Crystal Structure, Thermal Analysis, Spectroscopic Studies and DFT Calculations on Hexaaquamagnesium II Acesulfamate

Year 2016, Volume: 44 Issue: 1, 95 - 106, 01.03.2016

Ömer Yurdakul Güneş Demirtaş Necmi Dege Hasan Icbudak Dursun Ali Kose Orhan Büyükgüngör

Abstract

The crystal structure of the complex, [Mg H2O 6] C4H4NO4S 2, was determined at 296 K. The unit cell parame- ters of the crystal structure are a=6.9404 Å, b=8.5775 Å, c=8.7200 Å, α=68.564°, β=78.640°, γ=81.260° and Z=1. The complex crystallizes in the centrosymmetric triclinic space group P-1. The Mg II ion is coordinated by six O atoms from six aqua ligands and in the crystal structure, the anions and cations are linked with three dimensions via O—H···O and O—H···N interactions. In addition to the structure which was obtained by X-ray diffraction technique, the theoretical structure was calculated by using density functional theory B3LYP with the 6-31G basis sets. The molecular electrostatic potential, frontier molecular orbitals and theoretical IR studies were calculated by using DFT method. Besides, the experimental IR spectrum and thermal analysis were investigated for the complex.

Keywords

Magnesium, DFT Calculations, Coordination Chemistry, Crystal Structure, Thermal Characterization

Hekzaaquamagnezyum II Asesulfamat Molekülünün Kristal Yapısı, Termal Analizi, Spektroskopik Çalışmaları ve DFT

Abstract

Kompleksin kristal yapısı [Mg HO ] CHNOS , 296 K’de tayin edildi. Moleküler Kristal yapının birim hücre parametreleri a=6.9404 Å, b=8.5775 Å, c=8.7200 Å, α=68.564°, β=78.640°, γ=81.260° ve Z=1 olarak saptanmıştır. Kompleks merkezi simetrik triklinik yapıda kristallenmiş olup uzay grubu P-1’dir. Her bir Mg II iyonu altı mol su ligandının O atomları tarafından koordine edilmiştir. Kristal yapıda anyonlar ve katyonlar O—H···O ve O—H···N etkileşimleriyle üç boyutlu yapıyı oluştururlar. İlave olarak yoğunluk fonksiyonel teori DFT B3LYP yönteminin 6-31G temel setleri kullanılarak elde edilen hesaplanmış sonuçlarla deneysel X-ışınları kırınım sonuçları kıyaslanarak moleküler yapı oluşturulmuştur. Moleküler elektrostatik potansiyel, frontier moleküler orbitaller ve IR spektrumu DFT yöntemi kullanılarak hesaplanmıştır. Ayrıca, deneysel IR spektroskopi ve termal analiz yöntemleri ile yapı incelenmiştir

Keywords

Magnezyum, DFT Hesaplamaları, Koordinasyon Kimyası, Kristal Yapı, Termal Karakterizasyon.

References

• 1. V.D. Duffy and G. H. Anderson, Position of the American Dietetic Association: use of nutritive and nonnutritive sweeteners, J. Am. Diet. Assoc., 98 (1998) 580-587.
• 2. W.L. Hough-Troutman, M. Smiglak, S. Griffin, W.M. Reichert, I. Mirska, J. Jodynis-Liebert, T. Adamska, J. Nawrot, M. Stasiewicz, R.D. Rogers, J. Pernak, Ionic liquids with dual biological function: sweet and antimicrobial, hydrophobic quaternary ammonium-based salts, New J. Chem., 33 (2009) 26-33.
• 3. P. Nockemann, B. Thijs, K. Driesen, C.R. Janssen, K.V. Hecke, L.V. Meervelt, S. Kossmann, B. Kirchner, K. Binnemans, Choline saccharinate and choline acesulfamate: Ionic liquids with low toxicities, J. Phys. Chem. B, 111 (2007) 5254-5263.
• 4. H. İçbudak, E. Adıyaman, N. Çetin, A. Bulut, O. Büyükgüngör, Synthesis, structural characterization and chromotropism of a Ni(II) and a Co(II) compound with acesulfamate as a ligand, Trans. Met. Chem., 31 (2006) 666-672.
• 5. S.P. Velaga, V.R. Vangala, S. Basavoju, D. Boström, Polymorphism in acesulfame sweetener: structureproperty and stability relationships of bending and brittle crystals, Chem. Commun., 46 (2010) 3562- 3564.
• 6. B. Sirinivasan, S.Y. Shetgaonkar, C. Näther, W. Bensch, Solid state synthesis and characterization of a triple chain calcium(II) coordination polymer showing two different bridging 4-nitrobenzoate coordination modes, Polyhedron, 28 (2009) 534-540.
• 7. R.J. Elin, Assessment of magnesium status, Clin. Chem., 33 (1987) 1965-1970.
• 8. J.R. Purvis, A. Movahed, Magnesium disorders and cardiovascular diseases, Clin. Cardiol., 15 (1992) 556- 568.
• 9. L.E. Rabbani, E.M. Antman, The role of magnesium therapy in acute myocardial infarction, Clin. Cardiol., 19 (1996) 841-844.
• 10. M.A. Ralston, M.R. Murnane, R.E. Kelley, R.A. Altschuld, D.V. Unverferth, C.V. Leier, Magnesium content of serum, circulating mononuclear cells, skeletal muscle, and myocardium in congestive heart failure, Circulation, 80 (1989) 573-580.
• 11. P. Lim, E. Jacob, Magnesium deficiency in patients on long-term diuretic therapy for heart failure., Brit. Med. J., 3 (1972) 620-622.
• 12. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. . Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P.M. W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision E.01, Gaussian Inc., Wallingford CT, 2004.
• 13. J.P. Merrick, D. Moran, L. Radom, An Evaluation of Harmonic Vibrational Frequency Scale Factors, J. Phys. Chem., A111 (2007) 11683-11700.
• 14. A. Frisch, R. Dennington, T. Keith, J. Millam, A. B. Nielsen, A.J. Holder, J. Hiscocks, GaussView Reference Version 40, Gaussian Inc., Pittsburgh, 2007.
• 15. Stoe & Cie, X-AREA (Version 1.18) and X-RED32 (Version 1.04), Stoe & Cie, Darmstadt, Germany 2002. 16. G.M. Sheldrick, A short history of SHELX, Acta Crystallogr., A, 64 (2008) 112-122.
• 17. L.J. Farrugia, ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI), J. Appl. Crystallogr., 30 (1997) 565.
• 18. L.J. Farrugia, WinGX suite for small-molecule singlecrystal crystallography, J. Appl. Crystallogr., 32 (1999) 837-838.
• 19. A.L. Spek, Structure validation in chemical crystallography, Acta Crystallogr., 65 (2009) 148-155.
• 20. O.E. Piro, G.A. Echeverría, B.S. Parajón-Costa, E.J. Baran, Structural and IR-spectroscopic characterization of magnesium acesulfamate, Zeitschrift für Naturforschung B., 71 (2016) 51.
• 21. J.F. Wen, W.Z. Yin, Y.X. Qiao, Diaquabis[1-ethyl-6- fluoro-4-oxo-7(piperazin-1-yl)-1,4-dihydroquinoline3carboxylato]magnesium(II) hexahydrate, Acta Crystallogr., E66 (2010) m1388.
• 22. B.S. Zhang, J.P. Qiu, L.H. Liu, W.Xu, Tetraaqua- (2,2-bipyridine-κ2 N,N )magnesium(II) bis(4-fluorobenzoate), Acta Crystallogr., E66 (2010) m1624.
• 23. F. Huang, W.D. Song, Tetra-aqua-bis(1-hydr-oxy-2- naphthoato- O2)magnesium(II) Acta Crystallogr., E64 (2008) m552.
• 24. A. Bulut, H. İçbudak, G. Sezer, C. Kazak, Bis(acesulfamatoκ2N3,O4)bis(2-aminopyrimidine-N1)copper(II), Acta Crystallogr., C61 (2005) m228-m230.
• 25. H. İçbudak, A. Bulut, N. Çetin, C. Kazak, Bis(acesulfamato)teraaquacobalt(II), A c t a Crystallogr., 61 (2005) 1-3.
• 26. Z.S. Şahin, H. İçbudak, Ş. Işık, Di-μ-acesulfamato3N,O:O; 3O:N,O-bis[(acesulfamato- 2N,O)]bis(3- methylpyridine)cadmium(II)], Acta Crystallogr., C65 (2009) 463-465.
• 27. H. İçbudak, A. Uyanık, A. Bulut, C. Arıcı, D. Ülkü, Synthesis, thermal, spectroscopic and structural properties of di(aqua)bis(N, N -dimethylethylenediamine- 2 N, N ) copper(II) acesulfamate, Z. Kristallogr., 222 (2007) 432-436.
• 28. G. Demirtaş, N. Dege, H. İçbudak, Ö. Yurdakul, O. Büyükgüngör, Experimental and DFT studies on poly[diμ3-acesulfamato-O,O:O’;O’:O,O-di-μacesulfamato-O,O;N-di-μ-aqua-dicalcium(II)] complex, J. Inorg. Organomet. Polym. and Materials, 22 (2012) 671-679.
• 29. F. Jensen, Introduction to Computational Chemistry, Second Edition, John Wiley and Sons., Chichester, 2007, Chapter 2.
• 30. W. Hussein, C.G. Walker, Z. Peralta-Inga, J.S. Murray, Computed electrostatic potentials and average local ionization energies on the molecular surfaces of some tetracyclines, Int. J. Quantum Chem. 2001, 82, 160-169.
• 31. B. Stuart, Infrared Spectroscopy: Fundamentals and Applications, John Wiley and Sons., Chichester, 2004, Chapter 3.
• 32. D. A. Köse, F. Akkurt, O. Şahin, O. Büyükgüngör, Synthesis and Structural Characterization of a Binuclear Mixed-Ligand (Salicylate and N,Ndiethylnicotinamide) Nickel(II) Complex, Its Magnetic Properties. [Ni2 (µ-Sal)4(Dena)2 ]H2 O, J. Chinese Chem. Soc., 61 (2014) 1326-1332.
• 33. D.A. Köse, E. Toprak, A. Kaşarcı, E. Avcı, G.A. Avcı, O. Şahin, O. Büyükgüngör, ynthesis, Spectral, Thermal Studies of Co(II), Ni(II), Cu(II) and Zn(II)-arginato Complexes. Crystal Structure of Monoaquabis(arginato-κO, N)copper(II). [Cu(arg)2 (H2 O)].NaNO3 J. Chinese Chem. Soc., 61 (2014) 881-890.
• 34. O. Yurdakul, D.A. Köse, Mixed Ligand Complexes of Acesulfame/Nicotinamide with Earth Alkaline Metal Cations MgII, CaII, BaII and SrII. Synthesis and Characterization, Hittite J. Science and Engineering, 1 (2014) 51-57.