Extraction of a solid with the nominal composition "K2GeBi" with 1,2-diaminoethane (en) in the presence of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo8.8.8hexacosane (crypt-222) afforded the salt K(crypt-222)(4)(Ge4Bi14). The 18-atom Zintl anion (Ge4Bi14)(4-) has a heretofore unknown molecular topology, which can be thought of as the formal condensation product of two E-11(3-) cages along a shared Ge-4 waist. In this way, (Ge4Bi14)(4-) represents the largest and most structurally complex Bi-containing polyanion. We describe its stepwise formation, its geometric and electronic structure, and comment on relative stabilities of isomers with different distributions of the four Ge atoms on the 18 positions that were investigated using DFT calculations.
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