FORMATION AND X-RAY STRUCTURE OF A SILVER-IODIDE BASED POLYMERIC COMPLEX (AG5I6)(N)(PH(3)PCH(2)I)(N)

Compounds [(Ph(3)P)(2)AgS(2)CSR (R = Bu(t), TIPT(2,4,6-triisopropylthi ophenolato))], formed by inserting CS2 into the Ag-S bond in AgSR in t he presence of PPh(3), react with CH(2)I2 to give pale yellow crystals of (Ag5I6)(n)(Ph(3)PCH(2)I)(n), which consist of the polymeric anion (Ag5I6)(-)(n), and the cation (Ph(3)PCH(2))(+). The polyanion (Ag5I6)( n)(-) is composed of alternate I-5-pentagons and Ag-5-pentagons that a re connected by Ag-I bonds along the C axis to form a layered ''pagoda '' structure, in which there exists an unusual stereochemistry of iodi ne. Crystal data: monoclinic, space group P2(1)/c, a 15.004(12) Angstr om, b = 27.19(2) Angstrom, c = 7.898 Angstrom, beta = 97.18(5)degrees, V = 3205(4) Angstrom(3), Z = 4, R = 0.0673 for 2726 observed reflecti ons.