Na2MgVF7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(3), and four equivalent F(2) atoms. In the second Na site, Na(2) is bonded in a distorted body-centered cubic geometry to four equivalent F(1) and four equivalent F(2) atoms. Mg(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form MgF6 octahedra that share corners with two equivalent Mg(1)F6 octahedra and corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form VF6 octahedra that share corners with four equivalent Mg(1)F6 octahedra. The corner-sharing octahedral tilt angles are 42°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), two equivalent Na(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing FNa3V tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Mg(1), and one V(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1) and two equivalent Mg(1) atoms.
Na2MgVF7 crystallizes in the orthorhombic Imma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(3), and four equivalent F(2) atoms. Both Na(1)-F(1) bond lengths are 2.26 Å. Both Na(1)-F(3) bond lengths are 2.88 Å. All Na(1)-F(2) bond lengths are 2.56 Å. In the second Na site, Na(2) is bonded in a distorted body-centered cubic geometry to four equivalent F(1) and four equivalent F(2) atoms. All Na(2)-F(1) bond lengths are 2.46 Å. All Na(2)-F(2) bond lengths are 2.79 Å. Mg(1) is bonded to two equivalent F(3) and four equivalent F(2) atoms to form MgF6 octahedra that share corners with two equivalent Mg(1)F6 octahedra and corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. Both Mg(1)-F(3) bond lengths are 1.95 Å. All Mg(1)-F(2) bond lengths are 2.01 Å. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form VF6 octahedra that share corners with four equivalent Mg(1)F6 octahedra. The corner-sharing octahedral tilt angles are 42°. Both V(1)-F(1) bond lengths are 2.00 Å. All V(1)-F(2) bond lengths are 1.97 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), two equivalent Na(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing FNa3V tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Mg(1), and one V(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1) and two equivalent Mg(1) atoms.