U.V., E.P.R. and X.R.D. Spectral Analysis of Bromo Mn(II) Tetra Seleniazide Complex

The complex of Mn (II) compound with Se4N3Br synthesized, was analyzed by U.V., E.P.R. and X.R.D. spectra. From the results, it is evident that the complex is good conductor, having paramagnetic character and orthorhombic geometry. Key word: Se4N3Br, Orthorhombic, Geometry, Magnetic susceptibility. washed with D.M.F. and alcohol, dried and stored in vacuum desiccators over fused CaCl2. U.V.,E.P.R, and X.R.D. spectra of complex, were recorded subsequently on Perkin-ElmerLambda-15 spectrophotometer (200-800nm) Varian’s X-E-4 band spectrometer at room temperature and PW-1710 X-ray power diffractometer using  =1.5418 Å, CuK, as source of radiation in the 2 range 0o-80°. RESULTS AND DISCUSSION On the basis of the quantitative ,Mass & I.R. spectral analysis the complex bromo Mn(II) tetra seleniazide has been assigned as (Se4N3Br)2 MnCl2. 4H2O (loc. cit). The U.V. spectrum (fig-1) consist three prominent peaks at 200, 222.5, 282.5 nm. Former two bands 200, 222.5, corresponding 568 GUPTA & JADON, Orient. J. Chem., Vol. 30(2), 567-570 (2014) Table 1: U.V. and E.P.R. Spectral Data of the Complex U.V. Spectral Data E.P.R. Spectral Data Band Transition f×10-5 Eg (ev) Nc × 105 Magnetic gx = gy gz μeff A× Assigned Field H (B.M.) 10-3 nm (cm-1) (Gauss) (e.s.u.) 1 2 3 4 5 6 7 8 9 10 200 C.T. 3.15659 3251.90 1.9407 2.0790 1.7215 1.2352 (50,000) 222.5 C.T. 2.43540 0.3135 0.1299 (44943.82) 282.5 p d 0.46635 0.5920 6.0342 (35398.23) Table 2: X-ray Diffraction pattern of complex S. No. 2(o) Sin2  (h2 + k2 + l2)Q hkl d(Ao) Obs (theo) dhkl (Å) 1 2 3 4 5 6 1 10.48 0.00834 1×(0.00834) (100) 8.4408 (8.4339) 8.4404 2 13.81 0.01445 2(0.00725) (110) 6.4124 (6.4022) 5.9682 3 23.00 0.03974 5(0.007948) (210) 3.8668 (3.8635) 3.7746 4 27.29 0.05565 6(0.009275) (211) 3.2679 (3.2663) 3.4457 5 29.21 0.06358 8(0.007947) (220) 3.0573 (3.0557) 2.9841 6 31.61 0.07418 9(0.008242) (221) 2.8304 (2.8289) 2.8135 7 40.86 0.12184 14(0.00870) (321) 2.2085 (2.2066) 2.2557 8 43.11 0.13948 17(0.008204) (322) 2.06415 (2.0970) 2.04711 9 44.83 0.14539 18(0.008077) (330) 2.0217 (2.0204) 1.9894 10 51.21 0.18670 22(0.008486) (332) 1.7838 (1.7826) 1.7995 11 55.57 0.21730 25(0.00869) (430) 1.6537 (1.6526) 1.6881 12 66.18 0.25897 30(0.00863) (521) 1.5148 (1.5136) 1.5410 13 64.56 0.28521 34(0.008388) (530) 1.4434 (1.4423) 1.4475 14 69.62 0.32587 38(0.00857) (532) 1.3504 (1.3493) 1.3692 15 70.88 0.33622 40(0.008405) (620) 1.3294 (1.3284) 1.3345 Qav = 0.008343 a0 = 8.4399Å, b0 = 18.8723Å, c0 = 9.2454 Å and  = = = 90 6.2, and 5.57ev energy, showing the ionic environment are due to the charge transfer transition in the complex. The last band, 282.5nm is on account of p-d transition for Se4N3 ring present in the complex. This is also confirmed from the frequencies ratios 1/2 =1.27 less than 2. The oscillator strength ‘f’ of the order 10-5 (Table-1, Column-3) suggest the low spin Laporte forbidden transition in the complexes which is due to the sharing of electrons in Se4N3 ring. The low value of band gape energy, Eg (Table-1,Column-4) and high value of number of conducting electrons, Nc of the order of 10 5 expounds the good conductive nature of complex. A single broad peak of high intensity has occurred in E.P.R. spectrum (fig-2) suggesting the paramagnetic character of complexes which is supported by the low value of magnetic susceptibility, A =1.2352×10 -3 e.s.u. (Table-1, Column-10). The value of gx = gy = 1.9407 (Table569 GUPTA & JADON, Orient. J. Chem., Vol. 30(2), 567-570 (2014) Fig. 1: U.V. spectrum of the Complex Fig. 2: E.P.R. spectrum of the Complex Fig. 3: X.R.D. Pattern of the Complex 1,Column-7) less than two explore the presence of vacant 3d energy shells in Mn atom to accept the electron pairs form N atom of Se4N3 ring, forming coordinate bond. The value of gz =2.0790 (Table1,Column-8) greater than two indicate the sharing of electrons i.e. covalent bonding in Se4N3 ring of the complex. Thus bromo Mn(II) tetra seleniazide, (Se4N3Br)2MnCl24H2O possess ionic bond due to Mn2+ and 2Cl-, coordinate bond, Se-NMn and SeN, Se-Br covalent linkage with the 3d5 configuration of Mn2+ because the value of μeff=1.7215 is according to the presence of one unpaired electron. Thus the complex formed having quadridentated, coordinated linkage with square planar structure as reported (loc. cit) fig. 4. 570 GUPTA & JADON, Orient. J. Chem., Vol. 30(2), 567-570 (2014) The X.R.D. pattern of complex recorded in 2 range 0o-80° (fig-3) possesses a strong and intense peak at 29.21° for the Se4N3 ring. From the X-ray pattern the values of sin2, miller indices, hkl, and inter planar distances ‘d’, calculated, resembles to the theoretical values (Table-2). From these X.R.D. data, the values of axial ratio and axial angles (Table-2) calculated are corresponding a0b0c0 and ===90° for the orthorhombohedral geometrical packing of the molecule in the complex. ACKNOWLEDGMENTS Authors wish to express to thank to the Director SAIF, Punjab University Chandigarh, Director SAIF, IIT Bombay, Director ACMS IIT Kanpur to provide instrumental facilities.