Na4MgMn2O6 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(4), and one O(6) atom. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(6) atom. In the fourth Na site, Na(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NaO6 octahedra that share corners with four equivalent Mg(1)O4 tetrahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, edges with three equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O5 trigonal bipyramids. Mg(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form distorted MgO4 tetrahedra that share corners with four equivalent Na(4)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-69°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mg(1)O4 tetrahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Mg(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 65-83°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share corners with four equivalent Mg(1)O4 tetrahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, edges with three equivalent Na(4)O6 octahedra, and edges with two equivalent Mn(1)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Mg(1), and one Mn(2) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Mg(1), one Mn(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Mg(1), one Mn(1), and one Mn(2) atom. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(1), one Na(3), one Na(4), one Mg(1), one Mn(1), and one Mn(2) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Mn(1), and one Mn(2) atom.
Na4MgMn2O6 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.34 Å. The Na(1)-O(3) bond length is 2.49 Å. The Na(1)-O(5) bond length is 2.34 Å. The Na(1)-O(6) bond length is 2.30 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(4), and one O(6) atom. The Na(2)-O(1) bond length is 2.25 Å. The Na(2)-O(3) bond length is 2.32 Å. The Na(2)-O(4) bond length is 2.44 Å. The Na(2)-O(6) bond length is 2.34 Å. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(6) atom. The Na(3)-O(1) bond length is 2.30 Å. The Na(3)-O(2) bond length is 2.20 Å. The Na(3)-O(3) bond length is 2.63 Å. The Na(3)-O(5) bond length is 2.51 Å. The Na(3)-O(6) bond length is 2.30 Å. In the fourth Na site, Na(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NaO6 octahedra that share corners with four equivalent Mg(1)O4 tetrahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, edges with three equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O5 trigonal bipyramids. The Na(4)-O(1) bond length is 2.54 Å. The Na(4)-O(2) bond length is 2.40 Å. The Na(4)-O(3) bond length is 2.65 Å. The Na(4)-O(4) bond length is 2.45 Å. The Na(4)-O(5) bond length is 2.37 Å. The Na(4)-O(6) bond length is 2.67 Å. Mg(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form distorted MgO4 tetrahedra that share corners with four equivalent Na(4)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-69°. The Mg(1)-O(2) bond length is 1.93 Å. The Mg(1)-O(3) bond length is 2.02 Å. The Mg(1)-O(4) bond length is 1.92 Å. The Mg(1)-O(5) bond length is 2.03 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mg(1)O4 tetrahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Mg(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 65-83°. The Mn(1)-O(1) bond length is 2.08 Å. The Mn(1)-O(3) bond length is 2.07 Å. The Mn(1)-O(4) bond length is 2.09 Å. The Mn(1)-O(5) bond length is 2.04 Å. The Mn(1)-O(6) bond length is 1.97 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share corners with four equivalent Mg(1)O4 tetrahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, edges with three equivalent Na(4)O6 octahedra, and edges with two equivalent Mn(1)O5 trigonal bipyramids. The Mn(2)-O(1) bond length is 2.03 Å. The Mn(2)-O(2) bond length is 1.92 Å. The Mn(2)-O(3) bond length is 2.35 Å. The Mn(2)-O(4) bond length is 2.41 Å. The Mn(2)-O(5) bond length is 2.26 Å. The Mn(2)-O(6) bond length is 2.03 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Mg(1), and one Mn(2) atom. In the third O site, O(3) is bonded in a 7-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Mg(1), one Mn(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Mg(1), one Mn(1), and one Mn(2) atom. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(1), one Na(3), one Na(4), one Mg(1), one Mn(1), and one Mn(2) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), one Mn(1), and one Mn(2) atom.