Premium
Bismuth Polyanions in Solution: Synthesis and Structural Characterization of (2, 2, 2‐crypt‐A) 2 Bi 4 (A = K, Rb) and the Formation of the Laves Phases ABi 2 (A = K, Rb, Cs) from Solution
Author(s) -
Kuznetsov Alexei N.,
Fässler Thomas F.
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200211)628:11<2537::aid-zaac2537>3.0.co;2-a
Subject(s) - isostructural , chemistry , ethylenediamine , crystallography , ternary operation , denticity , bismuth , stereochemistry , inorganic chemistry , crystal structure , organic chemistry , programming language , computer science
The possibility to synthesize and isolate different types of bismuth polyanions by dissolving various intermetallic precursors (binary samples from A‐Bi or ternary samples from A‐A'‐Bi systems, A and A' = K, Rb, Cs) in ethylenediamine or dimethylform amide in the presence of sequestering agents (2, 2, 2‐crypt or 18‐crown‐6) was investigated. The crystals of (2, 2, 2‐crypt‐K) 2 Bi 4 ( 1 ) and (2, 2, 2‐crypt‐Rb) 2 Bi 4 ( 2 ) compound were obtained from such solutions, the latter for the first time, and their structures were determined. The two compounds are isostructural (P1, Z=1, a = 11.052(2) Å, b = 11.370(2) Å, c = 11.698(2) Å, α = 61.85(3) °, β = 82.58(3) °, γ = 81.87(3) °, R 1 = 0.058, wR 2 = 0.149 for 1 and a = 11.181(2) Å, b = 11.603(2) Å, c = 11.740(2) Å, α = 61.96(3) °, β = 81.45(3) °, γ = 82.26(3) °, R 1 = 0.041, wR 2 = 0.109) and contain Bi 4 2— square planar cluster anions and cryptated alkali metal cations. In the case of the presence of 18‐crown‐6 the Laves phases ABi 2 (A = K, Rb, Cs) could be isolated from the solutions. A mechanism for the formation of ABi 2 is proposed.