Oxidative Coupling of Ge94‐ Zintl Anions ‐ Hexagonal Rod Packing of Linear [Ge9=Ge9=Ge9=Ge9]8‐

The compound K(18‐crown‐6)]₈Ge₉=Ge₉=Ge₉=Ge₉] ˙ 8en ( 1 ) featuring a Ge₉=Ge₉=Ge₉=Ge₉]^8‐cluster anion was synthesized from K₄Ge₉ for the first time. The X‐ray single crystal analysis shows that, in many respects such as bond connection and packing style, compound 1 is quite different from the previously reported compounds Rb(18‐crown‐6)]₈Ge₉=Ge₉=Ge₉=Ge₉] ˙ 2en ( 2 ) and Rb(18‐crown‐6)]₈Ge₉=Ge₉=Ge₉=Ge₉] ˙ 6en ( 3 ). Crystal packing of 1 gives strong indications that the highly charged nano‐rods self assembly in a hexagonal rod packing.