Bismuth Polyanions in Solution: Synthesis and Structural Characterization of (2, 2, 2‐crypt‐A)2Bi4 (A = K,Rb) and the Formation of the Laves Phases ABi2 (A = K,Rb, Cs) from Solution |
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Authors: | Alexei N. Kuznetsov,Thomas F. Fä ssler |
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Abstract: | 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)2Bi4 ( 1 ) and (2, 2, 2‐crypt‐Rb)2Bi4 ( 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) °, R1 = 0.058, wR2 = 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) °, R1 = 0.041, wR2 = 0.109) and contain Bi42— square planar cluster anions and cryptated alkali metal cations. In the case of the presence of 18‐crown‐6 the Laves phases ABi2 (A = K, Rb, Cs) could be isolated from the solutions. A mechanism for the formation of ABi2 is proposed. |
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Keywords: | Bismuth polyanions Zintl ions Clusters Crystal structure Laves phases |
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