Polymorphs of Substituted p-Toluenesulfonanilide: Synthesis, Single-Crystal Analysis, Hirshfeld Surface Exploration, and Theoretical Investigation

Mehreen Riaz; Akbar Ali; Muhammad Ashfaq; Muhammad Ibrahim; Nadia Akram; Muhammad Nawaz Tahir; Aleksey Kuznetsov; Lyanne Rodríguez; Manal Y Sameeh; Mohammed A Assiri; Alexander Fernandez de la Torre

doi:10.1021/acsomega.3c04957

Polymorphs of Substituted p-Toluenesulfonanilide: Synthesis, Single-Crystal Analysis, Hirshfeld Surface Exploration, and Theoretical Investigation

ACS Omega. 2023 Sep 15;8(38):35307-35320. doi: 10.1021/acsomega.3c04957. eCollection 2023 Sep 26.

Authors

Affiliations

¹ Department of Applied Chemistry, Government College University Faisalabad, 38000 Faisalabad, Pakistan.
² Department of Chemistry, Government College University Faisalabad, 38000 Faisalabad, Pakistan.
³ Department of Physics, University of Sargodha, 40100 Sargodha, Pakistan.
⁴ Departamento de Química, Campus Santiago Vitacura, Universidad Técnica Federico Santa María, Vitacura 7660251, Chile.
⁵ Department of Clinical Biochemistry and Immunohaematology, Thrombosis Research Center, Medical Technology School, Faculty of Health Sciences, Universidad de Talca, Talca 3460000, Chile.
⁶ Chemistry Department, Faculty of Applied Sciences, Al-Leith University College, Umm Al-Qura University, Makkah 24831, Saudi Arabia.
⁷ Research center for Advanced Materials Science (RCAMS), King Khalid University, P.O. Box 9004, Abha 61514, Saudi Arabia.
⁸ Department of Chemistry, Faculty of Science, King Khalid University, P.O. Box 9004, Abha 61413, Saudi Arabia.
⁹ Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad de Concepción, Concepción 3801061, Chile.

Abstract

Polymorphism is an exciting feature of chemical systems where a compound can exist in different crystal forms. The present investigation is focused on the two polymorphic forms, triclinic (MSBT) and monoclinic (MSBM), of ethyl 3-iodo-4-((4-methylphenyl)sulfonamido)benzoate prepared from ethyl 4-amino-3-iodobenzoate. The prepared polymorphs were unambiguously confirmed by single-crystal X-ray diffraction (SC-XRD) analysis. According to the SC-XRD results, the molecular configurations of both structures are stabilized by intramolecular N-H···I and C-H···O bonding. The crystal packing of MSBT is different as compared to the crystal packing of MSBM because MSBT is crystallized in the triclinic crystal system with the space group P1̅, whereas MSBM is crystallized in the monoclinic crystal system with the space group P2₁/c. The molecules of MSBT are interlinked in the form of dimers through N-H···O bonding to form R₂²(8) loops, while the MSBM molecules are connected with each other in the form of an infinite chain through C-H···O bonding. The crystal packing of both compounds is further stabilized by off-set π···π stacking interactions between phenyl rings, which is found stronger in MSBM as compared to in MSBT. Moreover, Hirshfeld surface exploration of the polymorphs was carried out, and the results were compared with the closely related literature structure. Accordingly, the supramolecular assembly of these polymorphs is mainly stabilized by noncovalent interactions or intermolecular interactions. Furthermore, a density functional theory (DFT) study was also carried out, which provided good support for the SC-XRD and Hirshfeld studies, suggesting the formation of both intramolecular and intermolecular interactions for both compounds.