Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(8), 23-27, August (2015) Res. J. Chem. Sci. International Science Congress Association 23 Study on X-Ray Diffraction and Biological Activity of some Rear Earth Metal Complexes on the Basis of Mixed LigandsIngale V.D., Shinde V.G., Rajbhoj A.S. and Gaikwad S.T.*Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad, 431004, Maharashtra, INDIAAvailable online at: www.isca.in, www.isca.me Received 24th July 2015, revised 3rd August 2015, accepted 18th August 2015 AbstractStudies on the Powder x-ray diffraction parameter of metal complexes such as La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III) has been synthesized by 4-methoxyplenylmaine and salicylaldehyde, o-vanillin having equiamolar ratio of 1:1:1(metal : ligand : ligand)in the same solvent. The complexes were different physico-chemical properties such as different colour, different melting points and different crystal systems. The x-ray diffraction studies are orthorhombic, monoclinic, tetragonal crystal structure has been proposed for the mixed (Land L) ligands and their lanthanide (III) complexes. The x-ray diffraction data suggest that monoclinic crystal system for La(III), Ce(III) complexes and orthorhombic crystal system for Pr(III), Nd(III), Gd(III), Dy(III) and Tb(III) complexes and other were tetrahedral crystal system for Sm(III) complex. The x-ray diffraction data were also being used for the determination of various parameter, unit cell volume and miller indices values (h k l). The screened for their antibacterial activity against bacterium of Staphylococcus aurious, B.subtilis (Gram-positive) and Aspergillus Niger and Fusarium oxysporum(Gram- negative). The result indicated that the complexes exhibited good antibacterial, antifungal active than that of free ligands. Keywords: Lanthanide (III) complexes, x-ray diffraction studies, antibacterial and antifungal activity. Introduction Schiff bases derived from aromatic amines and aromatic aldehydes have a wide variety of applications in many fields, i.e. biological, inorganic and analytical chemistry1-5. Powder x-ray diffraction studies on the lanthanide (III) complexes of an instrumental technique that used to identify crystalline material. X-ray diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide information on unit cell dimensions. The analyzed material is finely ground, homogenized, and average bulk composition is determined . In this work, we wish to report lanthanide (III) complexes scanned in the range of 5-65at wavelength 1.540598Å. The diffractogram and associated data depict the 2 value of each peak, relative intensity and inter-planar spacing (d-values), but the systematic study on determination of mixed (Land L) ligands and their lanthanide (III) complexes i.e. La (III), Ce (III), Pr (III), Nd (III), Sm (III), Gd (III), Tb (III) and Dy (III). A diffraction pattern plots intensity against the angle of the detector 2. In a diffraction pattern, the peak position depends upon the wavelength. X-ray diffractometer with a radiation source of CuK was used8-9. The objective of x-ray diffraction measurement is to determine the dimensions and shape of unit cell and to identify the detailed structure of the molecule. To achieve this objective, we must be able to express mathematically the nature of the measured interference pattern in terms of the position of the various atoms within the crystal10Material and Methods The lanthanide (III) nitrates obtained from Rare Earth Ltd. (India) were used without further purification. Salicylaldehyde, o-vanillin and p-anisidine was obtained from Alfa Acer Chemicals and solvents were obtained from Aldrich Chemical Company. The powders XRD were characterized by recorded on Perkin Elmer TA/SDT-2960 and Philips 3701, respectively. Synthesis of Schiff base ligands and Metal complexes: The syntheses of Schiff base ligand (Land L) were prepared by modification of reported method11. In 50 ml solution of ethanol contain 0.001mol (0.122g) of salicylaldehyde, 0.001mol (0.152 g) of o-vanillin and 0.001mol (0.123 g) of 4-methoxyphenylamine were stirred for 4 hours at room temperature at show in scheme-I and scheme-II. The two different color was obtained by gray (L) and orange (L). The ligands are collected, filtered by using Buckner funnel, washed with ethanol and dried in the desiccators. Purity of the ligands was checked by TLC plates. The product was purification and recrystallization from a hot ethanol. Yield obtained by 80% L1 and 78% L. Synthesis of lanthanide (III) complexes the mixture of hot ethanolic solution (25ml) of ligands Land L in (0.01mol) simultaneously and lanthanide (III) nitrate (0.01mol) was added under constant stirring for 3 hours at room temperature. The precipitated complexes were filtered off washed with ethanol, diethyl ether and dried under vacuum over anhydrous calcium chloride (CaCl). Decomposition point of lanthanide (III) complexes was greater than 200 C. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(8), 23-27, August (2015) Res. J. Chem. Sci. International Science Congress Association 24 H O OH NH OMe + Ethanol, Stirringat 4hr.at room temp. N H OH OMe Scheme - I. Synthesis of ligand (L) H O OH NH OMe + Ethanol, Stirringat 4hr.at room temp. N H OH OMe OMe OMe Scheme - II. Synthesis of ligands ligand (L) Results and Discussion X-ray diffraction study: A good quality x-ray diffractograms of chelate polymers indicates semicrystallinity as well as amorphous nature of complexes. All the reflection has been indexed for h, k, l values using methods reported in the literature12. On the comparative study on powder x-ray diffraction of lanthanide (III) complexes of La (III), Ce (III), Pr (III), Nd (III), Sm (III), Gd (III), Dy (III) and Tb (III) complexes were mixed (L and L) Ligands scanned in the range of 5-65° at wavelength 1.540598Å. The diffractogram and associated data depict the 2 value each peak, relative intensity and inter-planar spacing (d-values) and lattice constants a, b, and c for each unit cell parameter show in table-1-3, figure-1-2. The x-ray diffraction pattern of these complexes with respect to major peak having relative intensity greater than 10% has been indexed by computer program13. The above indexing method also yields miller indices (h k l), unit cell parameters and unit cell volume; calculate the unit cell volume for each peak in following equation. The diffractogram of La (III) complex of mixed ligands had 14 reflections with maxima at 2 =41.29 corresponding to d value 2.18Å. The diffractogram of Ce (III) complex of mixed ligands had 12 reflections with maxima at =47.28 corresponding to d value 1.92Å. Miller indices (h k l), unit cell parameters and unit cell volume. In x-ray diffractogram figure show percentage of intensity vs. 2 values in systematic arrangement of metal complexes. The experimental density values of the complexes were determined by using specific gravity method14. They’d’ values of reflections were obtained using Bragg’s equation. = 2dsinTo calculate the unit cell volume of La (III) and Ce (III) complexes for monoclinic crystal system by the following equation was used. V = abcsin To calculate the unit cell volume of Pr (III), Nd (III), Gd (III), Tb (III) and Dy (III) complexes for orthorhombic crystal system by the following equation was used. V= abcTo calculate the unit cell volume of Sm (III) complex for tetragonal crystal system by the following equation was used. V = ac=Table-1 Lattice constant, Unit cell Volume, Crystal system, Inter-planar spacing of metalUnit cell of compounds Lattice Constant Unit cell Volume Edge length Inter axial angle Crystal system d-value (Å) a (Å) b (Å) c (Å) V (Å 3 ) La (III) 15.29 9.82 8.05 702.44 a b c = = 90 monoclinic 41.29 2.18 Ce (III) 10.39 10.35 7.53 471.10 a b c = = 90 monoclinic 47.28 1.92 Pr (III) 17.52 14.56 5.40 380.31 a b c = = = 90 orthorhombic 43.12 2.09 Nd (III) 15.82 11.52 8.52 535.73 a b c = = = 90 orthorhombic 46.17 1.96 Sm(III) 9.124 9.124 9.35 778.54 A = b c = = = 90 tetragonal 44.10 2.05 Gd (III) 17.26 14.32 10.2 533.71 a b c = = = 90 orthorhombic 34.02 2.61 Tb (III) 8.245 9.458 7.52 586.69 a b c = = = 90 orthorhombic 49.00 1.83 Dy (III) 9.124 9.123 7.75 645.70 a b c = = = 90 orthorhombic 50.89 1.79 Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(8), 23-27, August (2015) International Science Congress Association Millar indices and interplanar distances of La h k l Observed 1 0 0 9.488 1 0 0 10.137 0 0 1 12.491 1 1 0 13.530 0 1 1 15.210 1 0 1 16.272 X- ray diffraction data of [LaL Crystal system: Lattice Type: Monoclinic, Lattice Parameter: a=15.2982, b=9.8211, c=8.0524Å, Volume of unit cell V=702.4431(Å) 3. Millar indices and interplanar distances of Ce (III) complex H k l Observed 1 1 0 12.495 1 1 0 13.553 1 0 1 16.290 0 2 0 17.138 1 1 1 17.979 2 0 1 19.222 1 2 0 20.043 2 1 1 21.166 2 1 0 22.193 1 2 1 23.099 ______________________________ ___________________ International Science Congress Association Table-2 Millar indices and interplanar distances of La (III) complexCalculated d Observed d Calculated 9.504 9.314 9.298 9.504 8.719 9.298 12.541 7.080 7.052 13.101 6.539 6.752 15.456 5.820 5.728 15.759 5.443 5.618 Figure-1 ray diffraction data of [LaL and L(HO)NO] complexes Crystal system: Lattice Type: Monoclinic, Lattice Parameter: a=15.2982, b=9.8211, c=8.0524Å, Volume of unit cell Table-3 Millar indices and interplanar distances of Ce (III) complex Calculated d Observed d Calculated 13.021 7.078 6.793 13.021 6.528 6.793 16.380 5.436 5.407 17.114 5.169 5.177 18.496 4.929 4.793 19.330 4.613 4.588 19.766 4.426 4.487 21.163 4.194 4.194 21.509 4.002 4.128 23.775 3.847 3.739 ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 25 Relative Intensity (%) 100 3.38 45.72 35.39 9.15 11.45 Crystal system: Lattice Type: Monoclinic, Lattice Parameter: a=15.2982, b=9.8211, c=8.0524Å, Volume of unit cell Calculated Relative Intensity (%) 46.50 34.33 10.14 14.98 16.61 4.77 1.75 32.16 22.02 1.60 Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(8), 23-27, August (2015) International Science Congress Association X- ray diffraction data of [Ce L Crystal system: Lattice Type: Monoclinic, Lattice Parameter: a=10.3954, b=10.3541, c=7.5384Å Antimicrobial and Antifungal activity : activity of mixed (L and L ) ligand and lanthanide (III) complexes was tested in vitro against bacteria by using paper disc plate method15 . The ligands and Lanthanide (III) complexes have been teste d for their antibacterial activity against Staphylococcus aureus and Bacillus substilis activity Aspergillus Niger and Fusarium Oxysporum concentration 250 ppm and 500 ppm show antibacterial activity result reveal ed that the ligands and complexes show good activity. The ligands and metal complexes such as La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III) and Dy(III) complexes shows highly active as compared to ligands and standard drugs with inhibition zone of 1 13-18 mm, 13-17 mm, 11-15 mm, 12- 15 mm, 15 mm respectively. The Tb (III) complexes have exhibited good activity with the inhibition zone of 14- 21mm when compared to the standard drugs ciprofloxacin and ligands. The results show antiba cterial activity of Schiff base ligands and its metal complexes of following increasing order Tb(III), � Gd(III) � L � Ce(III) � La(III) Pr(III) � Sm(III) � Dy (III) � L The antifungal activity result revealed that the mixed ligands and its La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III) complexes have exhibition shows highly active with the inhibition zone of 16-19 mm, 22- 24 mm, 20 mm, 16-26 mm, 22-24 mm, 14-24 mm, 15- 23 mm as compared to the standard drug cipr ofloxacin. The antifungal activity of Schiff base ligand and the mixed (L and L ) ligand complexes is following order Ce (III) Gd (III) �Pr (III) � Sm (III) � La (III) �Dy (III) � Tb (III) � Nd (III) � L2 � L obtained it clearly indicates that the antibacterial activity of metal salts is high. From table- 4 it is found that the inhibition by ______________________________ ___________________ International Science Congress Association Figure-2 ray diffraction data of [Ce L and L (HO) 2NO] complex Crystal system: Lattice Type: Monoclinic, Lattice Parameter: a=10.3954, b=10.3541, c=7.5384Å V=471.1053(Å) 3. : The antibacterial ) ligand and lanthanide (III) complexes was tested in vitro against bacteria by using paper . The ligands and Lanthanide (III) complexes d for their antibacterial activity against Bacillus substilis and antifungal Fusarium Oxysporum at the same 500 ppm show in table-4. The ed that the ligands and complexes show good activity. The ligands and metal complexes such as La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III) and Dy(III) complexes shows highly active as compared to ligands and standard drugs with inhibition zone of 1 3-17 mm, 15 mm, 15 -16 mm, 11-17 mm respectively. The Tb (III) complexes have exhibited good 21mm when compared to the standard drugs ciprofloxacin and ligands. The results show cterial activity of Schiff base ligands and its metal complexes of following increasing order Tb(III), � Gd(III) � L 1 Pr(III) � Sm(III) � Dy (III) � L . The antifungal activity result revealed that the mixed ligands Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III) complexes have exhibition shows highly active with 24 mm, 20 -24 mm, 14-20 23 mm as compared ofloxacin. The antifungal activity of ) ligand complexes Gd (III) �Pr (III) � Sm (III) � La � L . From the result obtained it clearly indicates that the antibacterial activity of 4 it is found that the inhibition by metal complexes is higher than that of a free ligand and results are in good agreement with previous fin comparative activity of free ligand and its complexes corresponding metal salts against the same organism under experimental conditions. The metals salt used for the synthesis of complexes exhibit negligibly high antimicrobial The comparative study of all compounds both ligands and its all metal complexes shows higher antifungal activity against Aspergillus Niger at 500 ppm and at 250 ppm against Oxysporum. Conclusion The synthesis of mixed ligand metal Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Dy(III) and Tb(III) complexes with N and O donor Schiff base ligand derived from 4- methoxyphenylanaline,salicylaldehyde and o synthesized. A comparative study of crystal sy volume, edge length and Miller indices of powder XRD. The powder XRD study suggested that orthorhombic crystal system for Pr(III), Nd(III), Gd(III), Dy(III), Tb(III) complexes and monoclinic crystal system for La(III), Ce(III) complexes a tetragonal crystal system for Sm(III) complex. The mixed ligands and their metal complexes of antibacterial and antifungal activity are highly active compared to free ligand. Acknowledgement The authors are grateful to the Dr. Babasaheb Ambedkar Marath wada University, Aurangabad for the award of University Scholar Fellowship and providing the laboratory facilities. ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 26 Crystal system: Lattice Type: Monoclinic, Lattice Parameter: a=10.3954, b=10.3541, c=7.5384Å Volume of unit cell metal complexes is higher than that of a free ligand and results are in good agreement with previous fin dings with respect to comparative activity of free ligand and its complexes 16. The corresponding metal salts against the same organism under experimental conditions. The metals salt used for the synthesis of complexes exhibit negligibly high antimicrobial activity17-18. The comparative study of all compounds both ligands and its all metal complexes shows higher antifungal activity against at 500 ppm and at 250 ppm against Fusarium The synthesis of mixed ligand metal complexes like La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III), Dy(III) and Tb(III) O donor Schiff base ligand derived from methoxyphenylanaline,salicylaldehyde and o -vanilline were synthesized. A comparative study of crystal sy stem, unit cell volume, edge length and Miller indices of powder XRD. The powder XRD study suggested that orthorhombic crystal system for Pr(III), Nd(III), Gd(III), Dy(III), Tb(III) complexes and monoclinic crystal system for La(III), Ce(III) complexes a nd tetragonal crystal system for Sm(III) complex. The mixed ligands and their metal complexes of antibacterial and antifungal activity are highly active compared to free ligand. The authors are grateful to the Dr. Babasaheb Ambedkar wada University, Aurangabad for the award of University Scholar Fellowship and providing the laboratory Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(8), 23-27, August (2015) Res. J. Chem. Sci. International Science Congress Association 27 Table-4 Antibacterial and Antifungal activity of ligands and Lanthanide (III) complexes [Diameter of inhibition Zone in (mm)] Compounds Antibacterial activity Antifungal activity Staphylococcusaureus Bacillus Substilis Aspergillus Niger Fusarium Oxysporum 250 ppm 500 ppm 250 ppm 500 ppm 250 ppm 500 ppm 250 ppm 500 ppm C 14 H 13 NO 2 (L 1 ) nil 14 nil 16 nil 11 16 19 C 15 H 15 NO 3 (L 2 ) nil 16 nil 17 16 16 15 18 [La(L 1 L 2 )(H 2 O) 2 NO 3 ] 17 16 17 13 16 19 19 nil [Ce(L 1 L 2 )(H 2 O) 2 NO 3 ] 13 18 14 15 24 22 22 nil [Pr(L 1 L 2 )(H 2 O) 2 NO 3 ] 15 17 nil 13 20 24 24 nil [Nd(L 1 L 2 )(H 2 O) 2 NO 3 ] 14 14 11 15 18 20 19 14 [Sm(L 1 L 2 )(H 2 O) 2 NO 3 ] 12 16 14 15 21 16 26 19 [Gd(L 1 L 2 )(H 2 O) 2 NO 3 ] 16 15 nil 16 22 22 24 22 [Tb(L 1 L 2 )(H 2 O)2NO 3 ] 11 16 17 15 24 14 17 nil [Dy(L 1 L 2 )(H 2 O) 2 NO 3 ] 14 14 21 15 23 18 15 Nil Ciprofloxin 29 nil 27 nil 30 21 32 nil Reference 1.Cimerman Z, Miljanic S and Galic N, Croatica Chemical Acta.,73(1), 81-95 (2000)2.Singh P, Goel R.L. and Singh B.P., J Indian Chem. Soc., 52, 958-959 (1975) 3.Perry BF, Geezer AE, Miles RJ, Smith BW, Miller J and Nascimento MG, Microbois 45, 181 (1988) 4.Elmali A, Kabak M and Elerman Y.J., Mol. Strut 477, 151 (1999)5.Patel P.R., Thaker B.T. and Zele S, Indian J Chem., 38A, 563-566(1999) 6.Klop E.A. and Lammers M., Polymers,39, 5987 (1998)7.Cullity B.P., Elements of X-ray diffraction, Addison: Wesley Inc., (1978) 8.Bish DL and Post JE, Editors Modern Powder Diffraction, Reviews in Mineralogy, v. 20. Mineralogical Society of America (1990)9.Wall B., Driscoll C., Strong J. and Fisher E., The Suitability of Different Preparations of Thermo luminescent Lithium Borate for Medical Dosimetry, Physical Medical biology, 1023-1034, (1982)10.Azaroff and Burger, The Powder Method, McGraw Hill London (1958)11.Munde A.S, Jagdale A.N, Jadhav S.M. and Chondhekar T.K; Journal of the Korean Chemical society., 53, 407 2009) 12.Saxena N., Juneja H.D. and Munshi K.N., J. Indian Chem. Soc., 70, 943 (1993) 13.Carvajal J.R., Roisnel T. and Winplotr A, Graphic Tool for Powder Diffraction, Laboratories Leon brillouin (ceal / enrs) 91191 gif suryvette cedex, France, (2004) 14.Bhattacharya K.C., An Elementary Physics for Indian School, The Indian Press Ltd. Allahabad, 105 (1934)15.Munde A.S., Jagdale A.N., Jadhav S.M., Chondhekar T.K., J. Serb. Chem. Soc., 75(3), 349 (2010) 16.Madhure A.K. and Aswar A.S., Am. J. Pharm. Tech. Res., 3(6), 462-484 (2013)17.Singh P., Geol R.L. and Singh B.P., Indian J. Chem. Soc., 52, 958 (1975) 18.Patel P.R., Thaker B.T. and Zele S., Indian J. Chem., 38A, 563, (1999) 19.Prabhumirashi L.S. and Khoje J.K., Indian J. Chem., 43a, 299 (2004)20.Nakamura T., Niwa K., Fujiwara M. and Matsushita T., Chem. Lett., 1067 (1999)21.Choi Y.K., Kim W.S., Chung K.I., Chung M.W. and Nam H.P., Microchem. J., 65, 3, (2000)22.Yoon H., Wagler T.R., O’Connor K.J. and Burrows C.J., J. Am. Chem. Soc., 122, 4568 (1990) 23.Pan N.T.S., Brown D.H., Adams H., Spey S.E. and Styring P., J. Chem. Soc., Dalton Trans., , 1348 (2004) 24.Hussain R. and Juneja H.D.., Int. J. Chem. Sci., 7(2),632-638 (2009)25.Nagasudha B., Yellasubbaiah N. and Bharathi K., Int. J. Chem. Sci., 13(2), 837-848 (2015) 26.Ubani O.C., Oforka N.C., Ngochindo R.I. and Odokuma L.O., Synthesis, Characterization and Antimicrobial Studies of Cinnamaldehydebenzylamine Schiff base Metal ion Complexes Res. J. of Chem. Sci.,Vol. 5(3), 14-22, March (2015) 27.Malik GM1, Patel BA1 and Patel NC, Synthesis, Spectroscopic and Physico-chemical Characterization of Cu (II), Ni(II), Co(II) and Mn(II) Coordination compounds with 4-methoxy salycylaldehyde-4-(2’-carboxy-5’-sulphophenyl)-3-thiosemi-carbazone (4- MSCST)., Res. J. of Chem. Sci., Vol. 5(3), 49-52 (2015)