Na8MgW2(NO)4 crystallizes in the triclinic P1 space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Mg(1)N3O tetrahedra, corners with two equivalent W(1)N2O2 tetrahedra, and corners with two equivalent W(2)N2O2 tetrahedra. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one N(1), one N(2), one N(3), one N(4), and one O(3) atom. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one N(1), one N(2), one N(3), one N(4), and one O(1) atom. In the fifth Na site, Na(5) is bonded in a 4-coordinate geometry to one N(2), one N(4), one O(1), and one O(4) atom. In the sixth Na site, Na(6) is bonded in a 4-coordinate geometry to one N(1), one N(2), one N(3), and one N(4) atom. In the seventh Na site, Na(7) is bonded in a distorted bent 150 degrees geometry to one N(1) and one O(4) atom. In the eighth Na site, Na(8) is bonded in a 3-coordinate geometry to one N(2), one N(4), one O(1), and one O(2) atom. Mg(1) is bonded to one N(1), one N(2), one N(3), and one O(3) atom to form distorted MgN3O tetrahedra that share  a cornercorner with one Na(2)O4 tetrahedra,  a cornercorner with one W(1)N2O2 tetrahedra, and corners with three equivalent W(2)N2O2 tetrahedra. There are two inequivalent W sites. In the first W site, W(1) is bonded to one N(2), one N(4), one O(1), and one O(4) atom to form WN2O2 tetrahedra that share  a cornercorner with one Mg(1)N3O tetrahedra and corners with two equivalent Na(2)O4 tetrahedra. In the second W site, W(2) is bonded to one N(1), one N(3), one O(2), and one O(3) atom to form WN2O2 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra and corners with three equivalent Mg(1)N3O tetrahedra. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Na(3), one Na(4), one Na(6), one Na(7), one Mg(1), and one W(2) atom. In the second N site, N(2) is bonded in a 7-coordinate geometry to one Na(3), one Na(4), one Na(5), one Na(6), one Na(8), one Mg(1), and one W(1) atom. In the third N site, N(3) is bonded in a 5-coordinate geometry to one Na(3), one Na(4), one Na(6), one Mg(1), and one W(2) atom. In the fourth N site, N(4) is bonded to one Na(3), one Na(4), one Na(5), one Na(6), one Na(8), and one W(1) atom to form distorted NNa5W octahedra that share  a cornercorner with one O(2)Na3W tetrahedra and edges with two equivalent O(1)Na5W pentagonal pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(4), one Na(5), one Na(8), and one W(1) atom to form distorted ONa5W pentagonal pyramids that share corners with three equivalent O(2)Na3W tetrahedra and edges with two equivalent N(4)Na5W octahedra. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(8), and one W(2) atom to form distorted ONa3W tetrahedra that share  a cornercorner with one N(4)Na5W octahedra and corners with three equivalent O(1)Na5W pentagonal pyramids. The corner-sharing octahedral tilt angles are 70°. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one W(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(5), one Na(7), and one W(1) atom.
Na8MgW2(NO)4 crystallizes in the triclinic P1 space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Na(1)-O(1) bond length is 2.63 Å. The Na(1)-O(2) bond length is 2.35 Å. The Na(1)-O(3) bond length is 2.41 Å. The Na(1)-O(4) bond length is 2.54 Å. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Mg(1)N3O tetrahedra, corners with two equivalent W(1)N2O2 tetrahedra, and corners with two equivalent W(2)N2O2 tetrahedra. The Na(2)-O(1) bond length is 2.48 Å. The Na(2)-O(2) bond length is 2.34 Å. The Na(2)-O(3) bond length is 2.66 Å. The Na(2)-O(4) bond length is 2.57 Å. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one N(1), one N(2), one N(3), one N(4), and one O(3) atom. The Na(3)-N(1) bond length is 2.93 Å. The Na(3)-N(2) bond length is 2.66 Å. The Na(3)-N(3) bond length is 2.49 Å. The Na(3)-N(4) bond length is 2.45 Å. The Na(3)-O(3) bond length is 2.54 Å. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one N(1), one N(2), one N(3), one N(4), and one O(1) atom. The Na(4)-N(1) bond length is 2.73 Å. The Na(4)-N(2) bond length is 3.00 Å. The Na(4)-N(3) bond length is 2.60 Å. The Na(4)-N(4) bond length is 2.44 Å. The Na(4)-O(1) bond length is 2.50 Å. In the fifth Na site, Na(5) is bonded in a 4-coordinate geometry to one N(2), one N(4), one O(1), and one O(4) atom. The Na(5)-N(2) bond length is 2.52 Å. The Na(5)-N(4) bond length is 2.42 Å. The Na(5)-O(1) bond length is 2.47 Å. The Na(5)-O(4) bond length is 2.47 Å. In the sixth Na site, Na(6) is bonded in a 4-coordinate geometry to one N(1), one N(2), one N(3), and one N(4) atom. The Na(6)-N(1) bond length is 2.51 Å. The Na(6)-N(2) bond length is 2.44 Å. The Na(6)-N(3) bond length is 2.71 Å. The Na(6)-N(4) bond length is 2.49 Å. In the seventh Na site, Na(7) is bonded in a distorted bent 150 degrees geometry to one N(1) and one O(4) atom. The Na(7)-N(1) bond length is 2.56 Å. The Na(7)-O(4) bond length is 2.32 Å. In the eighth Na site, Na(8) is bonded in a 3-coordinate geometry to one N(2), one N(4), one O(1), and one O(2) atom. The Na(8)-N(2) bond length is 3.01 Å. The Na(8)-N(4) bond length is 2.40 Å. The Na(8)-O(1) bond length is 2.59 Å. The Na(8)-O(2) bond length is 2.20 Å. Mg(1) is bonded to one N(1), one N(2), one N(3), and one O(3) atom to form distorted MgN3O tetrahedra that share  a cornercorner with one Na(2)O4 tetrahedra,  a cornercorner with one W(1)N2O2 tetrahedra, and corners with three equivalent W(2)N2O2 tetrahedra. The Mg(1)-N(1) bond length is 2.07 Å. The Mg(1)-N(2) bond length is 2.20 Å. The Mg(1)-N(3) bond length is 2.06 Å. The Mg(1)-O(3) bond length is 2.05 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one N(2), one N(4), one O(1), and one O(4) atom to form WN2O2 tetrahedra that share  a cornercorner with one Mg(1)N3O tetrahedra and corners with two equivalent Na(2)O4 tetrahedra. The W(1)-N(2) bond length is 1.86 Å. The W(1)-N(4) bond length is 1.84 Å. The W(1)-O(1) bond length is 1.93 Å. The W(1)-O(4) bond length is 1.91 Å. In the second W site, W(2) is bonded to one N(1), one N(3), one O(2), and one O(3) atom to form WN2O2 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra and corners with three equivalent Mg(1)N3O tetrahedra. The W(2)-N(1) bond length is 1.91 Å. The W(2)-N(3) bond length is 1.90 Å. The W(2)-O(2) bond length is 1.97 Å. The W(2)-O(3) bond length is 2.06 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Na(3), one Na(4), one Na(6), one Na(7), one Mg(1), and one W(2) atom. In the second N site, N(2) is bonded in a 7-coordinate geometry to one Na(3), one Na(4), one Na(5), one Na(6), one Na(8), one Mg(1), and one W(1) atom. In the third N site, N(3) is bonded in a 5-coordinate geometry to one Na(3), one Na(4), one Na(6), one Mg(1), and one W(2) atom. In the fourth N site, N(4) is bonded to one Na(3), one Na(4), one Na(5), one Na(6), one Na(8), and one W(1) atom to form distorted NNa5W octahedra that share  a cornercorner with one O(2)Na3W tetrahedra and edges with two equivalent O(1)Na5W pentagonal pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(4), one Na(5), one Na(8), and one W(1) atom to form distorted ONa5W pentagonal pyramids that share corners with three equivalent O(2)Na3W tetrahedra and edges with two equivalent N(4)Na5W octahedra. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(8), and one W(2) atom to form distorted ONa3W tetrahedra that share  a cornercorner with one N(4)Na5W octahedra and corners with three equivalent O(1)Na5W pentagonal pyramids. The corner-sharing octahedral tilt angles are 70°. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Mg(1), and one W(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(5), one Na(7), and one W(1) atom.