Exploring the rare S—H…S hydrogen bond using charge density analysis in isomers of mercaptobenzoic acid

Experimental and theoretical charge density analyses on isomers of mercaptobenzoic acid have been carried out to quantify the hydrogen bonding of the hitherto less explored thiols, to assess the strength of the interactions using the topological features of the electron density. The electron density study offers interesting insights into the nature of the S—H…S interaction. The interaction energy is comparable with that of a weak hydrogen bond. The strength and directionality of the S—H…S hydrogen bond is demonstrated to be mainly due to the conformation locking potential of the intramolecular S…O chalcogen bond in 2‐mercaptobenzoic acid and is stronger than in 3‐mercaptobenzoic acid, which lacks the intramolecular S…O bond. The para‐substituted mercaptobenzoic acid depicts a type I S…S interaction. The appearance of an elusive S—H…S hydrogen bond with the S atom acting as a donor in 2‐, 3‐mercaptobenzoic acids has been analysed based on charge density calculations. The importance of the locking potential provided by an intramolecular S…O chalcogen bond is highlighted.