Herein, we report the crystal structures of the antimicrobial agent diiodomethyl-p-tolylsulfone and of three halogen bonded co-crystals demonstrating that the bioactive moiety -SO2CHI2 can function as a quite effective halogen bond based motif in the solid state and in solution, namely demonstrating that α-iodosulfones may become a new entry in the quite small group of alkyl-iodides functioning as reliable halogen bond-donors.