NaTe3 crystallizes in the trigonal P-3c1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form corner-sharing NaTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the second Na site, Na(2) is bonded to three equivalent Te(2) and three equivalent Te(3) atoms to form corner-sharing NaTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. In the third Na site, Na(3) is bonded to three equivalent Te(1) and three equivalent Te(3) atoms to form corner-sharing NaTe6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. There are three inequivalent Te sites. In the first Te site, Te(3) is bonded in a 2-coordinate geometry to one Na(2), one Na(3), and one Te(1) atom. In the second Te site, Te(1) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(3), one Te(1), and one Te(3) atom. In the third Te site, Te(2) is bonded in a distorted linear geometry to one Na(1) and one Na(2) atom.
NaTe3 crystallizes in the trigonal P-3c1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent Te(1) and three equivalent Te(2) atoms to form corner-sharing NaTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-12°. All Na(1)-Te(1) bond lengths are 3.25 Å. All Na(1)-Te(2) bond lengths are 3.18 Å. In the second Na site, Na(2) is bonded to three equivalent Te(2) and three equivalent Te(3) atoms to form corner-sharing NaTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-9°. All Na(2)-Te(2) bond lengths are 3.21 Å. All Na(2)-Te(3) bond lengths are 3.24 Å. In the third Na site, Na(3) is bonded to three equivalent Te(1) and three equivalent Te(3) atoms to form corner-sharing NaTe6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. All Na(3)-Te(1) bond lengths are 3.23 Å. All Na(3)-Te(3) bond lengths are 3.20 Å. There are three inequivalent Te sites. In the first Te site, Te(3) is bonded in a 2-coordinate geometry to one Na(2), one Na(3), and one Te(1) atom. The Te(3)-Te(1) bond length is 2.86 Å. In the second Te site, Te(1) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(3), one Te(1), and one Te(3) atom. The Te(1)-Te(1) bond length is 2.81 Å. In the third Te site, Te(2) is bonded in a distorted linear geometry to one Na(1) and one Na(2) atom.