title: Halogen and Hydrogen Bonding Benzothiophene Diol Derivatives: A Study Using ab initio Calculations and X-Ray Crystal Structure Measurements.
abstract: The aim of this study is to describe and compare the supramolecular interactions, in the solid state, of chloro-, bromo-, and iodobenzothiophene diols. The compounds were obtained through organo-catalyzed reactions starting from 3-substituted halobenzothiophene carbaldehydes. Energies of the noncovalent interactions were obtained by density functional theory calculations. Bond distances and angles were found to be in accordance with those determined by X-ray structure analysis. anti-Bromobenzothiophene derivatives showed strong halogen⋅⋅⋅π interactions between bromine and the heterocyclic phenyl ring, corresponding to an energy of 7.5 kcal mol(-1). syn-Bromo and syn-iodo derivatives appeared to be isostructural, showing X⋅⋅⋅O (carbonyl) interactions, π stacking, and formation of extended hydrogen bonding networks. In contrast, the chloro derivatives displayed no halogen bonding interactions.
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato SS 554, Bivio per Sestu, 90042, Monserrato, CA, Italy.
authors.forename: Enzo
authors.initials: E
authors.lastname: Cadoni
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato SS 554, Bivio per Sestu, 90042, Monserrato, CA, Italy.
authors.forename: Giulio
authors.initials: G
authors.lastname: Ferino
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato SS 554, Bivio per Sestu, 90042, Monserrato, CA, Italy.
authors.forename: Patrizia
authors.initials: P
authors.lastname: Pitzanti
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato SS 554, Bivio per Sestu, 90042, Monserrato, CA, Italy.
authors.forename: Francesco
authors.initials: F
authors.lastname: Secci
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato SS 554, Bivio per Sestu, 90042, Monserrato, CA, Italy.
authors.forename: Claudia
authors.initials: C
authors.lastname: Fattuoni
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Messina Salita Sperone 31, Villaggio S. Agata, 98166, Messina, Italy.
authors.forename: Francesco
authors.initials: F
authors.lastname: Nicolò
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Messina Salita Sperone 31, Villaggio S. Agata, 98166, Messina, Italy.
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Bruno
keywords: ab initio calculations; benzothiophenes; crystal structures; halogen bonding; hydrogen bonding