Na4SnO3 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted edge and corner-sharing NaO5 square pyramids. In the second Na site, Na(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted edge and corner-sharing NaO5 square pyramids. In the third Na site, Na(3) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. In the fourth Na site, Na(4) is bonded in a distorted bent 150 degrees geometry to two equivalent O(1) atoms. Sn(1) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(3) atom. 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), two equivalent Na(4), and one Sn(1) atom to form a mixture of distorted edge and corner-sharing ONa5Sn octahedra. The corner-sharing octahedral tilt angles range from 7-19°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Sn(1) atom to form a mixture of distorted edge and corner-sharing ONa5Sn octahedra. The corner-sharing octahedral tilt angles range from 16-25°. In the third O site, O(3) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Sn(1) atom to form a mixture of edge and corner-sharing ONa5Sn octahedra. The corner-sharing octahedral tilt angles range from 7-25°.
Na4SnO3 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted edge and corner-sharing NaO5 square pyramids. The Na(1)-O(1) bond length is 2.70 Å. There is one shorter (2.35 Å) and one longer (2.38 Å) Na(1)-O(2) bond length. There is one shorter (2.37 Å) and one longer (2.47 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted edge and corner-sharing NaO5 square pyramids. The Na(2)-O(1) bond length is 2.46 Å. There is one shorter (2.34 Å) and one longer (2.56 Å) Na(2)-O(2) bond length. There is one shorter (2.38 Å) and one longer (2.40 Å) Na(2)-O(3) bond length. In the third Na site, Na(3) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. The Na(3)-O(1) bond length is 2.26 Å. The Na(3)-O(2) bond length is 2.23 Å. The Na(3)-O(3) bond length is 2.25 Å. In the fourth Na site, Na(4) is bonded in a distorted bent 150 degrees geometry to two equivalent O(1) atoms. There is one shorter (2.25 Å) and one longer (2.26 Å) Na(4)-O(1) bond length. Sn(1) is bonded in a 3-coordinate geometry to one O(1), one O(2), and one O(3) atom. The Sn(1)-O(1) bond length is 2.04 Å. The Sn(1)-O(2) bond length is 2.03 Å. The Sn(1)-O(3) bond length is 2.03 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), two equivalent Na(4), and one Sn(1) atom to form a mixture of distorted edge and corner-sharing ONa5Sn octahedra. The corner-sharing octahedral tilt angles range from 7-19°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Sn(1) atom to form a mixture of distorted edge and corner-sharing ONa5Sn octahedra. The corner-sharing octahedral tilt angles range from 16-25°. In the third O site, O(3) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Sn(1) atom to form a mixture of edge and corner-sharing ONa5Sn octahedra. The corner-sharing octahedral tilt angles range from 7-25°.