Na4Sn2C4SO16 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), two equivalent O(3), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-82°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-82°. 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 edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. S(1) is bonded to four equivalent O(4) atoms to form SO4 tetrahedra that share edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one S(1) atom. In the second O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Sn(1), and one C(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Sn(1), and one C(1) atom. In the fourth O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Sn(1), and one C(1) atom.
Na4Sn2C4SO16 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), two equivalent O(3), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-82°. Both Na(1)-O(2) bond lengths are 2.48 Å. Both Na(1)-O(3) bond lengths are 2.44 Å. Both Na(1)-O(4) bond lengths are 2.33 Å. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Sn(1)O6 octahedra, and  an edgeedge with one S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-82°. Both Na(2)-O(1) bond lengths are 2.40 Å. Both Na(2)-O(2) bond lengths are 2.63 Å. Both Na(2)-O(4) bond lengths are 2.31 Å. 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 edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. Both Sn(1)-O(1) bond lengths are 2.26 Å. Both Sn(1)-O(2) bond lengths are 2.31 Å. Both Sn(1)-O(3) bond lengths are 2.28 Å. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(2) bond length is 1.31 Å. The C(1)-O(3) bond length is 1.30 Å. S(1) is bonded to four equivalent O(4) atoms to form SO4 tetrahedra that share edges with two equivalent Na(1)O6 octahedra and edges with two equivalent Na(2)O6 octahedra. All S(1)-O(4) bond lengths are 1.50 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one S(1) atom. In the second O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Sn(1), and one C(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Sn(1), and one C(1) atom. In the fourth O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Sn(1), and one C(1) atom.