The Reduced Nitridogermanates(III) Ca6[Ge2N6] and Sr6[Ge2N6] with Ge−Ge Bonds

Abstract

The first nitridogermanates(III) Ca6[Ge2N6] and Sr6[Ge2N6] 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 Ca6[Cr2N6]H in space group R (Formula presented.). They feature unprecedented, mutually isolated, ethane-like [GeIII2N6]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 Ca6[Ge2N6] and 0.2 eV for Sr6[Ge2N6].