Halogen and Hydrogen Bonding Benzothiophene Diol Derivatives: A Study Using ab initio Calculations and X‐Ray Crystal Structure Measurements

ChemistryOpen

Prof. Enzo Cadoni³  Dr. Giulio Ferino¹  Dr. Patrizia Pitzanti¹  Dr. Francesco Secci¹  Dr. Claudia Fattuoni¹  Prof. Francesco Nicolò² 

[1] Dipartimento di Scienze Chimiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, Monserrato, CA, Italy;Dipartimento di Scienze Chimiche, Università degli Studi di Messina, Messina, Italy;E-mail address: 关键词: ab initio calculations;    benzothiophenes;    crystal structures;    halogen bonding;    hydrogen bonding;   

DOI  :  10.1002/open.201402087

来源: Wiley

【 摘 要 】

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.

【 授权许可】

CC BY-NC-ND   
© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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