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Compounds <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> were first obtained in attempts to recrystallize <jats:bold>1<\/jats:bold> and <jats:bold>1<\/jats:bold>\u00b72HCl using acetone as solvent. This solvent reacted with the vicinal diamines present in the molecular structures, forming a 5<jats:italic>H<\/jats:italic>-1,5-benzodiazepine ring. In the crystal structure of <jats:bold>2<\/jats:bold>, the seven-membered ring of benzodiazepine adopts a boat-like conformation, while upon protonation, observed in the crystal structure of <jats:bold>3<\/jats:bold>, it adopts an envelope-like conformation. In both crystalline compounds, the tosylamide N atoms are not in resonance with the arene ring, mainly due to hydrogen bonds and steric hindrance caused by the large vicinal groups in the aromatic ring. At a supramolecular level, the crystal structure is maintained by a combination of hydrogen bonds and hydrophobic interactions. In <jats:bold>2<\/jats:bold>, amine-to-tosyl N\u2014H...O and amide-to-imine N\u2014H...N hydrogen bonds can be observed. In contrast, in <jats:bold>3<\/jats:bold>, the chloride counter-ion and water molecule result in most of the hydrogen bonds being of the amide-to-chloride and ammonium-to-chloride N\u2014H...Cl types, while the amine interacts with the tosyl group, as seen in <jats:bold>2<\/jats:bold>. In conclusion, we report the synthesis of <jats:bold>1<\/jats:bold>, <jats:bold>1<\/jats:bold>\u00b72HCl and <jats:bold>2<\/jats:bold>, as well as their chemical characterization. For <jats:bold>2<\/jats:bold>, two synthetic methods are described, <jats:italic>i.e.<\/jats:italic> solvent-mediated crystallization and synthesis <jats:italic>via<\/jats:italic> a more efficient and cleaner route as a polycrystalline material. Salt <jats:bold>3<\/jats:bold> was only obtained as presented, with only a few crystals being formed.<\/jats:p>","DOI":"10.1107\/s2053229624007320","type":"journal-article","created":{"date-parts":[[2024,8,23]],"date-time":"2024-08-23T15:12:18Z","timestamp":1724425938000},"page":"497-504","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":2,"title":["Crystal structures of two unexpected products of vicinal diamines left to crystallize in acetone"],"prefix":"10.1107","volume":"80","author":[{"given":"Bruno","family":"Dival","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-7836-8329","authenticated-orcid":true,"given":"Leonardo","family":"Pitinato","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Let\u00edcia","family":"Develly","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0722-5352","authenticated-orcid":true,"given":"Willian X. 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