here the preparation of 3 - acetyl - 4 - hydroxychromen - 2 - one from 4 - hydroxychrom e n - 2 - one by earlier reported method 11 with some modification and was condensed with aromatic amines such as aniline, 4 - toluidine, 4 - chloroaniline and 4 - anisidine to synthesize 4 - hydroxy - 3 - (1 - (arylimino)ethyl)chromen - 2 - one (L 1 to L 4 ). Using these ligands their complexes were synthesized with cu II and Ni II metal ions. The structure of the complexes has been established using analytical, magnetic susceptibility, IR, electronic spectral data and powder XRD technique. The results obtaine d are in good agreement with the ligand – field splitting energy (10Dq). Material and Methods All the chemicals and solvents used were of A.R. grade. All chemicals used were of E - Merck and S.D. fine Ltd. Melting points were determined in an open capillary tube and are uncorrected. The purity of the compound has been checked by TLC. Elemental a nalyses (C, H and N) were performed on a Perkin - Elmer 2400 CHN elemental Analyzer . IR spectra were recorded in CHC l 3 on a Shimadzu FTIR - 8300 spectrophotometer. The 1 HNMR (300 MHz) and 13 CNMR (70 MHz) were run on a Bruker Avance DPX - 250 spectrometer in CDCl 3 using tetramethylsilane as an internal standard. Chemical shift values are given in d scale. Mass spectra were recorded on Finnigan Mat LCQ Mass Spectrometer using methanol as mobile phase. The electronic spectral measurements were made on Systronics UV - visible spectrophotometer (model 119). The metal contents in complexes were determined by atomic spectra on Perk ins Elmer atomic absorption spectrophotometer (model 2380). The conductivity of dilute solutions (1x10 - 4 M) in DMSO is measured on conductivity meter. Magnetic measurements at rootpraturwrcarrioutusigGouy’salac. Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ______ ISSN 2277 - 2502 Vol. 1( ISC - 2011 ), 1 10 - 116 (201 2 ) Res.J.Recent.Sci International Science Congress Association 111 S ynthesis of 3 - acetyl - 4 - hydroxychrom e n – 2 - one: To a solution of 4 - hydroxy - chromen - 2 - one (3g, 18.6 mmoles) in acetic acid (16 ml) phosphrous oxychloride (5.6 ml) was added. The mixture was heated at reflux for 30 minutes. After cooling, the precipitate was collected and recrystallized from ethanol. 3 - acetyl - 4 - hydroxy - chromen - 2 - one is collected as white needles. Yield of 2.7 g (90%), mp 134 - 36 0 C. S ynthesis of 4 - hydroxy - 3 - (1 - (arylimino)ethyl)chromen - 2 - one: The ligands L 1 - L 4 ( scheme 1) were prepared by mixing equimolar solu tions of 3 - acetyl - 4 - hydroxy - chromen - 2 - one and the corresponding aromatic amine in ethanol and refluxing the mixture for 4 hrs. After cooling, the product was crystallized from ethanol. The purity of the ligands was checked by m.p., TLC and elemental analys is. These are also characterized by IR, 1 HNMR, 13 CNMR and mass spectral studies. General procedure for the synthesis complexes: To a hot solution of Ligand ( 0.02 Moles in 40ml of methanol), 0.01 moles of metal salt dissolved in 25ml of methanol was added drop wise. The contents were refluxed for four hours. The precipitated complex was further digested for one hour. The complex formed was filtered and washed with alcohol and followed by petroleum ether (40 – 60 0 C). It was dried in vacuum desiccators over calcium chloride. Results and Discussion Ligands ( L 1 - L 4 ) are synthesized as shown in scheme 1. Commercially available (1) is acetylated with acetic acid and phosphorus oxychloride in a hood as safety meas ure according to literature procedure 11 to afford (2). The ligands 4 - hydroxy - 3 - (1 - (arylimino)ethyl)chromen - 2 - ones ( L 1 - L 4 ) are obtained by condensation of (2) with aromatic amines as aniline, 4 - toludine, 4 - chloroaniline and 4 - anisidine. Investigations are carried out to establish the structures of ligands (L 1 - L 4 ) , both in the solid state and in solution using various spectroscopic techniques. Physical, analytical and spectral data of the ligands are listed in t able 1. The synthesized com plexes are stable at room temperature, insoluble in water, partially soluble in methanol and ethanol, completely soluble in DMF and DMSO. The elemental analysis, magnetic moments and molar conductance data given in ( t able 1) are consistent with the general formula [M(L) 2 ].2H 2 O. The ligand is a bidentate coordinating through azomethine nitrogen, phenolic oxygen of coumarin moiety via deprotonation. The molar conductance values in DMSO in 10 - 3 M fall in the range 22 - 0Ω - 1 indicating non - electrolytic nature of the complexes 12 . All ligands show a high intensity band observed ca . at 1632 - 1626 cm - 1 is assigned to ν (C=N) vibration suggesting the formation of Schiff base. Broad weak band around 3500 - 2600 cm - 1 is assigned to H b onded – OH in the Schiff base. The band at 1567 - 1483 cm - 1 is assigned to the combination of ν (C=C) of the aromatic ring. A high intensity band in the region 1338 - 1335 cm - 1 is assigned to phenolic ν (C - O) vibration and 1720 - 1709 cm - 1 for lactone carbonyl. The ν (C=N) of ligand (L 1 - L 4 ) appeared at 1632 - 1626 cm - 1 has shifted to 1611 - 1605 cm - 1 in the metal complexes. This lower shift supports the coordination of metal ion with azomethine nitrogen. The disappearance of the band at 1338 - 1335 cm - 1 and appearance o f new medium intensity bands in the region 1398 - 1394 cm - 1 for ν (C - O) supports the coordination of phenolic oxygen to the metal ion via deprotonation 9 . The unaltered position of ν (C=O) confirms the non - involvement of lactone in the coordination. A broad band at 3500 - 3300 cm - 1 and a peak at 955 - 948 cm - 1 in the complexes indicates the presence of coordinated water molecules. 13 Further the presence of coordinated and non coordinated water molecules is confirmed by the TGA studies. The appearance of two stron g bands at 528 - 492 cm - 1 and at 415 - 405 cm - 1 are assignable to ν (M - N) and ν (M - O) vibrations respectively 14 - 15 . In thermal studies, no weight loss was found on constant heating for 1 h at 120 o C which is indicative of the presence of coordinated water. The TG analysis shows the percentage loss corresponding to two coordinated water molecules in cu II and Ni II complexes. The loss of water in these complexes was found to be one - step process as only one endothermic peak was observed at 200 - 220 o C 16 . The electronic spectra of the Cu II complexes shows a band in the 16260 - 16666 (  = 40.50) cm - 1 assignable to 2 E g  2 T 2g characteristic of distorted octahedral stereochemistry with D 4h geometry 17 . Beside the above bands, the band observed at ~ 27700 cm - 1 may be assigned due to charge transfer. The cu II complex exhibit normal magnetic moment which are in the range 1.73 - 1.82 BM support the octahedral structure. The ESR spectra of the Cu(II) complexes were recorded at room temperature t able 3 . The anisotropi c G values have calculatyKuuhl’stho 18 G= (g || - 2.003) / (g  - 2.003) which measures the exchange interaction between copper(II) centers. One unpaired electron in Cu(II) complex with 2 B 1g as ground state lies in d x2 - y2 spectrum of Cu(II) compl ex of ligand orbital and follows the trend g || � g  �g e (g e = 2.0036 free ion value). The axial spectrum with g || � g  � 2.03 is consistent with a distorted octahedral geometry Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ______ ISSN 2277 - 2502 Vol. 1( ISC - 2011 ), 1 10 - 116 (201 2 ) Res.J.Recent.Sci International Science Congress Association 112 around the Copper(II) ion 19 . The spectra [Cu(L 1 ) 2 (H 2 O) 2 ] , [Cu(L 2 ) 2 (H 2 O) 2 ], [Cu(L 3 ) 2 (H 2 O) 2 ] and [Cu(L 4 ) 2 (H 2 O) 2 ] exhibited pronounced peak at g ┴ =2.07 0.02 and a broad and shallow quadruplet at g || =2.280.04. Such spectral features are characteristic of the Cu 2+ ions present in axially distorted octahedral . sites 20 . The calculated G value for the present complexes appeared in the range 3.13 to 3.66 indicate the existence of a negligible exchange interaction between copper, as G 4 21 . The Ni II complexes exhibit three absorption bonds 12987 - 13333 (  = 8) (  1 ), 19417 - 19802 (  = 6) (  2 ) and 27777 - 29411 (  = 20) (  3 ) which may attributed to the 3 A 2g (F)  3 T 2g (F) (  1 ), 3 A 2g (F)  3 T 1g (F) (  2 ), 3 A 2g F)  3 T 1g (P) (  3 ), respectively indicating octahedral geometry 22 - 23 . The magnetic values are in normal range (3.11 – 3.37 B.M.) of octahedral structure. This structure is further confirmed by the ratio V 2 /V 1 (1.44 – 1.50), the value expected for octahedral structure. The reduction of Racah parameters (B 1 = 527.43 - 601.83) form the free ion value 1080 and  = 0.488 - 0.557, less than unity suggest appreciable amount of covalent character in the metal – ligand bonds 24,25 . X - ray diffraction pattern of Cu[L 1 ] 2. 2H 2 O and Ni[L 1 ] 2. 2H 2 O revealed sharp refluxes suggesting highly crystalline monoclinic nature for the complexes 26 . The position of each reflux was accurately measured and by using Bragg's equation the inter planar distance d was calculated. The d - spacing values of each reflux were used to calculate lattice parameters assuming the probable crystal monoclinic system. Table - 1 Physical, analytical and spectral data of the ligands S.No Specification Data of Ligand L 1 Data of Ligand L 2 Data of Ligand L 3 Data of Ligand L 4 1 Yield 90% 85% 82% 83% 2 Colour Yellowish Green Yellowish Green Yellowish Green Yellowish Green 3 Melting Point 203 0 C 210 0 C 237 0 C 243 0 C 4 IR (KBr, cm - 1 ) 3600 - 2600 (broad pholicν OH ) , 70(ν C=O ) lactone , 28(ν C=N ) of imine, 1564, 1483 aromatic (ν C=c ) 5(ν C - O ) phenolic 3600 - 2600 (broad pholicν OH ) , 709(ν C=O ) lactone , 0(ν C=N ) of imine, 1567, 1483 aromatic (ν C=c ) (ν C - O ) phenolic 3600 - 2600 (broad pholicν OH ) , 720(ν C=O ) lactone , 2(ν C=N ) of imine, 1565, 1484 aromatic (ν C=c ) (ν C - O ) phenolic 3600 - 2600 (broad pholicν OH ) , 70(ν C=O ) lactone , 2(ν C=N ) of imine, 1563, 1483 aromatic (ν C=c ) 8(ν C - O ) phenolic 5 1 H - NMR (CDCl 3 ) in  (300 MHz) 2.66 (S,3H, – CH 3 ), 7.5 - 7.0 ( m, 5H, Ph – H), 8.06 and 7.5 - 7.2 (Ar - H of coumarin moiety), 15.75 ( S,1H, O – H). 2.65 ( S, 3H, imne – CH 3 ), 2.38 ( S, 3H, for p - Phenyl - CH 3 ) 7.5 and 7.08 dd, 4H, ( - C 6 H 4 - p ) 8.04 and 7.2 - 7.5 ( Ar - H of coumarin moiety), 15.74 ( S,1H, O – H). 2.68( S, 3H, imne – CH 3 ), 7.19 and 7.47dd, 4H, ( - C 6 H 4 - p ) 8.04 and 7.2 - 7.5( Ar - H of coumarin moiety), 15.92 ( S,1H, O – H). 2.66 ( S, 3H, imne – CH 3 ), 3.84 ( S, 3H, for p - Phenyl - 0CH 3 ) 6.97 and 7.14dd, 4H, (C 6 H 4 - p ) 8.05 and 7.2 - 7.5( Ar - H of coumarin moiety), 15.68 ( S,1H, O – H). 6 13 C - NMR (CDCl 3 ) in  (300 MHz) 20.39 (imine - CH 3 carbon), 98.12 for 3 C, 138 - 116 for aromatic carbons, 154 for 9 C, 162.4 for lactone carbon, 175.9 for 4 C, and 181.7 for imine carbon 20.38 (imine - CH 3 carbon), 21.04 ( p - CH 3 ) 98.07 for 3 C, 138 - 116 for aromatic carbons, 154 for 9 C, 162.38 for lactone carbo n, 175.99 for 4 C, and 181.78 for imine carbon 20.43 (imine - CH 3 carbon), 98.07 for 3 C, 133.9 - 116.7 for aromatic carbons, 154.1 for 9 C, 162.12 for lactone carbon, 176.13 for 4 C, and 182.11 for imine carbon 20.34 (imine - CH 3 carbon), 55.60 ( p - OCH 3 carbon) 98.04 for 3 C, 138.8 - 114.9 for aromatic carbons, 154 for 9 C, 159.7 for lactone carbon, 176.07 for 4 C, and 181.59 for imine carbon 7 Mass Spectra [M + ]=279.08 [M + ]=294.35 [M + ]=314.23 and 316.19 (in isotopic ratio of Chlorine ) [M + ]=309.98 Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ______ ISSN 2277 - 2502 Vol. 1( ISC - 2011 ), 1 10 - 116 (201 2 ) Res.J.Recent.Sci International Science Congress Association 113 Table - 2 Analytical Data o f Complexes Table - 3 ESR data of the Cu(II) complexes of the ligand L 1 and L 3 Complex g  g   g av G  eff Cu(L 1 ) 2 (2H 2 O) 2.3303 2.0935 2.174 3.666 1.882 Cu(L 2 ) 2 (2H 2 O) 2.2674 2.0788 2.141 3.486 1.854 Cu(L 3 ) 2 (2H 2 O) 2.2625 2.0830 2.142 3.242 1.855 Cu(L 4 ) 2 (2H 2 O) 2.2826 2.0923 2.155 3.130 1.866 S. No. Complexes Colour Found / (calc), %  eff . B.M. Ligand field parameters C H N M 10 Dq (cm - 1 ) LFSE kcal - mol - 1   (cm - 1 )   V 2 / V 1 1 [Cu(L 1 ) 2 (H 2 O) 2 ] Green 62.27 (62.24) 4.35 (4.30) 4.23 (4.27) 10.1 (9.68) 1.78   37.60 - - - 2 [Cu(L 2 ) 2 (H 2 O) 2 ] Green 59.93 (63.20) 4.60 (4.71) 4.42 (4.09) 9.60 (9.29) 1.73 1316 37.60 - - - 3 [Cu(L 3 ) 2 (H 2 O) 2 ] Pale Green 56.50 (56.32) 3.46 (3.61) 3.52 (3.86) 10.15 (9.78) 1.82 1333 38.03 - - - 4 [Cu(L 4 ) 2 (H 2 O) 2 ] Green 60.60 (60.37) 4.26 (4.50) 3.63 (3.91) 8.70 (8.87) 1.76 1333 38.03 - - - 5 [Ni(L 1 ) 2 (H 2 O) 2 ] Yellow ish Green 62.46 (62.70) 4.60 (4.33) 4.50 (4.30) 9.28 (9.01) 3.11 1298 37.11 601.8 0.557 1.50 6 [Ni(L 2 ) 2 (H 2 O) 2 ] Yellow ish Green 63.28 (63.65) 4.66 (4.75) 4.20 (4.12) 8.50 (8.64) 3.17 1316 37.60 527.4 0.488 1.49 7 [Ni(L 3 ) 2 (H 2 O) 2 ] Yellow ish Green 56.92 (56.70) 3.46 (3.64) 3.62 (3.89) 8.36 (8.15) 3.20 1333 38.10 576.1 0.533 1.44 8 [Ni(L 4 ) 2 (H 2 O) 2 ] Yellow ish Green 60.90 (60.78) 4.60 (4.53) 3.68 (3.94) 8.10 (8.25) 3.37 1333 38.10 558.2 0.516 1.49 Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ______ ISSN 2277 - 2502 Vol. 1( ISC - 2011 ), 1 10 - 116 (201 2 ) Res.J.Recent.Sci International Science Congress Association 114 Table - 4 Anti Bacterial activity Compound Zone of Inhibition (diameter in mm) E. coli S. typhi S.aureus B. subtilis Penicillin 24 18 21 14 (L 1 ) 16 - 13 7 Cu(L 1 ) 2 (2H 2 O) 22 11 17 10 Ni(L 1 ) 2 (2H 2 O) 19 9 13 7 (L 2 ) 11 - 9 8 Cu(L 2 ) 2 (2H 2 O) 15 6 10 5 Ni(L 2 ) 2 (2H 2 O) 11 - 5 - (L 3 ) 20 7 14 11 Cu(L 3 ) 2 (2H 2 O) 24 12 17 13 Ni(L 3 ) 2 (2H 2 O) 22 10 15 12 (L 4 ) 18 - 11 8 Cu(L 4 ) 2 (2H 2 O) 23 5 14 11 Ni(L 4 ) 2 (2H 2 O) 20 - 12 9 Table - 5 Anti fungal activity Compound Growth of Fungi A. niger P .chrysogenum F. moneliforme A. flavus Gresiofulvin - - - - (L 1 ) + ++ ++ + Cu(L 1 ) 2 (2H 2 O) - - - - Ni(L 1 ) 2 (2H 2 O) - + + - (L 2 ) + ++ ++ + Cu(L 2 ) 2 (2H 2 O) - - - - Ni(L 2 ) 2 (2H 2 O) - + + - (L 3 ) - - + - Cu(L 3 ) 2 (2H 2 O) - - - - Ni(L 3 ) 2 (2H 2 O) - - - - (L 4 ) + ++ ++ + Cu(L 4 ) 2 (2H 2 O) - - - - Ni(L 4 ) 2 (2H 2 O) - + + - Moderate growth ( ++ ), Reduced growth ( + ) and No growth ( - ) of fungi Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ______ ISSN 2277 - 2502 Vol. 1( ISC - 2011 ), 1 10 - 116 (201 2 ) Res.J.Recent.Sci International Science Congress Association 115 Biological Activity: The antibacterial activity was measured by agar cup method 27 . The bacterial cultures selected were, two gram negative cultures viz. Escherichia coli, Salmonella typ hi and two Gram positive cultures viz. Staphylococcus aureu, Bacillus subtilis. Results were recorded by measuring the zone of inhibition in millimeter (mm) using zone reader ( t able - 4). Antifungal activity was performed by Poison plate method.[20] The medium used was Potato Dextrose Agar (Himedia) 27 . Aspergillus niger, Penicillium chrysogenum, Fusarium moneliforme, Aspergillus fla vus were selected as test fungal cultures. Results were recorded ( t able - 5) as moderate growth of fungi (++), reduced growth of fungi (+) and no growth of inoculated fungi ( - ) antifungal activity. ThSchiff’sassathirCu(II)aNi(II)coplxs we re evaluated for anti - bacterial and anti - fungal activity with different strains of bacteria and fungi. Results are shown in t able - 4 and t able - 5. All have shown lesser activity against E. coli, S. aureus and B. subtilis compared with penicillin taken as standard. The activity of ligand L 3 and its complexes was higher in comparison and has also shown activity against S. typhi and fungi. Antifungal activity observed against Aspergillus species was encouraging in comparison with Penicillium chrysogenum and Fusarium moneliforme. Conclusion Thus from the elemental analysis, molar conductivity measurements, magnetic susceptibilities, electronic absorption and infrared spectral studies and XRD stu dies, it is concluded that the complexes of Cu II , Ni II , have crystalline monoclinic system with monomeric octahedral geometry scheme 2 . It may be concluded from results that antibacterial activity and antifungal activity of Cu(II) complexes was greater tha n Ni(II) complexes. Acknowledgement The authors thank Principal, N.S.B. College, Nanded, Maharashtra for providing laboratory facility. 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