Interaction in molecular crystals, 162. Di(arylsulfonyl)amines - Ligands for lipophilically wrapped polyion aggregates with Cs-circle plus-layers of variable thickness

Di(arylsulfonyl)amides are presented as novel anionic ligands for polycatio n aggregates. Starting from the structures of Ag+ and Na+ salts registered in the Cambridge Structural Database, the largest alkali cation Cs+ with hi gh coordination number has been selected and in extreme low gradient crysta llisation single crystals of both cesium-di(benzenesulfonyl)amide and cesiu m-di(4-toluenesulfonyl)amide were grown. Their structure determinations rev ealed that both polymeric salts contain cation layers (Cs+)(infinity.) The one lipophilically wrapped by di(benzenesulfonyl)amide ligands exhibits hex agonal (Cs+)(6) subunits, whereas the methyl-substituted di(4-toluenesulfon yl)amide ligands of the other one are interspersed within (Cs+)(infinity) l ayers. The resulting lipophilically wrapped sheets with Cs+ cations of ten- and twelve-fold coordination to disulfonyl O and C centers vary in their o verall thickness of 1.77 nm and 1.39 nm because the toluene substituents in the thinner one are tilted. The remarkable effects caused by the 4-methyl substitution of the phenyl rings determine the structures of the parent di( arylsulfonyl)amines as well: Contrary to the polymeric phenyl substituted d erivative, the toluene homologue crystallizes in dimers. The single crystal s grown of the closely related di(arylsulfonyl)amides with or without para methyl substituents and their poly(Cs+) aggregates without any solvent incl usion show hitherto unknown structural motifs and, therefore, further impro ve our knowledge of alkali salt self-organisation phenomena in crystals.