IODOPLUMBATES WITH POLYMERIC ANIONS - SYN THESIS AND CRYSTAL-STRUCTURES OF [NA-3(OCME(2))(12)][PB4I11(OCME(2))], (PH(4)P)(2)[PB5I12], AND (PH(4)P)(4)[PB15I34(DMF)(6)]

Reactions of PbI2 with NaI in polar organic solvents followed by cryst allization with large cations yield iodoplumbate complexes with variou s compositions and structures. [Na-3(OCMe(2))(12)][Pb4I11(OCMe(2))] 3, (Ph(4)P)(2)[Pb5I12] 4 and (Ph(4)P)(4)[Pb15I34(dmf)(6)] 7 contain one- dimensional infinite anionic chains of face- or edge-sharing PbI6 or P bI(5)L (L = acetone, DMF) octahedra. [Na-3(OCMe(2))(12)][Pb4I11(OCMe(2 ))] 3: Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608. 3(8) pm, alpha = 74.64(4), beta = 70.40(4), gamma = 85.24(4)degrees, V = 2071(2). 10(6) pm(3); (Ph(4)P)(2)[Pb5I12] 4: Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5)pm, beta = 96.240(13) degrees, V = 6885(2). 10(6) pm(3); (Ph(4)P)(4)[Pb15I34(dmf)(6)] 7: Spa ce group P2(1)/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, beta = 114.432(13)degrees, V = 9678(3). 10(6) pm(3).