Polysulfonylamine, CLXXIX [1]. Intermolekulare Wechselwirkungen in kristallinen Di(organosulfonyl)aminen. Teil 4 [2]. Di(4-iodbenzolsulfonyl)amin und zwei Methylpyridinium-di(4-iodbenzolsulfonyl)amide: Iod-Sauerstoff vs. Iod-Iod-Wechselwirkungen / Polysulfonylamines, CLXXIX [1]. Intermolecular Interactions in Crystalline Di(organosulfonyl) amines. Part 4 [2]. Di(4-iodobenzenesulfonyl)amine and Two Methylpyridinium Di(4-iodobenzenesulfonyl) amides: Iodine-Oxygen vs. Iodine-Iodine Interactions

Abstract

Low-temperature X-ray structures and crystal packing arrangements are presented for di(4-iodobenzenesulfonyl)amine (4, monoclinic, P21/c, Z ' = 1, isostructural to a previously described dimorph of the corresponding bromo homologue), 2,4-dimethylpyridinium di(4- iodobenzenesulfonyl)amide (5, monoclinic, P21/n, Z ' = 1, isostructural to the corresponding bromo compound), and 3-methylpyridinium di(4-iodobenzenesulfonyl)amide (6, orthorhombic, Pna21, Z '= 1). The packing of 4 consists of non-lamellar layers, in which the molecules are connected by N-H···O hydrogen bonds in one and by Iδ+···Oδ− interactions in the other dimension. Structure 5 involves strands of formula units, whereby the anions form catemers via Iδ+···Oδ− interactions and the cations are isotactically connected to the anion backbone by an N+ -H(···O)2 three-centre bond. Short I···I contacts are absent from structures 4 and 5. In contrast, structure 6 displays lamellar layers comprising an inner lamella of cations and N(SO2)2 groups connected by an N+ -H···N− two-centre bond, and peripheral regions of 4-iodophenyl rings. Thus, the iodine atoms are efficiently shielded from the oxygen atoms, but in appropriate positions to form Iδ+···Iδ− interlayer contacts. Each structure is reinforced by a parallel-displaced π···π stacking arrangement of aromatic rings and an abundance of short C-H···A contacts (A = acceptor).