Na5CeO6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Ce(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Ce(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Ce(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Ce(1)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, edges with three equivalent Ce(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. In the fourth Na site, Na(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ce(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-14°. Ce(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CeO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ce(1) atom to form a mixture of edge and corner-sharing ONa5Ce octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second O site, O(1) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ce(1) atom to form a mixture of distorted edge and corner-sharing ONa5Ce octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(2) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ce(1) atom to form a mixture of edge and corner-sharing ONa5Ce octahedra. The corner-sharing octahedral tilt angles range from 0-10°.
Na5CeO6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Ce(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Ce(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. There is one shorter (2.43 Å) and one longer (2.45 Å) Na(1)-O(1) bond length. There is one shorter (2.42 Å) and one longer (2.56 Å) Na(1)-O(2) bond length. There is one shorter (2.39 Å) and one longer (2.61 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Ce(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Ce(1)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. Both Na(2)-O(1) bond lengths are 2.72 Å. Both Na(2)-O(2) bond lengths are 2.39 Å. Both Na(2)-O(3) bond lengths are 2.38 Å. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, edges with three equivalent Ce(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-14°. Both Na(3)-O(1) bond lengths are 2.42 Å. Both Na(3)-O(2) bond lengths are 2.43 Å. Both Na(3)-O(3) bond lengths are 2.47 Å. In the fourth Na site, Na(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ce(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-14°. Both Na(4)-O(1) bond lengths are 2.42 Å. Both Na(4)-O(2) bond lengths are 2.46 Å. Both Na(4)-O(3) bond lengths are 2.42 Å. Ce(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CeO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both Ce(1)-O(1) bond lengths are 2.13 Å. Both Ce(1)-O(2) bond lengths are 2.18 Å. Both Ce(1)-O(3) bond lengths are 2.18 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ce(1) atom to form a mixture of edge and corner-sharing ONa5Ce octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second O site, O(1) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ce(1) atom to form a mixture of distorted edge and corner-sharing ONa5Ce octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(2) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Ce(1) atom to form a mixture of edge and corner-sharing ONa5Ce octahedra. The corner-sharing octahedral tilt angles range from 0-10°.