Na5SbO5 crystallizes in the monoclinic C2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form distorted NaO5 square pyramids that share corners with two equivalent Na(2)O5 square pyramids, corners with three equivalent Na(1)O5 square pyramids, edges with three equivalent Sb(1)O6 octahedra, edges with two equivalent Na(1)O5 square pyramids, and edges with three equivalent Na(2)O5 square pyramids. In the second Na site, Na(2) is bonded to one O(1), one O(3), and three equivalent O(2) atoms to form distorted NaO5 square pyramids that share corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Na(1)O5 square pyramids, corners with three equivalent Na(2)O5 square pyramids, edges with two equivalent Sb(1)O6 octahedra, edges with two equivalent Na(2)O5 square pyramids, and edges with three equivalent Na(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 3-7°. In the third Na site, Na(3) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Sb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Na(2)O5 square pyramids, edges with four equivalent Na(2)O5 square pyramids, and edges with six equivalent Na(1)O5 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), three equivalent Na(1), and one Sb(1) atom to form distorted ONa5Sb octahedra that share corners with four equivalent O(1)Na5Sb octahedra, edges with two equivalent O(1)Na5Sb octahedra, edges with three equivalent O(3)Na4Sb2 octahedra, and edges with five equivalent O(2)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 1-24°. In the second O site, O(2) is bonded to one Na(1), one Na(3), three equivalent Na(2), and one Sb(1) atom to form ONa5Sb octahedra that share corners with two equivalent O(3)Na4Sb2 octahedra, corners with four equivalent O(2)Na5Sb octahedra, edges with two equivalent O(3)Na4Sb2 octahedra, edges with two equivalent O(2)Na5Sb octahedra, and edges with five equivalent O(1)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 1-29°. In the third O site, O(3) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Sb(1) atoms to form ONa4Sb2 octahedra that share corners with two equivalent O(3)Na4Sb2 octahedra, corners with four equivalent O(2)Na5Sb octahedra, edges with four equivalent O(2)Na5Sb octahedra, and edges with six equivalent O(1)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-16°.
Na5SbO5 crystallizes in the monoclinic C2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form distorted NaO5 square pyramids that share corners with two equivalent Na(2)O5 square pyramids, corners with three equivalent Na(1)O5 square pyramids, edges with three equivalent Sb(1)O6 octahedra, edges with two equivalent Na(1)O5 square pyramids, and edges with three equivalent Na(2)O5 square pyramids. The Na(1)-O(2) bond length is 2.39 Å. The Na(1)-O(3) bond length is 2.37 Å. There are a spread of Na(1)-O(1) bond distances ranging from 2.24-2.29 Å. In the second Na site, Na(2) is bonded to one O(1), one O(3), and three equivalent O(2) atoms to form distorted NaO5 square pyramids that share corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Na(1)O5 square pyramids, corners with three equivalent Na(2)O5 square pyramids, edges with two equivalent Sb(1)O6 octahedra, edges with two equivalent Na(2)O5 square pyramids, and edges with three equivalent Na(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 3-7°. The Na(2)-O(1) bond length is 2.37 Å. The Na(2)-O(3) bond length is 2.45 Å. There are a spread of Na(2)-O(2) bond distances ranging from 2.26-2.47 Å. In the third Na site, Na(3) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Na(3)-O(1) bond lengths are 2.20 Å. Both Na(3)-O(2) bond lengths are 2.32 Å. Sb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Na(2)O5 square pyramids, edges with four equivalent Na(2)O5 square pyramids, and edges with six equivalent Na(1)O5 square pyramids. The corner-sharing octahedra are not tilted. Both Sb(1)-O(1) bond lengths are 1.98 Å. Both Sb(1)-O(2) bond lengths are 2.01 Å. There is one shorter (2.12 Å) and one longer (2.27 Å) Sb(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), three equivalent Na(1), and one Sb(1) atom to form distorted ONa5Sb octahedra that share corners with four equivalent O(1)Na5Sb octahedra, edges with two equivalent O(1)Na5Sb octahedra, edges with three equivalent O(3)Na4Sb2 octahedra, and edges with five equivalent O(2)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 1-24°. In the second O site, O(2) is bonded to one Na(1), one Na(3), three equivalent Na(2), and one Sb(1) atom to form ONa5Sb octahedra that share corners with two equivalent O(3)Na4Sb2 octahedra, corners with four equivalent O(2)Na5Sb octahedra, edges with two equivalent O(3)Na4Sb2 octahedra, edges with two equivalent O(2)Na5Sb octahedra, and edges with five equivalent O(1)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 1-29°. In the third O site, O(3) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Sb(1) atoms to form ONa4Sb2 octahedra that share corners with two equivalent O(3)Na4Sb2 octahedra, corners with four equivalent O(2)Na5Sb octahedra, edges with four equivalent O(2)Na5Sb octahedra, and edges with six equivalent O(1)Na5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-16°.