Synthesis and Single Crystal X‐ray Characterization of [Sn₅Bi₃]³⁻

The extraction of the solid state materials “M SnBi x “ ( M / x =Cs/1, Na/3) in liquid ammonia in the presence of different chelating agents yielded the novel Zintl anion [Sn 5 Bi 3 ] 3− . The anion could be crystallized and characterized via single crystal X‐ray diffraction in [Cs@[18]crown‐6] 3 [Sn 5 Bi 3 ] ⋅ 7NH 3 , [K@[18]crown‐6] 1.5 [Cs@[18]crown‐6][Cs@([18]crown‐6) 2 ] 0.5 [Sn 5 Bi 3 ] ⋅ 3.98NH 3 , [Na@DB[18]crown‐6] 2 [Na(NH 3 ) 6 ][Sn 5 Bi 3 ] ⋅ 14NH 3 and [Cs@[2.2.2]crypt] 6 [Sn 5 Bi 3 ] 2 ⋅ 9.53NH 3 . The [Sn 5 Bi 3 ] 3− anion is further investigated by mass spectrometry and DFT calculations to confirm its composition and elucidate its electronic structure.