Na3BiO4 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2) and four equivalent O(1) 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(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-15°. In the second Na site, Na(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. In the third Na site, Na(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. Bi(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form BiO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Bi(1) atom to form ONa5Bi octahedra that share corners with two equivalent O(1)Na5Bi octahedra, corners with four equivalent O(2)Na4Bi2 octahedra, edges with six equivalent O(2)Na4Bi2 octahedra, and edges with six equivalent O(1)Na5Bi octahedra. The corner-sharing octahedral tilt angles range from 6-17°. In the second O site, O(2) is bonded to one Na(1), one Na(2), two equivalent Na(3), and two equivalent Bi(1) atoms to form ONa4Bi2 octahedra that share corners with two equivalent O(2)Na4Bi2 octahedra, corners with four equivalent O(1)Na5Bi octahedra, edges with six equivalent O(2)Na4Bi2 octahedra, and edges with six equivalent O(1)Na5Bi octahedra. The corner-sharing octahedral tilt angles range from 6-12°.
Na3BiO4 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2) and four equivalent O(1) 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(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-15°. Both Na(1)-O(2) bond lengths are 2.41 Å. There are two shorter (2.35 Å) and two longer (2.43 Å) Na(1)-O(1) bond lengths. In the second Na site, Na(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. Both Na(2)-O(2) bond lengths are 2.67 Å. There are two shorter (2.30 Å) and two longer (2.46 Å) Na(2)-O(1) bond lengths. In the third Na site, Na(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. Both Na(3)-O(1) bond lengths are 2.31 Å. There are two shorter (2.37 Å) and two longer (2.54 Å) Na(3)-O(2) bond lengths. Bi(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form BiO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. Both Bi(1)-O(1) bond lengths are 2.07 Å. There are two shorter (2.18 Å) and two longer (2.20 Å) Bi(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Bi(1) atom to form ONa5Bi octahedra that share corners with two equivalent O(1)Na5Bi octahedra, corners with four equivalent O(2)Na4Bi2 octahedra, edges with six equivalent O(2)Na4Bi2 octahedra, and edges with six equivalent O(1)Na5Bi octahedra. The corner-sharing octahedral tilt angles range from 6-17°. In the second O site, O(2) is bonded to one Na(1), one Na(2), two equivalent Na(3), and two equivalent Bi(1) atoms to form ONa4Bi2 octahedra that share corners with two equivalent O(2)Na4Bi2 octahedra, corners with four equivalent O(1)Na5Bi octahedra, edges with six equivalent O(2)Na4Bi2 octahedra, and edges with six equivalent O(1)Na5Bi octahedra. The corner-sharing octahedral tilt angles range from 6-12°.