Na2SnO3 is Caswellsilverite-like structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Sn(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Sn(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the second Na site, Na(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Sn(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. In the third Na site, Na(3) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with six equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. Sn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) 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 two equivalent Na(1)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Sn(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-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(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Na(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.
Na2SnO3 is Caswellsilverite-like structured and crystallizes in the monoclinic Cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Sn(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Sn(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. The Na(1)-O(3) bond length is 2.28 Å. The Na(1)-O(4) bond length is 2.28 Å. Both Na(1)-O(1) bond lengths are 2.48 Å. Both Na(1)-O(2) bond lengths are 2.48 Å. In the second Na site, Na(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Sn(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. The Na(2)-O(3) bond length is 2.42 Å. The Na(2)-O(4) bond length is 2.42 Å. There is one shorter (2.32 Å) and one longer (2.51 Å) Na(2)-O(1) bond length. There is one shorter (2.32 Å) and one longer (2.52 Å) Na(2)-O(2) bond length. In the third Na site, Na(3) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with six equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. The Na(3)-O(3) bond length is 2.34 Å. The Na(3)-O(4) bond length is 2.34 Å. Both Na(3)-O(1) bond lengths are 2.34 Å. Both Na(3)-O(2) bond lengths are 2.34 Å. Sn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) 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 two equivalent Na(1)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Sn(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. The Sn(1)-O(3) bond length is 2.11 Å. The Sn(1)-O(4) bond length is 2.11 Å. Both Sn(1)-O(1) bond lengths are 2.10 Å. Both Sn(1)-O(2) bond lengths are 2.10 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-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(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Na(1), one Na(3), two equivalent Na(2), and two equivalent Sn(1) atoms to form a mixture of corner and edge-sharing ONa4Sn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.