Na6N4Te crystallizes in the tetragonal P4_2/nmc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. In the second Na site, Na(2) is bonded to four equivalent N(1) atoms to form distorted NaN4 tetrahedra that share corners with two equivalent Te(1)N4 tetrahedra, corners with eight equivalent Na(2)N4 tetrahedra,  an edgeedge with one Te(1)N4 tetrahedra, and edges with two equivalent Na(2)N4 tetrahedra. N(1) is bonded in a 7-coordinate geometry to two equivalent Na(1), four equivalent Na(2), and one Te(1) atom. Te(1) is bonded to four equivalent N(1) atoms to form TeN4 tetrahedra that share corners with eight equivalent Na(2)N4 tetrahedra and edges with four equivalent Na(2)N4 tetrahedra.
Na6N4Te crystallizes in the tetragonal P4_2/nmc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. There are two shorter (2.37 Å) and two longer (2.78 Å) Na(1)-N(1) bond lengths. In the second Na site, Na(2) is bonded to four equivalent N(1) atoms to form distorted NaN4 tetrahedra that share corners with two equivalent Te(1)N4 tetrahedra, corners with eight equivalent Na(2)N4 tetrahedra,  an edgeedge with one Te(1)N4 tetrahedra, and edges with two equivalent Na(2)N4 tetrahedra. There are two shorter (2.48 Å) and two longer (2.52 Å) Na(2)-N(1) bond lengths. N(1) is bonded in a 7-coordinate geometry to two equivalent Na(1), four equivalent Na(2), and one Te(1) atom. The N(1)-Te(1) bond length is 2.00 Å. Te(1) is bonded to four equivalent N(1) atoms to form TeN4 tetrahedra that share corners with eight equivalent Na(2)N4 tetrahedra and edges with four equivalent Na(2)N4 tetrahedra.