Na2BiO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 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(2)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. 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 Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. 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(4)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)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 2-13°. 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(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second Bi site, Bi(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°.
Na2BiO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 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(2)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Na(1)-O(1) bond lengths are 2.39 Å. Both Na(1)-O(2) bond lengths are 2.49 Å. Both Na(1)-O(3) bond lengths are 2.44 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 Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. Both Na(2)-O(1) bond lengths are 2.68 Å. Both Na(2)-O(2) bond lengths are 2.41 Å. Both Na(2)-O(3) bond lengths are 2.36 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(4)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)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 2-13°. Both Na(3)-O(1) bond lengths are 2.41 Å. Both Na(3)-O(2) bond lengths are 2.45 Å. Both Na(3)-O(3) bond lengths are 2.58 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(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-13°. Both Na(4)-O(1) bond lengths are 2.46 Å. Both Na(4)-O(2) bond lengths are 2.57 Å. Both Na(4)-O(3) bond lengths are 2.39 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(4)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. Both Bi(1)-O(1) bond lengths are 2.14 Å. Both Bi(1)-O(2) bond lengths are 2.15 Å. Both Bi(1)-O(3) bond lengths are 2.16 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(4)O6 octahedra, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. Both Bi(2)-O(1) bond lengths are 2.35 Å. Both Bi(2)-O(2) bond lengths are 2.38 Å. Both Bi(2)-O(3) bond lengths are 2.38 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Bi(1), and one Bi(2) atom to form a mixture of corner and edge-sharing ONa4Bi2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°.