Na2Mn3Te4 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Te(2), one Te(3), two equivalent Te(1), and two equivalent Te(4) atoms to form distorted NaTe6 octahedra that share  a cornercorner with one Mn(1)Te4 tetrahedra,  a cornercorner with one Mn(2)Te4 tetrahedra, corners with five equivalent Mn(3)Te4 tetrahedra, edges with two equivalent Na(1)Te6 octahedra, edges with four equivalent Na(2)Te6 octahedra,  an edgeedge with one Mn(3)Te4 tetrahedra, edges with two equivalent Mn(1)Te4 tetrahedra, and edges with two equivalent Mn(2)Te4 tetrahedra. In the second Na site, Na(2) is bonded to one Te(1), one Te(4), two equivalent Te(2), and two equivalent Te(3) atoms to form NaTe6 octahedra that share  a cornercorner with one Mn(3)Te4 tetrahedra, corners with five equivalent Mn(1)Te4 tetrahedra, corners with five equivalent Mn(2)Te4 tetrahedra, edges with two equivalent Na(2)Te6 octahedra, edges with four equivalent Na(1)Te6 octahedra,  an edgeedge with one Mn(1)Te4 tetrahedra,  an edgeedge with one Mn(2)Te4 tetrahedra, and edges with two equivalent Mn(3)Te4 tetrahedra. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one Te(2), one Te(4), and two equivalent Te(3) atoms to form distorted MnTe4 tetrahedra that share  a cornercorner with one Na(1)Te6 octahedra, corners with five equivalent Na(2)Te6 octahedra, corners with two equivalent Mn(1)Te4 tetrahedra,  an edgeedge with one Na(2)Te6 octahedra, edges with two equivalent Na(1)Te6 octahedra,  an edgeedge with one Mn(3)Te4 tetrahedra, and edges with two equivalent Mn(2)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 18-50°. In the second Mn site, Mn(2) is bonded to one Te(1), one Te(3), and two equivalent Te(2) atoms to form MnTe4 tetrahedra that share  a cornercorner with one Na(1)Te6 octahedra, corners with five equivalent Na(2)Te6 octahedra, corners with two equivalent Mn(2)Te4 tetrahedra, corners with four equivalent Mn(3)Te4 tetrahedra,  an edgeedge with one Na(2)Te6 octahedra, edges with two equivalent Na(1)Te6 octahedra, and edges with two equivalent Mn(1)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-54°. In the third Mn site, Mn(3) is bonded to one Te(2), one Te(4), and two equivalent Te(1) atoms to form MnTe4 tetrahedra that share  a cornercorner with one Na(2)Te6 octahedra, corners with five equivalent Na(1)Te6 octahedra, corners with two equivalent Mn(3)Te4 tetrahedra, corners with four equivalent Mn(2)Te4 tetrahedra,  an edgeedge with one Na(1)Te6 octahedra, edges with two equivalent Na(2)Te6 octahedra, and  an edgeedge with one Mn(1)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-59°. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded to one Na(2), two equivalent Na(1), one Mn(2), and two equivalent Mn(3) atoms to form TeNa3Mn3 octahedra that share  a cornercorner with one Te(3)Na3Mn3 octahedra, corners with five equivalent Te(4)Na3Mn2 square pyramids, edges with two equivalent Te(1)Na3Mn3 octahedra, edges with two equivalent Te(3)Na3Mn3 octahedra, and  an edgeedge with one Te(4)Na3Mn2 square pyramid. The corner-sharing octahedral tilt angles are 68°. In the second Te site, Te(2) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), one Mn(1), one Mn(3), and two equivalent Mn(2) atoms. In the third Te site, Te(3) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and two equivalent Mn(1) atoms to form distorted TeNa3Mn3 octahedra that share  a cornercorner with one Te(1)Na3Mn3 octahedra, corners with two equivalent Te(4)Na3Mn2 square pyramids, edges with two equivalent Te(1)Na3Mn3 octahedra, edges with two equivalent Te(3)Na3Mn3 octahedra, and edges with two equivalent Te(4)Na3Mn2 square pyramids. The corner-sharing octahedral tilt angles are 68°. In the fourth Te site, Te(4) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and one Mn(3) atom to form distorted TeNa3Mn2 square pyramids that share corners with two equivalent Te(3)Na3Mn3 octahedra, corners with five equivalent Te(1)Na3Mn3 octahedra, corners with two equivalent Te(4)Na3Mn2 square pyramids,  an edgeedge with one Te(1)Na3Mn3 octahedra, and edges with two equivalent Te(3)Na3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 3-90°.
Na2Mn3Te4 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Te(2), one Te(3), two equivalent Te(1), and two equivalent Te(4) atoms to form distorted NaTe6 octahedra that share  a cornercorner with one Mn(1)Te4 tetrahedra,  a cornercorner with one Mn(2)Te4 tetrahedra, corners with five equivalent Mn(3)Te4 tetrahedra, edges with two equivalent Na(1)Te6 octahedra, edges with four equivalent Na(2)Te6 octahedra,  an edgeedge with one Mn(3)Te4 tetrahedra, edges with two equivalent Mn(1)Te4 tetrahedra, and edges with two equivalent Mn(2)Te4 tetrahedra. The Na(1)-Te(2) bond length is 3.48 Å. The Na(1)-Te(3) bond length is 3.27 Å. Both Na(1)-Te(1) bond lengths are 3.38 Å. Both Na(1)-Te(4) bond lengths are 3.15 Å. In the second Na site, Na(2) is bonded to one Te(1), one Te(4), two equivalent Te(2), and two equivalent Te(3) atoms to form NaTe6 octahedra that share  a cornercorner with one Mn(3)Te4 tetrahedra, corners with five equivalent Mn(1)Te4 tetrahedra, corners with five equivalent Mn(2)Te4 tetrahedra, edges with two equivalent Na(2)Te6 octahedra, edges with four equivalent Na(1)Te6 octahedra,  an edgeedge with one Mn(1)Te4 tetrahedra,  an edgeedge with one Mn(2)Te4 tetrahedra, and edges with two equivalent Mn(3)Te4 tetrahedra. The Na(2)-Te(1) bond length is 3.32 Å. The Na(2)-Te(4) bond length is 3.17 Å. Both Na(2)-Te(2) bond lengths are 3.41 Å. Both Na(2)-Te(3) bond lengths are 3.24 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one Te(2), one Te(4), and two equivalent Te(3) atoms to form distorted MnTe4 tetrahedra that share  a cornercorner with one Na(1)Te6 octahedra, corners with five equivalent Na(2)Te6 octahedra, corners with two equivalent Mn(1)Te4 tetrahedra,  an edgeedge with one Na(2)Te6 octahedra, edges with two equivalent Na(1)Te6 octahedra,  an edgeedge with one Mn(3)Te4 tetrahedra, and edges with two equivalent Mn(2)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 18-50°. The Mn(1)-Te(2) bond length is 2.89 Å. The Mn(1)-Te(4) bond length is 2.66 Å. Both Mn(1)-Te(3) bond lengths are 2.78 Å. In the second Mn site, Mn(2) is bonded to one Te(1), one Te(3), and two equivalent Te(2) atoms to form MnTe4 tetrahedra that share  a cornercorner with one Na(1)Te6 octahedra, corners with five equivalent Na(2)Te6 octahedra, corners with two equivalent Mn(2)Te4 tetrahedra, corners with four equivalent Mn(3)Te4 tetrahedra,  an edgeedge with one Na(2)Te6 octahedra, edges with two equivalent Na(1)Te6 octahedra, and edges with two equivalent Mn(1)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 17-54°. The Mn(2)-Te(1) bond length is 2.73 Å. The Mn(2)-Te(3) bond length is 2.73 Å. Both Mn(2)-Te(2) bond lengths are 2.82 Å. In the third Mn site, Mn(3) is bonded to one Te(2), one Te(4), and two equivalent Te(1) atoms to form MnTe4 tetrahedra that share  a cornercorner with one Na(2)Te6 octahedra, corners with five equivalent Na(1)Te6 octahedra, corners with two equivalent Mn(3)Te4 tetrahedra, corners with four equivalent Mn(2)Te4 tetrahedra,  an edgeedge with one Na(1)Te6 octahedra, edges with two equivalent Na(2)Te6 octahedra, and  an edgeedge with one Mn(1)Te4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-59°. The Mn(3)-Te(2) bond length is 2.93 Å. The Mn(3)-Te(4) bond length is 2.66 Å. Both Mn(3)-Te(1) bond lengths are 2.79 Å. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded to one Na(2), two equivalent Na(1), one Mn(2), and two equivalent Mn(3) atoms to form TeNa3Mn3 octahedra that share  a cornercorner with one Te(3)Na3Mn3 octahedra, corners with five equivalent Te(4)Na3Mn2 square pyramids, edges with two equivalent Te(1)Na3Mn3 octahedra, edges with two equivalent Te(3)Na3Mn3 octahedra, and  an edgeedge with one Te(4)Na3Mn2 square pyramid. The corner-sharing octahedral tilt angles are 68°. In the second Te site, Te(2) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), one Mn(1), one Mn(3), and two equivalent Mn(2) atoms. In the third Te site, Te(3) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and two equivalent Mn(1) atoms to form distorted TeNa3Mn3 octahedra that share  a cornercorner with one Te(1)Na3Mn3 octahedra, corners with two equivalent Te(4)Na3Mn2 square pyramids, edges with two equivalent Te(1)Na3Mn3 octahedra, edges with two equivalent Te(3)Na3Mn3 octahedra, and edges with two equivalent Te(4)Na3Mn2 square pyramids. The corner-sharing octahedral tilt angles are 68°. In the fourth Te site, Te(4) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and one Mn(3) atom to form distorted TeNa3Mn2 square pyramids that share corners with two equivalent Te(3)Na3Mn3 octahedra, corners with five equivalent Te(1)Na3Mn3 octahedra, corners with two equivalent Te(4)Na3Mn2 square pyramids,  an edgeedge with one Te(1)Na3Mn3 octahedra, and edges with two equivalent Te(3)Na3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 3-90°.