K5H3S5O14 crystallizes in the monoclinic C2/m space group. There are six inequivalent K sites. In the first K site, K(1) is bonded to two equivalent O(3) and four equivalent O(8) atoms to form KO6 octahedra that share corners with four equivalent S(5)HO3 tetrahedra and edges with two equivalent K(6)O7 pentagonal bipyramids. In the second K site, K(2) is bonded in a distorted body-centered cubic geometry to four equivalent O(2) and four equivalent O(6) atoms. In the third K site, K(3) is bonded in a 9-coordinate geometry to two equivalent O(1), two equivalent O(4), two equivalent O(6), and three equivalent O(7) atoms. In the fourth K site, K(4) is bonded in a 9-coordinate geometry to one O(9), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms. In the fifth K site, K(5) is bonded to one O(9), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form distorted KO7 pentagonal bipyramids that share  a cornercorner with one S(5)HO3 tetrahedra, corners with two equivalent S(3)HO3 tetrahedra,  an edgeedge with one K(6)O7 pentagonal bipyramid, and  an edgeedge with one S(4)HO3 tetrahedra. In the sixth K site, K(6) is bonded to one O(5), two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms to form distorted KO7 pentagonal bipyramids that share corners with two equivalent S(5)HO3 tetrahedra, corners with three equivalent S(3)HO3 tetrahedra,  an edgeedge with one K(1)O6 octahedra, and  an edgeedge with one K(5)O7 pentagonal bipyramid. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one S(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one S(4) atom. In the third H site, H(3) is bonded in a single-bond geometry to one S(5) atom. There are five inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to two equivalent O(1) atoms. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one O(3) and two equivalent O(2) atoms. In the third S site, S(3) is bonded to one H(1), one O(5), and two equivalent O(4) atoms to form SHO3 tetrahedra that share corners with two equivalent K(5)O7 pentagonal bipyramids and corners with three equivalent K(6)O7 pentagonal bipyramids. In the fourth S site, S(4) is bonded to one H(2), one O(7), and two equivalent O(6) atoms to form SHO3 tetrahedra that share  an edgeedge with one K(5)O7 pentagonal bipyramid. In the fifth S site, S(5) is bonded to one H(3), one O(9), and two equivalent O(8) atoms to form SHO3 tetrahedra that share corners with two equivalent K(1)O6 octahedra,  a cornercorner with one K(5)O7 pentagonal bipyramid, and corners with two equivalent K(6)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 56°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(3), one K(4), one K(6), and one S(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(2), one K(4), one K(5), and one S(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(4), and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one K(3), one K(5), one K(6), and one S(3) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one K(6) and one S(3) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one K(2), one K(3), one K(5), and one S(4) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to three equivalent K(3) and one S(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one K(1), one K(4), one K(6), and one S(5) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one K(4), one K(5), and one S(5) atom.
K5H3S5O14 crystallizes in the monoclinic C2/m space group. There are six inequivalent K sites. In the first K site, K(1) is bonded to two equivalent O(3) and four equivalent O(8) atoms to form KO6 octahedra that share corners with four equivalent S(5)HO3 tetrahedra and edges with two equivalent K(6)O7 pentagonal bipyramids. Both K(1)-O(3) bond lengths are 2.71 Å. All K(1)-O(8) bond lengths are 2.75 Å. In the second K site, K(2) is bonded in a distorted body-centered cubic geometry to four equivalent O(2) and four equivalent O(6) atoms. All K(2)-O(2) bond lengths are 3.05 Å. All K(2)-O(6) bond lengths are 2.82 Å. In the third K site, K(3) is bonded in a 9-coordinate geometry to two equivalent O(1), two equivalent O(4), two equivalent O(6), and three equivalent O(7) atoms. Both K(3)-O(1) bond lengths are 2.83 Å. Both K(3)-O(4) bond lengths are 3.28 Å. Both K(3)-O(6) bond lengths are 2.89 Å. There is one shorter (2.81 Å) and two longer (3.32 Å) K(3)-O(7) bond lengths. In the fourth K site, K(4) is bonded in a 9-coordinate geometry to one O(9), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms. The K(4)-O(9) bond length is 2.78 Å. Both K(4)-O(1) bond lengths are 2.81 Å. Both K(4)-O(2) bond lengths are 3.02 Å. Both K(4)-O(3) bond lengths are 3.11 Å. Both K(4)-O(8) bond lengths are 2.89 Å. In the fifth K site, K(5) is bonded to one O(9), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form distorted KO7 pentagonal bipyramids that share  a cornercorner with one S(5)HO3 tetrahedra, corners with two equivalent S(3)HO3 tetrahedra,  an edgeedge with one K(6)O7 pentagonal bipyramid, and  an edgeedge with one S(4)HO3 tetrahedra. The K(5)-O(9) bond length is 2.84 Å. Both K(5)-O(2) bond lengths are 2.74 Å. Both K(5)-O(4) bond lengths are 2.75 Å. Both K(5)-O(6) bond lengths are 2.85 Å. In the sixth K site, K(6) is bonded to one O(5), two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms to form distorted KO7 pentagonal bipyramids that share corners with two equivalent S(5)HO3 tetrahedra, corners with three equivalent S(3)HO3 tetrahedra,  an edgeedge with one K(1)O6 octahedra, and  an edgeedge with one K(5)O7 pentagonal bipyramid. The K(6)-O(5) bond length is 2.89 Å. Both K(6)-O(1) bond lengths are 3.01 Å. Both K(6)-O(4) bond lengths are 2.86 Å. Both K(6)-O(8) bond lengths are 2.84 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one S(3) atom. The H(1)-S(3) bond length is 1.37 Å. In the second H site, H(2) is bonded in a single-bond geometry to one S(4) atom. The H(2)-S(4) bond length is 1.36 Å. In the third H site, H(3) is bonded in a single-bond geometry to one S(5) atom. The H(3)-S(5) bond length is 1.36 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to two equivalent O(1) atoms. Both S(1)-O(1) bond lengths are 1.51 Å. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one O(3) and two equivalent O(2) atoms. The S(2)-O(3) bond length is 1.48 Å. Both S(2)-O(2) bond lengths are 1.49 Å. In the third S site, S(3) is bonded to one H(1), one O(5), and two equivalent O(4) atoms to form SHO3 tetrahedra that share corners with two equivalent K(5)O7 pentagonal bipyramids and corners with three equivalent K(6)O7 pentagonal bipyramids. The S(3)-O(5) bond length is 1.46 Å. Both S(3)-O(4) bond lengths are 1.47 Å. In the fourth S site, S(4) is bonded to one H(2), one O(7), and two equivalent O(6) atoms to form SHO3 tetrahedra that share  an edgeedge with one K(5)O7 pentagonal bipyramid. The S(4)-O(7) bond length is 1.47 Å. Both S(4)-O(6) bond lengths are 1.48 Å. In the fifth S site, S(5) is bonded to one H(3), one O(9), and two equivalent O(8) atoms to form SHO3 tetrahedra that share corners with two equivalent K(1)O6 octahedra,  a cornercorner with one K(5)O7 pentagonal bipyramid, and corners with two equivalent K(6)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 56°. The S(5)-O(9) bond length is 1.47 Å. Both S(5)-O(8) bond lengths are 1.47 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(3), one K(4), one K(6), and one S(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(2), one K(4), one K(5), and one S(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(4), and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one K(3), one K(5), one K(6), and one S(3) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one K(6) and one S(3) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one K(2), one K(3), one K(5), and one S(4) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to three equivalent K(3) and one S(4) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one K(1), one K(4), one K(6), and one S(5) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one K(4), one K(5), and one S(5) atom.