Na2MgV2(OF)4 crystallizes in the monoclinic Pm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), two equivalent F(2), and two equivalent F(3) atoms. In the second Na site, Na(2) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(4) atoms to form distorted NaOF5 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O4F2 octahedra, corners with two equivalent Mg(1)O4F trigonal bipyramids, and edges with two equivalent Na(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 38-66°. Mg(1) is bonded to one O(1), one O(4), two equivalent O(2), and one F(2) atom to form distorted MgO4F trigonal bipyramids that share  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent Na(2)OF5 octahedra, corners with two equivalent Mg(1)O4F trigonal bipyramids,  an edgeedge with one V(1)O4F2 octahedra, and edges with two equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 13-71°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), two equivalent O(3), one F(2), and one F(3) atom to form distorted VO4F2 octahedra that share corners with two equivalent Na(2)OF5 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, edges with two equivalent V(2)O4F2 octahedra, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-66°. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(4), one F(1), and one F(4) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent Na(2)OF5 octahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with two equivalent Mg(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-59°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Mg(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Mg(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted square co-planar geometry to one Mg(1), one V(1), and two equivalent V(2) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one V(2) atom. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), one Mg(1), and one V(1) atom to form distorted corner-sharing FNa3MgV trigonal bipyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Na(2) and one V(2) atom.
Na2MgV2(OF)4 crystallizes in the monoclinic Pm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(2), one F(1), two equivalent F(2), and two equivalent F(3) atoms. The Na(1)-O(2) bond length is 2.46 Å. The Na(1)-F(1) bond length is 2.23 Å. Both Na(1)-F(2) bond lengths are 2.51 Å. Both Na(1)-F(3) bond lengths are 2.27 Å. In the second Na site, Na(2) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(4) atoms to form distorted NaOF5 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O4F2 octahedra, corners with two equivalent Mg(1)O4F trigonal bipyramids, and edges with two equivalent Na(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 38-66°. The Na(2)-O(1) bond length is 2.29 Å. The Na(2)-F(2) bond length is 2.57 Å. Both Na(2)-F(1) bond lengths are 2.56 Å. Both Na(2)-F(4) bond lengths are 2.27 Å. Mg(1) is bonded to one O(1), one O(4), two equivalent O(2), and one F(2) atom to form distorted MgO4F trigonal bipyramids that share  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent Na(2)OF5 octahedra, corners with two equivalent Mg(1)O4F trigonal bipyramids,  an edgeedge with one V(1)O4F2 octahedra, and edges with two equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 13-71°. The Mg(1)-O(1) bond length is 1.99 Å. The Mg(1)-O(4) bond length is 2.42 Å. Both Mg(1)-O(2) bond lengths are 2.03 Å. The Mg(1)-F(2) bond length is 2.03 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), two equivalent O(3), one F(2), and one F(3) atom to form distorted VO4F2 octahedra that share corners with two equivalent Na(2)OF5 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, edges with two equivalent V(2)O4F2 octahedra, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-66°. The V(1)-O(1) bond length is 1.70 Å. The V(1)-O(4) bond length is 2.16 Å. Both V(1)-O(3) bond lengths are 1.99 Å. The V(1)-F(2) bond length is 2.17 Å. The V(1)-F(3) bond length is 1.94 Å. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(4), one F(1), and one F(4) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent Na(2)OF5 octahedra, edges with two equivalent V(1)O4F2 octahedra, and edges with two equivalent Mg(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-59°. The V(2)-O(2) bond length is 1.83 Å. The V(2)-O(3) bond length is 1.92 Å. Both V(2)-O(4) bond lengths are 1.95 Å. The V(2)-F(1) bond length is 2.01 Å. The V(2)-F(4) bond length is 1.95 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Mg(1), and one V(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Mg(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted square co-planar geometry to one Mg(1), one V(1), and two equivalent V(2) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one V(2) atom. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), one Mg(1), and one V(1) atom to form distorted corner-sharing FNa3MgV trigonal bipyramids. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Na(2) and one V(2) atom.