Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(10), 1-6, October (2015) Res. J. Chem. Sci. International Science Congress Association 1 Study on X-Ray Diffraction of some Mn (II), Fe (III), Co(II), Ni(II), Cu(II), Zn(II), Complexes on the basis of Mixed ligandsShinde V.G., Ingale V.D., Rajbhoj A.S. and Gaikwad S.T.* Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad, 431004, MH, INDIAAvailable online at: www.isca.in, www.isca.me Received 19th August 2015, revised 13th September 2015, accepted 16th October 2015 AbstractComparative studies on the x-ray diffraction parameter of some transition metal complexes such as Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II), has been synthesized by 4-methoxyplenylmaine and salicylaldehyde, o-vanillin having equiamolar ratio of 1:1:1(metal : L : L) in the same solvent. These complexes were different physico-chemical properties such as different color, different melting points and different crystal systems. All the complexes of XRD studies indicate that monoclinic crystal structure has been proposed for the mixed ligands metal complexes. The XRD data were also being used for the determination of various parameter, unit cell volume and miller indices values (h, k, l). The XRD measurement is to be determine the dimensions and shape of unit cell and to identify the detailed structure of the molecule such as tetrahedral, octahedral or square planer geometry. Keywords: Mixed Schiff ligand, x-ray diffraction studies, 4-methoxyplenylmaine, salicylaldehyde, o-vanillin. Introduction The wavelengths are important part of crystal system of complexes to determine the peak position, miller (h k l) value, unit cell parameters and 2 value with a radiation source of CuK by used as x-ray diffractometer range1-2. The objectivity of complexes to identify the detailed structure of the molecule is x-ray diffraction. 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 crystal3 To identify crystalline materials they are using XRD instrumental technique In the present work, literature survey reveals that transition metal complexes generally crystalline as well as amorphous in nature with tetrahedral, octahedral or square planer geometry. In this work the powder x-ray diffraction of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) complexes were mixed ligands scanned in the range of 5°-65° at wavelength 1.540598Å. The diffract gram and associated data depict the 2 value each peak, relative intensity and inter-planar spacing (d-values). The position of the various atoms within the crystal to measured mathematical expression. Material and Methods Experimental: All chemicals and solvents used were of A.R. grade. The transition metal (II) 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 recorded on Perkin Elmer TA/SDT-2960 and Philips 3701, respectively at the range of 5°-65at wavelength 1.540598Å. Synthesis of Schiff base ligand: The synthesis of Schiff base ligand were prepared by reported method . The synthesis of L in 50 ml solution of ethanol contain 0.001mol of salicylaldehyde (0.122g), and 0.001 mol of o-vanilline (0.152 g) were continuously stirred for 4 hours at room temperature. The gray color was obtained. The ligands were collected, filtered by using Buckner funnel, washed with ethanol and dried in the desiccator. Purity of the ligands was checked by thin layer chromatography in silica gel plates. The product was purified and recrystallized with a hot ethanol. Obtainedyield were 80%. The synthesis of L in 50 ml solution of ethanol contain 0.001mol of o-vanilline (0.152 g) and 0.001mol of 4methoxyphenylamine (0.123 g) were continuous stirred for 4 hours at room temperature. The orange color was obtained. The ligands were collected, filtered by using Buckner funnel, washed with ethanol and dried in the desiccators. Purity of the ligand was checked by thin layer chromatography in silica gel plates. The product was purified and recrystallized with a hot ethanol. Obtained yield were 78%. Synthesis of metal complexes: Synthesis of some transition metal (II) complexes, the mixture of (0.01mol) ligands 2-(E)-[4-methoxybenzylideneamine]phenol (L) and 2-(E)-[4-methoxy phenylimino methyl] -6-methoxy phenol (L) dissolve in 25 ml hot ethanol solution simultaneously and other metal (II) nitrate (0.01mol) 25 ml of hot ethanol was added under constant stirring for 3 hours at room temperature. The precipitated complexes were filtered off washed with diethyl ether, ethanol and dried vacuum under anhydrous calcium chloride (CaCl). Decomposition points of transition (II) complexes were above 200C. Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(10), 1-6, October (2015) International Science Congress Association Results and Discussion An x- ray diffractogram of some transition mixed ligand (II) complex indicates that they are crystalline as well as amorphous in nature. To calculate the h, k, l values of reflection by using reported methods . All the mixed ligand metal complexes except the amorphous complexes found to be crystal system were monoclinic. These values of sin 2d for each peak have been calculated with the help of cell parameters and corresponding h, k, l, values. The lattice constants a, b and c for each unit cell have been found out and are given in XRD patter ns the major peak, which showed relative intensity greater than 10% indexed by computer program indexing method also yields miller indices (h, k, l), unit cell parameters and unit cell volume. To calculate the experimental Lattice constant, Unit cell Volume, Crystal system, Inter Unit cell of complexes Lattice Constant Unit cell Volume a (Å) b (Å) c (Å) V (Å Mn (II) 14.24 9.51 9.32 733.47 Fe(III) 12.53 9.23 7.12 478.98 Co (II) 12.54 10.35 7.42 559.64 Ni(II) 14.23 9.23 7.25 553.67 Cu(II) 14.47 11.54 9.25 898.23 Zn(II) 11.25 9.25 6.32 382.58 X- ray diffraction data of [MnL ______________________________ ___________________ International Science Congress Association ray diffractogram of some transition mixed ligand metal (II) complex indicates that they are crystalline as well as amorphous in nature. To calculate the h, k, l values of reflection . All the mixed ligand metal complexes except the amorphous complexes found to be crystal were monoclinic. These values of sin 2d for each peak have been calculated with the help of cell parameters and corresponding h, k, l, values. The lattice constants a, b and c for each unit cell have been found out and are given in table-1. The ns the major peak, which showed relative intensity greater than 10% indexed by computer program . The above indexing method also yields miller indices (h, k, l), unit cell parameters and unit cell volume. To calculate the experimental density values of the complexes by using specific gravity method10 In a figure-1- 6 show in that the relative intensity vs values. They’d’ values of reflections were obtained using Bragg’s equation. = 2d sin To calculate the unit cell volume of Mn(II), Fe(III), Co Ni(III), Cu(III) and Zn (II) complexes for monoclinic system of crystal by the following equation was used V = abc sin Table-1 Lattice constant, Unit cell Volume, Crystal system, Inter - planar spacing of metal Unit cell Volume Edge length Inter axial angle Crystal system Reflections V (Å ) 733.47 a b c = = 90 monoclinic 478.98 a b c = = 90 monoclinic 559.64 a b c = = 90 monoclinic 553.67 a b c = = 90 monoclinic 898.23 a b c = = 90 monoclinic 382.58 a b c = = 90 monoclinic Figure-1 ray diffraction data of [MnL - L2 (HO) 2] complex ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 2 complexes by using specific gravity 6 show in that the relative intensity vs They’d’ values of reflections were obtained using Bragg’s To calculate the unit cell volume of Mn(II), Fe(III), Co (III), Ni(III), Cu(III) and Zn (II) complexes for monoclinic system of crystal by the following equation was used . planar spacing of metal Reflections d-value (Å) 9 26.11 3.40 14 8.724 10.12 11 12.13 7.28 11 16.94 5.68 15 13.63 6.48 12 14.60 6.05 Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(10), 1-6, October (2015) International Science Congress Association Millar indices and interplanar distances of Mn h k l -1 0 0 -1 0 0 -1 0 0 -1 0 0 0 0 1 X- ray diffraction data of [FeL Millar indices and interplanar distances of Fe h k l -1 0 0 -1 0 0 -1 0 0 -1 1 0 0 1 0 0 1 0 ______________________________ ___________________ International Science Congress Association Table-2 Millar indices and interplanar distances of Mn (II) complex (Obs) 2 (Cal) d (Obs) d (Cal) 6.56 7.16 13.46 12.33 7.17 7.16 12.30 12.33 7.54 7.16 11.71 12.33 7.94 7.16 11.12 12.33 9.62 9.47 9.18 9.32 Figure-2 ray diffraction data of [FeL - L (HO) 2] ComplexTable-3 Millar indices and interplanar distances of Fe (III) complex (Obs) 2 (Cal) d (Obs) d (Cal) 7.89 8.13 11.18 10.85 8.52 8.13 10.36 10.85 8.72 8.13 10.12 10.85 10.09 9.84 8.75 8.97 10.50 10.94 8.41 8.07 10.76 10.94 8.21 8.07 ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 3 d (Cal) Relative intensity 0.56 0.54 0.53 0.68 22.27 d (Cal) Relative intensity 4.53 5.42 5.46 1.60 0.52 0.40 Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(10), 1-6, October (2015) International Science Congress Association X- ray diffraction data of [CoL Millar indices and interplanar distances of Co h k l -1 0 0 0 1 0 0 0 1 -1 0 1 -2 0 0 -1 2 0 X- ray diffraction data of [NiL ______________________________ ___________________ International Science Congress Association Figure-3 ray diffraction data of [CoL -L (HO) 2] ComplexTable-4 Millar indices and interplanar distances of Co (II) complex (Obs) 2 (Cal) d (Obs) d (Cal) 7.81 8.13 11.30 10.86 9.51 9.85 9.28 8.96 12.13 11.91 7.28 7.42 14.66 14.44 6.03 6.12 16.61 16.30 5.33 5.43 17.21 17.19 5.14 5.15 Figure-4 ray diffraction data of [NiL -L (HO) 2] Complex ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 4 d (Cal) Relative intensity 10.86 133.33 73.08 15.52 7.25 38.2 13.00 Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(10), 1-6, October (2015) International Science Congress Association Millar indices and interplanar distances of Ni h k l -1 0 0 -2 1 0 -1 0 1 -2 0 0 -1 1 1 X- ray diffraction data of [CuL Millar indices and interplanar h k l -1 0 0 -1 1 0 0 1 0 0 0 1 0 1 1 1 1 0 ______________________________ ___________________ International Science Congress Association Table-5 Millar indices and interplanar distances of Ni (II) complex (Obs) 2 (Cal) d (Obs) d (Cal) 7.213 7.16 12.24 12.32 12.76 13.02 6.92 6.79 13.63 14.15 6.48 6.25 14.88 14.35 5.94 6.16 15.56 15.60 5.69 5.67 Figure-5 ray diffraction data of [CuL - L2 (HO)] ComplexTable-6 Millar indices and interplanar distances of Cu (II) complex (Obs) 2 (Cal) d (Obs) d (Cal) 6.51 7.04 13.55 12.53 7.70 8.09 11.47 10.91 8.46 8.83 10.43 9.99 10.14 9.54 8.71 9.25 13.17 13.02 6.71 6.79 13.63 13.80 6.4 6.40 ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 5 d (Cal) Relative intensity 12.32 226.31 6.79 58.94 6.25 47.25 6.16 93.15 5.67 40.26 d (Cal) Relative intensity 12.53 322.18 10.91 126.26 78.54 36.58 72.74 74.35 Research Journal of Chemical Sciences ___ ______________________________ Vol. 5(10), 1-6, October (2015) International Science Congress Association X- ray diffraction data of [ZnL Millar indices and interplanar distances of Zn h k l -1 1 0 0 1 0 0 0 1 0 0 1 -2 1 0 0 1 1 Conclusion All synthesized metal complexes like Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) complexes with N, O donor mixed ligand Schiff base derived from 4- methoxyphenylanaline, salicylaldehyde and o-vanilline studied by x- ray diffraction and it is found that N i(II), Cu(II), Zn(II) complexes are amorphous in nature and Mn(II), Fe(III), Co(II) are crystalline in nature. They are monoclinic crystal system. References 1.Bish D.L. and Post J.E., Editors , Diffraction, Reviews in Mineralogy, Mineralogical Society of America (1990) 2.Wall B., Driscoll C., Strong J. and Suitability of Different Preparations of Thermo luminescent Lithium Borate for Medical Dosimetry Physical Medical biology, 1023-1034 (1982) 3.Azaroff and Burger, the Powde r Method, McGraw Hill London (1958)4.Klop E.A .and Lammers M., Polymers , ______________________________ ___________________ International Science Congress Association Figure-6 ray diffraction data of [ZnL -L (HO) 2] ComplexTable-7 Millar indices and interplanar distances of Zn (II) complex (Obs) 2 (Cal) d (Obs) d (Cal) 10.09 10.18 8.75 8.67 11.09 11.02 7.96 8.01 14.00 13.99 6.31 6.32 14.60 13.99 6.05 6.32 15.12 15.85 5.85 5.58 17.96 17.84 4.93 4.96 All synthesized metal complexes like Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) complexes with N, O donor mixed ligand methoxyphenylanaline, ray diffraction and i(II), Cu(II), Zn(II) complexes are amorphous in nature and Mn(II), Fe(III), Co(II) are crystalline in nature. , Modern Powder Reviews in Mineralogy, V, 20, (1990) and Fisher E., The Suitability of Different Preparations of Thermo luminescent Lithium Borate for Medical Dosimetry , (1982) r Method, McGraw Hill , 39, 5987 (1998)5. Sleema B. and Parameshwaran G., 961 (2002)6. Azaroff and Burger, The Powder Method, McGraw Hill London (1958) 7.Dutt N.K. and Rahut S., J. Inorg. Nucl. (1970)8. Saxena N., Juneja H.D. and Munshi K.N., Chem. Soc., 70, 943 (1993)9. Carvajal J.R., Roisnel T. and Winplotr A., Graphic Tool for Powder Diffraction, Laboratories Leon brillouin (ceal / enrs) 91191 gif suryvette cedex, France, 10.Bhattacharya K.C., A n Elementary Physics for Indian School, the Indian Press Ltd , 11. Suryawanshi D.D., Gaikwad S.T., Suryawanshi A.D. Rajbhoj A.S., International Journal of recent Technology and engineering ISSN : 227 - 12. Suryawanshi D.D., Gaikwad S.T. and Rajbhoj A.S., Chemical Science Tranction, ___________________ _______ ISSN 2231-606X Res. J. Chem. Sci. 6 d (Cal) Relative intensity 8.67 330.91 8.01 450.35 6.32 620.46 6.32 179.54 5.58 34.80 4.96 79.11 Sleema B. and Parameshwaran G., Asian J. Chem., 14, Azaroff and Burger, The Powder Method, McGraw Hill J. Inorg. Nucl. Chem., 32 2105 Saxena N., Juneja H.D. and Munshi K.N., J. Indian Carvajal J.R., Roisnel T. and Winplotr A., Graphic Tool for Powder Diffraction, Laboratories Leon brillouin (ceal / enrs) 91191 gif suryvette cedex, France, (2004) n Elementary Physics for Indian , Allahabad, 105 (1934) Suryawanshi D.D., Gaikwad S.T., Suryawanshi A.D. and International Journal of recent Technology - 3878, 2(3),(2013) Suryawanshi D.D., Gaikwad S.T. and Rajbhoj A.S., Chemical Science Tranction, 3(1), 117-122 (2014)