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Crystallization of silver di(4-methylbenzenesulfonyl)amide [Ag(MA)], silver di(4-nitrobenzenesulfonyl) amide [Ag(NA)], silver di(4-bromobenzenesulfonyl)amide [Ag(BA)] or silver di(4-fluorobenzenesulfonyl) amide [Ag(FA)] from acetonitrile solutions under slightly different conditions afforded single crystals of the following complexes, which were structurally authenticated by X-ray diffraction at low temperatures: (MeCN)Ag(MA) (1, triclinic, space group P1, Z’ = 1), (MeCN) 2 Ag(NA) (2, monoclinic, P2 1 /c, Z’ = 1), (MeCN) 2 Ag(BA) (3, monoclinic, P2 1 /c, Z’ = 1), (MeCN) 2 Ag(BA) (4, monoclinic, P21/c, Z’ = 2), and [(MeCN) 3 Ag][Ag(FA) 2 ]・MeCN (5, triclinic , Z’ = 1). In each structure, the inner coordination sphere of silver is formed by the ligand nitrogen atoms, leading to a linear NAgN core for the molecular complex 1 and the complex anion of 5, or to a trigonal planar AgN 3  core for the molecular complex 2, the molecular polymorphs 3 and 4, and the complex cation of 5. The flexible di(arenesulfonyl)amide ligands adopt extended pseudo-C 2  symmetric conformations in 1, 2 and 5, but folded pseudo-mirror symmetric conformations in 3 and 4. The molecules of 1 are associated into inversion-symmetric dimers via a short Ag・ ・ ・O contact; the dimers form stacks by translation along the a axis, causing the silver ions to segregate in zigzag chains. The arrangement of the molecules in 2 is controlled mainly by a centered C-H・ ・ ・Ph hydrogen bond, a dipolar nitro-nitro and a dipolar nitro-sulfonyl interaction, giving rise to layers oriented parallel to the bc plane. The packing motifs of polymorphs 3 and 4 are very similar. Both forms consist of layers in which the molecules act as 4-connecting nodes in a network based upon C-Br・ ・ ・O=S halogen bonds. In the Z’ = 1 structure of 3, the layers are generated by 2 l  screw axes and display one short and one long halogen bond, whereas in the Z’ = 2 structure of 4, the layers are realized by glide planes and are based on four independent halogen bonds that are all reasonably short. The packing of 5 exhibits alternating layers comprised of complex anions or of complex cations and acetonitrile solvent molecules, respectively. This Z’ = 2 structure may be viewed as a kinetic polymorph of a more symmetric Z’ = 1 crystal

zeitschrift für naturforschung b

Polysulfonylamine, CLXXXVII [1]. Strukturvielfalt in (Acetonitril)silber(I)-di(arensulfonyl)amiden: Zwei Molek¨ulkristalle mit Z'= 1, ein Ionenkristall mit Z' = 2 und zwei auf Halogenbr¨ucken C–Br···O=S beruhende molekulare Polymorphe mit Z' = 1 beziehungsweise Z' = 2 in der gleichen Raumgruppe / Polysulfonylamines, CLXXXVII. Structural Diversity in (Acetonitrile)silver(I) Di(arenesulfonyl)- amides: Two Molecular Z' = 1 Crystals, an Ionic Z' = 2 Crystal, and Two Molecular Polymorphs Based upon C–Br· · ·O=S Halogen Bonds and Featuring Z' = 1 or Z' = 2 in the Same Space Group