Na4Mo(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 two equivalent Na(3)N4O square pyramids, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent Mo(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 corners with three equivalent Na(3)N4O square pyramids,  a cornercorner with one Mo(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, edges with three equivalent Na(3)N4O square pyramids,  an edgeedge with one Na(4)N2O2 tetrahedra, and edges with two equivalent Mo(1)N2O2 tetrahedra. In the third Na site, Na(3) is bonded to two equivalent N(1), two equivalent N(2), and one O(1) atom to form distorted NaN4O square pyramids that share corners with three equivalent Na(2)N4O square pyramids,  a cornercorner with one Na(4)N2O2 tetrahedra, corners with two equivalent Na(1)O4 tetrahedra, corners with three equivalent Mo(1)N2O2 tetrahedra, edges with two equivalent Na(3)N4O square pyramids, edges with three equivalent Na(2)N4O square pyramids,  an edgeedge with one Mo(1)N2O2 tetrahedra, and edges with two equivalent Na(4)N2O2 tetrahedra. 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  a cornercorner with one Na(3)N4O square pyramid, corners with three equivalent Na(2)N4O square pyramids, corners with four equivalent Na(1)O4 tetrahedra, corners with four equivalent Mo(1)N2O2 tetrahedra,  an edgeedge with one Na(2)N4O square pyramid, and edges with two equivalent Na(3)N4O square pyramids. Mo(1) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form MoN2O2 tetrahedra that share  a cornercorner with one Na(2)N4O square pyramid, corners with three equivalent Na(3)N4O square pyramids, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra,  an edgeedge with one Na(3)N4O square pyramid, 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 Mo(1) atom to form distorted NNa5Mo octahedra that share corners with two equivalent N(2)Na5Mo octahedra, corners with two equivalent O(1)Na5Mo octahedra, corners with two equivalent O(2)Na3Mo tetrahedra, edges with two equivalent N(1)Na5Mo octahedra, edges with two equivalent O(1)Na5Mo octahedra, and edges with four equivalent N(2)Na5Mo octahedra. The corner-sharing octahedral tilt angles range from 13-34°. In the second N site, N(2) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one Mo(1) atom to form distorted NNa5Mo octahedra that share corners with two equivalent N(1)Na5Mo octahedra, corners with two equivalent O(2)Na3Mo tetrahedra, edges with two equivalent N(2)Na5Mo octahedra, edges with three equivalent O(1)Na5Mo octahedra, and edges with four equivalent N(1)Na5Mo octahedra. The corner-sharing octahedral tilt angles range from 17-34°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Mo(1) atom to form distorted ONa5Mo octahedra that share corners with two equivalent N(1)Na5Mo octahedra, corners with six equivalent O(2)Na3Mo tetrahedra,  an edgeedge with one O(1)Na5Mo octahedra, edges with two equivalent N(1)Na5Mo octahedra, and edges with three equivalent N(2)Na5Mo octahedra. The corner-sharing octahedral tilt angles range from 13-14°. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(1), and one Mo(1) atom to form ONa3Mo tetrahedra that share corners with two equivalent N(1)Na5Mo octahedra, corners with two equivalent N(2)Na5Mo octahedra, corners with six equivalent O(1)Na5Mo octahedra, and  an edgeedge with one O(2)Na3Mo tetrahedra. The corner-sharing octahedral tilt angles range from 55-69°.
Na4Mo(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 two equivalent Na(3)N4O square pyramids, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent Mo(1)N2O2 tetrahedra, and edges with two equivalent Na(1)O4 tetrahedra. There is one shorter (2.39 Å) and one longer (2.42 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 corners with three equivalent Na(3)N4O square pyramids,  a cornercorner with one Mo(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, edges with three equivalent Na(3)N4O square pyramids,  an edgeedge with one Na(4)N2O2 tetrahedra, and edges with two equivalent Mo(1)N2O2 tetrahedra. There is one shorter (2.48 Å) and one longer (2.51 Å) Na(2)-N(1) bond length. There is one shorter (2.52 Å) and one longer (2.68 Å) Na(2)-N(2) bond length. The Na(2)-O(1) bond length is 2.48 Å. In the third Na site, Na(3) is bonded to two equivalent N(1), two equivalent N(2), and one O(1) atom to form distorted NaN4O square pyramids that share corners with three equivalent Na(2)N4O square pyramids,  a cornercorner with one Na(4)N2O2 tetrahedra, corners with two equivalent Na(1)O4 tetrahedra, corners with three equivalent Mo(1)N2O2 tetrahedra, edges with two equivalent Na(3)N4O square pyramids, edges with three equivalent Na(2)N4O square pyramids,  an edgeedge with one Mo(1)N2O2 tetrahedra, and edges with two equivalent Na(4)N2O2 tetrahedra. 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 (2.54 Å) Na(3)-N(2) bond length. The Na(3)-O(1) bond length is 2.78 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  a cornercorner with one Na(3)N4O square pyramid, corners with three equivalent Na(2)N4O square pyramids, corners with four equivalent Na(1)O4 tetrahedra, corners with four equivalent Mo(1)N2O2 tetrahedra,  an edgeedge with one Na(2)N4O square pyramid, and edges with two equivalent Na(3)N4O square pyramids. The Na(4)-N(1) bond length is 2.43 Å. The Na(4)-N(2) bond length is 2.42 Å. The Na(4)-O(1) bond length is 2.40 Å. The Na(4)-O(2) bond length is 2.35 Å. Mo(1) is bonded to one N(1), one N(2), one O(1), and one O(2) atom to form MoN2O2 tetrahedra that share  a cornercorner with one Na(2)N4O square pyramid, corners with three equivalent Na(3)N4O square pyramids, corners with four equivalent Na(4)N2O2 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra,  an edgeedge with one Na(3)N4O square pyramid, and edges with two equivalent Na(2)N4O square pyramids. The Mo(1)-N(1) bond length is 1.82 Å. The Mo(1)-N(2) bond length is 1.82 Å. The Mo(1)-O(1) bond length is 1.91 Å. The Mo(1)-O(2) bond length is 1.90 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 Mo(1) atom to form distorted NNa5Mo octahedra that share corners with two equivalent N(2)Na5Mo octahedra, corners with two equivalent O(1)Na5Mo octahedra, corners with two equivalent O(2)Na3Mo tetrahedra, edges with two equivalent N(1)Na5Mo octahedra, edges with two equivalent O(1)Na5Mo octahedra, and edges with four equivalent N(2)Na5Mo octahedra. The corner-sharing octahedral tilt angles range from 13-34°. In the second N site, N(2) is bonded to one Na(4), two equivalent Na(2), two equivalent Na(3), and one Mo(1) atom to form distorted NNa5Mo octahedra that share corners with two equivalent N(1)Na5Mo octahedra, corners with two equivalent O(2)Na3Mo tetrahedra, edges with two equivalent N(2)Na5Mo octahedra, edges with three equivalent O(1)Na5Mo octahedra, and edges with four equivalent N(1)Na5Mo octahedra. The corner-sharing octahedral tilt angles range from 17-34°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Mo(1) atom to form distorted ONa5Mo octahedra that share corners with two equivalent N(1)Na5Mo octahedra, corners with six equivalent O(2)Na3Mo tetrahedra,  an edgeedge with one O(1)Na5Mo octahedra, edges with two equivalent N(1)Na5Mo octahedra, and edges with three equivalent N(2)Na5Mo octahedra. The corner-sharing octahedral tilt angles range from 13-14°. In the second O site, O(2) is bonded to one Na(4), two equivalent Na(1), and one Mo(1) atom to form ONa3Mo tetrahedra that share corners with two equivalent N(1)Na5Mo octahedra, corners with two equivalent N(2)Na5Mo octahedra, corners with six equivalent O(1)Na5Mo octahedra, and  an edgeedge with one O(2)Na3Mo tetrahedra. The corner-sharing octahedral tilt angles range from 55-69°.