Na2ZrO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three 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(2)O6 octahedra, corners with four equivalent Na(3)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Zr(1)O6 octahedra, edges with three equivalent Zr(2)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. 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(1)O6 octahedra, corners with two equivalent Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with two equivalent Zr(2)O6 octahedra, and edges with six equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. 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(1)O6 octahedra, corners with two equivalent Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with two equivalent Zr(2)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(3)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Zr(2)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-12°. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(3)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Zr(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(1), one Na(2), two equivalent Na(3), one Zr(1), and one Zr(2) atom to form a mixture of corner and edge-sharing ONa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(1) is bonded to one Na(1), one Na(2), two equivalent Na(3), one Zr(1), and one Zr(2) atom to form a mixture of corner and edge-sharing ONa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the third O site, O(2) is bonded to one Na(1), one Na(2), two equivalent Na(3), one Zr(1), and one Zr(2) atom to form a mixture of corner and edge-sharing ONa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°.
Na2ZrO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three 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(2)O6 octahedra, corners with four equivalent Na(3)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Zr(1)O6 octahedra, edges with three equivalent Zr(2)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. Both Na(1)-O(1) bond lengths are 2.37 Å. Both Na(1)-O(2) bond lengths are 2.37 Å. Both Na(1)-O(3) bond lengths are 2.37 Å. 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(1)O6 octahedra, corners with two equivalent Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with two equivalent Zr(2)O6 octahedra, and edges with six equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Na(2)-O(1) bond lengths are 2.52 Å. Both Na(2)-O(2) bond lengths are 2.52 Å. Both Na(2)-O(3) bond lengths are 2.29 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(1)O6 octahedra, corners with two equivalent Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with two equivalent Zr(2)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. There is one shorter (2.34 Å) and one longer (2.54 Å) Na(3)-O(1) bond length. There is one shorter (2.34 Å) and one longer (2.54 Å) Na(3)-O(2) bond length. Both Na(3)-O(3) bond lengths are 2.45 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(3)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Zr(2)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-12°. Both Zr(1)-O(1) bond lengths are 2.12 Å. Both Zr(1)-O(2) bond lengths are 2.12 Å. Both Zr(1)-O(3) bond lengths are 2.13 Å. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(3)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Zr(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. Both Zr(2)-O(1) bond lengths are 2.11 Å. Both Zr(2)-O(2) bond lengths are 2.12 Å. Both Zr(2)-O(3) bond lengths are 2.14 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(1), one Na(2), two equivalent Na(3), one Zr(1), and one Zr(2) atom to form a mixture of corner and edge-sharing ONa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(1) is bonded to one Na(1), one Na(2), two equivalent Na(3), one Zr(1), and one Zr(2) atom to form a mixture of corner and edge-sharing ONa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the third O site, O(2) is bonded to one Na(1), one Na(2), two equivalent Na(3), one Zr(1), and one Zr(2) atom to form a mixture of corner and edge-sharing ONa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°.