Structural Characterization of 6-Bromo-5-nitroquinoline-1-oxide: A Quantum Chemical Study and XRD Investigations
Abstract
The chemical properties of recently synthesized
6-bromo-5-nitroquinoline-1-oxide under a mild reaction condition by regioselective
nitration of 6-bromoquinoline-1-oxide
at C5 on going our research were investigated as theoretical. The crystal
structure of 6-bromo-5-nitroquinoline-1-oxide, C9H5BrN2O3, was determined
by X-ray analysis. Crystallized in Pmc21
in the orthorhombic space group with a
= 13.6694 (13) Å, b = 9.6036 (10)
Å, c = 14.1177 (16) Å, Z = 8, Dx = 1.929 mg/m3. In this study, theoretical calculations were performed using the
GaussView 4.1 molecular imaging program and the Gaussian03W packet program. In
the ground state, stable structures of the wholes molecule in the gaseous phase
are investigated based on Density Functional Theory (DFT). Molecularly
optimized geometries, dipole moments, charge density, thermodynamic properties
(heat capacity, enthalpy, entropy), chemical shift values (1H
NMR and 13C NMR), energies, molecular
electrostatic potentials and frontier orbitals (HOMO and LUMO)
B3LYP/6-311G(d,p) base set. Thus, the results obtained by the X-ray diffraction
method are supported by theoretical foundations. Finally, the distribution of
interactions between molecules in the crystal structure of
6-bromo-5-nitroquinoline-1-oxide (3) was
investigated by analysis using Hirshfeld surface production and two-dimensional
fingerprinting.
References
- [1] Paloque L., Verhaeghe P., Casanova M., Castera-Ducros C., Dumètre A., Mbatchi L., Hutter S., Kraiem-Mrabet M., Laget M., Remusat V., Rault S., Rathelot P., Azas N. and Vanelle P., Discovery of A New Antileishmanial Hit in 8-Nitroquinoline Series, Eur. J. Med. Chem., 54 (2012) 75-86.
- [2] Nunoshiba T. and Demple B., Potent Intracellular Oxidative Stress Exerted by the Carcinogen 4-Nitroquinoline-N-oxide, Cancer Res., 53-14 (1993) 3250-3252.
- [3] Wu J., Cui X., Chen L., Jiang G.and Wu Y., Palladium-Catalyzed Alkenylation of Quinoline-N-oxides via C-H Activation under External-Oxidant-Free Conditions, J. Am. Chem. Soc., 131 (2009) 13888-13889.
- [4] Wengryniuk S.E., Weickgenannt A., Reiher C., Strotman N.A., Chen K., Eastgate M.D. and Baran P.S., Regioselective Bromination of Fused Heterocyclic N-Oxides, Org. Lett., 15-4 (2013) 792-795.
- [5] Romanov V.V., Nizhnik Y.P. and Fofanov A.D., Conformational and Structural Analysis of Bis(4-chloroquinoline-N-oxide)hydrogen Tribromide, J. Struct. Chem., 56-2 (2015) 365-369.
- [6] Pool J., Scott B. and Kiplinger J.A., A New Mode of Reactivity for Pyridine N-Oxide: C-H Activation with Uranium (IV) and Thorium (IV) Bis(alkyl) Complexes, J. Am. Chem. Soc., 127-5 (2005) 1338-1339.
- [7] Çakmak O. and Ökten S., Regioselective Bromination: Synthesis of Brominated Methoxyquinolines, Tetrahedron, 73-36 (2017) 5389-5396.
- [8] Ökten S., Eyigün D. and Çakmak O., Synthesis of Brominated Quinolines, Sigma J. Eng. Nat. Sci., 33 (2015) 8-15
- [9] Ökten S. and Çakmak O., Synthesis of Novel Cyano Quinoline Derivatives, Tetrahedron Lett., 56-39 (2015) 5337-5340.
- [10] Çakmak O., Ökten S., Alımlı D., Saddiqa A. and Ersanlı C.C., Activation of 6-Bromoquinoline by Nitration and N-oxidation: Synthesis of Substituted Quinolines, Arkivoc, iii, (2018) 362-374.
- [11] APEX-II, SAINT and SADABS; Bruker AXS Inc.: Madison, WI, 2014.
- [12] Sheldrick G.M., SHELXS-97 and SHELXL-97, Program for Solution Crystal Structure and Refinement, University of Göttingen, Göttingen, 1997.
- [13] Frisch A., Nielsen A.B. and Holder A.J., GaussView Users Manual, Gaussian Inc., Pittsburgh, PA., 2001.
- [14] Dennington R.I., Keith T., Millam J., Eppinnett K. and Hovell W., GaussView Version 4.1, 2003.
- [15] Miertus S., Scrocco E. and Tomasi J., Electrostatic Interaction of a Solute with a Continuum. A Direct Utilizaion of ab-initio Molecular Potentials for The Prevision of Solvent Effects, Chem. Phys., 74 (1981) 117-129.
- [16] London F., Quantum Theory of Interatomic Currents in Aromatic Compounds. J. Phys. Radium, 8 (1937) 397-409.
- [17] Tanak H., Crystal Structure, Spectroscopy, and Quantum Chemical Studies of (E)-2-[(2-Chlorophenyl)iminomethyl]-4-trifluoromethoxyphenol J. Phys. Chem. A, 115 (2011) 13865-13876
- [18] Babu G.A. and Ramasamy P., Growth and characterization of an organic NLO material ammonium malate, Current Appl. Phys., 10-1 (2010) 214-220.
- [19] Fukui K., Role of Frontier Orbitals in Chemical Reactions, Science, 218 (1982) 747-754.
- [20] Parr R.G. and Chattaraj P.K., Principle of Maximum Hardness, J. Am. Chem. Soc., 113-5 (1991) 1854-1855.
- [21] Kalinowski H.O., Berger S. and Braun S., Carbon-13 NMR Spectroscopy, 4th ed. Chichester: John Wiley & Sons, 1988; pp 512-543.
- [22] Spackman M.A. and Jayatilaka D., Hirshfeld Surface Analysis, Crystal engineering communications, 11 (2009) 19-32.
6-Bromo-5-nitrokinolin-1-oksit’in Yapısal Karekterizasyonu: Bir Kuantum Kimyasal Çalışma ve XRD Bulguları
Abstract
Devam eden çalışmalarımız kapsamında
6-bromokinolin-1-oksit’in ılıman reaksiyon şartlarında C5 konumundan yerseçici
olarak nitrolanmasıyla yakın zamanda sentezlenen
6-bromo-5-nitrokinolin-1-oksit’in kimyasal özellikleri teorik olarak
araştırıldı. Bu çalışmaya ilaveten 6-bromo-5-nitrokinolin-1-oksit’in, C9H5BrN2O3,
yapısı X-ışınları difraksiyon analizi ile belirlendi. Bu bileşik, elde edilen
veriler ile, a=13.6694(13) Å, b=9.6036(10) Å, c=14.1177(16) Å, Z=8, Dx=1.929 mg/m3,ortorombik kristal yapısında olduğu belirlendi. Bu çalışmada, kuramsal
hesaplar GaussView 4.1 molekül görüntüleme programı ve Gaussian03W paket
programı kullanılarak yapılmıştır. Temel halde, tüm molekülün gaz fazında
yalıtılmış halde bulunan kararlı yapıları, Yoğunluk Fonksiyonel Kuramı (YFT)
temel alınarak incelenmiştir. Söz konusu molekülün optimize edilmiş
geometrileri, dipol momentleri, yük yoğunluğu, termodinamik özellikler (ısı
sığası, entalpi, entropi), kimyasal kayma değerleri (1H NMR and 13C NMR), enerjileri, moleküler elektrostatik potansiyelleri ve öncü
orbitalleri (HOMO ve LUMO) B3LYP/6-311G(d,p) baz seti kullanılarak elde
edilmiştir. Böylece X-ışını kırınım yöntemi ile elde edilen sonuçlar kuramsal
temeller aracılığı ile desteklenmiştir. Son olarak, Hirshfeld yüzey üretimi ve iki boyutlu parmak izi grafikleri
kullanılarak yapılan analiz ile bileşiğin kristal yapısındaki moleküllerarası
etkileşimleri araştırıldı.
Keywords
Nitrolama N-oksitleme İşlevselleştirme 6-Bromokinolin-1-oksit X-ışınları difraksiyon Yoğunluk Fonksiyonel Teori
References
- [1] Paloque L., Verhaeghe P., Casanova M., Castera-Ducros C., Dumètre A., Mbatchi L., Hutter S., Kraiem-Mrabet M., Laget M., Remusat V., Rault S., Rathelot P., Azas N. and Vanelle P., Discovery of A New Antileishmanial Hit in 8-Nitroquinoline Series, Eur. J. Med. Chem., 54 (2012) 75-86.
- [2] Nunoshiba T. and Demple B., Potent Intracellular Oxidative Stress Exerted by the Carcinogen 4-Nitroquinoline-N-oxide, Cancer Res., 53-14 (1993) 3250-3252.
- [3] Wu J., Cui X., Chen L., Jiang G.and Wu Y., Palladium-Catalyzed Alkenylation of Quinoline-N-oxides via C-H Activation under External-Oxidant-Free Conditions, J. Am. Chem. Soc., 131 (2009) 13888-13889.
- [4] Wengryniuk S.E., Weickgenannt A., Reiher C., Strotman N.A., Chen K., Eastgate M.D. and Baran P.S., Regioselective Bromination of Fused Heterocyclic N-Oxides, Org. Lett., 15-4 (2013) 792-795.
- [5] Romanov V.V., Nizhnik Y.P. and Fofanov A.D., Conformational and Structural Analysis of Bis(4-chloroquinoline-N-oxide)hydrogen Tribromide, J. Struct. Chem., 56-2 (2015) 365-369.
- [6] Pool J., Scott B. and Kiplinger J.A., A New Mode of Reactivity for Pyridine N-Oxide: C-H Activation with Uranium (IV) and Thorium (IV) Bis(alkyl) Complexes, J. Am. Chem. Soc., 127-5 (2005) 1338-1339.
- [7] Çakmak O. and Ökten S., Regioselective Bromination: Synthesis of Brominated Methoxyquinolines, Tetrahedron, 73-36 (2017) 5389-5396.
- [8] Ökten S., Eyigün D. and Çakmak O., Synthesis of Brominated Quinolines, Sigma J. Eng. Nat. Sci., 33 (2015) 8-15
- [9] Ökten S. and Çakmak O., Synthesis of Novel Cyano Quinoline Derivatives, Tetrahedron Lett., 56-39 (2015) 5337-5340.
- [10] Çakmak O., Ökten S., Alımlı D., Saddiqa A. and Ersanlı C.C., Activation of 6-Bromoquinoline by Nitration and N-oxidation: Synthesis of Substituted Quinolines, Arkivoc, iii, (2018) 362-374.
- [11] APEX-II, SAINT and SADABS; Bruker AXS Inc.: Madison, WI, 2014.
- [12] Sheldrick G.M., SHELXS-97 and SHELXL-97, Program for Solution Crystal Structure and Refinement, University of Göttingen, Göttingen, 1997.
- [13] Frisch A., Nielsen A.B. and Holder A.J., GaussView Users Manual, Gaussian Inc., Pittsburgh, PA., 2001.
- [14] Dennington R.I., Keith T., Millam J., Eppinnett K. and Hovell W., GaussView Version 4.1, 2003.
- [15] Miertus S., Scrocco E. and Tomasi J., Electrostatic Interaction of a Solute with a Continuum. A Direct Utilizaion of ab-initio Molecular Potentials for The Prevision of Solvent Effects, Chem. Phys., 74 (1981) 117-129.
- [16] London F., Quantum Theory of Interatomic Currents in Aromatic Compounds. J. Phys. Radium, 8 (1937) 397-409.
- [17] Tanak H., Crystal Structure, Spectroscopy, and Quantum Chemical Studies of (E)-2-[(2-Chlorophenyl)iminomethyl]-4-trifluoromethoxyphenol J. Phys. Chem. A, 115 (2011) 13865-13876
- [18] Babu G.A. and Ramasamy P., Growth and characterization of an organic NLO material ammonium malate, Current Appl. Phys., 10-1 (2010) 214-220.
- [19] Fukui K., Role of Frontier Orbitals in Chemical Reactions, Science, 218 (1982) 747-754.
- [20] Parr R.G. and Chattaraj P.K., Principle of Maximum Hardness, J. Am. Chem. Soc., 113-5 (1991) 1854-1855.
- [21] Kalinowski H.O., Berger S. and Braun S., Carbon-13 NMR Spectroscopy, 4th ed. Chichester: John Wiley & Sons, 1988; pp 512-543.
- [22] Spackman M.A. and Jayatilaka D., Hirshfeld Surface Analysis, Crystal engineering communications, 11 (2009) 19-32.
Details
| Primary Language | English |
|---|---|
| Journal Section | Natural Sciences |
| Authors | |
| Publication Date | December 24, 2018 |
| Submission Date | May 16, 2018 |
| Acceptance Date | November 8, 2018 |
| Published in Issue | Year 2018 |