Na2MgV2(OF)4 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted NaOF5 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O4F2 octahedra, edges with two equivalent Na(1)OF5 octahedra, edges with two equivalent Na(2)OF5 octahedra, and edges with two equivalent Mg(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 14-60°. 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,  a cornercorner with one Mg(1)O4F trigonal bipyramid, edges with two equivalent Na(1)OF5 octahedra, and edges with two equivalent Na(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. Mg(1) is bonded to one O(1), one O(4), two equivalent O(2), and one F(3) atom to form distorted MgO4F trigonal bipyramids that share  a cornercorner with one Na(2)OF5 octahedra,  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent Mg(1)O4F trigonal bipyramids,  an edgeedge with one V(1)O4F2 octahedra, edges with two equivalent Na(1)OF5 octahedra, and edges with two equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 27-91°. 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, corners with four equivalent Na(1)OF5 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 14-60°. 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 Na(1)OF5 octahedra, 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 14-59°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped 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 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 rectangular see-saw-like 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 to one Na(1), two equivalent Na(2), and one V(2) atom to form distorted FNa3V trigonal pyramids that share corners with two equivalent F(3)Na2MgV trigonal pyramids, corners with two equivalent F(1)Na3V trigonal pyramids, and edges with two equivalent F(2)Na3V trigonal pyramids. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form distorted FNa3V trigonal pyramids that share corners with two equivalent F(2)Na3V trigonal pyramids, corners with three equivalent F(3)Na2MgV trigonal pyramids,  an edgeedge with one F(3)Na2MgV trigonal pyramid, and edges with two equivalent F(1)Na3V trigonal pyramids. In the third F site, F(3) is bonded to two equivalent Na(1), one Mg(1), and one V(1) atom to form FNa2MgV trigonal pyramids that share corners with two equivalent F(3)Na2MgV trigonal pyramids, corners with two equivalent F(1)Na3V trigonal pyramids, corners with three equivalent F(2)Na3V trigonal pyramids, and  an edgeedge with one F(2)Na3V trigonal pyramid. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one V(2) atom.
Na2MgV2(OF)4 crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted NaOF5 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent V(1)O4F2 octahedra, edges with two equivalent Na(1)OF5 octahedra, edges with two equivalent Na(2)OF5 octahedra, and edges with two equivalent Mg(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 14-60°. The Na(1)-O(2) bond length is 2.50 Å. The Na(1)-F(1) bond length is 2.33 Å. Both Na(1)-F(2) bond lengths are 2.37 Å. There is one shorter (2.38 Å) and one longer (2.40 Å) Na(1)-F(3) bond length. 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,  a cornercorner with one Mg(1)O4F trigonal bipyramid, edges with two equivalent Na(1)OF5 octahedra, and edges with two equivalent Na(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. The Na(2)-O(1) bond length is 2.46 Å. The Na(2)-F(2) bond length is 2.40 Å. Both Na(2)-F(1) bond lengths are 2.39 Å. There is one shorter (2.39 Å) and one longer (2.41 Å) Na(2)-F(4) bond length. Mg(1) is bonded to one O(1), one O(4), two equivalent O(2), and one F(3) atom to form distorted MgO4F trigonal bipyramids that share  a cornercorner with one Na(2)OF5 octahedra,  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent Mg(1)O4F trigonal bipyramids,  an edgeedge with one V(1)O4F2 octahedra, edges with two equivalent Na(1)OF5 octahedra, and edges with two equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 27-91°. The Mg(1)-O(1) bond length is 2.04 Å. The Mg(1)-O(4) bond length is 2.21 Å. There is one shorter (2.11 Å) and one longer (2.12 Å) Mg(1)-O(2) bond length. The Mg(1)-F(3) bond length is 2.00 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, corners with four equivalent Na(1)OF5 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 14-60°. The V(1)-O(1) bond length is 1.70 Å. The V(1)-O(4) bond length is 2.22 Å. Both V(1)-O(3) bond lengths are 1.98 Å. The V(1)-F(2) bond length is 1.94 Å. The V(1)-F(3) bond length is 2.10 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 Na(1)OF5 octahedra, 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 14-59°. The V(2)-O(2) bond length is 1.81 Å. The V(2)-O(3) bond length is 1.94 Å. Both V(2)-O(4) bond lengths are 1.93 Å. The V(2)-F(1) bond length is 1.96 Å. The V(2)-F(4) bond length is 2.04 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped 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 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 rectangular see-saw-like 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 to one Na(1), two equivalent Na(2), and one V(2) atom to form distorted FNa3V trigonal pyramids that share corners with two equivalent F(3)Na2MgV trigonal pyramids, corners with two equivalent F(1)Na3V trigonal pyramids, and edges with two equivalent F(2)Na3V trigonal pyramids. In the second F site, F(2) is bonded to one Na(2), two equivalent Na(1), and one V(1) atom to form distorted FNa3V trigonal pyramids that share corners with two equivalent F(2)Na3V trigonal pyramids, corners with three equivalent F(3)Na2MgV trigonal pyramids,  an edgeedge with one F(3)Na2MgV trigonal pyramid, and edges with two equivalent F(1)Na3V trigonal pyramids. In the third F site, F(3) is bonded to two equivalent Na(1), one Mg(1), and one V(1) atom to form FNa2MgV trigonal pyramids that share corners with two equivalent F(3)Na2MgV trigonal pyramids, corners with two equivalent F(1)Na3V trigonal pyramids, corners with three equivalent F(2)Na3V trigonal pyramids, and  an edgeedge with one F(2)Na3V trigonal pyramid. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one V(2) atom.