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Ionic cocrystals of dithiobispyridines: the role of I…I halogen bonds in the building of iodine frameworks and the stabilization of crystal structures
Author(s) -
Wzgarda-Raj Kinga,
Nawrot Martyna,
Rybarczyk-Pirek Agnieszka J.,
Palusiak Marcin
Publication year - 2021
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229621006306
Subject(s) - triiodide , halogen , iodide , iodine , chemistry , ionic bonding , pyridinium , protonation , chalcogen , halogen bond , hydrogen bond , crystal structure , crystallography , molecule , inorganic chemistry , medicinal chemistry , ion , organic chemistry , alkyl , electrode , dye sensitized solar cell , electrolyte
It has been confirmed that mercaptopyridines undergo spontaneous condensation in redox reaction with iodine‐forming dithiopyridines. In the solid state, these compounds are protonated at the N atoms and cocrystallize with iodine forming salt structures, namely, 2‐[(pyridin‐2‐yl)disulfanyl]pyridinium triiodide sesquiiodine, C 10 H 9 N 2 S 2 + ·I 3 − ·1.5I 2 , and 4,4′‐(disulfanediyl)dipyridinium pentaiodide triiodide, C 10 H 10 N 2 S 2 2+ ·I 5 − ·I 3 − . Dithiopyridine cations are packed among three‐dimensional frameworks built from iodide anions and neutral iodine molecules, and are linked by hydrogen, halogen and chalcogen interactions. Quantum chemical computations indicated that dithiopyridines exhibit anomalously high nitrogen basicity which qualify them as potential proton sponges.