Na2MgV4O10 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra and corners with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 74°. Mg(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(6) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(5) atoms. In the second V site, V(2) is bonded to one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Na(2)O6 octahedra and corners with three equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 55°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one V(1) atom. In the second O site, O(2) is bonded to two equivalent Na(2) and two equivalent V(1) atoms to form corner-sharing ONa2V2 tetrahedra. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Mg(1), one V(1), and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Mg(1), and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(2), one V(2), and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Mg(1), and one V(2) atom.
Na2MgV4O10 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms. Both Na(1)-O(3) bond lengths are 2.60 Å. Both Na(1)-O(4) bond lengths are 2.40 Å. Both Na(1)-O(6) bond lengths are 2.33 Å. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra and corners with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 74°. Both Na(2)-O(1) bond lengths are 2.38 Å. Both Na(2)-O(2) bond lengths are 2.39 Å. Both Na(2)-O(5) bond lengths are 2.65 Å. Mg(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(6) atoms. Both Mg(1)-O(3) bond lengths are 2.24 Å. Both Mg(1)-O(4) bond lengths are 2.40 Å. All Mg(1)-O(6) bond lengths are 2.48 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(5) atoms. The V(1)-O(1) bond length is 1.65 Å. The V(1)-O(2) bond length is 1.90 Å. The V(1)-O(3) bond length is 2.17 Å. Both V(1)-O(5) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to one O(4), one O(5), one O(6), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Na(2)O6 octahedra and corners with three equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 55°. The V(2)-O(4) bond length is 2.01 Å. The V(2)-O(5) bond length is 1.88 Å. The V(2)-O(6) bond length is 1.72 Å. Both V(2)-O(3) bond lengths are 1.96 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one V(1) atom. In the second O site, O(2) is bonded to two equivalent Na(2) and two equivalent V(1) atoms to form corner-sharing ONa2V2 tetrahedra. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Mg(1), one V(1), and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Mg(1), and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(2), one V(2), and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Mg(1), and one V(2) atom.