K2S5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one S(5), two equivalent S(2), two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. In the second K site, K(2) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(2), three equivalent K(1), and one S(2) atom to form a mixture of distorted corner and edge-sharing SK5S octahedra. The corner-sharing octahedral tilt angles range from 11-42°. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent K(1), two equivalent K(2), one S(1), and one S(5) atom. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent K(1), four equivalent K(2), and one S(4) atom. In the fourth S site, S(4) is bonded in a distorted pentagonal planar geometry to one K(2), two equivalent K(1), one S(3), and one S(5) atom. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one S(2), and one S(4) atom.
K2S5 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one S(5), two equivalent S(2), two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. The K(1)-S(5) bond length is 3.46 Å. There is one shorter (3.50 Å) and one longer (3.55 Å) K(1)-S(2) bond length. There is one shorter (3.33 Å) and one longer (3.80 Å) K(1)-S(3) bond length. There is one shorter (3.32 Å) and one longer (3.46 Å) K(1)-S(4) bond length. There are a spread of K(1)-S(1) bond distances ranging from 3.22-3.34 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. The K(2)-S(4) bond length is 3.39 Å. There is one shorter (3.34 Å) and one longer (3.44 Å) K(2)-S(1) bond length. There is one shorter (3.37 Å) and one longer (3.38 Å) K(2)-S(2) bond length. There are a spread of K(2)-S(3) bond distances ranging from 3.29-3.73 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to two equivalent K(2), three equivalent K(1), and one S(2) atom to form a mixture of distorted corner and edge-sharing SK5S octahedra. The corner-sharing octahedral tilt angles range from 11-42°. The S(1)-S(2) bond length is 2.05 Å. In the second S site, S(2) is bonded in a 6-coordinate geometry to two equivalent K(1), two equivalent K(2), one S(1), and one S(5) atom. The S(2)-S(5) bond length is 2.08 Å. In the third S site, S(3) is bonded in a 7-coordinate geometry to two equivalent K(1), four equivalent K(2), and one S(4) atom. The S(3)-S(4) bond length is 2.05 Å. In the fourth S site, S(4) is bonded in a distorted pentagonal planar geometry to one K(2), two equivalent K(1), one S(3), and one S(5) atom. The S(4)-S(5) bond length is 2.07 Å. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one S(2), and one S(4) atom.