KSnAsS5 crystallizes in the orthorhombic Pbam space group. K(1) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(2) atoms. Sn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing SnS6 octahedra. As(1) is bonded in a trigonal non-coplanar geometry to one S(4) and two equivalent S(2) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to two equivalent Sn(1) and one S(4) atom. In the second S site, S(2) is bonded to two equivalent K(1), one Sn(1), and one As(1) atom to form a mixture of corner and edge-sharing SK2SnAs trigonal pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1) and two equivalent Sn(1) atoms. In the fourth S site, S(4) is bonded in a distorted water-like geometry to one As(1) and one S(1) atom.
KSnAsS5 crystallizes in the orthorhombic Pbam space group. K(1) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(2) atoms. There is one shorter (3.17 Å) and one longer (3.78 Å) K(1)-S(3) bond length. There are two shorter (3.22 Å) and two longer (3.45 Å) K(1)-S(2) bond lengths. Sn(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing SnS6 octahedra. Both Sn(1)-S(1) bond lengths are 2.69 Å. Both Sn(1)-S(2) bond lengths are 2.59 Å. Both Sn(1)-S(3) bond lengths are 2.51 Å. As(1) is bonded in a trigonal non-coplanar geometry to one S(4) and two equivalent S(2) atoms. The As(1)-S(4) bond length is 2.31 Å. Both As(1)-S(2) bond lengths are 2.22 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to two equivalent Sn(1) and one S(4) atom. The S(1)-S(4) bond length is 2.02 Å. In the second S site, S(2) is bonded to two equivalent K(1), one Sn(1), and one As(1) atom to form a mixture of corner and edge-sharing SK2SnAs trigonal pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1) and two equivalent Sn(1) atoms. In the fourth S site, S(4) is bonded in a distorted water-like geometry to one As(1) and one S(1) atom.