Synthesis and Single Crystal X‐ray Characterization of Sn5Bi33−

Abstract 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@[18crown‐6] 3 Sn 5 Bi 3 ⋅ 7NH 3 , K@[18crown‐6] 1.5 Cs@[18crown‐6]Cs@([18crown‐6) 2 ] 0.5 Sn 5 Bi 3 ⋅ 3.98NH 3 , Na@DB[18crown‐6] 2 Na(NH 3 ) 6 Sn 5 Bi 3 ⋅ 14NH 3 and Cs@[2.2.2crypt] 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.