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NaGe 6 As 6  is a ternary arsenide prepared by reaction of the elements at 650 °C. It crystallizes in a new monoclinic structure type [space group  C 2/ m ,  Z  = 2,  a  = 22.063(2),  b  = 3.8032(4),  c  = 7.2020(8) Å,  β  = 92.7437(15)°] that can be considered to be derived by inserting guest Na atoms between [Ge 6 As 6 ] layers identical to those found in the layered binary arsenide GeAs. An unusual feature in both structures is the presence of ethane-like Ge 2 As 6  units in staggered conformation, with Ge–Ge dumbbells oriented either parallel or perpendicular to the layers. Electronic band structure calculations have shown that the electron excess in NaGe 6 As 6  is accommodated by raising the Fermi level across a 0.6 eV band gap in semiconducting GeAs so that it cuts the bottom of the conduction band, resulting in an  n -doped semiconductor.

NaGe 6 As 6 : Insertion of sodium into the layered semiconductor germanium arsenide GeAs