Na4W(NO)2 is Aluminum carbonitride-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(2)N4O square pyramids, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent W(1)N2O2 tetrahedra, and edges with two equivalent Na(1)O4 tetrahedra. In the second Na site, Na(2) is bonded to two equivalent N(1), two equivalent N(2), and one O(1) atom to form distorted NaN4O square pyramids that share  a cornercorner with one W(1)N2O2 tetrahedra, corners with two equivalent Na(1)O4 tetrahedra, corners with three equivalent Na(4)N2O2 tetrahedra, edges with two equivalent Na(2)N4O square pyramids,  an edgeedge with one Na(4)N2O2 tetrahedra, and edges with two equivalent W(1)N2O2 tetrahedra. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to two equivalent N(1), two equivalent N(2), and one O(1) atom. In the fourth Na site, Na(4) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form distorted NaN2O2 tetrahedra that share corners with three equivalent Na(2)N4O square pyramids, corners with four equivalent Na(1)O4 tetrahedra, corners with four equivalent W(1)N2O2 tetrahedra, and  an edgeedge with one Na(2)N4O square pyramid. W(1) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form WN2O2 tetrahedra that share  a cornercorner with one Na(2)N4O square pyramid, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and edges with two equivalent Na(2)N4O square pyramids. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one W(1) atom to form distorted NNa5W octahedra that share corners with two equivalent N(2)Na5W octahedra, corners with two equivalent O(2)Na3W tetrahedra, edges with two equivalent N(1)Na5W octahedra, and edges with four equivalent N(2)Na5W octahedra. The corner-sharing octahedral tilt angles range from 19-38°. In the second N site, N(2) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one W(1) atom to form distorted NNa5W octahedra that share corners with two equivalent N(1)Na5W octahedra, corners with two equivalent O(2)Na3W tetrahedra, edges with two equivalent N(2)Na5W octahedra, and edges with four equivalent N(1)Na5W octahedra. The corner-sharing octahedral tilt angles range from 19-38°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one W(1) atom. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(1), and one W(1) atom to form ONa3W tetrahedra that share corners with two equivalent N(1)Na5W octahedra, corners with two equivalent N(2)Na5W octahedra, and  an edgeedge with one O(2)Na3W tetrahedra. The corner-sharing octahedral tilt angles range from 62-69°.
Na4W(NO)2 is Aluminum carbonitride-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(2)N4O square pyramids, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent W(1)N2O2 tetrahedra, and edges with two equivalent Na(1)O4 tetrahedra. There is one shorter (2.38 Å) and one longer (2.43 Å) Na(1)-O(1) bond length. There is one shorter (2.32 Å) and one longer (2.33 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) is bonded to two equivalent N(1), two equivalent N(2), and one O(1) atom to form distorted NaN4O square pyramids that share  a cornercorner with one W(1)N2O2 tetrahedra, corners with two equivalent Na(1)O4 tetrahedra, corners with three equivalent Na(4)N2O2 tetrahedra, edges with two equivalent Na(2)N4O square pyramids,  an edgeedge with one Na(4)N2O2 tetrahedra, and edges with two equivalent W(1)N2O2 tetrahedra. There is one shorter (2.48 Å) and one longer (2.53 Å) Na(2)-N(1) bond length. There is one shorter (2.53 Å) and one longer (2.68 Å) Na(2)-N(2) bond length. The Na(2)-O(1) bond length is 2.53 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to two equivalent N(1), two equivalent N(2), and one O(1) atom. There is one shorter (2.49 Å) and one longer (2.54 Å) Na(3)-N(1) bond length. There is one shorter (2.46 Å) and one longer (2.53 Å) Na(3)-N(2) bond length. The Na(3)-O(1) bond length is 2.91 Å. In the fourth Na site, Na(4) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form distorted NaN2O2 tetrahedra that share corners with three equivalent Na(2)N4O square pyramids, corners with four equivalent Na(1)O4 tetrahedra, corners with four equivalent W(1)N2O2 tetrahedra, and  an edgeedge with one Na(2)N4O square pyramid. The Na(4)-N(1) bond length is 2.41 Å. The Na(4)-N(2) bond length is 2.41 Å. The Na(4)-O(1) bond length is 2.40 Å. The Na(4)-O(2) bond length is 2.37 Å. W(1) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form WN2O2 tetrahedra that share  a cornercorner with one Na(2)N4O square pyramid, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and edges with two equivalent Na(2)N4O square pyramids. The W(1)-N(1) bond length is 1.85 Å. The W(1)-N(2) bond length is 1.85 Å. The W(1)-O(1) bond length is 1.91 Å. The W(1)-O(2) bond length is 1.91 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one W(1) atom to form distorted NNa5W octahedra that share corners with two equivalent N(2)Na5W octahedra, corners with two equivalent O(2)Na3W tetrahedra, edges with two equivalent N(1)Na5W octahedra, and edges with four equivalent N(2)Na5W octahedra. The corner-sharing octahedral tilt angles range from 19-38°. In the second N site, N(2) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one W(1) atom to form distorted NNa5W octahedra that share corners with two equivalent N(1)Na5W octahedra, corners with two equivalent O(2)Na3W tetrahedra, edges with two equivalent N(2)Na5W octahedra, and edges with four equivalent N(1)Na5W octahedra. The corner-sharing octahedral tilt angles range from 19-38°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one W(1) atom. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(1), and one W(1) atom to form ONa3W tetrahedra that share corners with two equivalent N(1)Na5W octahedra, corners with two equivalent N(2)Na5W octahedra, and  an edgeedge with one O(2)Na3W tetrahedra. The corner-sharing octahedral tilt angles range from 62-69°.