Conformational preferences and supramolecular aggregation in 2-nitrophenylthiolates: Disulfides and thiosulfonates

Article abstract of DOI:10.1107/S0108768100007114

In each of the asymmetrically substituted disulfides 2-nitro-4′-methyldiphenyl disulfide, C₁₃H₁₁NO₂S₂ (1), 2-nitro-4′-chlorodiphenyl disulfide, C₁₂H₈ClNO₂S₂ (2), 2,4-dinitro-4′-methyldiphenyl disulfide, C₁₃H₁₀N₂O₄S₂ (3), and 2,4-dinitrophenyl-2′-methoxycarbonylmethyl disulfide, C₉H₈N₂O₆S₂ (4), and in both of the symmetrically substituted disulfides bis(2-nitrophenyl) disulfide, C₁₂H₈N₂O₄S₂ (5), and bis(2-nitro-4-trifluoromethylphenyl) disulfide, C₁₄H₆F₆N₂O₄S₂ (6), the 2-nitro groups are essentially coplanar with the adjacent aryl ring and the S atom remote from the nitrated aryl ring is also essentially coplanar and transoid to the nitro group. In S-(2-nitrophenyl) 2-nitrobenzene thiosulfonate, C₁₂H₈N₂O₆S₂ (7), which contains three independent molecules in the asymmetric unit, all six of the independent nitro groups are twisted out of the plane of the adjacent aryl rings. The crystal structures of (1)-(3) contain isolated molecules, that of (4) contains centrosymmetric dimers held together by C-H...O hydrogen bonds, while in the structures of (5)-(7), respectively, the C-H...O hydrogen bonds generate one-, two-and three-dimensional arrays. The interplay between molecular conformation and supramolecular aggregation is discussed.