Na2SnO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fddd space group. There are two 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(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with five equivalent Na(2)O6 octahedra, and edges with five equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. 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 Sn(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with four equivalent Sn(1)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. Sn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form SnO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with three equivalent Sn(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 5-9°.
Na2SnO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fddd space group. There are two 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(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with five equivalent Na(2)O6 octahedra, and edges with five equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both Na(1)-O(2) bond lengths are 2.30 Å. There are two shorter (2.39 Å) and two longer (2.41 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 Sn(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with four equivalent Sn(1)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. Both Na(2)-O(2) bond lengths are 2.41 Å. There are two shorter (2.32 Å) and two longer (2.48 Å) Na(2)-O(1) bond lengths. Sn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form SnO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with three equivalent Sn(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. Both Sn(1)-O(2) bond lengths are 2.11 Å. There are two shorter (2.10 Å) and two longer (2.11 Å) Sn(1)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 5-9°.