Synthesis and Structural Analysis of Powder Complex of Tris(bipyridine)cobalt(II) Trifluoromethanesulfonate Octahydrate
Kristian Handoyo Sugiyarto(1*), Cahyorini Kusumawardani(2), Kristanti Eka Wulandari(3)
(1) Department of Chemistry Education, Yogyakarta State University, Jl. Colombo No. 1, Yogyakarta 55281, Indonesia
(2) Department of Chemistry Education, Yogyakarta State University, Jl. Colombo No. 1, Yogyakarta 55281, Indonesia
(3) Department of Chemistry Education, Yogyakarta State University, Jl. Colombo No. 1, Yogyakarta 55281, Indonesia
(*) Corresponding Author
Abstract
The powder complex of tris(bipyridine)cobalt(II) trifluoromethanesulfonate octahydrate has been synthesized by direct interaction of the corresponding aqueous solutions (and drops of ethanol) of cobalt(II) nitrate, bipyridine, and potassium triflate. The yellow-orange powder produced was filtered off and allowed to dry on an aeration for characterization. AAS measurement showed the content of metal to be 6.06%, corresponding to the theoretical value of 6.06% in [Co(bipy)3](CF3SO3)2.8H2O. The analysis of conductance producing the charge ratio of cation to anion to be 2:1, confirms the formula. The magnetic moment, µeff, of this complex which was to be 4.5-4.9 BM, indicates that the complex is paramagnetic corresponding to the three unpaired electrons with a significantly orbital contribution. UV-Vis spectrum of the complex reveals the first band observed at about 11100 cm–1, which is associated with the spin-allowed transition, 4T1g → 4T2g. A distinct shoulder at only about 16100 cm–1 should be associated with the spin-forbidden transition of 4T1g → 2T2g,2T2g (G). The expected second and third bands which are associated with spin-allowed transitions of 4T1g → 4T1g(P) and 4T1g → 4A2g at higher energy were not well resolved. The infrared spectrum shows absorptions of the functional group of ligand which is influenced by the metal-ligand interaction in this complex. The powder XRD of this complex was refined using Le Bail method of Rietica program and found to be fit as monoclinic symmetry with a space group of C2/c.
Keywords
Full Text:
Full Text PDFReferences
[1] Cooke, K.,Olenev, A.V.,and Kovnir, K., 2013, Tris(ethylenediamine)cobalt(II) dichloride, Acta Crystallogr., Sect. E: Struct. Rep. Online, 69 (Pt 6), m332.
[2] Tao, B., Xia, H., Zhu, Y.F., and Wang, X., 2012, Synthesis, crystal structure and electrochemical properties of [Co(phen)3].(H3btec).(H2btec)0.5.DMF.6H2O, Russ. J. Inorg. Chem., 57 (6), 822–826.
[3] Palmer, R.A., and Piper, T.S., 1966, 2,2’-Bipyridine complexes. I. Polarized crystal spectra of tris(2,2’-bipyridine)copper(II), -nickel(II), -cobalt(II), -iron(II), and -ruthenium(II), Inorg. Chem., 5 (5), 864–878.
[4] Yao, J.C., Ma, L.F., and Yao, F.J., 2005, Crystal structure of tris(2,2'-bipyridine)cobalt(II) diperchlorate, [Co(C10 H8N2)3][ClO4]2, Ζ. Krist.-New Cryst. St., 220, 483-484.
[5] Ellis, H, Jiang, R., Ye, S., Hagfeldt, A., and Boschloo, G., 2016, Development of high efficiency 100% aqueous cobalt electrolyte dye-sensitised solar cells, Phys. Chem. Chem. Phys., 18 (12), 8419–8427.
[6] Raamat, E., Kaupmees, K., Ovsjannikov, G., Trummal, A., Kütt, A., Saame, J., Koppel, I., Kaljurand, I., Lipping, L., Rodima, T., Pihl, V., Koppel, I.A., and Leito, I., 2012, Acidities of strong neutral Brønsted acids in different media, J. Phys. Org. Chem., 26 (2), 162–170.
[7] Ignat’ev, N.V., Barthen, P., Kucheryna, A., Willner, H., and Sartori, P., 2012, A convenient synthesis of triflate anion ionic liquids and their properties, Molecules, 17 (5), 5319–5338.
[8] Prijamboedi, Z.B., Nugroho, A.A., and Ismunandar, 2009, Synthesis and structure analysis of aurivillius phases Pb1-xBi4+xTi4-xMnxO15, J. Chin. Chem. Soc., 56 (6), 1108–1111.
[9] Wallwork, K.S., Pring, A., Taylor, M.R., and Hunter, B.A., 2003, A model for the structure of the hydrated aluminum phosphate, kingite determined by ab initio powder diffraction methods, Am. Mineral., 88 (1), 235–239.
[10] Wallwork, K.S., James, M., and Carter, M.L., 2006, The crystal chemistry, structure and properties of a synthetic carnotite-type compound, Ba2[UO2)2Ti2O8], Can. Mineral., 44 (2), 433–442.
[11] Lee, R.H., Griswold, E., and Kleinberg, J., 1964, Studies on the stepwise controlled decomposition of 2,2’-bipyridine complexes of cobalt(II) and nickel(II) chlorides, Inorg. Chem., 3 (9), 1278–1283.
[12] Wojciechowska, A., Staszak, Z., Bronowska, W., Pietraszko, A., and Cieślak-Golonka, M., 2003, Crystal structure and 4.2 K electronic spectrum of [Co(bpy)3](CrO4)0.5NO3·7H2O, a double salt containing uncoordinated chromate ion, J. Mol. Struct., 654 (1-3), 197–204.
[13] Sinha, S.P., 1964, 2,2'-Dipyridyl complexes of rare earths. I: Preparation, infrared and some other spectroscopic data, Spectrochim. Acta, 20, 879–886.
[14] Strukl, J.S., and Walter, J.L., 1971, Infrared and raman spectra of heterocyclic compounds-III: The infrared studies and normal vibrations of 2,2’-bipyridine, Spectrochim. Acta, Part A, 27 (2), 209–221.
[15] Czakis-Sulikowska, D., and Czylkowska, A., 2003, Thermal and other properties of complexes of Mn(II), Co(II) and Ni(II) with 2,2’-bipyridine and trichloroacetates, J. Therm. Anal. Calorim., 74 (1), 349–360.
[16] Czakis-Sulikowska, D., and Czylkowska, A., 2005, New 2,2’-bipyridine-chloroacetato complexes of transition metals(II), J. Therm. Anal. Calorim., 82 (1), 69–75.
[17] Szalda, D.J., Creutz, C., Mahajan, D., and Sutin, N., 1983, Electron-transfer barriers and metal-ligand bonding as a function of metal oxidation state. 2. Crystal and molecular structures of tris(2,2'-bipyridine)cobalt(II) dichloride-2-water-ethanol and tris(2,2'-bipyridine)cobalt(I) chloride-water, Inorg. Chem., 22 (17), 2372–2379.
[18] Zhu, J.H., Wu, H.X., and Le Bail, A., 1999, Structure of [Co(NH3)5CO3]NO3.H2O, Solid State Sci., 1 (1), 55–62.
[19] Marques, J., Anjo, L., Marques, M.P.M., Santos, T.M., Paz, F.A.A., and Braga, S.S., 2008, Structural studies on supramolecular adducts of cyclodextrins with the complex [Ru([9]aneS3)(bpy)Cl]Cl, J. Organomet. Chem., 693 (18), 3021–3028.
[20] Martak, F., Onggo, D., Ismunandar, Nugroho, A.A., Mufti, N., and Yamin, B.M., 2009, Synthesis and characterization of a bimetallic oxalate-based magnet: [(C4H9)4P][M(II)Cr(ox)3], M(II) = Mn, Fe, Co, Ni, Cu, Current Research in Chemistry, 1 (1), 1–7.
[21] Sugiyarto, K.H., Saputra, H.W., Permanasari, L., and Kusumawardani, C., 2017, Structural analysis of powder complex of [Mn(phen)3](CF3SO3)2.6.5H2O, AIP Conf. Proc., 1847 (1), 040006.
[22] Kusumawardani, C., Kainastiti, F., and Sugiyarto, K.H., 2018, Structural Analysis of Powder Complex of Cu(bipy)3(CF3SO3)2(H2O)x (x = 0.5, 1), Chiang Mai J. Sci., 45 (4),1944–1952.
[23] Toby, B.H., 2006, R factors in Rietveld analysis: How good is good enough?, Powder Diffr., 21 (1), 67–70.
DOI: https://doi.org/10.22146/ijc.26833
Article Metrics
Abstract views : 3516 | views : 3487Copyright (c) 2018 Indonesian Journal of Chemistry
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.
View The Statistics of Indones. J. Chem.