Unexpectedly low affinity of aromatic disulfides for π-stacking interactions of the arene–polyfluoroarene type

1,2,3,4,5-Pentafluorodiphenyl disulfide (1) was synthesized from C6F5SCl and C6H5SSiMe3 in quantitative yield. The homo-crystals of disulfide 1 and co-crystals of 1,1′,2,2′,3,3′,4,4′,5,5′-decafluorodiphenyl disulfide (2) with naphthalene (stoichiometry 1:2, complex 4) and diphenyl disulfide (3) with octafluoronaphthalene (stoichiometry 2:1, complex 5) were prepared followed by XRD characterization. In the crystal lattice of 1, face-to-face and face-to-edge PhH/PhF orientations of neighboring rings were observed together with face-to-edge PhF/PhF orientations. For the face-to-face PhH/PhF orientation, the large offset of PhH and PhF groups excludes their π-stacking interaction which is very non-typical of the field. The crystal lattice of 4 reveals standard π-stacking interactions of the arene–polyfluoroarene type. While in the lattice of 4 each PhF ring interacts alternating with naphthalenes, in 5 two disulfides 3 are bridged by one octafluoronaphthalene with only one of the PhH rings of each disulfide interacting with the polyfluoroarene π-system. The large offset of neighboring molecules excludes however their π-stacking interactions in complex 5. An attempt to prepare 2/3 co-crystals failed.