Na3GeTe3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent Te(1), two equivalent Te(2), and two equivalent Te(3) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent Te(1), two equivalent Te(2), and two equivalent Te(3) atoms. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one Te(3), two equivalent Te(1), and two equivalent Te(2) atoms. Ge(1) is bonded to one Ge(1), one Te(1), one Te(2), and one Te(3) atom to form distorted GeGeTe3 tetrahedra that share  a cornercorner with one Te(1)Na6Ge pentagonal bipyramid. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ge(1) atom to form distorted TeNa6Ge pentagonal bipyramids that share  a cornercorner with one Ge(1)GeTe3 tetrahedra and faces with two equivalent Te(1)Na6Ge pentagonal bipyramids. In the second Te site, Te(2) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ge(1) atom. In the third Te site, Te(3) is bonded in a 6-coordinate geometry to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ge(1) atom.
Na3GeTe3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent Te(1), two equivalent Te(2), and two equivalent Te(3) atoms. There is one shorter (3.19 Å) and one longer (3.38 Å) Na(1)-Te(1) bond length. There is one shorter (3.27 Å) and one longer (3.56 Å) Na(1)-Te(2) bond length. There is one shorter (3.23 Å) and one longer (3.56 Å) Na(1)-Te(3) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent Te(1), two equivalent Te(2), and two equivalent Te(3) atoms. There is one shorter (3.49 Å) and one longer (3.57 Å) Na(2)-Te(1) bond length. There is one shorter (3.34 Å) and one longer (3.39 Å) Na(2)-Te(2) bond length. There is one shorter (3.19 Å) and one longer (3.25 Å) Na(2)-Te(3) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one Te(3), two equivalent Te(1), and two equivalent Te(2) atoms. The Na(3)-Te(3) bond length is 3.13 Å. There is one shorter (3.15 Å) and one longer (3.28 Å) Na(3)-Te(1) bond length. There is one shorter (3.37 Å) and one longer (3.74 Å) Na(3)-Te(2) bond length. Ge(1) is bonded to one Ge(1), one Te(1), one Te(2), and one Te(3) atom to form distorted GeGeTe3 tetrahedra that share  a cornercorner with one Te(1)Na6Ge pentagonal bipyramid. The Ge(1)-Ge(1) bond length is 2.50 Å. The Ge(1)-Te(1) bond length is 2.62 Å. The Ge(1)-Te(2) bond length is 2.61 Å. The Ge(1)-Te(3) bond length is 2.62 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ge(1) atom to form distorted TeNa6Ge pentagonal bipyramids that share  a cornercorner with one Ge(1)GeTe3 tetrahedra and faces with two equivalent Te(1)Na6Ge pentagonal bipyramids. In the second Te site, Te(2) is bonded in a 7-coordinate geometry to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Ge(1) atom. In the third Te site, Te(3) is bonded in a 6-coordinate geometry to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Ge(1) atom.