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Correlation of the solid‐state reactivities of racemic 2,4(6)‐di‐ O ‐benzoyl‐ myo ‐inositol 1,3,5‐orthoformate and its 4,4′‐bipyridine cocrystal with their crystal structures
Author(s) -
Tamboli Majid I.,
Bahadur Vir,
Gonnade Rajesh G.,
Shashidhar Mysore S.
Publication year - 2014
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/s2053229614021834
Subject(s) - cocrystal , chemistry , molecule , electrophile , crystallography , intermolecular force , 4,4' bipyridine , bipyridine , hydrogen bond , stereochemistry , crystal engineering , nucleophile , crystal structure , organic chemistry , catalysis
Racemic 2,4(6)‐di‐ O ‐benzoyl‐ myo ‐inositol 1,3,5‐orthoformate, C 21 H 18 O 8 , (1) , shows a very efficient intermolecular benzoyl‐group migration reaction in its crystals. However, the presence of 4,4′‐bipyridine molecules in its cocrystal, C 21 H 18 O 8 ·C 10 H 8 N 2 , (1)·BP , inhibits the intermolecular benzoyl‐group transfer reaction. In (1) , molecules are assembled around the crystallographic twofold screw axis ( b axis) to form a helical self‐assembly through conventional O—H...O hydrogen‐bonding interactions. This helical association places the reactive C6‐ O ‐benzoyl group (electrophile, El) and the C4‐hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal (1)·BP , the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid‐state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl‐transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.