Na3LaN6 crystallizes in the orthorhombic Fddd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form NaN6 octahedra that share corners with two equivalent La(1)N6 octahedra, corners with four equivalent Na(2)N6 octahedra, edges with two equivalent La(1)N6 octahedra, and edges with four equivalent Na(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the second Na site, Na(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form NaN6 octahedra that share corners with two equivalent Na(1)N6 octahedra, corners with two equivalent Na(2)N6 octahedra, edges with two equivalent Na(1)N6 octahedra, edges with two equivalent Na(2)N6 octahedra, and edges with three equivalent La(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. La(1) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form LaN6 octahedra that share corners with two equivalent Na(1)N6 octahedra, edges with two equivalent Na(1)N6 octahedra, and edges with six equivalent Na(2)N6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent N sites. In the first N site, N(1) is bonded in a square co-planar geometry to one Na(1), two equivalent Na(2), and one La(1) atom. In the second N site, N(2) is bonded in a see-saw-like geometry to one Na(1), two equivalent Na(2), and one La(1) atom.
Na3LaN6 crystallizes in the orthorhombic Fddd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form NaN6 octahedra that share corners with two equivalent La(1)N6 octahedra, corners with four equivalent Na(2)N6 octahedra, edges with two equivalent La(1)N6 octahedra, and edges with four equivalent Na(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. Both Na(1)-N(1) bond lengths are 2.71 Å. All Na(1)-N(2) bond lengths are 2.61 Å. In the second Na site, Na(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form NaN6 octahedra that share corners with two equivalent Na(1)N6 octahedra, corners with two equivalent Na(2)N6 octahedra, edges with two equivalent Na(1)N6 octahedra, edges with two equivalent Na(2)N6 octahedra, and edges with three equivalent La(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. Both Na(2)-N(1) bond lengths are 2.64 Å. There are two shorter (2.40 Å) and two longer (2.59 Å) Na(2)-N(2) bond lengths. La(1) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form LaN6 octahedra that share corners with two equivalent Na(1)N6 octahedra, edges with two equivalent Na(1)N6 octahedra, and edges with six equivalent Na(2)N6 octahedra. The corner-sharing octahedra are not tilted. Both La(1)-N(1) bond lengths are 2.48 Å. All La(1)-N(2) bond lengths are 2.37 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a square co-planar geometry to one Na(1), two equivalent Na(2), and one La(1) atom. In the second N site, N(2) is bonded in a see-saw-like geometry to one Na(1), two equivalent Na(2), and one La(1) atom.