TY - JOUR T1 - 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 JF - Acta Crystallographica Section C-Structural Chemistry Y1 - 2014 A1 - Tamboli, Majid I. A1 - Bahadur, Vir A1 - Gonnade, Rajesh G. A1 - Shashidhar, Mysore S. KW - acyl transfer KW - cocrystal KW - crystal structure KW - design of functional solids KW - helical assembly KW - hydrogen bonding KW - myo-inositol KW - solid-state reactions AB -

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8, (1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4 `-bipyridine molecules in its cocrystal, C21H18O8 center dot C10H8N2, (1)center dot 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 center dot center dot center dot 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 center dot center dot center dot Nu geometry favourable for the acyl transfer reaction. In the cocrystal (1)center dot BP, the dibenzoate and bipyridine molecules are arranged alternately through OH center dot center dot center dot 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.

PB - WILEY-BLACKWELL CY - 111 RIVER ST, HOBOKEN 07030-5774, NJ USA VL - 70 IS - Part : 11 U3 -

Foreign

U4 -

0.479

ER -