Na4N3Br crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent Br(1) atoms. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one N(1), two equivalent N(2), and three equivalent Br(1) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent Br(1) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to one Na(2), two equivalent Na(1), and four equivalent Na(3) atoms. In the second N site, N(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), and two equivalent Na(3) atoms. Br(1) is bonded in a 9-coordinate geometry to two equivalent Na(1), three equivalent Na(2), and four equivalent Na(3) atoms.
Na4N3Br crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent Br(1) atoms. Both Na(1)-N(1) bond lengths are 2.91 Å. Both Na(1)-N(2) bond lengths are 2.41 Å. Both Na(1)-Br(1) bond lengths are 3.35 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one N(1), two equivalent N(2), and three equivalent Br(1) atoms. The Na(2)-N(1) bond length is 2.49 Å. Both Na(2)-N(2) bond lengths are 2.33 Å. There are a spread of Na(2)-Br(1) bond distances ranging from 2.88-3.47 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent Br(1) atoms. There is one shorter (2.80 Å) and one longer (2.90 Å) Na(3)-N(1) bond length. There is one shorter (2.38 Å) and one longer (2.39 Å) Na(3)-N(2) bond length. There is one shorter (3.00 Å) and one longer (3.34 Å) Na(3)-Br(1) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to one Na(2), two equivalent Na(1), and four equivalent Na(3) atoms. In the second N site, N(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), and two equivalent Na(3) atoms. Br(1) is bonded in a 9-coordinate geometry to two equivalent Na(1), three equivalent Na(2), and four equivalent Na(3) atoms.