Na3(Mn2Te3)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form NaTe6 octahedra that share corners with eight equivalent Mn(1)Te4 tetrahedra, edges with three equivalent Na(1)Te6 octahedra, edges with three equivalent Na(2)Te6 octahedra, and edges with four equivalent Mn(1)Te4 tetrahedra. In the second Na site, Na(2) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form NaTe6 octahedra that share corners with eight equivalent Mn(1)Te4 tetrahedra, edges with six equivalent Na(1)Te6 octahedra, and edges with four equivalent Mn(1)Te4 tetrahedra. Mn(1) is bonded to one Te(1) and three equivalent Te(2) atoms to form MnTe4 tetrahedra that share corners with two equivalent Na(2)Te6 octahedra, corners with four equivalent Na(1)Te6 octahedra, corners with three equivalent Mn(1)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 18-57°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one Na(2), two equivalent Na(1), and two equivalent Mn(1) atoms to form TeNa3Mn2 square pyramids that share corners with six equivalent Te(2)Na3Mn3 pentagonal pyramids,  a cornercorner with one Te(1)Na3Mn2 square pyramid, edges with six equivalent Te(2)Na3Mn3 pentagonal pyramids, and  an edgeedge with one Te(1)Na3Mn2 square pyramid. In the second Te site, Te(2) is bonded to one Na(2), two equivalent Na(1), and three equivalent Mn(1) atoms to form distorted TeNa3Mn3 pentagonal pyramids that share corners with three equivalent Te(2)Na3Mn3 pentagonal pyramids, corners with three equivalent Te(1)Na3Mn2 square pyramids, edges with six equivalent Te(2)Na3Mn3 pentagonal pyramids, and edges with three equivalent Te(1)Na3Mn2 square pyramids.
Na3(Mn2Te3)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form NaTe6 octahedra that share corners with eight equivalent Mn(1)Te4 tetrahedra, edges with three equivalent Na(1)Te6 octahedra, edges with three equivalent Na(2)Te6 octahedra, and edges with four equivalent Mn(1)Te4 tetrahedra. Both Na(1)-Te(1) bond lengths are 3.21 Å. There are two shorter (3.32 Å) and two longer (3.36 Å) Na(1)-Te(2) bond lengths. In the second Na site, Na(2) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form NaTe6 octahedra that share corners with eight equivalent Mn(1)Te4 tetrahedra, edges with six equivalent Na(1)Te6 octahedra, and edges with four equivalent Mn(1)Te4 tetrahedra. Both Na(2)-Te(1) bond lengths are 3.18 Å. All Na(2)-Te(2) bond lengths are 3.39 Å. Mn(1) is bonded to one Te(1) and three equivalent Te(2) atoms to form MnTe4 tetrahedra that share corners with two equivalent Na(2)Te6 octahedra, corners with four equivalent Na(1)Te6 octahedra, corners with three equivalent Mn(1)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 18-57°. The Mn(1)-Te(1) bond length is 2.66 Å. There are two shorter (2.75 Å) and one longer (2.76 Å) Mn(1)-Te(2) bond length. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one Na(2), two equivalent Na(1), and two equivalent Mn(1) atoms to form TeNa3Mn2 square pyramids that share corners with six equivalent Te(2)Na3Mn3 pentagonal pyramids,  a cornercorner with one Te(1)Na3Mn2 square pyramid, edges with six equivalent Te(2)Na3Mn3 pentagonal pyramids, and  an edgeedge with one Te(1)Na3Mn2 square pyramid. In the second Te site, Te(2) is bonded to one Na(2), two equivalent Na(1), and three equivalent Mn(1) atoms to form distorted TeNa3Mn3 pentagonal pyramids that share corners with three equivalent Te(2)Na3Mn3 pentagonal pyramids, corners with three equivalent Te(1)Na3Mn2 square pyramids, edges with six equivalent Te(2)Na3Mn3 pentagonal pyramids, and edges with three equivalent Te(1)Na3Mn2 square pyramids.