Iodoplumbates with polymeric anions - Synthesis 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 crystallization with large cations yield iodoplumbate complexes with various 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 PbI(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: Space 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).