Reactions of bismuth iodide with ammonium, phosphonium, and bismuthonium salts

Abstract

The reactions of ammonium, phosphonium, and bismuthonium salts with bismuth iodide were used to synthesize a series of complex compounds with bismuth-containing anions: [(HOC2H4)3NH]+ 4[Bi4I16]4−, [Ph3EtP] 3 + [Bi2I9]3−, and [Ph4Bi] 3 + [Bi5I18]3−. X-ray diffraction data show that the nitrogen atoms in the two types of crystallographically independent cations of the nitrogen-containing complex possess a distorted tetrahedral coordination [the CNC angles are 110.3(9)°–113.2(9)°]. In the tetranuclear centrosymmetric [Bi4I16]4− anion, the bismuth atoms have an octahedral coordination: Two types of groups, BiI2 and BiI3, are bound with one another by four μ2-and two μ3-iodine bridges (the Bi-I-μ2, Bi-I-μ3, and Bi-I-μ1 distances are 3.1296(10), 3.2808(8); 3.3210(8) and 2.8670(8)–2.9108(9) A, respectively). The coordination of the phosphorus atom in the [Ph3EtP]+ cations of the phosphorus-containing complex is close to tetrahedral (the CPC angles are 107.5°–114.1°). In the binuclear [Bi2I9]3− anions, the bismuth atoms have an octahedral coordination. The axial I-Bi-I angles are 167.52(2)°, 169.84(2)°, and 174.97(2)°. The terminal BiI3 fragments [Bi2-I7,8,9 2.9238(7), 2.9236(7), and 2.9522(7) A] are in the eclipsed conformation.