K5NaS4(O6Cl)2 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a distorted q4 geometry to eight equivalent O(2) and two equivalent Cl(1) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent O(1), four equivalent O(2), and two equivalent Cl(1) atoms. Na(1) is bonded in an octahedral geometry to four equivalent O(1) and two equivalent Cl(1) atoms. S(1) is bonded in a trigonal non-coplanar geometry to one O(1) and two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(2), and one S(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to two equivalent K(2), one Na(1), and one S(1) atom. Cl(1) is bonded to one K(1), four equivalent K(2), and one Na(1) atom to form corner-sharing ClK5Na octahedra. The corner-sharing octahedral tilt angles range from 0-28°.
K5NaS4(O6Cl)2 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a distorted q4 geometry to eight equivalent O(2) and two equivalent Cl(1) atoms. All K(1)-O(2) bond lengths are 3.26 Å. Both K(1)-Cl(1) bond lengths are 3.11 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent O(1), four equivalent O(2), and two equivalent Cl(1) atoms. Both K(2)-O(1) bond lengths are 3.26 Å. There are two shorter (2.91 Å) and two longer (2.94 Å) K(2)-O(2) bond lengths. Both K(2)-Cl(1) bond lengths are 3.19 Å. Na(1) is bonded in an octahedral geometry to four equivalent O(1) and two equivalent Cl(1) atoms. All Na(1)-O(1) bond lengths are 2.39 Å. Both Na(1)-Cl(1) bond lengths are 2.78 Å. S(1) is bonded in a trigonal non-coplanar geometry to one O(1) and two equivalent O(2) atoms. The S(1)-O(1) bond length is 1.47 Å. Both S(1)-O(2) bond lengths are 1.47 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(2), and one S(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to two equivalent K(2), one Na(1), and one S(1) atom. Cl(1) is bonded to one K(1), four equivalent K(2), and one Na(1) atom to form corner-sharing ClK5Na octahedra. The corner-sharing octahedral tilt angles range from 0-28°.