Na3V6N11 crystallizes in the tetragonal P4bm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one N(4), two equivalent N(1), and four equivalent N(2) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to four equivalent N(1) and four equivalent N(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form corner-sharing VN4 tetrahedra. In the second V site, V(2) is bonded to one N(3), one N(4), and two equivalent N(2) atoms to form corner-sharing VN4 tetrahedra. There are four inequivalent N sites. In the first N site, N(3) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second N site, N(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent V(2) atoms. In the third N site, N(1) is bonded to one Na(1), one Na(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing NNa2V2 trigonal pyramids. In the fourth N site, N(2) is bonded in a distorted bent 120 degrees geometry to one Na(2), two equivalent Na(1), one V(1), and one V(2) atom.
Na3V6N11 crystallizes in the tetragonal P4bm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one N(4), two equivalent N(1), and four equivalent N(2) atoms. The Na(1)-N(4) bond length is 2.69 Å. Both Na(1)-N(1) bond lengths are 2.63 Å. There are two shorter (2.92 Å) and two longer (2.99 Å) Na(1)-N(2) bond lengths. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to four equivalent N(1) and four equivalent N(2) atoms. All Na(2)-N(1) bond lengths are 2.80 Å. All Na(2)-N(2) bond lengths are 2.77 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form corner-sharing VN4 tetrahedra. The V(1)-N(2) bond length is 1.80 Å. The V(1)-N(3) bond length is 1.88 Å. There is one shorter (1.78 Å) and one longer (1.79 Å) V(1)-N(1) bond length. In the second V site, V(2) is bonded to one N(3), one N(4), and two equivalent N(2) atoms to form corner-sharing VN4 tetrahedra. The V(2)-N(3) bond length is 1.88 Å. The V(2)-N(4) bond length is 1.79 Å. Both V(2)-N(2) bond lengths are 1.79 Å. There are four inequivalent N sites. In the first N site, N(3) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second N site, N(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent V(2) atoms. In the third N site, N(1) is bonded to one Na(1), one Na(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing NNa2V2 trigonal pyramids. In the fourth N site, N(2) is bonded in a distorted bent 120 degrees geometry to one Na(2), two equivalent Na(1), one V(1), and one V(2) atom.