The Role of Organic Fluorine in the Supramolecular Assembly of Halogenated β-Hydroxysulphoxides Diastereomers

A series of optically pure γ-halogenated β-hydroxysulphoxides containing two stereogenic centers have been prepared, and the X-ray crystal structures have been determined. The conformational behavior in the solid state and the crystal packing of the different β-hydroxysulphoxide diastereoisomers have been determined. The intermolecular and intramolecular interactions present have been studied in both halogenated and nonhalogenated β-hydroxysulphoxides to establish the influence of the halogen atom in the supramolecular structure. The main intermolecular hydrogen bond OH···OS is always present and produces molecular chains. Self-assembly of these chains includes weak CH···F, C−F···F−C, and C−F···π interactions. While the C−F···F−C and C−F···π interactions present do not appear to drive the crystal packing, partially fluorinated methyl groups induce C−H···F−C hydrogen bridges within C_F−H···F−C crystal homosynthons that clearly change the packing mode.