European Journal of Chemistry

The crystal magnification, characterization, X-ray single crystal structure, thermal behavior, and computational studies of the 2,4,6-trimethylpyridinium picrate

Crossmark


Main Article Content

Nahide Burcu Arslan
Fatma Aydin

Abstract

A crystal of organic salt, 2,4,6-trimethylpyridinium picrate (TMPPc), was synthesized and magnified by slow evaporation in a polar aprotic solvent and characterized by 1H NMR, 13C NMR, and FT-IR spectroscopic methods. X-ray diffraction analysis of the crystal structure of the compound TMPPc showed the presence of a monoclinic space group with a = 4.0174(4) Å, b = 27.863(3) Å, c = 13.9247(17) Å, β = 95.741(4)°, = 1550.9(3) Å3, Z = 4, T = 296 K, μ(MoKα) = 0.123 mm-1, Dcalc = 1.500 g/cm3, 62749 reflections measured (5.88° ≤ 2Θ ≤ 57.058°), 3911 unique (Rint = 0.0536, Rsigma = 0.0226) which were used in all calculations. The final R1 was 0.0569 (I > 2σ(I)) and wR2 was 0.1710 (all data). Detailed investigation of molecular packing of the TMPPc molecule indicated the presence of intermolecular hydrogen bond between N4-H44···O1 and C13-H13B···O4 that generates C22(14) chain running parallel to the [001] direction. The infrared and Raman spectra of the prepared TMPPc compound were recorded and discussed. The thermal stability of the obtained TMPPc crystal was analysed by TGA/DTG technique and revealed that the crystal was stable up to 162 °C. Density functional theory calculations such as the value of the HOMO and LUMO energy gap, the parameters of the molecular electrostatic potential, the global reactivity and thermodynamic properties of the compound TMPPc were also performed using the DFT/B3LYP method with the level of the 6-311G (d, p) basis set.


icon graph This Abstract was viewed 297 times | icon graph Article PDF downloaded 116 times icon graph Article CIF FILE downloaded 0 times

How to Cite
(1)
Arslan, N. B.; Aydin, F. The Crystal Magnification, Characterization, X-Ray Single Crystal Structure, Thermal Behavior, and Computational Studies of the 2,4,6-Trimethylpyridinium Picrate. Eur. J. Chem. 2022, 13, 468-477.

Article Details

Share
Crossref - Scopus - Google - European PMC
References

[1]. Sherman, A. R. 2,4,6-Collidine. Encyclopedia of Reagents for Organic Synthesis 2001.
https://doi.org/10.1002/047084289X.rc190

[2]. Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. 2,4,6-Trimethyl-pyridine-bishydrofluoride: a novel fluorinating reagent for organo transition-metal alkyls. Chem. Commun. (Camb.) 1996, 29-30.
https://doi.org/10.1039/CC9960000029

[3]. Xue, X.-S.; Wang, Y.; Li, M.; Cheng, J.-P. Comprehensive energetic scale for quantitatively estimating the fluorinating potential of N-F reagents in electrophilic fluorinations. J. Org. Chem. 2016, 81, 4280-4289.
https://doi.org/10.1021/acs.joc.6b00683

[4]. Rozatian, N.; Ashworth, I. W.; Sandford, G.; Hodgson, D. R. W. A quantitative reactivity scale for electrophilic fluorinating reagents. Chem. Sci. 2018, 9, 8692-8702.
https://doi.org/10.1039/C8SC03596B

[5]. André, V.; Lahrache, H.; Robin, S.; Rousseau, G. Reaction of unsaturated phosphonate monoesters with bromo- and iodo(bis-collidine) hexafluorophosphates. Tetrahedron 2007, 63, 10059-10066.
https://doi.org/10.1016/j.tet.2007.07.032

[6]. CRC handbook of chemistry and physics; Haynes, W. M., Ed.; 95th ed.; CRC Press: London, England, 2014.

[7]. Handbook of reagents for organic synthesis: Acidic and basic reagents; Reich, H. J.; Rigby, J. H., Eds.; John Wiley & Sons: Chichester, England, 1999.

[8]. Aditya Prasad, A.; Muthu, K.; Rajasekar, M.; Meenatchi, V.; Meenakshisundaram, S. P. Synthesis, crystal growth, characterization and theoretical studies of 4-aminobenzophenonium picrate. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2015, 135, 46-54.
https://doi.org/10.1016/j.saa.2014.06.154

[9]. Dhanabal, T.; Amirthaganesan, G.; Dhandapani, M.; Das, S. K. Synthesis, structure, thermal and NLO characterization of 4-hydroxy tetra-methylpiperazinium picrate crystals. J. Chem. Sci. (Bangalore) 2012, 124, 951-961.
https://doi.org/10.1007/s12039-012-0289-2

[10]. Chandramohan, A.; Bharathikannan, R.; Chandrasekaran, J.; Maadeswaran, P.; Renganathan, R.; Kandavelu, V. Synthesis, crystal growth and characterization of a new organic NLO material: Caffeinium picrate (CAFP)-A charge transfer molecular complex salt. J. Cryst. Growth 2008, 310, 5409-5415.
https://doi.org/10.1016/j.jcrysgro.2008.09.020

[11]. Sudharsana, N.; Muthunatesan, S.; Jasmine Priya, G.; Krishnakumar, V.; Nagalakshmi, R. Experimental and theoretical studies of 2,5-dichloroanilinium picrate. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2014, 121, 53-62.
https://doi.org/10.1016/j.saa.2013.10.047

[12]. Chandramohan, A.; Bharathikannan, R.; Kandavelu, V.; Chandrasekaran, J.; Kandhaswamy, M. A. Synthesis, crystal growth, structural, thermal and optical properties of naphthalene picrate an organic NLO material. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2008, 71, 755-759.
https://doi.org/10.1016/j.saa.2008.01.036

[13]. Hankin, S. M.; John, P.; Smith, G. P. Laser time-of-flight mass spectrometry of PAH−Picrate complexes. Anal. Chem. 1997, 69, 2927-2930.
https://doi.org/10.1021/ac970222o

[14]. Koizumi, S.; Matsunaga, Y. The phenanthrene/anthracene-picric acid system. Bull. Chem. Soc. Jpn. 1974, 47, 9-13.
https://doi.org/10.1246/bcsj.47.9

[15]. Akhavan, J. The chemistry of explosives; Royal Society of Chemistry: Cambridge, England, 1998.

[16]. Peng, Y.; Zhang, A.-J.; Dong, M.; Wang, Y.-W. A colorimetric and fluorescent chemosensor for the detection of an explosive-2,4,6-trinitrophenol (TNP). Chem. Commun. (Camb.) 2011, 47, 4505.
https://doi.org/10.1039/c1cc10400d

[17]. Schechter, B.; Arnon, R.; Freedman, Y.; Chen, L.; Wilchek, M. Liver accumulation of TNP-modified streptavidin and avidin: Potential use for targeted radio- and chemotherapy. J. Drug Target. 1996, 4, 171-179.
https://doi.org/10.3109/10611869609015974

[18]. Stilinović, V.; Kaitner, B. Hydrogen bonding in pyridinium picrates: From discrete ion pairs to 3D networks. Cryst. Growth Des. 2011, 11, 4110-4119.
https://doi.org/10.1021/cg200684x

[19]. Bruker (2008). SHELXL-97. Bruker AXS Inc., Madison, Wisconsin, USA.

[20]. Bruker (1997). SHELXS-97. Bruker AXS Inc., Madison, Wisconsin, USA.

[21]. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 09, Revision E.01, Gaussian, Inc., Wallingford CT, 2009.

[22]. Aditya Prasad, A.; Muthu, K.; Rajasekar, M.; Meenatchi, V.; Meenakshisundaram, S. P. Crystal growth, characterization and theoretical studies of 4-aminopyridinium picrate. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2015, 135, 805-813.
https://doi.org/10.1016/j.saa.2014.07.069

[23]. Srivastava, K. K.; Shubha, S.; Tanweer, A.; Rituraj An Overview of Picric Acid. Der Pharma Chemica 2017, 9, 64-75.

[24]. Coates, J. Interpretation of infrared spectra, A practical approach. Encyclopedia of Analytical Chemistry 2006.
https://doi.org/10.1002/9780470027318.a5606

[25]. Smith, B. C. Infrared spectral interpretation: A systematic approach; CRC Press: Boca Raton, FL, 1998.

[26]. Hendra, P.; etc.; Jones, C.; Warnes, G. Fourier transform Raman spectroscopy: Instrumental and chemical applications; Ellis Horwood Ltd, Publisher: Harlow, England, 1991.

[27]. Clarkson, J.; Smith, W. E.; Batchelder, D. N.; Smith, D. A.; Coats, A. M. A theoretical study of the structure and vibrations of 2,4,6-trinitrotolune. J. Mol. Struct. 2003, 648, 203-214.
https://doi.org/10.1016/S0022-2860(03)00024-3

[28]. Aydın, F.; Arslan, N. B. Synthesis, spectral properties, crystal structure and theoretical calculations of a new geminal diamine: 2,2,2-Trichloro-N,N׳-bis(2-nitrophenyl)-ethane-1,1-diamine. J. Mol. Struct. 2021, 1232, 129976.
https://doi.org/10.1016/j.molstruc.2021.129976

[29]. Tauc, J.; Grigorovici, R.; Vancu, A. Optical properties and electronic structure of amorphous germanium. Phys. Status Solidi B Basic Res. 1966, 15, 627-637.
https://doi.org/10.1002/pssb.19660150224

[30]. Fukui, K.; Yonezawa, T.; Shingu, H. A molecular orbital theory of reactivity in aromatic hydrocarbons. J. Chem. Phys. 1952, 20, 722-725.
https://doi.org/10.1063/1.1700523

[31]. Parr, R. G.; Szentpály, L. v.; Liu, S. Electrophilicity index. J. Am. Chem. Soc. 1999, 121, 1922-1924.
https://doi.org/10.1021/ja983494x

[32]. Murray, J. S. Molecular electrostatic potentials: Concepts and applications; Murray, J. S.; Sen, K., Eds.; Elsevier Science & Technology, 1996.

[33]. Geerlings, P.; Proft, F. D.; Ayers, P. W. Chapter 1 Chemical reactivity and the shape function. In Theoretical and Computational Chemistry; Elsevier, 2007; pp. 1-17.
https://doi.org/10.1016/S1380-7323(07)80002-1

[34]. Jauhar, R. O. M. U.; Viswanathan, V.; Vivek, P.; Vinitha, G.; Velmurugan, D.; Murugakoothan, P. A new organic NLO material isonicotinamidium picrate (ISPA): crystal structure, structural modeling and its physico-chemical properties. RSC Adv. 2016, 6, 57977-57985.
https://doi.org/10.1039/C6RA10477K

[35]. Bevan Ott, J.; Boerio-Goates, J. Chemical thermodynamics: Advanced applications: Advanced applications; Academic Press: San Diego, CA, 2000.

TrendMD

Dimensions - Altmetric - scite_ - PlumX

Downloads and views

Downloads

Download data is not yet available.

Metrics

Metrics Loading ...
License Terms

License Terms

by-nc

Copyright © 2024 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at https://www.eurjchem.com/index.php/eurjchem/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution, or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (https://www.eurjchem.com/index.php/eurjchem/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry).