European Journal of Chemistry 2021, 12(4), 439-449 | doi: https://doi.org/10.5155/eurjchem.12.4.439-449.2196 | Get rights and content

Issue cover




Crossmark

  Open Access OPEN ACCESS | Open Access PEER-REVIEWED | RESEARCH ARTICLE | DOWNLOAD PDF | VIEW FULL-TEXT PDF | TOTAL VIEWS

Crystal structure, Hirshfeld surface analysis, and DFT studies of N-(2-chlorophenylcarbamothioyl)cyclohexanecarboxamide


Cemal Koray Ozer (1) orcid , Ummuhan Solmaz (2,*) orcid , Hakan Arslan (3) orcid

(1) Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, TR 33343, Turkey
(2) Department of Chemistry and Chemical Processing Technologies, Technical Science Vocational School, Mersin University, Mersin, TR 33343, Turkey
(3) Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, TR 33343, Turkey
(*) Corresponding Author

Received: 22 Oct 2021 | Revised: 14 Nov 2021 | Accepted: 20 Nov 2021 | Published: 31 Dec 2021 | Issue Date: December 2021

Abstract


N-(2-Chlorophenylcarbamothioyl)cyclohexanecarboxamide was characterized by a single crystal X-ray diffraction study. Crystal data for this compound, C14H17ClN2OS; Monoclinic, space group P21/n with Z = 4, a = 5.2385(10) Å, b = 17.902(4) Å, c = 15.021(3) Å, β = 90.86(3)°, = 1408.5(5) Å3T = 153(2) K, μ(MoKα) = 0.413 mm-1Dcalc = 1.400 g/cm3, 9840 reflections measured (7.082° ≤ 2Θ ≤ 50.378°), 2519 unique (Rint = 0.0406, Rsigma = 0.0335) which were used in all calculations. The final R1 was 0.0397 (I > 2σ(I)) and wR2 was 0.0887 (all data). The puckering parameters (q2 = 0.019(3) Å, q3 = 0.578(3) Å, θ = 1.0(3)° and φ = 51(8)°) of the title compound show that the cyclohexane ring adopts a chair conformation. The molecular conformation of the title compound is stabilized by intramolecular hydrogen bonds (N2-H2⋅⋅⋅Cl1, N2-H2⋅⋅⋅O1, and C2-H2A⋅⋅⋅S1) and intermolecular hydrogen bonds (N1-H1⋅⋅⋅S1i and C9-HA⋅⋅⋅S1ii: 2-x, 2-y, 1-z). The intramolecular hydrogen bonds (N2-H2⋅⋅⋅O1 and C2-H2A⋅⋅⋅S1) are also form two pseudo-six-membered rings. Density functional theory optimized structure in the gaseous phase at B3LYP/6-311G(d,p) level of theory has been compared with the experimentally defined molecular structure. The molecular orbitals HOMO and LUMO with the energy gap for the title compound are calculated and the estimated energy gap (ΔE) between the HOMO and LUMO energies levels of the title compound is 3.5399 eV, which implies that the title molecule is very reactive. The Hirshfeld surface analysis reveals that the most important contributions to crystal packing are from H···H (49.0%), H···C/C···H (12.5%), H···Cl/Cl···H (10.9%), and H···S/S···H (10.0%) interactions. The energy-framework calculations are used to analyze and visualize the three-dimensional topology of the crystal packing. The intermolecular energy analysis confirmed a significant contribution of dispersion to the stabilization of molecular packings in the title compound.


Keywords


Benzoylthiourea; Chair conformation; Cyclohexanecarboxamide; Crystal structure analysis; Hirshfeld surface analysis; Density Functional Theory (DFT)

Full Text:

PDF
PDF    Open Access

DOI: 10.5155/eurjchem.12.4.439-449.2196

Links for Article


| | | | | | |

| | | | | | |

| | | |

Related Articles




Article Metrics

icon graph This Abstract was viewed 141 times | icon graph PDF Article downloaded 46 times

Funding information


Mersin University Research Fund [Project No: BAP-SBETB (CKÖ) 2007-1], Mersin, Turkey.

References


[1]. Karakus, S.; Rollas, S. Farmaco 2002, 57 (7), 577-581.
https://doi.org/10.1016/S0014-827X(02)01252-1

[2]. Solomon, V. R.; Haq, W.; Smilkstein, M.; Srivastava, K.; Puri, S. K.; Katti, S. B. Eur. J. Med. Chem. 2010, 45 (11), 4990-4996.
https://doi.org/10.1016/j.ejmech.2010.07.068

[3]. Saeed, A.; Flörke, U.; Erben, M. F. J. Sulphur Chem. 2014, 35 (3), 318-355.
https://doi.org/10.1080/17415993.2013.834904

[4]. Beyer, L.; Hoyer, E.; Liebscher, J.; Hartmann, H. Z. Chem. 2010, 21 (3), 81-91.
https://doi.org/10.1002/zfch.19810210302

[5]. Mühl, P.; Gloe, K.; Dietze, F.; Hoyer, E.; Beyer, L. Z. Chem. 2010, 26 (3), 81-94.
https://doi.org/10.1002/zfch.19860260302

[6]. Duque, J.; Estevez-Hernandez, O.; Reguera, E.; Ellena, J.; Correa, R. S. J. Coord. Chem. 2009, 62 (17), 2804-2813.
https://doi.org/10.1080/00958970902926795

[7]. Estevez-Hernandez, O.; Duque, J.; Rodríguez-Hernandez, J.; Reguera, E. Polyhedron 2015, 97, 148-156.
https://doi.org/10.1016/j.poly.2015.05.028

[8]. Yesilkaynak, T. J. Therm. Anal. Calorim. 2016, 124 (2), 1029-1037.
https://doi.org/10.1007/s10973-015-5221-9

[9]. Correa, R. S.; de Oliveira, K. M.; Delolo, F. G.; Alvarez, A.; Mocelo, R.; Plutin, A. M.; Cominetti, M. R.; Castellano, E. E.; Batista, A. A. J. Inorg. Biochem. 2015, 150, 63-71.
https://doi.org/10.1016/j.jinorgbio.2015.04.008

[10]. Sternberg, M.; Rust, J.; Lehmann, C. W.; Mohr, F. Helv. Chim. Acta 2013, 96 (2), 280-288.
https://doi.org/10.1002/hlca.201200386

[11]. Hassan, S. S.; Shoukry, M. M.; Shallan, R. N.; van Eldik, R. J. Coord. Chem. 2017, 70 (10), 1761-1775.
https://doi.org/10.1080/00958972.2017.1312357

[12]. Hussain, S.; Imtiaz-ud-Din; Raheel, A.; Hussain, S.; Tahir, M. N.; Hussain, I. J. Coord. Chem. 2020, 73 (7), 1191-1207.
https://doi.org/10.1080/00958972.2020.1771558

[13]. Teixeira, E. I.; Schwalm, C. S.; Casagrande, G. A.; Tirloni, B.; Schwade, V. D. J. Mol. Struct. 2020, 1210 (127999), 127999.
https://doi.org/10.1016/j.molstruc.2020.127999

[14]. Barnard, I.; Koch, K. R.; Gerber, W. J. J. Mol. Struct. 2021, 1244 (131009), 131009.
https://doi.org/10.1016/j.molstruc.2021.131009

[15]. Lapasam, A.; Kollipara, M. R. Phosphorus Sulfur Silicon Relat. Elem. 2020, 195 (10), 779-804.
https://doi.org/10.1080/10426507.2020.1764956

[16]. Ketchemen, K. I. Y.; Khan, M. D.; Mlowe, S.; Akerman, M. P.; Vitorica-Yrezabal, I.; Whitehead, G.; Nyamen, L. D.; Ndifon, P. T.; Revaprasadu, N.; O'Brien, P. J. Mol. Struct. 2021, 1229 (129791), 129791.
https://doi.org/10.1016/j.molstruc.2020.129791

[17]. Cunha, B. N.; Luna-Dulcey, L.; Plutin, A. M.; Silveira, R. G.; Honorato, J.; Cairo, R. R.; de Oliveira, T. D.; Cominetti, M. R.; Castellano, E. E.; Batista, A. A. Inorg. Chem. 2020, 59 (7), 5072-5085.
https://doi.org/10.1021/acs.inorgchem.0c00319

[18]. Nkabyo, H. A.; Barnard, I.; Koch, K. R.; Luckay, R. C. Coord. Chem. Rev. 2021, 427 (213588), 213588.
https://doi.org/10.1016/j.ccr.2020.213588

[19]. Tudor, C. A.; Iliş, M.; Secu, M.; Ferbinteanu, M.; Cîrcu, V. Polyhedron 2022, 211 (115542), 115542.
https://doi.org/10.1016/j.poly.2021.115542

[20]. Mitrea, D. G.; Circu, V. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2021, 258 (119860), 119860.
https://doi.org/10.1016/j.saa.2021.119860

[21]. Plutín, A. M.; Ramos, R.; Mocelo, R.; Alvarez, A.; Castellano, E. E.; Cominetti, M. R.; Oliveira, K. M.; Donizeth de Oliveira, T.; Silva, T. E. M.; S. Correa, R.; Batista, A. A. Polyhedron 2020, 184 (114543), 114543.
https://doi.org/10.1016/j.poly.2020.114543

[22]. Yuan, Y. F.; Wang, J. T.; Gimeno, M. C.; Laguna, A.; Jones, P. G. Inorganica Chim. Acta 2001, 324 (1-2), 309-317.
https://doi.org/10.1016/S0020-1693(01)00661-2

[23]. Zhang, Y. M.; Wei, T. B.; Xian, L.; Gao, L. M. Phosphorus Sulfur Silicon Relat. Elem. 2004, 179 (10), 2007-2013.
https://doi.org/10.1080/10426500490473456

[24]. You-Ming, Z.; Tai-Bao, W.; Xiu-Chun, W.; Su-You, Y. Indian J. Chem. 1998, 37B, 604-606.

[25]. Weiqun, Z.; Baolong, L.; Liming, Z.; Jiangang, D.; Yong, Z.; Lude, L.; Xujie, Y. J. Mol. Struct. 2004, 690 (1-3), 145-150.
https://doi.org/10.1016/j.molstruc.2003.11.029

[26]. Ozer, C. K.; Binzet, G.; Arslan, H. Eur. J. Chem. 2020, 11 (4), 319-323.
https://doi.org/10.5155/eurjchem.11.4.319-323.2047

[27]. Ozer, C. K.; Arslan, H.; VanDerveer, D.; Külcü, N. Molecules 2009, 14 (2), 655-666.
https://doi.org/10.3390/molecules14020655

[28]. Arslan, B., MSc Thesis, Mersin University, Mersin, Turkey, 2017.

[29]. Binzet, G.; Arslan, H.; Flörke, U.; Külcü, N.; Duran, N. J. Coord. Chem. 2006, 59 (12), 1395-1406.
https://doi.org/10.1080/00958970500512633

[30]. Arslan, H.; Flörke, U.; Külcü, N.; Emen, M. F. J. Coord. Chem. 2006, 59 (2), 223-228.
https://doi.org/10.1080/00958970500270992

[31]. Binzet, G.; Gumus, I.; Dogen, A.; Flörke, U.; Kulcu, N.; Arslan, H. J. Mol. Struct. 2018, 1161, 519-529.
https://doi.org/10.1016/j.molstruc.2018.02.073

[32]. Arslan, H.; Flörke, U.; Külcü, N. Acta Crystallogr. Sect. E Struct. Rep. Online 2003, 59 (5), o641-o642.
https://doi.org/10.1107/S1600536803007992

[33]. Arslan, H.; Flörke, U.; Külcü, N. J. Chem. Crystallogr. 2003, 33 (12), 919-924.
https://doi.org/10.1023/A:1027429814989

[34]. Ozpozan, N.; Arslan, H.; Ozpozan, T.; Merdivan, M.; Külcü, N. J. Therm. Anal. Calorim. 2000, 61 (3), 955-965.
https://doi.org/10.1023/A:1010171230450

[35]. Solmaz, U.; Gumus, I.; Yilmaz, M. K.; Ince, S.; Arslan, H. Appl. Organomet. Chem. 2021, 35 (10), e6348.
https://doi.org/10.1002/aoc.6348

[36]. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Crystallogr. 2009, 42 (2), 339-341.
https://doi.org/10.1107/S0021889808042726

[37]. Palatinus, L.; Chapuis, G. J. Appl. Crystallogr. 2007, 40 (4), 786-790.
https://doi.org/10.1107/S0021889807029238

[38]. Palatinus, L.; van der Lee, A. J. Appl. Crystallogr. 2008, 41 (6), 975-984.
https://doi.org/10.1107/S0021889808028185

[39]. Palatinus, L.; Prathapa, S. J.; van Smaalen, S. J. Appl. Crystallogr. 2012, 45 (3), 575-580.
https://doi.org/10.1107/S0021889812016068

[40]. Sheldrick, G. M. Acta Crystallogr. C Struct. Chem. 2015, 71 (Pt 1), 3-8.
https://doi.org/10.1107/S2053229614024218

[41]. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Revision C.01, Gaussian, Inc., Wallingford CT, 2016.

[42]. Becke, A. D. J. Chem. Phys. 1993, 98 (7), 5648-5652.
https://doi.org/10.1063/1.464913

[43]. Lee, C. T.; Yang, W.T.; Parr, R.G. Phys. Rev. B. 1988, 37 (2), 785-789.
https://doi.org/10.1103/PhysRevB.37.785

[44]. Dennington, R.; Keith, T. A.; Millam, J. M. GaussView, Version 6, Semichem Inc., Shawnee Mission, KS, 2016.

[45]. McKinnon, J. J.; Jayatilaka, D.; Spackman, M. A. Chem. Commun. (Camb.) 2007, No. 37, 3814-3816.
https://doi.org/10.1039/b704980c

[46]. Spackman, M. A.; Jayatilaka, D. CrystEngComm 2009, 11 (1), 19-32.
https://doi.org/10.1039/B818330A

[47]. Spackman, P. R.; Turner, M. J.; McKinnon, J. J.; Wolff, S. K.; Grimwood, D. J.; Jayatilaka, D.; Spackman, M. A. J. Appl. Cryst. 2021, 54 (3), 1006-1011.
https://doi.org/10.1107/S1600576721002910

[48]. Spackman, M. A.; McKinnon, J. J. CrystEngComm 2002, 4 (66), 378-392.
https://doi.org/10.1039/B203191B

[49]. Spackman, M. A.; McKinnon, J. J.; Jayatilaka, D. CrystEngComm 2008, 10 (4), 377-388.

[50]. Jayatilaka, D.; Grimwood, D. J. Tonto: A FORTRAN Based Object-Oriented System for Quantum Chemistry and Crystallography. In Lecture Notes in Computer Science; Springer Berlin Heidelberg: Berlin, Heidelberg, 2003; pp 142-151.
https://doi.org/10.1007/3-540-44864-0_15

[51]. Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Guy Orpen, A.; Taylor, R. J. Chem. Soc. Perkin Trans. 2 1987, 12, S1-S19.
https://doi.org/10.1039/p298700000s1

[52]. Arslan, H.; Külcü, N.; Flörke, U. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2006, 64 (4), 1065-1071.
https://doi.org/10.1016/j.saa.2005.09.016

[53]. Arslan, H.; Florke, U.; Kulcu, N.; Kayhan, E. Turk. J. Chem 2006, 30, 429-440.

[54]. Khawar Rauf, M.; Badshah, A.; Bolte, M. Acta Crystallogr. Sect. E Struct. Rep. Online 2007, 63 (4), o1676-o1678.
https://doi.org/10.1107/S1600536807010185

[55]. Arslan, H.; Florke, U.; Kulcu, N. Acta Chim. Slov 2004, 51, 787-792.

[56]. Shen, X.; Shi, X.; Kang, B.; Tong, Y.; Liu, Y.; Gu, L.; Liu, Q.; Huang, Y. Polyhedron 1998, 18 (1-2), 33-37.
https://doi.org/10.1016/S0277-5387(98)00264-2

[57]. Yamin, B. M.; Yusof, M. S. M. Acta Crystallogr. Sect. E Struct. Rep. Online 2003, 59 (2), o151-o152.
https://doi.org/10.1107/S1600536802023711

[58]. Yusof, M. S. M.; Asroh, F. S. M.; Kadir, M. A.; Yamin, B. M. Acta Crystallogr. Sect. E Struct. Rep. Online 2007, 63 (3), o1190-o1191.
https://doi.org/10.1107/S1600536807001900

[59]. Cremer, D.; Pople, J. A. J. Am. Chem. Soc. 1975, 97 (6), 1354-1358.
https://doi.org/10.1021/ja00839a011

[60]. Evans, D. G.; Boeyens, J. C. A. Acta Crystallogr. B 1989, 45 (6), 581-590.
https://doi.org/10.1107/S0108768189008190

[61]. Chermette, H. J. Comput. Chem. 1999, 20 (1), 129-154.
https://doi.org/10.1002/(SICI)1096-987X(19990115)20:1<129::AID-JCC13>3.0.CO;2-A

[62]. Baumgärtner, A. J. Chem. Phys. 1993, 98 (9), 7496-7501.
https://doi.org/10.1063/1.464689

[63]. Bogolubov, N. N. Jr; Kien, F. L.; Shumovsky, A. S. J. Phys. A Math. Gen. 1986, 19 (2), 191-203.
https://doi.org/10.1088/0305-4470/19/2/015

[64]. Meyer, A. Y. Chem. Soc. Rev. 1986, 15 (4), 449-474.
https://doi.org/10.1039/cs9861500449

[65]. Mackenzie, C. F.; Spackman, P. R.; Jayatilaka, D.; Spackman, M. A. IUCrJ 2017, 4 (Pt 5), 575-587.
https://doi.org/10.1107/S205225251700848X

[66]. Edwards, A. J.; Mackenzie, C. F.; Spackman, P. R.; Jayatilaka, D.; Spackman, M. A. Faraday Discuss. 2017, 203, 93-112.
https://doi.org/10.1039/C7FD00072C

[67]. Scrocco, E.; Tomasi, J. The Electrostatic Molecular Potential as a Tool for the Interpretation of Molecular Properties. In Topics in Current Chemistry Fortschritte der Chemischen Forschung; Springer Berlin Heidelberg: Berlin, Heidelberg, 2007; pp 95-170.
https://doi.org/10.1007/3-540-06399-4_6

[68]. Mulliken, R. S. J. Chem. Phys. 1955, 23 (10), 1833-1840.
https://doi.org/10.1063/1.1740588


Supporting information


The Supplementary Material for this article can be found online at: Supplementary files

How to cite


Ozer, C.; Solmaz, U.; Arslan, H. Eur. J. Chem. 2021, 12(4), 439-449. doi:10.5155/eurjchem.12.4.439-449.2196
Ozer, C.; Solmaz, U.; Arslan, H. Crystal structure, Hirshfeld surface analysis, and DFT studies of N-(2-chlorophenylcarbamothioyl)cyclohexanecarboxamide. Eur. J. Chem. 2021, 12(4), 439-449. doi:10.5155/eurjchem.12.4.439-449.2196
Ozer, C., Solmaz, U., & Arslan, H. (2021). Crystal structure, Hirshfeld surface analysis, and DFT studies of N-(2-chlorophenylcarbamothioyl)cyclohexanecarboxamide. European Journal of Chemistry, 12(4), 439-449. doi:10.5155/eurjchem.12.4.439-449.2196
Ozer, Cemal, Ummuhan Solmaz, & Hakan Arslan. "Crystal structure, Hirshfeld surface analysis, and DFT studies of N-(2-chlorophenylcarbamothioyl)cyclohexanecarboxamide." European Journal of Chemistry [Online], 12.4 (2021): 439-449. Web. 17 Jan. 2022
Ozer, Cemal, Solmaz, Ummuhan, AND Arslan, Hakan. "Crystal structure, Hirshfeld surface analysis, and DFT studies of N-(2-chlorophenylcarbamothioyl)cyclohexanecarboxamide" European Journal of Chemistry [Online], Volume 12 Number 4 (31 December 2021)

The other citation formats (EndNote | Reference Manager | ProCite | BibTeX | RefWorks) for this article can be found online at: How to cite item



DOI Link: https://doi.org/10.5155/eurjchem.12.4.439-449.2196

CrossRef | Scilit | GrowKudos | Researchgate | Publons | Microsoft | scibey | Scite | Lens | OUCI

WorldCat Paperbuzz | LibKey Citeas | Dimensions | Semanticscholar | Plumx | Kopernio | Zotero | Mendeley

ZoteroSave to Zotero MendeleySave to Mendeley



European Journal of Chemistry 2021, 12(4), 439-449 | doi: https://doi.org/10.5155/eurjchem.12.4.439-449.2196 | Get rights and content

Refbacks

  • There are currently no refbacks.




Copyright (c) 2021 Authors

Creative Commons License
This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at http://www.eurjchem.com/index.php/eurjchem/pages/view/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 (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry).



© Copyright 2010 - 2022  Atlanta Publishing House LLC All Right Reserved.

The opinions expressed in all articles published in European Journal of Chemistry are those of the specific author(s), and do not necessarily reflect the views of Atlanta Publishing House LLC, or European Journal of Chemistry, or any of its employees.

Copyright 2010-2022 Atlanta Publishing House LLC. All rights reserved. This site is owned and operated by Atlanta Publishing House LLC whose registered office is 2850 Smith Ridge Trce Peachtree Cor GA 30071-2636, USA. Registered in USA.