Na2SnO3 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(3)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, corners with two equivalent Sn(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, edges with two equivalent Sn(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 11-13°. 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(3)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, corners with two equivalent Sn(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, edges with two equivalent Sn(2)O6 octahedra, and edges with six equivalent Na(1)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(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Sn(1)O6 octahedra, edges with three equivalent Sn(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SnO6 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 Sn(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. In the second Sn site, Sn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SnO6 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 Sn(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Sn(1), and one Sn(2) atom to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Sn(1), and one Sn(2) atom to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Sn(1), and one Sn(2) atom to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°.
Na2SnO3 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(3)O6 octahedra, corners with two equivalent Sn(1)O6 octahedra, corners with two equivalent Sn(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, edges with two equivalent Sn(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 11-13°. Both Na(1)-O(1) bond lengths are 2.43 Å. There is one shorter (2.32 Å) and one longer (2.51 Å) Na(1)-O(2) bond length. There is one shorter (2.32 Å) and one longer (2.50 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 Sn(1)O6 octahedra, corners with two equivalent Sn(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, edges with two equivalent Sn(2)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Na(2)-O(1) bond lengths are 2.28 Å. Both Na(2)-O(2) bond lengths are 2.49 Å. Both Na(2)-O(3) bond lengths are 2.49 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 Sn(1)O6 octahedra, edges with three equivalent Sn(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. Both Na(3)-O(1) bond lengths are 2.34 Å. Both Na(3)-O(2) bond lengths are 2.34 Å. Both Na(3)-O(3) bond lengths are 2.34 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SnO6 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 Sn(2)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. Both Sn(1)-O(1) bond lengths are 2.11 Å. Both Sn(1)-O(2) bond lengths are 2.10 Å. Both Sn(1)-O(3) bond lengths are 2.10 Å. In the second Sn site, Sn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SnO6 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 Sn(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. Both Sn(2)-O(1) bond lengths are 2.11 Å. Both Sn(2)-O(2) bond lengths are 2.10 Å. Both Sn(2)-O(3) bond lengths are 2.10 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Sn(1), and one Sn(2) atom to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Sn(1), and one Sn(2) atom to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Sn(1), and one Sn(2) atom to form a mixture of edge and corner-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°.