Na8SnO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form NaO4 tetrahedra that share corners with two equivalent Sn(1)O4 tetrahedra, corners with six equivalent Na(1)O4 tetrahedra, corners with four equivalent Na(2)O4 trigonal pyramids, edges with two equivalent Na(3)O4 tetrahedra, and edges with three equivalent Na(2)O4 trigonal pyramids. In the second Na site, Na(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted NaO4 trigonal pyramids that share corners with four equivalent Na(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra, corners with six equivalent Na(2)O4 trigonal pyramids,  an edgeedge with one Sn(1)O4 tetrahedra, and edges with three equivalent Na(1)O4 tetrahedra. In the third Na site, Na(3) is bonded to one O(2) and three equivalent O(1) atoms to form NaO4 tetrahedra that share corners with three equivalent Na(3)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, corners with six equivalent Na(2)O4 trigonal pyramids, and edges with three equivalent Na(1)O4 tetrahedra. Sn(1) is bonded to one O(3) and three equivalent O(1) atoms to form SnO4 tetrahedra that share corners with six equivalent Na(1)O4 tetrahedra, corners with six equivalent Na(3)O4 tetrahedra, and edges with three equivalent Na(2)O4 trigonal pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), two equivalent Na(3), and one Sn(1) atom to form ONa4Sn trigonal bipyramids that share corners with two equivalent O(2)Na7 pentagonal bipyramids, corners with six equivalent O(1)Na4Sn trigonal bipyramids, and edges with two equivalent O(2)Na7 pentagonal bipyramids. In the second O site, O(2) is bonded to one Na(3), three equivalent Na(1), and three equivalent Na(2) atoms to form distorted ONa7 pentagonal bipyramids that share corners with three equivalent O(1)Na4Sn trigonal bipyramids, edges with three equivalent O(2)Na7 pentagonal bipyramids, and edges with three equivalent O(1)Na4Sn trigonal bipyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and one Sn(1) atom.
Na8SnO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form NaO4 tetrahedra that share corners with two equivalent Sn(1)O4 tetrahedra, corners with six equivalent Na(1)O4 tetrahedra, corners with four equivalent Na(2)O4 trigonal pyramids, edges with two equivalent Na(3)O4 tetrahedra, and edges with three equivalent Na(2)O4 trigonal pyramids. The Na(1)-O(1) bond length is 2.31 Å. The Na(1)-O(3) bond length is 2.40 Å. Both Na(1)-O(2) bond lengths are 2.32 Å. In the second Na site, Na(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted NaO4 trigonal pyramids that share corners with four equivalent Na(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra, corners with six equivalent Na(2)O4 trigonal pyramids,  an edgeedge with one Sn(1)O4 tetrahedra, and edges with three equivalent Na(1)O4 tetrahedra. The Na(2)-O(1) bond length is 2.31 Å. The Na(2)-O(3) bond length is 2.57 Å. Both Na(2)-O(2) bond lengths are 2.29 Å. In the third Na site, Na(3) is bonded to one O(2) and three equivalent O(1) atoms to form NaO4 tetrahedra that share corners with three equivalent Na(3)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, corners with six equivalent Na(2)O4 trigonal pyramids, and edges with three equivalent Na(1)O4 tetrahedra. The Na(3)-O(2) bond length is 2.40 Å. All Na(3)-O(1) bond lengths are 2.33 Å. Sn(1) is bonded to one O(3) and three equivalent O(1) atoms to form SnO4 tetrahedra that share corners with six equivalent Na(1)O4 tetrahedra, corners with six equivalent Na(3)O4 tetrahedra, and edges with three equivalent Na(2)O4 trigonal pyramids. The Sn(1)-O(3) bond length is 2.01 Å. All Sn(1)-O(1) bond lengths are 1.97 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), two equivalent Na(3), and one Sn(1) atom to form ONa4Sn trigonal bipyramids that share corners with two equivalent O(2)Na7 pentagonal bipyramids, corners with six equivalent O(1)Na4Sn trigonal bipyramids, and edges with two equivalent O(2)Na7 pentagonal bipyramids. In the second O site, O(2) is bonded to one Na(3), three equivalent Na(1), and three equivalent Na(2) atoms to form distorted ONa7 pentagonal bipyramids that share corners with three equivalent O(1)Na4Sn trigonal bipyramids, edges with three equivalent O(2)Na7 pentagonal bipyramids, and edges with three equivalent O(1)Na4Sn trigonal bipyramids. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and one Sn(1) atom.