Polysulfonylamine, CLXXXVIII [1]. Kristallstrukturen von drei Dimethylammonium-di(4-halogenbenzolsulfonyl)amiden (Halogen = Cl, Br, I) und von Dimethylammonium-di(4-methylbenzolsulfonyl)amid: Eine isotype Reihe mit strukturbestimmenden starken Wasserstoffbrücken und beiläufigen Halogenbrücken/ Polysulfonylamines, CLXXXVIII. Crystal Structures of Three Dimethylammonium Di(4-halobenzenesulfonyl)amides (Halogen = Cl, Br, I) and of Dimethylammonium Di(4-methylbenzenesulfonyl)amide: An Isotypical Ser

• Published in: Zeitschrift für Naturforschung. B, A journal of chemical sciences Vol. 65; no. 10; pp. 1258 - 1266
• Main Authors: Wölper, Christoph, Rodríguez-Gimeno, Alejandra, Freytag, Matthias, Jones, Peter G., Blaschette, Armand
• Format: Journal Article
• Language: English
• Published: Verlag der Zeitschrift für Naturforschung 01-10-2010
• Subjects: Halogen Bonding; Halogen-Methyl Exchange; Hydrogen Bonding; Isotypical Structures; Sulfonamides
• ISSN: 0932-0776; 1865-7117
• DOI: 10.1515/znb-2010-1013

The four title compounds, Me
NH
·(4-Cl/Br/I/Me-C
-SO
, were obtained by metathesis of dimethylammonium chloride with the corresponding silver di(arenesulfonyl)amides. The products crystallize isotypically in the monoclinic space group Cc (Z = 4, Z´ = 1). In each structure, the ionic entities associate into hydrogen-bonded chains, which propagate along the c axis of the crystals and consist of alternating cations and anions held together by charge-assisted N
-H· · ·N− and N
- H(· · ·O)
hydrogen bonds. In the three structures containing 4-halobenzenesulfonyl groups, each hydrogen-bonded chain is linked to four neighboring chains by pairs of C-Cl/Br/I· · ·O halogen bonds, which at first sight seem to be the causative factor in the formation of catemeric head-to-tail arrays of anions propagating along the ab face diagonals. On suppressing these halogen bonds by means of halogen-methyl exchange, all essential features of the packing architecture, including the anion headto- tail arrays, are precisely maintained. It may be thus inferred that the halogen bonds occurring in the first three compounds are supportive incidentals, but do not play any structure-determining role.