Benzothienoiodolium Cations Doubly Bonded to Anions via Halogen–Chalcogen and Halogen–Hydrogen Supramolecular Synthons

The simultaneous binding of a molecular entity through two interactions is a frequently pursued recognition mode due to the advantages it offers in securing molecular self-assembly. Here, we report how the planarity of the benzothienoiodolium (BTI) cation allows for preorganizing in the cation plane the hydrogen, halogen, and chalcogen bonds (HBs, XBs, and ChBs, respectively) formed by the phenyl hydrogen, iodolium iodine, and thienyl sulfur. Crystallographic analyses of some BTI salts show how this interaction coplanarity enables their coupling to point toward a single anion that is coordinated via the supramolecular and heteroditopic synthon XB/HB or XB/ChB, the latter observed here for the first time. These synthons adopt a Janus-like arrangement around iodine. Crystallographic information suggests that interactions of the synthons act synergistically, e.g., when resulting in the unusually short ChBs formed by the thienyl sulfur. Determination of the molecular electrostatic potential, Bader’s quantum theory of “atoms-in-molecules” analysis, and natural bond orbital investigations give information on the nature and energetic aspects of the short contacts observed in crystals.