Na6MgV2(SO3)2 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one O(1), one O(3), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one S(2), one O(1), one O(2), and one O(5) atom. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one S(2), one O(1), one O(3), and one O(6) atom. In the fourth Na site, Na(4) is bonded in a 3-coordinate geometry to one S(2), one O(1), one O(2), one O(4), and one O(5) atom. In the fifth Na site, Na(5) is bonded in a distorted square co-planar geometry to one O(2), one O(3), one O(4), and one O(6) atom. In the sixth Na site, Na(6) is bonded in a 3-coordinate geometry to one S(1), one S(2), one O(2), and one O(4) atom. Mg(1) is bonded in a 2-coordinate geometry to one S(1), one S(2), one O(3), one O(4), and one O(6) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted tetrahedral geometry to one S(1), one O(1), one O(2), and one O(3) atom. In the second V site, V(2) is bonded in a distorted tetrahedral geometry to one S(2), one O(4), one O(5), and one O(6) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Mg(1), and one V(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Na(6), one Mg(1), and one V(2) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), and one V(1) atom to form distorted ONa4V trigonal bipyramids that share  a cornercorner with one O(5)Na3V tetrahedra,  a cornercorner with one O(2)Na4V trigonal bipyramid,  an edgeedge with one O(5)Na3V tetrahedra, and  an edgeedge with one O(2)Na4V trigonal bipyramid. In the second O site, O(2) is bonded to one Na(2), one Na(4), one Na(5), one Na(6), and one V(1) atom to form distorted ONa4V trigonal bipyramids that share corners with two equivalent O(5)Na3V tetrahedra,  a cornercorner with one O(1)Na4V trigonal bipyramid, and  an edgeedge with one O(1)Na4V trigonal bipyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Mg(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(4), one Na(5), one Na(6), one Mg(1), and one V(2) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(4), and one V(2) atom to form a mixture of distorted corner and edge-sharing ONa3V tetrahedra. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Mg(1), and one V(2) atom.
Na6MgV2(SO3)2 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one O(1), one O(3), one O(5), and one O(6) atom. The Na(1)-S(1) bond length is 3.05 Å. The Na(1)-S(2) bond length is 2.94 Å. The Na(1)-O(1) bond length is 2.49 Å. The Na(1)-O(3) bond length is 2.86 Å. The Na(1)-O(5) bond length is 2.33 Å. The Na(1)-O(6) bond length is 2.93 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one S(2), one O(1), one O(2), and one O(5) atom. The Na(2)-S(2) bond length is 3.05 Å. The Na(2)-O(1) bond length is 2.35 Å. The Na(2)-O(2) bond length is 2.28 Å. The Na(2)-O(5) bond length is 2.28 Å. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one S(2), one O(1), one O(3), and one O(6) atom. The Na(3)-S(2) bond length is 2.95 Å. The Na(3)-O(1) bond length is 2.46 Å. The Na(3)-O(3) bond length is 2.44 Å. The Na(3)-O(6) bond length is 2.33 Å. In the fourth Na site, Na(4) is bonded in a 3-coordinate geometry to one S(2), one O(1), one O(2), one O(4), and one O(5) atom. The Na(4)-S(2) bond length is 2.80 Å. The Na(4)-O(1) bond length is 2.49 Å. The Na(4)-O(2) bond length is 2.50 Å. The Na(4)-O(4) bond length is 2.90 Å. The Na(4)-O(5) bond length is 2.36 Å. In the fifth Na site, Na(5) is bonded in a distorted square co-planar geometry to one O(2), one O(3), one O(4), and one O(6) atom. The Na(5)-O(2) bond length is 2.51 Å. The Na(5)-O(3) bond length is 2.54 Å. The Na(5)-O(4) bond length is 2.42 Å. The Na(5)-O(6) bond length is 2.44 Å. In the sixth Na site, Na(6) is bonded in a 3-coordinate geometry to one S(1), one S(2), one O(2), and one O(4) atom. The Na(6)-S(1) bond length is 2.73 Å. The Na(6)-S(2) bond length is 3.29 Å. The Na(6)-O(2) bond length is 2.22 Å. The Na(6)-O(4) bond length is 2.29 Å. Mg(1) is bonded in a 2-coordinate geometry to one S(1), one S(2), one O(3), one O(4), and one O(6) atom. The Mg(1)-S(1) bond length is 2.48 Å. The Mg(1)-S(2) bond length is 2.81 Å. The Mg(1)-O(3) bond length is 1.93 Å. The Mg(1)-O(4) bond length is 1.98 Å. The Mg(1)-O(6) bond length is 2.66 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted tetrahedral geometry to one S(1), one O(1), one O(2), and one O(3) atom. The V(1)-S(1) bond length is 2.36 Å. The V(1)-O(1) bond length is 1.76 Å. The V(1)-O(2) bond length is 1.78 Å. The V(1)-O(3) bond length is 1.86 Å. In the second V site, V(2) is bonded in a distorted tetrahedral geometry to one S(2), one O(4), one O(5), and one O(6) atom. The V(2)-S(2) bond length is 2.38 Å. The V(2)-O(4) bond length is 1.89 Å. The V(2)-O(5) bond length is 1.75 Å. The V(2)-O(6) bond length is 1.78 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Mg(1), and one V(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Na(6), one Mg(1), and one V(2) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), and one V(1) atom to form distorted ONa4V trigonal bipyramids that share  a cornercorner with one O(5)Na3V tetrahedra,  a cornercorner with one O(2)Na4V trigonal bipyramid,  an edgeedge with one O(5)Na3V tetrahedra, and  an edgeedge with one O(2)Na4V trigonal bipyramid. In the second O site, O(2) is bonded to one Na(2), one Na(4), one Na(5), one Na(6), and one V(1) atom to form distorted ONa4V trigonal bipyramids that share corners with two equivalent O(5)Na3V tetrahedra,  a cornercorner with one O(1)Na4V trigonal bipyramid, and  an edgeedge with one O(1)Na4V trigonal bipyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Mg(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(4), one Na(5), one Na(6), one Mg(1), and one V(2) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(4), and one V(2) atom to form a mixture of distorted corner and edge-sharing ONa3V tetrahedra. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Mg(1), and one V(2) atom.