Tris-(2,2'-bipiridil)bakır(II)perklorat, {[Cu(bpy)3](ClO4)2} Sentezi ve Kristal Yapısının Yeniden Belirlenmesi

2,2'-bipiridin ligandı ve bakır(II)asetat tuzu ile elde edilen kompleks, sulu sodyum perklorat çözeltisi ile çöktürülerek, perklorat tuzu haline getirildi. İzole edilen mavi renkli {Cu(bipy)3(C104)2} kompleksi, dimetilformamit (DMF)’de yeniden kristallendirildi. Kompleksin molekül yapısı, tek kristal x-ışını kırınımı yöntemi ile yeniden belirlendi. Çarpık-oktahedral geometride olan kompleks; triklinik kristal yapıda, P-1 uzay grubunda, a = 7.920(4) Å, b = 10.970(6) Å, c = 18.374(11) Å, α=100.43(3) °, β=90.05(2) °, γ=97.84(2)° ve Z=2 birim hücre parametrelerinde kristallenmiştir. Ekvatoryel pozisyondaki Cu-N bağları hemen hemen aynı uzunlukta olup (Ort. 2,025 Å), eksenel pozisyonundaki Cu-N(2) ve Cu-N(4) bağ uzunlukları ise sırasıyla 2.224(3) ve 2.440(3) Å’ dur. Kompleksin kristal istiflenmesi; C–H⋯O ve π⋯O etkileşimleri ile kararlı bir 3D ağ oluşturmuştur.

Anahtar Kelimeler:

Bipiridin, Bakır Kompleksi, Tris ligant, Perklorat, Kristal Yapı

Synthesis of tris-(2,2'-bipyridyl)copper(II)perchlorate, {[Cu(bpy)3](ClO4)2} and Redetermination of the Crystal Structure

The complex obtained with 2,2'-bipyridine ligand and copper(II) acetate was precipitated with aqueous sodium perchlorate solution to become the perchlorate salt. The isolated blue colored {Cu(bipy)3(C104)2} complex was recrystallized in dimethylformamide (DMF). The molecular structure of the complex was redetermined by single crystal x-ray diffraction method. Crystals in distorted-octahedral geometry are triclinic, space group P-1, with Z=2 in a unit cell of dimensions: a = 7.920(4) Å, b = 10.970(6) Å, c = 18.374(11) Å, α=100.43(3 ) °, β=90.05(2) °, γ=97.84(2)°. Cu-N bonds in the equatorial position are almost the same length (average 2.025 Å), while the Cu-N(2) and Cu-N(4) bond lengths in the axial position are 2.224(3) and 2.440(3) Å, respectively. Crystal packaging of the complex; It formed a stable 3D network with C–H⋯O and π⋯O interactions.

Keywords:

Bipyridine, Copper Complex, Tris ligand, Perchlorate, Crystal Structure,

PDF

___

Anderson, O. P., 1972. Crystal and Molecular Structure of Tris-(2,2′-Bipyridyl) Copper (II) Perchlorate. Journal of the Chemical Society, Dalton Transactions, 23, 2597–2601.
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A., & Puschmann, H., 2015. The Anatomy of a Comprehensive Constrained, Restrained Refinement Program for the Modern Computing Environment--Olex2 Dissected. Acta Crystallographica Section A: Foundations and Advances, 71(1), 59–75.
Campos-Vallette, M. M., Clavijo, R. E., Mendizabal, F., Zamudio, W., Baraona, R., & Diaz, G., 1996. Infrared Spectrum of the Bis-(1,10-Phenanthroline) Cu(I) and Cu(II) Perchlorate Complexes. Vibrational Spectroscopy, 12(1), 37–44.
Chamayou, A. C., Biswas, C., Janiak, C., & Ghosh, A., 2007. Tris(2,2′-Bipyridine-K2 N,N′)Copper(II) Bis-(Tetra-Fluorido-Borate). Acta Crystallographica Section E: Structure Reports Online, 63(7), 2597–2601.
Cheung, E. Y., Fujii, K., Guo, F., Harris, K. D., Hasebe, S., & Kuroda, R., 2011. Structural Chemistry of a New Chiral Anhydrous Phase of Ru(Bipy) 3(ClO4)2 Established from Powder X-Ray Diffraction Analysis. Crystal Growth and Design, 11(8), 3313–3317.
Constable, E. C. and Housecroft, C. E., 2019. The Early Years of 2, 2′-Bipyridine—A Ligand in Its Own Lifetime. Molecules, 24(21), 3951.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A., & Puschmann, H., 2009. OLEX2: A Complete Structure Solution, Refinement and Analysis Program. Journal of Applied Crystallography, 42(2), 339–341.
Liu, Z. M., Jiang, Z. H., Liao, D. Z., Wang, G. L., Yao, X. K., & Wang, H. G., 1991. X-Ray Crystal Structure of Cu(Bipy)3(ClO4)2. Polyhedron, 10(1), 101–102.
Ranjbar, Z. R., Morsali, A., Zhu, L. G., 2007. Two Different 2,2′-Bipyridine Cadmium(II) Perchlorate Complexes, [Cd(2,2′-Bipy)2(H2O)(ClO4)]ClO4 and [Cd(2,2′Bipy)3] (ClO4)2·0.5 2,2′-Bipy, Syntheses, Characterization, Thermal and Structural Studies. Journal of Coordination Chemistry, 60(6), 667–676.
Yao, J. C., Ma, L. F., Yao, F. J., 2005. Crystal Structure of Tris(2,2’-Bipyridine)Cobalt(II) Diperchlorate. Zeitschrift für Kristallographie-New Crystal Structures, 220, 483–484.
Yilmaz, İ., 2022. Synthesis, Structural Characterization, and Thermal Properties of Octahedral Diperchlorato Complexes of Copper(II) with the Chelating 2-Aminomethylpiperidine and 2-Aminomethylpyridine Ligands. Inorganic and Nano-Metal Chemistry, early access, 1–7.