The reaction of 2,2′-thiodiethanol with chloramine-T (sodium N-chlorotoluene-p-sulphonamide): crystal and molecular structures of 2,2′-(p-tolylsulphonylimino-λ4-sulphanyl)diethanol monohydrate and 2,2′-sulphinyldiethanol

Abstract

Chloramine-T, sodium N-chlorotoluene-p-sulphonamide reacts with 2,2′-thiodiethanol in weakly acidic methanol to yield 2,2′-(p-tolylsulphonylimino-λ⁴-sulphanyl)diethanol monohydrate, MeC₆H₄SO₂NS(CH₂CH₂OH)₂·H₂O (1) and 2,2′-sulphinyldiethanol, OS(CH₂CH₂OH)₂(2), in yields of 23 and 36%, respectively. Crystals of (1) are monoclinic, space group P2₁/c, with a= 7.497(1), b= 16.291(2), c= 11.843(2)Å, β= 92.52(1)°, and Z= 4. The structure was refined from diffractometer data to an R value of 0.033. The structure consists of a hydrogen-bonded array of MeC₆H₄SO₂NS(CH₂CH₂OH)₂ molecules and of water molecules, in which each molecule participates in three hydrogen bonds. Within the MeC₆H₄SO₂NS(CH₂CH₂OH)₂ molecules the S(VI)–N and N–S(IV) bond lengths are 1.602(2) and 1.629(2)Å, and there is a short intramolecular O ⋯ S contact distance of 2.931 Å. The structural data indicate a highly polarised, ylidic, molecule. Crystals of (2) are monoclinic, space group P2₁/n with a= 11.057(4), b= 4.837(2), c= 12.332(4)Å, β= 103.61(3)°, and Z= 4. The crystals are always twinned, but by careful photographic and diffractometer studies a complete structural analysis was possible; R= 0.044 from 1 056 diffractometer data. The structure contains OS(CH₂CH₂OH)₂ molecules which are not maximally extended but which are linked by O–H ⋯ O hydrogen bonds to form centrosymmetric dimers, further linked into infinite spirals. The sulphur atom in (2) is pyramidal [O–Ŝ–C, 105.8(1) and 105.9(1)°, C–Ŝ–C, 96.7(1)°] with an S–O distance of 1.514(3)Å and S–C distances of 1.789(3) and 1.791 (3)Å.