Na2SnF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Sn(1)F6 octahedra,  an edgeedge with one Na(1)F6 octahedra, and  an edgeedge with one Sn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. Sn(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form SnF6 octahedra that share corners with eight equivalent Na(1)F6 octahedra and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Sn(1) atom. In the second F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one Sn(1) atom.
Na2SnF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Na(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Sn(1)F6 octahedra,  an edgeedge with one Na(1)F6 octahedra, and  an edgeedge with one Sn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-60°. Both Na(1)-F(1) bond lengths are 2.27 Å. There are two shorter (2.22 Å) and two longer (2.33 Å) Na(1)-F(2) bond lengths. Sn(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form SnF6 octahedra that share corners with eight equivalent Na(1)F6 octahedra and edges with two equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. Both Sn(1)-F(1) bond lengths are 1.98 Å. All Sn(1)-F(2) bond lengths are 1.98 Å. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one Sn(1) atom. In the second F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one Sn(1) atom.