Structures of ionic di(arenesulfonyl)amides.: 4.: Cross-linking lamellar layers by O-H•••O hydrogen bonds:: Structures of M⊕⊖N(SO2C6H4-4-COOH)2 (M⊕ = K⊕, Rb⊕, Cs⊕)

Syntheses and low-temperature X-ray crystal structures are reported for (MN)-N-I(SO2C6H4-4-COOII)(2), where M = K (monoclinic, space group P2(1)/c, Z = 4, Z' = 1), M = Rb (monoclinic, P2(1), Z = 4, Z' = 2), or M = Cs (monoclinic, P2(1)/c, Z = 4, Z' = 1), The three compounds are examples of layered inorgano-organic solids where the inorganic component is comprised of metal cations and N(SO2)(2) groups and the outer regions are formed by the 4-carboxy substituted phenyl rings of the folded anions. In the two-dimensional coordination networks, K-circle plus and Cs-circle plus adopt irregular and chemically distinct [MN1O7] octacoordinations, whereas the independent Rb-circle plus cations attain irregular nonacoordinations of type [RbN2O7] or [RbO9] respectively. The crystal packings of the compounds are governed by self-assembly of parallel layers through exhaustive hydrogen bonding between carboxylic acid groups, resulting in a dense array of cyclic (COOH)(2) motifs within the interlamellar regions.