Na3AuN2 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to two equivalent N(1) atoms. In the second Na site, Na(2) is bonded to four equivalent N(1) atoms to form a mixture of distorted edge and corner-sharing NaN4 tetrahedra. Au(1) is bonded in a distorted linear geometry to two equivalent N(1) atoms. N(1) is bonded to one Na(1), four equivalent Na(2), and one Au(1) atom to form a mixture of edge and corner-sharing NNa5Au octahedra. The corner-sharing octahedral tilt angles range from 0-80°.
Na3AuN2 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to two equivalent N(1) atoms. Both Na(1)-N(1) bond lengths are 2.26 Å. In the second Na site, Na(2) is bonded to four equivalent N(1) atoms to form a mixture of distorted edge and corner-sharing NaN4 tetrahedra. There are two shorter (2.65 Å) and two longer (2.71 Å) Na(2)-N(1) bond lengths. Au(1) is bonded in a distorted linear geometry to two equivalent N(1) atoms. Both Au(1)-N(1) bond lengths are 1.93 Å. N(1) is bonded to one Na(1), four equivalent Na(2), and one Au(1) atom to form a mixture of edge and corner-sharing NNa5Au octahedra. The corner-sharing octahedral tilt angles range from 0-80°.