Na4MgV2O6 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(3), two equivalent O(1), and two equivalent O(2) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share edges with six equivalent V(1)O6 octahedra. Mg(1) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(3) atoms. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO6 octahedra that share edges with three equivalent Na(3)O6 octahedra and edges with three equivalent V(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), one Mg(1), and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and two equivalent V(1) atoms.
Na4MgV2O6 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(3), two equivalent O(1), and two equivalent O(2) atoms. The Na(1)-O(3) bond length is 2.60 Å. There is one shorter (2.24 Å) and one longer (2.31 Å) Na(1)-O(1) bond length. There is one shorter (2.28 Å) and one longer (2.35 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(2)-O(1) bond lengths are 2.46 Å. Both Na(2)-O(2) bond lengths are 2.52 Å. Both Na(2)-O(3) bond lengths are 2.28 Å. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share edges with six equivalent V(1)O6 octahedra. Both Na(3)-O(1) bond lengths are 2.55 Å. Both Na(3)-O(2) bond lengths are 2.53 Å. Both Na(3)-O(3) bond lengths are 2.50 Å. Mg(1) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Mg(1)-O(2) bond lengths are 2.18 Å. Both Mg(1)-O(3) bond lengths are 1.97 Å. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO6 octahedra that share edges with three equivalent Na(3)O6 octahedra and edges with three equivalent V(1)O6 octahedra. There is one shorter (2.04 Å) and one longer (2.12 Å) V(1)-O(1) bond length. There is one shorter (2.06 Å) and one longer (2.27 Å) V(1)-O(2) bond length. There is one shorter (2.11 Å) and one longer (2.13 Å) V(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Na(2), one Na(3), two equivalent Na(1), one Mg(1), and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and two equivalent V(1) atoms.