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The ternary complexes 18C6 · 4H 2 O · 2HN(SO 2 Ph) 2  (3) and 18C6 · 2H 2 O · 2HN(SO 2 C 6 H 4⁻ 4-F) 2  (4) were obtained by co-crystallization of 18-crown-6 (18C6) with the appropriate di(arenesulfonyl)amine from aqueous solutions and characterized by low-temperature X-ray diffraction. The crystal structures consist of monomeric formula units displaying crystallographic C i , symmetry for 3 (monoclinic, space group C2/c) and approximate C i  symmetry for 4 (monoclinic, space group P2 1 /c). In 3, hydrogen-bonded water dimers H 2 O ··· H - OʹH (H ··· O 182 pm) act as links between the two di(benzenesulfonyl)amine molecules and the crown ring. Each dimer accepts an N - H ··· Oʹ bond (H ··· Oʹ 194 pm) and is attached by its remaining protons to a set of three alternate crown oxygen atoms O c  (OʹH ··· O c  202, OH ··· O c  207 and 208 pm). The overall topological features of 3 strongly resemble those of the known supramolecule 18C6 ­· 2MeOH · 2HN(SO 2 Ph) 2 . In 4, each amine molecule is N - H ··· O bonded to a water monomer (H ··· O 184 and 187 pm) that is connected to two O c  atoms of the crown (OH ··· O c  202 - 210 pm). The crown rings of both complexes adopt the frequently observed pseudo D 3d  symmetry. In the crystal of the pure compound HN(SO 2 C 6 H 4⁻ 4-F) 2  (5; monoclinic, space group C2/c), the molecules are associated into chains in the z direction through a relatively weak N - H ··· Oʹ bond (H ··· Oʹ 215 pm). The conformations of the HN(SO 2 R) 2  entities in 3, 4, 5 and some related solids are compared and discussed.

zeitschrift für naturforschung b

Polysulfonylamine, LXIV. Wasser-Dimere und Wasser-Monomere als Bindeglieder in Komplexen von 18-Krone-6 mit ungeladenen aciden Molekülen: Synthese und Kristallstrukturen von (CH 2 CH 2 O) 6  · 4H 2 O · 2HN(SO 2 Ph) 2  und (CH 2 CH 2 O) 6  · 2H 2 O · 2HN(SO 2 C 6 H 4⁻ 4–F) 2  sowie Struktur des freien HN(SO 2 C 6 H 4⁻ 4–F) 2  / Polysulfonylamines, LXIV Water Dimers and Water Monomers as Links in 18-Crown-6 Complexes with Uncharged Acidic Molecules: Syntheses and Crystal Structures of  (CH 2 CH 2 O) 6  · 4H 2 O · 2HN(SO 2 Ph) 2  und (CH 2 CH 2 O) 6  · 2H 2 O · 2HN(SO 2 C 6 H 4⁻ 4-F) 2  and Structure of Free HN(SO 2 C 6 H 4⁻ 4–F) 2