Na5(InTe3)2 crystallizes in the orthorhombic Cmc2_1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to one Te(2), one Te(3), one Te(5), one Te(6), one Te(8), and one Te(9) atom to form NaTe6 octahedra that share corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent In(2)Te4 tetrahedra, corners with two equivalent In(3)Te4 tetrahedra, edges with two equivalent Na(1)Te6 octahedra,  an edgeedge with one In(1)Te4 tetrahedra,  an edgeedge with one In(4)Te4 tetrahedra, and faces with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-61°. In the second Na site, Na(2) is bonded to one Te(2), one Te(3), one Te(5), one Te(6), one Te(8), and one Te(9) atom to form NaTe6 octahedra that share corners with four equivalent Na(1)Te6 octahedra, corners with two equivalent In(1)Te4 tetrahedra, corners with two equivalent In(4)Te4 tetrahedra, edges with two equivalent Na(2)Te6 octahedra,  an edgeedge with one In(2)Te4 tetrahedra,  an edgeedge with one In(3)Te4 tetrahedra, and faces with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-61°. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Te(1), one Te(10), one Te(3), one Te(6), one Te(7), and one Te(9) atom. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one Te(10), one Te(2), one Te(4), one Te(5), one Te(7), and one Te(8) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Te(1), one Te(10), one Te(4), one Te(5), one Te(6), and one Te(7) atom. There are four inequivalent In sites. In the first In site, In(1) is bonded to one Te(4), one Te(9), and two equivalent Te(6) atoms to form InTe4 tetrahedra that share corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent In(4)Te4 tetrahedra, and edges with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 41-65°. In the second In site, In(2) is bonded to one Te(10), one Te(2), and two equivalent Te(5) atoms to form distorted InTe4 tetrahedra that share corners with four equivalent Na(1)Te6 octahedra, corners with two equivalent In(3)Te4 tetrahedra, and edges with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. In the third In site, In(3) is bonded to one Te(1), one Te(8), and two equivalent Te(5) atoms to form InTe4 tetrahedra that share corners with four equivalent Na(1)Te6 octahedra, corners with two equivalent In(2)Te4 tetrahedra, and edges with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 41-65°. In the fourth In site, In(4) is bonded to one Te(3), one Te(7), and two equivalent Te(6) atoms to form distorted InTe4 tetrahedra that share corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent In(1)Te4 tetrahedra, and edges with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. There are ten inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to two equivalent Na(3), two equivalent Na(5), one In(3), and one Te(4) atom. In the second Te site, Te(2) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(4), and one In(2) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(3)Na6In pentagonal bipyramids, corners with two equivalent Te(9)Na6In pentagonal bipyramids,  an edgeedge with one Te(3)Na6In pentagonal bipyramid,  an edgeedge with one Te(9)Na6In pentagonal bipyramid, edges with two equivalent Te(6)Na4In2 pentagonal pyramids, edges with four equivalent Te(5)Na4In2 pentagonal pyramids, and faces with two equivalent Te(8)Na6In pentagonal bipyramids. In the third Te site, Te(3) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one In(4) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(2)Na6In pentagonal bipyramids, corners with two equivalent Te(8)Na6In pentagonal bipyramids,  an edgeedge with one Te(2)Na6In pentagonal bipyramid,  an edgeedge with one Te(8)Na6In pentagonal bipyramid, edges with two equivalent Te(5)Na4In2 pentagonal pyramids, edges with four equivalent Te(6)Na4In2 pentagonal pyramids, and faces with two equivalent Te(9)Na6In pentagonal bipyramids. In the fourth Te site, Te(4) is bonded in a 6-coordinate geometry to two equivalent Na(4), two equivalent Na(5), one In(1), and one Te(1) atom. In the fifth Te site, Te(5) is bonded to one Na(1), one Na(2), one Na(4), one Na(5), one In(2), and one In(3) atom to form distorted TeNa4In2 pentagonal pyramids that share corners with two equivalent Te(5)Na4In2 pentagonal pyramids, corners with three equivalent Te(6)Na4In2 pentagonal pyramids,  an edgeedge with one Te(3)Na6In pentagonal bipyramid,  an edgeedge with one Te(9)Na6In pentagonal bipyramid, edges with two equivalent Te(2)Na6In pentagonal bipyramids, and edges with two equivalent Te(8)Na6In pentagonal bipyramids. In the sixth Te site, Te(6) is bonded to one Na(1), one Na(2), one Na(3), one Na(5), one In(1), and one In(4) atom to form distorted TeNa4In2 pentagonal pyramids that share corners with two equivalent Te(6)Na4In2 pentagonal pyramids, corners with three equivalent Te(5)Na4In2 pentagonal pyramids,  an edgeedge with one Te(2)Na6In pentagonal bipyramid,  an edgeedge with one Te(8)Na6In pentagonal bipyramid, edges with two equivalent Te(3)Na6In pentagonal bipyramids, and edges with two equivalent Te(9)Na6In pentagonal bipyramids. In the seventh Te site, Te(7) is bonded in a 7-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), and one In(4) atom. In the eighth Te site, Te(8) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(4), and one In(3) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(3)Na6In pentagonal bipyramids, corners with two equivalent Te(9)Na6In pentagonal bipyramids,  an edgeedge with one Te(3)Na6In pentagonal bipyramid,  an edgeedge with one Te(9)Na6In pentagonal bipyramid, edges with two equivalent Te(6)Na4In2 pentagonal pyramids, edges with four equivalent Te(5)Na4In2 pentagonal pyramids, and faces with two equivalent Te(2)Na6In pentagonal bipyramids. In the ninth Te site, Te(9) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one In(1) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(2)Na6In pentagonal bipyramids, corners with two equivalent Te(8)Na6In pentagonal bipyramids,  an edgeedge with one Te(2)Na6In pentagonal bipyramid,  an edgeedge with one Te(8)Na6In pentagonal bipyramid, edges with two equivalent Te(5)Na4In2 pentagonal pyramids, edges with four equivalent Te(6)Na4In2 pentagonal pyramids, and faces with two equivalent Te(3)Na6In pentagonal bipyramids. In the tenth Te site, Te(10) is bonded in a 7-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), and one In(2) atom.
Na5(InTe3)2 crystallizes in the orthorhombic Cmc2_1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to one Te(2), one Te(3), one Te(5), one Te(6), one Te(8), and one Te(9) atom to form NaTe6 octahedra that share corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent In(2)Te4 tetrahedra, corners with two equivalent In(3)Te4 tetrahedra, edges with two equivalent Na(1)Te6 octahedra,  an edgeedge with one In(1)Te4 tetrahedra,  an edgeedge with one In(4)Te4 tetrahedra, and faces with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-61°. The Na(1)-Te(2) bond length is 3.29 Å. The Na(1)-Te(3) bond length is 3.29 Å. The Na(1)-Te(5) bond length is 3.17 Å. The Na(1)-Te(6) bond length is 3.27 Å. The Na(1)-Te(8) bond length is 3.53 Å. The Na(1)-Te(9) bond length is 3.36 Å. In the second Na site, Na(2) is bonded to one Te(2), one Te(3), one Te(5), one Te(6), one Te(8), and one Te(9) atom to form NaTe6 octahedra that share corners with four equivalent Na(1)Te6 octahedra, corners with two equivalent In(1)Te4 tetrahedra, corners with two equivalent In(4)Te4 tetrahedra, edges with two equivalent Na(2)Te6 octahedra,  an edgeedge with one In(2)Te4 tetrahedra,  an edgeedge with one In(3)Te4 tetrahedra, and faces with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 49-61°. The Na(2)-Te(2) bond length is 3.30 Å. The Na(2)-Te(3) bond length is 3.32 Å. The Na(2)-Te(5) bond length is 3.29 Å. The Na(2)-Te(6) bond length is 3.18 Å. The Na(2)-Te(8) bond length is 3.33 Å. The Na(2)-Te(9) bond length is 3.47 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Te(1), one Te(10), one Te(3), one Te(6), one Te(7), and one Te(9) atom. The Na(3)-Te(1) bond length is 3.39 Å. The Na(3)-Te(10) bond length is 3.34 Å. The Na(3)-Te(3) bond length is 3.33 Å. The Na(3)-Te(6) bond length is 3.25 Å. The Na(3)-Te(7) bond length is 3.52 Å. The Na(3)-Te(9) bond length is 3.26 Å. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one Te(10), one Te(2), one Te(4), one Te(5), one Te(7), and one Te(8) atom. The Na(4)-Te(10) bond length is 3.46 Å. The Na(4)-Te(2) bond length is 3.34 Å. The Na(4)-Te(4) bond length is 3.40 Å. The Na(4)-Te(5) bond length is 3.26 Å. The Na(4)-Te(7) bond length is 3.32 Å. The Na(4)-Te(8) bond length is 3.27 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one Te(1), one Te(10), one Te(4), one Te(5), one Te(6), and one Te(7) atom. The Na(5)-Te(1) bond length is 3.15 Å. The Na(5)-Te(10) bond length is 3.15 Å. The Na(5)-Te(4) bond length is 3.14 Å. The Na(5)-Te(5) bond length is 3.33 Å. The Na(5)-Te(6) bond length is 3.36 Å. The Na(5)-Te(7) bond length is 3.16 Å. There are four inequivalent In sites. In the first In site, In(1) is bonded to one Te(4), one Te(9), and two equivalent Te(6) atoms to form InTe4 tetrahedra that share corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent In(4)Te4 tetrahedra, and edges with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 41-65°. The In(1)-Te(4) bond length is 2.86 Å. The In(1)-Te(9) bond length is 2.74 Å. Both In(1)-Te(6) bond lengths are 2.84 Å. In the second In site, In(2) is bonded to one Te(10), one Te(2), and two equivalent Te(5) atoms to form distorted InTe4 tetrahedra that share corners with four equivalent Na(1)Te6 octahedra, corners with two equivalent In(3)Te4 tetrahedra, and edges with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. The In(2)-Te(10) bond length is 2.81 Å. The In(2)-Te(2) bond length is 2.76 Å. Both In(2)-Te(5) bond lengths are 2.86 Å. In the third In site, In(3) is bonded to one Te(1), one Te(8), and two equivalent Te(5) atoms to form InTe4 tetrahedra that share corners with four equivalent Na(1)Te6 octahedra, corners with two equivalent In(2)Te4 tetrahedra, and edges with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 41-65°. The In(3)-Te(1) bond length is 2.85 Å. The In(3)-Te(8) bond length is 2.74 Å. Both In(3)-Te(5) bond lengths are 2.84 Å. In the fourth In site, In(4) is bonded to one Te(3), one Te(7), and two equivalent Te(6) atoms to form distorted InTe4 tetrahedra that share corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent In(1)Te4 tetrahedra, and edges with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 44-59°. The In(4)-Te(3) bond length is 2.75 Å. The In(4)-Te(7) bond length is 2.80 Å. Both In(4)-Te(6) bond lengths are 2.85 Å. There are ten inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to two equivalent Na(3), two equivalent Na(5), one In(3), and one Te(4) atom. The Te(1)-Te(4) bond length is 2.90 Å. In the second Te site, Te(2) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(4), and one In(2) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(3)Na6In pentagonal bipyramids, corners with two equivalent Te(9)Na6In pentagonal bipyramids,  an edgeedge with one Te(3)Na6In pentagonal bipyramid,  an edgeedge with one Te(9)Na6In pentagonal bipyramid, edges with two equivalent Te(6)Na4In2 pentagonal pyramids, edges with four equivalent Te(5)Na4In2 pentagonal pyramids, and faces with two equivalent Te(8)Na6In pentagonal bipyramids. In the third Te site, Te(3) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one In(4) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(2)Na6In pentagonal bipyramids, corners with two equivalent Te(8)Na6In pentagonal bipyramids,  an edgeedge with one Te(2)Na6In pentagonal bipyramid,  an edgeedge with one Te(8)Na6In pentagonal bipyramid, edges with two equivalent Te(5)Na4In2 pentagonal pyramids, edges with four equivalent Te(6)Na4In2 pentagonal pyramids, and faces with two equivalent Te(9)Na6In pentagonal bipyramids. In the fourth Te site, Te(4) is bonded in a 6-coordinate geometry to two equivalent Na(4), two equivalent Na(5), one In(1), and one Te(1) atom. In the fifth Te site, Te(5) is bonded to one Na(1), one Na(2), one Na(4), one Na(5), one In(2), and one In(3) atom to form distorted TeNa4In2 pentagonal pyramids that share corners with two equivalent Te(5)Na4In2 pentagonal pyramids, corners with three equivalent Te(6)Na4In2 pentagonal pyramids,  an edgeedge with one Te(3)Na6In pentagonal bipyramid,  an edgeedge with one Te(9)Na6In pentagonal bipyramid, edges with two equivalent Te(2)Na6In pentagonal bipyramids, and edges with two equivalent Te(8)Na6In pentagonal bipyramids. In the sixth Te site, Te(6) is bonded to one Na(1), one Na(2), one Na(3), one Na(5), one In(1), and one In(4) atom to form distorted TeNa4In2 pentagonal pyramids that share corners with two equivalent Te(6)Na4In2 pentagonal pyramids, corners with three equivalent Te(5)Na4In2 pentagonal pyramids,  an edgeedge with one Te(2)Na6In pentagonal bipyramid,  an edgeedge with one Te(8)Na6In pentagonal bipyramid, edges with two equivalent Te(3)Na6In pentagonal bipyramids, and edges with two equivalent Te(9)Na6In pentagonal bipyramids. In the seventh Te site, Te(7) is bonded in a 7-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), and one In(4) atom. In the eighth Te site, Te(8) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(4), and one In(3) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(3)Na6In pentagonal bipyramids, corners with two equivalent Te(9)Na6In pentagonal bipyramids,  an edgeedge with one Te(3)Na6In pentagonal bipyramid,  an edgeedge with one Te(9)Na6In pentagonal bipyramid, edges with two equivalent Te(6)Na4In2 pentagonal pyramids, edges with four equivalent Te(5)Na4In2 pentagonal pyramids, and faces with two equivalent Te(2)Na6In pentagonal bipyramids. In the ninth Te site, Te(9) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one In(1) atom to form distorted TeNa6In pentagonal bipyramids that share corners with two equivalent Te(2)Na6In pentagonal bipyramids, corners with two equivalent Te(8)Na6In pentagonal bipyramids,  an edgeedge with one Te(2)Na6In pentagonal bipyramid,  an edgeedge with one Te(8)Na6In pentagonal bipyramid, edges with two equivalent Te(5)Na4In2 pentagonal pyramids, edges with four equivalent Te(6)Na4In2 pentagonal pyramids, and faces with two equivalent Te(3)Na6In pentagonal bipyramids. In the tenth Te site, Te(10) is bonded in a 7-coordinate geometry to two equivalent Na(3), two equivalent Na(4), two equivalent Na(5), and one In(2) atom.