title: 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.
abstract: 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·C10H8N2, (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.
authors.affiliation: Division of Organic Chemistry, CSIR-National Chemical Laboratory, Pune 411 008, India.
authors.forename: Majid I
authors.initials: MI
authors.lastname: Tamboli
authors.affiliation: Division of Organic Chemistry, CSIR-National Chemical Laboratory, Pune 411 008, India.
authors.forename: Vir
authors.initials: V
authors.lastname: Bahadur
authors.affiliation: Center for Materials Characterization, CSIR-National Chemical Laboratory, Pune 411 008, India.
authors.forename: Rajesh G
authors.initials: RG
authors.lastname: Gonnade
authors.affiliation: Division of Organic Chemistry, CSIR-National Chemical Laboratory, Pune 411 008, India.
authors.forename: Mysore S
authors.initials: MS
authors.lastname: Shashidhar
mesh_terms: D001565:Benzoates / Q000737:chemistry*; D005561:Formates / Q000737:chemistry*; D006860:Hydrogen Bonding; D007294:Inositol / Q000031:analogs & derivatives* / Q000737:chemistry*; D015394:Molecular Structure; D011725:Pyridines / Q000737:chemistry*
chemical_list: C000596809:2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate; D001565:Benzoates; D005561:Formates; D011725:Pyridines; D007294:Inositol; C034306:4,4'-bipyridyl
keywords: acyl transfer; cocrystal; crystal structure; design of functional solids; helical assembly; hydrogen bonding; myo-inositol; solid-state reactions