Synthesis and crystal structures of (Ph(4)P)(4)[Bi8I28], ((n)Bu(4)N)[Bi2I7], and (Et(3)PhN)(2)[Bi3I11] - Bismuth Iodo complexes with isolated and polymeric anions

Solutions of BiI3 in methanol react with NaI and ((n)Bu(4)N)(PF6) or (Et(3)NPh)(PF6) to form anionic bismuth iodo complexes ((n)Bu(4)N)[Bi2I7] 1 and (Et(3)PhN)(2)[Bi3I11] 2. In 1 Bi4I16 units, and in 2 Bi6I24 units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI3 with (Ph(4)P)(PF6) in methanol yields (Ph(4)P)(4)[Bi8I28] 3. The anions of 1-3 consist of edge-sharing BiI6 octahedra. ((n)Bu(4)N)[Bi2I7] 1: Space group I2/m (No. 13), a = 1082.3(5), b = 2597.1(13), c = 1206.1(6)pm, beta = 93.17(2)degrees, V = 3385(3). 10(6)pm(3); (Et(3)PhN)(2)[Bi3I11] 2: Space group P (1) over bar (No. 2), a = 1283.5(6), b = 1345.9(7), c = 1546.3(8)pm, alpha = 83.87(2), beta = 74.24(2), = 68.26(2)degrees V = 2388(2).10(6)pm(3); (Ph(4)P)(4)[Bi8I28] 3: Space group P1 (No.2), a=1329.3(4), b = 1337.0(4), c = 2193.1(5) pm, alpha = 104.20(2), beta = 99.73(2), gamma = 100.44(2)degrees, V = 3 622(2).10(6)pm(3).