Isobornanyl sulfoxides and isobornanyl sulfone: Physicochemical characteristics and the features of crystal structure

• Published in: Journal of molecular structure 2021-09, Vol.1239, p.130491, Article 130491
• Main Authors: Lodochnikova, Olga A., Islamov, Daut R., Gerasimova, Daria P., Zakharychev, Dmitry V., Saifina, Alina F., Pestova, Svetlana V., Izmest'ev, Evgeny S., Rubtsova, Svetlana A., Pavelyev, Roman S., Rakhmatullin, Ilfat Z., Klochkov, Vladimir V., Ostolopovskaya, Olga V., Nikitina, Liliya E., Rollin, Patrick
• Format: Article
• Language: English
• Subjects: Diastereomeric sulfoxides; Eutectic mixture; Monoterpenoids; Sulfone; Supramolecular synthon; Thermochemistry
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2021.130491

•Found the absence of reproducibility of the dimeric β-hydroxysulfoxide synthon in the series of sulfur-containing derivatives of bornane.•According to the X-ray data, the supramolecular open-chain S=O⋅⋅⋅H–O synthon is built up in the crystals of diastereomeric sulfoxides.•The isobornanyl sulfone crystal is formed in a complex way – two crystallographically independent molecules playing different roles in the formation of H-bonds.•Based on thermochemical data, the form of the phase diagram of the system was reconstructed, showing that diastereomers have significantly different melting points. The physico-chemical characteristics and crystal structure of newly synthesized isobornanyl sulfoxides and sulfone are presented. After purification, diastereomeric sulfoxides were obtained in a 2:1 eutectic ratio, which did not allow either separation or enrichment of the mixture. Based on thermochemical data, the form of the phase diagram of the system was reconstructed, showing that diastereomers have significantly different melting points. According to the X-ray data, the same supramolecular open–chain S=O⋅⋅⋅H–O synthon is built up in the crystals of diastereomeric sulfoxides. The isobornanyl sulfone crystal is formed in a complex way – two crystallographically independent molecules playing different roles in the formation of H-bonds. The IR spectra of a diastereomeric sulfoxides mixture demonstrate the averaging of the synthon-forming functional groups bands. In a counterbalance, the IR spectrum of isobornanyl sulfone shows a doubling of the key bands of synthon-forming functional groups belonging to homochirally homogeneous but crystallographically nonequivalent molecules. [Display omitted]