Na3Mo2N5 crystallizes in the tetragonal I4_1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(4), and two equivalent N(2) atoms. In the second Na site, Na(2) is bonded in a distorted trigonal non-coplanar geometry to one N(1), one N(4), and one N(5) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent N(2), two equivalent N(3), and two equivalent N(5) atoms. In the fourth Na site, Na(4) is bonded in a square co-planar geometry to two equivalent N(1) and two equivalent N(2) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one N(1), one N(5), and two equivalent N(3) atoms to form corner-sharing MoN4 tetrahedra. In the second Mo site, Mo(2) is bonded to one N(2), one N(5), and two equivalent N(4) atoms to form corner-sharing MoN4 tetrahedra. There are five inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(4), and one Mo(1) atom. In the second N site, N(2) is bonded to one Na(3), one Na(4), two equivalent Na(1), and one Mo(2) atom to form distorted NNa4Mo trigonal bipyramids that share corners with two equivalent N(2)Na4Mo trigonal bipyramids, corners with three equivalent N(5)Na2Mo2 trigonal pyramids, and  an edgeedge with one N(2)Na4Mo trigonal bipyramid. In the third N site, N(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), and two equivalent Mo(1) atoms. In the fourth N site, N(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), and two equivalent Mo(2) atoms. In the fifth N site, N(5) is bonded to one Na(2), one Na(3), one Mo(1), and one Mo(2) atom to form distorted NNa2Mo2 trigonal pyramids that share corners with three equivalent N(2)Na4Mo trigonal bipyramids and  a cornercorner with one N(5)Na2Mo2 trigonal pyramid.
Na3Mo2N5 crystallizes in the tetragonal I4_1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(4), and two equivalent N(2) atoms. The Na(1)-N(1) bond length is 2.48 Å. The Na(1)-N(3) bond length is 2.58 Å. The Na(1)-N(4) bond length is 2.71 Å. There is one shorter (2.53 Å) and one longer (2.58 Å) Na(1)-N(2) bond length. In the second Na site, Na(2) is bonded in a distorted trigonal non-coplanar geometry to one N(1), one N(4), and one N(5) atom. The Na(2)-N(1) bond length is 2.41 Å. The Na(2)-N(4) bond length is 2.59 Å. The Na(2)-N(5) bond length is 2.34 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent N(2), two equivalent N(3), and two equivalent N(5) atoms. Both Na(3)-N(2) bond lengths are 2.54 Å. Both Na(3)-N(3) bond lengths are 2.80 Å. Both Na(3)-N(5) bond lengths are 2.93 Å. In the fourth Na site, Na(4) is bonded in a square co-planar geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Na(4)-N(1) bond lengths are 2.35 Å. Both Na(4)-N(2) bond lengths are 2.39 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one N(1), one N(5), and two equivalent N(3) atoms to form corner-sharing MoN4 tetrahedra. The Mo(1)-N(1) bond length is 1.75 Å. The Mo(1)-N(5) bond length is 1.97 Å. Both Mo(1)-N(3) bond lengths are 1.91 Å. In the second Mo site, Mo(2) is bonded to one N(2), one N(5), and two equivalent N(4) atoms to form corner-sharing MoN4 tetrahedra. The Mo(2)-N(2) bond length is 1.76 Å. The Mo(2)-N(5) bond length is 1.92 Å. There is one shorter (1.93 Å) and one longer (1.94 Å) Mo(2)-N(4) bond length. There are five inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(4), and one Mo(1) atom. In the second N site, N(2) is bonded to one Na(3), one Na(4), two equivalent Na(1), and one Mo(2) atom to form distorted NNa4Mo trigonal bipyramids that share corners with two equivalent N(2)Na4Mo trigonal bipyramids, corners with three equivalent N(5)Na2Mo2 trigonal pyramids, and  an edgeedge with one N(2)Na4Mo trigonal bipyramid. In the third N site, N(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), and two equivalent Mo(1) atoms. In the fourth N site, N(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), and two equivalent Mo(2) atoms. In the fifth N site, N(5) is bonded to one Na(2), one Na(3), one Mo(1), and one Mo(2) atom to form distorted NNa2Mo2 trigonal pyramids that share corners with three equivalent N(2)Na4Mo trigonal bipyramids and  a cornercorner with one N(5)Na2Mo2 trigonal pyramid.