S–(CF3)Thianthrenium and S–(CF3)dibenzothiophenium cations form potent chalcogen bonds (ChBs) with [Mo(CO)5CN]−, yielding S2N2 supramolecular motifs. Crystal structures reveal shorter S⋯N contacts opposite the CF3 group compared to the aryl substituents. The energetic features of the ChBs have been studied using DFT calculations demonstrating the structure guiding role of ChBs.
