POLYSULFONYL AMINES .57. 2 SILVER(I) DI(ORGANOSULFONYL)-AMIDES WITH SILVER-ETA-2-ARYL OR SILVER-SILVER INTERACTIONS - CRYSTAL-STRUCTURES OF SILVER DI(BENZENESULFONYL)AMIDE-WATER (1/0.5) AND OF ANHYDROUS SILVER DI(4-TOLUENESULFONYL)-AMIDE

Crystals of [(PhSO2)2NAg(mu-H2O)AgN(SO2Ph)2]n (5) and [(4-Me-C6H4SO2)2NAgAgN(SO2C6H4-4-Me)2]n (6) were obtained from aqueous solutions. The crystallographic data are for 5 (at -95-degrees-C): monoclinic, space group C2/c, a = 2743.8(5), b = 600.49(12), c = 1664.5(3) pm, beta = 101.143(15)-degree, V = 2.6908 nm3, Z = 8, D(x) = 2.040 Mg m-3; for 6 (at -130-degrees-C): monoclinic, space group P2(1)/n, a = 1099.8(5), b = 563.7(3), c = 2487.7(13) pm, beta = 99.68(4)-degrees, V = 1.5203 nm3, Z = 4, D(x) = 1.888 Mg m-3. In both crystals, the silver atom has a fivefold coordination. The structure of 5 displays [(RSO2)2N-Ag(mu-H2O)Ag'-N(SO2R)2] units with Ag-N 226.9 pm, Ag-O 236.7 pm and Ag-O-Ag' 95.3-degrees; the water oxygen lies on a crystallographic twofold axis. These units are extended to two fused six-membered rings by intramolecular dative bonds (S)O--> Ag' and S(O)' --> Ag (249.3 pm). One phenyl group from each (PhSO2)2N moiety is eta2-coordinated with its p-C and one m-C atom to a silver atom of a neighbouring bicyclic unit related by a glide plane to form infinite parallel strands (p-C-Ag 252.2, m-C-Ag 263.9 pm). The strands are interconnected into parallel layers through hydrogen bonds between H2O and sulfonyl oxygens [O...O(S) 276.1 pm]. These layers consist of a hydrophilic inner region containing metal ions, N(SO2)2 fragments and water molecules, and hydrophobic surfaces formed by phenyl groups. The structure of 6 features centrosymmetric [(RSO2)2N-Ag-Ag'-N(SO2R)2] units with two intramolecular dative bonds (S)O --> Ag' and (S)O' --> Ag (Ag-Ag' 295.4, Ag-N 226.0, Ag-O 229.4 pm). These bi-pentacyclic units are associated by translation parallel to y into infinite strands by two dative (S)O --> Ag bonds per silver atom (Ag-O 243.2 and 253.3 pm).