Na3NbN2 is Brookite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted bent 120 degrees geometry to one N(1) and one N(2) atom. In the second Na site, Na(2) is bonded in a distorted T-shaped geometry to one N(1) and two equivalent N(2) atoms. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Nb(1) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), two equivalent Na(3), and two equivalent Nb(1) atoms. In the second N site, N(2) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(3), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing NNa5Nb octahedra. The corner-sharing octahedral tilt angles are 63°.
Na3NbN2 is Brookite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted bent 120 degrees geometry to one N(1) and one N(2) atom. The Na(1)-N(1) bond length is 2.58 Å. The Na(1)-N(2) bond length is 2.45 Å. In the second Na site, Na(2) is bonded in a distorted T-shaped geometry to one N(1) and two equivalent N(2) atoms. The Na(2)-N(1) bond length is 2.72 Å. There is one shorter (2.43 Å) and one longer (2.54 Å) Na(2)-N(2) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. There is one shorter (2.65 Å) and one longer (2.97 Å) Na(3)-N(1) bond length. There is one shorter (2.44 Å) and one longer (2.46 Å) Na(3)-N(2) bond length. Nb(1) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) atoms. The Nb(1)-N(2) bond length is 1.87 Å. There is one shorter (2.01 Å) and one longer (2.03 Å) Nb(1)-N(1) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), two equivalent Na(3), and two equivalent Nb(1) atoms. In the second N site, N(2) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(3), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing NNa5Nb octahedra. The corner-sharing octahedral tilt angles are 63°.