Polysulfonylamine, LXIII [1] / Polysulfonylamines, LXIII [1]

Abstract

Complexes of Uncharged Molecules, Crystal StructureThe thermally labile ternary complexes 18C6 · 2MeOH · 2 HN(SO2Ph)2 (2a), 18C6 · 2MeOH · 2HN(SO2–C6H4-4-Cl)2 (2b) and 18C6 · 3 MeOH · HN(SO2Me)(SO2Ph) (3) were obtained by co-crystallization of 18-crown-6 (18C6) and the appropriate di(organosulfonyl)amine from methanolic solutions and characterized by low-temperature X-ray diffraction. The crystal structures of 2a (monoclinic, space group P21/n) and 2b (triclinic, space group P1̄) consist of monomeric, centrosymmetric formula units. Each di(arenesulfonyl)-amine molecule is connected to a methanol molecule by an N-Η ··· O hydrogen bond (H ··· O 203 pm in 2a, 190 pm in 2b). The methanol molecules are linked to three alternate crown oxygen atoms via one O-Η ··· O(crown) hydrogen-bond and two weaker C-Η ··· O(crown) interactions (OH ··· O 201 pm in 2a, 186 pm in 2b; CH ··· O 236 and 247 pm in 2a, 240 and 254 pm in 2b); two symmetry-related oxygen atoms of the crown are involved in O-Η ··· O and the other four in C-Η ··· O interactions. The structure of complex 3 (monoclinic, space group P21) is built of infinite chains parallel to [101]. The methyl group of the di(organosulfonyl)amine is bonded by C-Η ··· O(crown) interactions to a set of three alternate oxygen atoms of the cyclic polyether (H ··· O 228, 245 and 247 pm). Starting from the acidic NH function, a sequence of three methanol molecules catenated by hydrogen bonds curves around the bulky phenyl group and links with its terminal MeOH through one O-H ··· O(crown) and two C-Η ··· O(crown) bonds to the second set of alternate oxygen atoms in the adjacent symmetry-equivalent crown (OH ··· O 193 pm, CH ··· O 248 and 250 pm). Within the chain sequence N-H ··· O′(Me)H′ ··· O″(Me)H″ ··· O‴(Me)H, the H ··· O distances are H ··· O′ 184, H′ ··· O″ 189 and H″··· O‴ 183 pm. In the structures of 2a, 2b and 3, the crown rings adopt the frequently observed D3d pseudosymmetry.