The Reduced Nitridogermanates(III) Ca(6)[Ge(2)N(6)] and Sr(6)[Ge(2)N(6)] with Ge−Ge Bonds

The first nitridogermanates(III) Ca(6)[Ge(2)N(6)] and Sr(6)[Ge(2)N(6)] were synthesized from sodium flux and structurally characterized by powder and single crystal X‐ray diffraction, respectively. They crystallize isostructurally to each other and homeotypic to Ca(6)[Cr(2)N(6)]H in space group R [Formula: see text] . They feature unprecedented, mutually isolated, ethane‐like [Ge(III) (2)N(6)](12−) anions in a staggered conformation. The compounds are semiconductors according to resistivity measurements and electronic structure calculations, yielding band gaps of 1.1 eV for Ca(6)[Ge(2)N(6)] and 0.2 eV for Sr(6)[Ge(2)N(6)].