Polysulfonylamine. CLXXXIII. Neues aus der Festkörperchemie der Di(arensulfonyl)amine: Silber(I)‐di(4‐iod‐ benzolsulfonyl)amid, eine Schichtverbindung mit strukturdirigierenden Ag–I–C‐Motiven, und Di(4‐fluorbenzolsulfonyl)amin‐Monohydrat, eine Säulenstruktur mit intracolumnaren Wasserketten und intercolumnaren Wasserstoffbrücken C–H···F–C

• Published in: Zeitschrift für anorganische und allgemeine Chemie (1950) Vol. 634; no. 3; pp. 519 - 528
• Main Authors: Wölper, Christoph, Kandula, Maja, Graumann, Tobias, Hartwig, Sven, Blume, Eike, Jones, Peter G., Blaschette, Armand
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag 01-03-2008
• Subjects: Columnarcompounds; Hydrogen bonding; Layered compounds; Metal‐halocarbon interactions; Silver; Sulfonamides; Water chains
• ISSN: 0044-2313; 1521-3749
• DOI: 10.1002/zaac.200700420

Polysulfonylamines. CLXXXIII. Novel Solid‐State Aspects of Di(arenesulfonyl)amines: Silver(I) Di(4‐iodobenzenesulfonyl)amide, a Layer Compound Displaying Structure‐Directing Ag–I–C Motifs, and Di(4‐fluorobenzenesulfonyl)amine Monohydrate, a Column Structure Exhibiting Intracolumnar Water Chains and Intercolumnar C–H···F–C Hydrogen Bonds
Low‐temperature X‐ray structures are reported for (4‐I–C6H4SO2)2NAg (1, triclinic, $P{\bar 1}$, Z′ = 1) and (4‐F–C6H4SO2)2NH·H2O (2, orthorhombic, Pna21, Z′ = 2). Whereas metal di(arenesulfonyl)amides usually display folded anions (C–S···S′–C′ synperiplanar) and crystallize in lamellar layers, compound 1 has an extended anion (C–S···S′–C′ antiperiplanar) and forms non‐lamellar striated layers in which the ions are connected by Ag–N/Ag–O bonds in one dimension and by Ag–I–C interactions, C–I···O halogen bonds and weak π/π ring interactions in the other dimension. The silver ion adopts a trigonal‐bipyramidal pentacoordination comprising two long axial Ag–O bonds (259 and 261 pm), one short Ag–N bond (228 pm) and two structure‐determining Ag–I bonds (289 and 294 pm, Ag–I–C 107 and 109°). An analysis of Ag···I–C contacts < 340 pm extracted from the Cambridge Structural Database (25 structures, 63 contacts) reveals that the Ag–I–C angles lie between 90 and 110° for contacts < 300 pm, whereas for longer interactions, the directionality rapidly becomes weaker; this result is in keeping with the electrophile/nucleophile model for interactions involving halogen atoms bonded to carbon. In the structure of compound 2, a dimer of two independent water molecules is repeated via glide planes to give a chain in which water 1 acts as a difunctional hydrogen bond donor and water 2 as a difunctional acceptor. The extended disulfonylamine molecules are connected to water 1 by N–H···O(w), to water 2 by O(w)–H···O=S bonds. The resulting supramolecular polymer is a square column that is reinforced by C–H···O=S hydrogen bonds and π/π interactions and bears four one‐dimensional sets of fluorine atoms at the vertices. Dense packing of these columns causes all the fluorine atoms to segregate into parallel tunnels and to form short C–H···F–C intercolumnar contacts strongly suggestive of weak hydrogen bonding (H···F 240–250 pm, C···F 328–346 pm, C–H···F 137–148°).