ISSN:
0044-2313
Keywords:
Iodobismuthate
;
[Bi2I7]-, [Bi3I11]2-, [Bi8I28]4-, crystal structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesis and Crystal Structures of (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7], and (Et3PhN)2[Bi3I11] - Bismuth Iodo Complexes with Isolated and Polymeric AnionsSolutions of BiI3 in methanol react with NaI and (nBu4N)(PF6) or (Et3NPh)(PF6) to form anionic bismuth iodo complexes (nBu4N)[Bi2I7] 1 and (Et3PhN)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 (Ph4P)(PF6) in methanol yields (Ph4P)4[Bi8I28] 3. The anions of 1-3 consist of edge-sharing BiI6 octahedra.(nBu4N)[Bi2I7] 1: Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 106 pm3;(Et3PhN)2[Bi3I11] 2: Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 106 pm3;(Ph4P)4[Bi8I28] 3: Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 106 pm3.
Notes:
BiI3 reagiert in methanolischer Lösung mit NaI und (nBu4N)(PF6) bzw. (Et3PhN)(PF6) zu (nBu4N)[Bi2I7] 1 und (Et3PhN)2[Bi3I11] 2 mit Iodobismutatanionen. In 1 liegen unendliche Stränge von über gemeinsame I-Atome verknüpften Bi4I16-Einheiten vor. In 2 bilden verkettete Bi6I24-Einheiten polymere Anionen. Führt man die Umsetzung von BiI3 mit (Ph4P)(PF6) ohne NaI durch, so kristallisiert aus Methanol (Ph4P)4[Bi8I28] 3. Die Anionen von 1-3 bestehen aus kantenverknüpften BiI6-Oktaedern.(nBu4N)[Bi2I7] 1: Raumgruppe I2/m (Nr. 13), a = 1 082,3(5), b = 2 597,1(13), c = 1 206,1(6) pm, β = 93,17(2)°, V = 3 385(3) · 106 pm3;(Et3PhN)2[Bi3I11] 2: Raumgruppe P1 (Nr. 2), a = 1 283,5(6), b = 1 345,9(7), c = 1 546,3(8) pm, α = 83,87(2), b = 74,24(2), γ = 68,26(2)°, V = 2 388(2) · 106 pm3;(Ph4P)4[Bi8I28] 3: Raumgruppe P1 (Nr. 2), a = 1 329,3(4), b = 1 337,0(4), c = 2 193,1(5) pm, α = 104,20(2), β = 99,73(2), γ = 100,44(2)°, V = 3 622(2) · 106 pm3.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19956211212
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