Na4OBr2 is (La,Ba)CuO4 structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1) and five equivalent Br(1) atoms to form a mixture of distorted corner and edge-sharing NaBr5O octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Na site, Na(2) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent Br(1) atoms. O(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form corner-sharing ONa6 octahedra. The corner-sharing octahedra are not tilted. Br(1) is bonded in a 9-coordinate geometry to four equivalent Na(2) and five equivalent Na(1) atoms.
Na4OBr2 is (La,Ba)CuO4 structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1) and five equivalent Br(1) atoms to form a mixture of distorted corner and edge-sharing NaBr5O octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Na(1)-O(1) bond length is 2.26 Å. There is one shorter (2.93 Å) and four longer (3.16 Å) Na(1)-Br(1) bond lengths. In the second Na site, Na(2) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent Br(1) atoms. Both Na(2)-O(1) bond lengths are 2.24 Å. All Na(2)-Br(1) bond lengths are 3.16 Å. O(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form corner-sharing ONa6 octahedra. The corner-sharing octahedra are not tilted. Br(1) is bonded in a 9-coordinate geometry to four equivalent Na(2) and five equivalent Na(1) atoms.