Molecular complexes of octafluoronaphthalene with catenated chalcogen–nitrogen compounds C6H5–X–NSN–SiMe3 (X = S, Se)

Mismatched molecular 1:1 complexes of C10F8 with catenated chalcogen–nitrogen compounds C6H5–X–NSN–SiMe3 (X = S, Se) were prepared and characterized by X-ray crystallography. The complexes provide examples of structurally non-rigid polyheteroatom molecules involved in non-covalent arene–polyfluoroarene π-stacking interactions. In going from homocrystals to the co-crystals, the molecular Z, E configuration of the catenated compounds changes from noticeably non-planar to perfectly planar, i.e. C10F8 acts as “molecular iron”. On the other hand, C10H8 does not produce complexes with C6F5–X–NSN–SiMe3 (X = S, Se).