Unusually large 254 Atoms Counter‐Ion for 5 Atoms [Ge5]2– Cluster.

Abstract. With the attempt to synthesize Nb‐enclosed germanium Zintl cluster ion in ethylenediamine (en) / toluene solution, the reaction of K4Ge9/Na4Ge9 with Nb(mes)2 (mes = mesitylene) gives unexpected 18‐crown‐6 cleavage product of [K14Na2(NbO2)2(C8H16O5)8](Ge5) (en)·solv in the form of very air‐sensitive, light‐brown, plate‐like crystals. This unique compound crystallizes in monoclinic Pn (No. 7) space group, the cleavage of crown linked the 14 potassium, 2 sodium, and 2 niobium atoms into the bulky 2+ charged cation, which balances the [Ge5]2– anion. This compound represents the rare example of heteronuclear metal alkoxide / Zintl ion hybrid. [ABSTRACT FROM AUTHOR]