Na6MgV2(S3O)2 crystallizes in the monoclinic Cm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and one O(1) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), and one O(1) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), and one O(2) atom. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one S(2), two equivalent S(3), two equivalent S(4), and one O(2) atom. Mg(1) is bonded in a 5-coordinate geometry to two equivalent S(1), two equivalent S(3), and one O(2) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted tetrahedral geometry to one S(4), two equivalent S(1), and one O(2) atom. In the second V site, V(2) is bonded in a distorted tetrahedral geometry to one S(2), two equivalent S(3), and one O(1) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(3), one Mg(1), and one V(1) atom. In the second S site, S(2) is bonded to one Na(4), two equivalent Na(1), two equivalent Na(3), and one V(2) atom to form distorted SNa5V octahedra that share corners with two equivalent S(2)Na5V octahedra,  a cornercorner with one O(1)Na3V tetrahedra, corners with three equivalent O(2)Na3MgV trigonal bipyramids, edges with two equivalent S(4)Na5V octahedra, and  an edgeedge with one O(1)Na3V tetrahedra. The corner-sharing octahedral tilt angles are 2°. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Na(4), two equivalent Na(2), two equivalent Na(3), one Mg(1), and one V(2) atom. In the fourth S site, S(4) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(4), and one V(1) atom to form SNa5V octahedra that share corners with two equivalent S(4)Na5V octahedra, corners with three equivalent O(1)Na3V tetrahedra,  a cornercorner with one O(2)Na3MgV trigonal bipyramid, edges with two equivalent S(2)Na5V octahedra, and  an edgeedge with one O(2)Na3MgV trigonal bipyramid. The corner-sharing octahedral tilt angles are 1°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(2), and one V(2) atom to form distorted ONa3V tetrahedra that share  a cornercorner with one S(2)Na5V octahedra, corners with three equivalent S(4)Na5V octahedra, and  an edgeedge with one S(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 8-78°. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(3), one Mg(1), and one V(1) atom to form distorted ONa3MgV trigonal bipyramids that share  a cornercorner with one S(4)Na5V octahedra, corners with three equivalent S(2)Na5V octahedra, and  an edgeedge with one S(4)Na5V octahedra. The corner-sharing octahedral tilt angles range from 1-73°.
Na6MgV2(S3O)2 crystallizes in the monoclinic Cm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and one O(1) atom. The Na(1)-S(4) bond length is 2.80 Å. Both Na(1)-S(1) bond lengths are 3.32 Å. There is one shorter (2.81 Å) and one longer (2.99 Å) Na(1)-S(2) bond length. The Na(1)-O(1) bond length is 2.37 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(3), and one O(1) atom. The Na(2)-S(4) bond length is 2.96 Å. There is one shorter (2.96 Å) and one longer (3.32 Å) Na(2)-S(1) bond length. There is one shorter (2.89 Å) and one longer (2.97 Å) Na(2)-S(3) bond length. The Na(2)-O(1) bond length is 2.40 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), and one O(2) atom. The Na(3)-S(2) bond length is 2.69 Å. There is one shorter (2.96 Å) and one longer (3.00 Å) Na(3)-S(1) bond length. There is one shorter (3.04 Å) and one longer (3.19 Å) Na(3)-S(3) bond length. The Na(3)-O(2) bond length is 2.47 Å. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one S(2), two equivalent S(3), two equivalent S(4), and one O(2) atom. The Na(4)-S(2) bond length is 2.90 Å. Both Na(4)-S(3) bond lengths are 3.31 Å. There is one shorter (2.84 Å) and one longer (2.95 Å) Na(4)-S(4) bond length. The Na(4)-O(2) bond length is 2.64 Å. Mg(1) is bonded in a 5-coordinate geometry to two equivalent S(1), two equivalent S(3), and one O(2) atom. Both Mg(1)-S(1) bond lengths are 2.62 Å. Both Mg(1)-S(3) bond lengths are 2.65 Å. The Mg(1)-O(2) bond length is 2.04 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted tetrahedral geometry to one S(4), two equivalent S(1), and one O(2) atom. The V(1)-S(4) bond length is 2.22 Å. Both V(1)-S(1) bond lengths are 2.28 Å. The V(1)-O(2) bond length is 1.79 Å. In the second V site, V(2) is bonded in a distorted tetrahedral geometry to one S(2), two equivalent S(3), and one O(1) atom. The V(2)-S(2) bond length is 2.26 Å. Both V(2)-S(3) bond lengths are 2.31 Å. The V(2)-O(1) bond length is 1.71 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(3), one Mg(1), and one V(1) atom. In the second S site, S(2) is bonded to one Na(4), two equivalent Na(1), two equivalent Na(3), and one V(2) atom to form distorted SNa5V octahedra that share corners with two equivalent S(2)Na5V octahedra,  a cornercorner with one O(1)Na3V tetrahedra, corners with three equivalent O(2)Na3MgV trigonal bipyramids, edges with two equivalent S(4)Na5V octahedra, and  an edgeedge with one O(1)Na3V tetrahedra. The corner-sharing octahedral tilt angles are 2°. In the third S site, S(3) is bonded in a 7-coordinate geometry to one Na(4), two equivalent Na(2), two equivalent Na(3), one Mg(1), and one V(2) atom. In the fourth S site, S(4) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(4), and one V(1) atom to form SNa5V octahedra that share corners with two equivalent S(4)Na5V octahedra, corners with three equivalent O(1)Na3V tetrahedra,  a cornercorner with one O(2)Na3MgV trigonal bipyramid, edges with two equivalent S(2)Na5V octahedra, and  an edgeedge with one O(2)Na3MgV trigonal bipyramid. The corner-sharing octahedral tilt angles are 1°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(2), and one V(2) atom to form distorted ONa3V tetrahedra that share  a cornercorner with one S(2)Na5V octahedra, corners with three equivalent S(4)Na5V octahedra, and  an edgeedge with one S(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 8-78°. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(3), one Mg(1), and one V(1) atom to form distorted ONa3MgV trigonal bipyramids that share  a cornercorner with one S(4)Na5V octahedra, corners with three equivalent S(2)Na5V octahedra, and  an edgeedge with one S(4)Na5V octahedra. The corner-sharing octahedral tilt angles range from 1-73°.