NaKSnF6 crystallizes in the orthorhombic Pna2_1 space group. K(1) is bonded in a 8-coordinate geometry to one F(1), one F(2), one F(4), one F(5), two equivalent F(3), and two equivalent F(6) atoms. Na(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form NaF6 octahedra that share corners with four equivalent Sn(1)F6 octahedra and  an edgeedge with one Sn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-45°. Sn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form SnF6 octahedra that share corners with four equivalent Na(1)F6 octahedra and  an edgeedge with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-45°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Na(1), and one Sn(1) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the sixth F site, F(6) is bonded to two equivalent K(1), one Na(1), and one Sn(1) atom to form distorted corner-sharing FK2NaSn tetrahedra.
NaKSnF6 crystallizes in the orthorhombic Pna2_1 space group. K(1) is bonded in a 8-coordinate geometry to one F(1), one F(2), one F(4), one F(5), two equivalent F(3), and two equivalent F(6) atoms. The K(1)-F(1) bond length is 2.72 Å. The K(1)-F(2) bond length is 2.77 Å. The K(1)-F(4) bond length is 2.73 Å. The K(1)-F(5) bond length is 2.73 Å. There is one shorter (2.69 Å) and one longer (2.80 Å) K(1)-F(3) bond length. There is one shorter (2.70 Å) and one longer (2.76 Å) K(1)-F(6) bond length. Na(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form NaF6 octahedra that share corners with four equivalent Sn(1)F6 octahedra and  an edgeedge with one Sn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-45°. The Na(1)-F(1) bond length is 2.23 Å. The Na(1)-F(2) bond length is 2.18 Å. The Na(1)-F(3) bond length is 2.45 Å. The Na(1)-F(4) bond length is 2.26 Å. The Na(1)-F(5) bond length is 2.24 Å. The Na(1)-F(6) bond length is 2.28 Å. Sn(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form SnF6 octahedra that share corners with four equivalent Na(1)F6 octahedra and  an edgeedge with one Na(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-45°. The Sn(1)-F(1) bond length is 1.97 Å. The Sn(1)-F(2) bond length is 1.97 Å. The Sn(1)-F(3) bond length is 1.99 Å. The Sn(1)-F(4) bond length is 1.98 Å. The Sn(1)-F(5) bond length is 1.97 Å. The Sn(1)-F(6) bond length is 2.00 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Na(1), and one Sn(1) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one K(1), one Na(1), and one Sn(1) atom. In the sixth F site, F(6) is bonded to two equivalent K(1), one Na(1), and one Sn(1) atom to form distorted corner-sharing FK2NaSn tetrahedra.