Structures of ionic di(arenesulfonyl) amides.: 3.: Four sodium di(arenesulfonyl)amides:: Lamellar layers exhibiting short C-H•••O(nitro), C-H•••F-C, or C-I•••I-C interlayer contacts

Low-temperature X-ray crystal structures are reported for NaN(SO2C6H4-4-X)(2) . nH(2)O, where X = NO2 and n = 3 (1, monoclinic, space group P2(1), Z = 2), X = F and n = 3 (2, monoclinic, P2(1)/c, Z = 4), X = F and n = 1 (3, orthorhombic, Peen, Z = 8), or X = I and n = 1 (4, monocli- nic, P2(1)/c, Z = 4). The four compounds are examples of layered inorgano-organic solids where the inorganic component is comprised of metal cations, N(SO2)(2) groups and H2O molecules and the outer regions are formed by the 4-subsituted phenyl rings of the folded anions. In the two-dimensional coordination networks, the cations adopt either an octahedral [Na(O-S)(2)(OH2)(4)] (1, 2) or a distorted monocapped octahedral [NaN(O-S)(4)(OH2)(2)] (3, 4) environment. Taking into account the differing crystal symmetries within the two pairs of compounds, it is remarkable that the trihydrates 1/2 and the monohydrates 3/4 each display chemically identical and nearly isometric Na-O or Na-O/N networks. In the crystal packings, parallel layers are connected through weak hydrogen bonds C-H...O(nitro) (1) or C-H...F (2, 3), or through short "typeI" I...I contacts (4). There is good evidence that the strikingly distinct crystal symmetries in the halogenated homologues 3/4 are determined by the specific complementarity requirements of the interlayer binding centres.