K4Mn2H16S4O23 crystallizes in the triclinic P1 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 3-coordinate geometry to one O(10), one O(20), and one O(6) atom. In the second K site, K(2) is bonded in a 9-coordinate geometry to one H(15), one O(12), one O(14), one O(15), one O(19), one O(20), one O(4), one O(6), and one O(8) atom. In the third K site, K(3) is bonded in a 8-coordinate geometry to one H(2), one H(6), one O(11), one O(17), one O(19), one O(3), one O(7), and one O(9) atom. In the fourth K site, K(4) is bonded in a 8-coordinate geometry to one H(12), one H(2), one O(13), one O(15), one O(17), one O(22), one O(3), and one O(5) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(15), one O(2), one O(21), one O(23), and one O(7) atom to form MnO6 octahedra that share  a cornercorner with one S(2)O4 tetrahedra and  a cornercorner with one S(3)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(10), one O(13), one O(14), one O(16), one O(8), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one S(4)O4 tetrahedra. There are sixteen inequivalent H sites. In the first H site, H(1) is bonded in a distorted linear geometry to one O(1) and one O(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one K(3), one K(4), and one O(23) atom. In the third H site, H(3) is bonded in a single-bond geometry to one O(9) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(9) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(7) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one K(3) and one O(7) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(10) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(10) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one O(13) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one O(13) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one O(15) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one K(4) and one O(15) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one O(14) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one O(14) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one K(2) and one O(1) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one O(23) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one O(4), one O(6), and one O(8) atom. In the second S site, S(2) is bonded to one O(11), one O(2), one O(3), and one O(5) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 40°. In the third S site, S(3) is bonded to one O(12), one O(18), one O(20), and one O(21) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 46°. In the fourth S site, S(4) is bonded to one O(16), one O(17), one O(19), and one O(22) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. There are twenty-three inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Mn(1), one H(1), and one H(15) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(1) and one S(2) atom. In the third O site, O(3) is bonded in a single-bond geometry to one K(3), one K(4), and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one K(2), one H(1), and one S(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one K(4) and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one K(1), one K(2), and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted water-like geometry to one K(3), one Mn(1), one H(5), and one H(6) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one K(2), one Mn(2), and one S(1) atom. In the ninth O site, O(9) is bonded in a distorted water-like geometry to one K(3), one Mn(2), one H(3), and one H(4) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one K(1), one Mn(2), one H(7), and one H(8) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one K(3) and one S(2) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one K(2) and one S(3) atom. In the thirteenth O site, O(13) is bonded in a distorted water-like geometry to one K(4), one Mn(2), one H(10), and one H(9) atom. In the fourteenth O site, O(14) is bonded in a distorted water-like geometry to one K(2), one Mn(2), one H(13), and one H(14) atom. In the fifteenth O site, O(15) is bonded in a distorted water-like geometry to one K(2), one K(4), one Mn(1), one H(11), and one H(12) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Mn(2) and one S(4) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one K(3), one K(4), and one S(4) atom. In the eighteenth O site, O(18) is bonded in a single-bond geometry to one S(3) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one K(2), one K(3), and one S(4) atom. In the twentieth O site, O(20) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one S(3) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one S(3) atom. In the twenty-second O site, O(22) is bonded in a single-bond geometry to one K(4) and one S(4) atom. In the twenty-third O site, O(23) is bonded in a distorted water-like geometry to one Mn(1), one H(16), and one H(2) atom.
K4Mn2H16S4O23 crystallizes in the triclinic P1 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 3-coordinate geometry to one O(10), one O(20), and one O(6) atom. The K(1)-O(10) bond length is 2.77 Å. The K(1)-O(20) bond length is 2.70 Å. The K(1)-O(6) bond length is 2.61 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one H(15), one O(12), one O(14), one O(15), one O(19), one O(20), one O(4), one O(6), and one O(8) atom. The K(2)-H(15) bond length is 2.92 Å. The K(2)-O(12) bond length is 3.09 Å. The K(2)-O(14) bond length is 2.75 Å. The K(2)-O(15) bond length is 3.14 Å. The K(2)-O(19) bond length is 3.21 Å. The K(2)-O(20) bond length is 2.70 Å. The K(2)-O(4) bond length is 2.95 Å. The K(2)-O(6) bond length is 2.77 Å. The K(2)-O(8) bond length is 2.83 Å. In the third K site, K(3) is bonded in a 8-coordinate geometry to one H(2), one H(6), one O(11), one O(17), one O(19), one O(3), one O(7), and one O(9) atom. The K(3)-H(2) bond length is 2.81 Å. The K(3)-H(6) bond length is 3.03 Å. The K(3)-O(11) bond length is 2.97 Å. The K(3)-O(17) bond length is 2.66 Å. The K(3)-O(19) bond length is 2.88 Å. The K(3)-O(3) bond length is 2.75 Å. The K(3)-O(7) bond length is 3.04 Å. The K(3)-O(9) bond length is 2.82 Å. In the fourth K site, K(4) is bonded in a 8-coordinate geometry to one H(12), one H(2), one O(13), one O(15), one O(17), one O(22), one O(3), and one O(5) atom. The K(4)-H(12) bond length is 2.88 Å. The K(4)-H(2) bond length is 2.91 Å. The K(4)-O(13) bond length is 2.79 Å. The K(4)-O(15) bond length is 2.92 Å. The K(4)-O(17) bond length is 2.64 Å. The K(4)-O(22) bond length is 2.92 Å. The K(4)-O(3) bond length is 2.76 Å. The K(4)-O(5) bond length is 2.97 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(15), one O(2), one O(21), one O(23), and one O(7) atom to form MnO6 octahedra that share  a cornercorner with one S(2)O4 tetrahedra and  a cornercorner with one S(3)O4 tetrahedra. The Mn(1)-O(1) bond length is 2.27 Å. The Mn(1)-O(15) bond length is 2.40 Å. The Mn(1)-O(2) bond length is 2.06 Å. The Mn(1)-O(21) bond length is 2.07 Å. The Mn(1)-O(23) bond length is 2.36 Å. The Mn(1)-O(7) bond length is 2.43 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(13), one O(14), one O(16), one O(8), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one S(4)O4 tetrahedra. The Mn(2)-O(10) bond length is 2.40 Å. The Mn(2)-O(13) bond length is 2.42 Å. The Mn(2)-O(14) bond length is 2.42 Å. The Mn(2)-O(16) bond length is 2.04 Å. The Mn(2)-O(8) bond length is 2.03 Å. The Mn(2)-O(9) bond length is 2.37 Å. There are sixteen inequivalent H sites. In the first H site, H(1) is bonded in a distorted linear geometry to one O(1) and one O(4) atom. The H(1)-O(1) bond length is 1.02 Å. The H(1)-O(4) bond length is 1.65 Å. In the second H site, H(2) is bonded in a single-bond geometry to one K(3), one K(4), and one O(23) atom. The H(2)-O(23) bond length is 0.98 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(9) atom. The H(3)-O(9) bond length is 0.99 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(9) atom. The H(4)-O(9) bond length is 1.00 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(7) atom. The H(5)-O(7) bond length is 0.99 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one K(3) and one O(7) atom. The H(6)-O(7) bond length is 0.99 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(10) atom. The H(7)-O(10) bond length is 0.99 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(10) atom. The H(8)-O(10) bond length is 0.99 Å. In the ninth H site, H(9) is bonded in a single-bond geometry to one O(13) atom. The H(9)-O(13) bond length is 1.00 Å. In the tenth H site, H(10) is bonded in a single-bond geometry to one O(13) atom. The H(10)-O(13) bond length is 0.99 Å. In the eleventh H site, H(11) is bonded in a single-bond geometry to one O(15) atom. The H(11)-O(15) bond length is 0.99 Å. In the twelfth H site, H(12) is bonded in a single-bond geometry to one K(4) and one O(15) atom. The H(12)-O(15) bond length is 0.99 Å. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one O(14) atom. The H(13)-O(14) bond length is 1.00 Å. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one O(14) atom. The H(14)-O(14) bond length is 0.98 Å. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one K(2) and one O(1) atom. The H(15)-O(1) bond length is 0.98 Å. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one O(23) atom. The H(16)-O(23) bond length is 0.98 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one O(4), one O(6), and one O(8) atom. The S(1)-O(4) bond length is 1.56 Å. The S(1)-O(6) bond length is 1.51 Å. The S(1)-O(8) bond length is 1.56 Å. In the second S site, S(2) is bonded to one O(11), one O(2), one O(3), and one O(5) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 40°. The S(2)-O(11) bond length is 1.49 Å. The S(2)-O(2) bond length is 1.49 Å. The S(2)-O(3) bond length is 1.49 Å. The S(2)-O(5) bond length is 1.50 Å. In the third S site, S(3) is bonded to one O(12), one O(18), one O(20), and one O(21) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 46°. The S(3)-O(12) bond length is 1.49 Å. The S(3)-O(18) bond length is 1.51 Å. The S(3)-O(20) bond length is 1.48 Å. The S(3)-O(21) bond length is 1.49 Å. In the fourth S site, S(4) is bonded to one O(16), one O(17), one O(19), and one O(22) atom to form SO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. The S(4)-O(16) bond length is 1.50 Å. The S(4)-O(17) bond length is 1.48 Å. The S(4)-O(19) bond length is 1.49 Å. The S(4)-O(22) bond length is 1.50 Å. There are twenty-three inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one Mn(1), one H(1), and one H(15) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(1) and one S(2) atom. In the third O site, O(3) is bonded in a single-bond geometry to one K(3), one K(4), and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one K(2), one H(1), and one S(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one K(4) and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one K(1), one K(2), and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted water-like geometry to one K(3), one Mn(1), one H(5), and one H(6) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one K(2), one Mn(2), and one S(1) atom. In the ninth O site, O(9) is bonded in a distorted water-like geometry to one K(3), one Mn(2), one H(3), and one H(4) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one K(1), one Mn(2), one H(7), and one H(8) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one K(3) and one S(2) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one K(2) and one S(3) atom. In the thirteenth O site, O(13) is bonded in a distorted water-like geometry to one K(4), one Mn(2), one H(10), and one H(9) atom. In the fourteenth O site, O(14) is bonded in a distorted water-like geometry to one K(2), one Mn(2), one H(13), and one H(14) atom. In the fifteenth O site, O(15) is bonded in a distorted water-like geometry to one K(2), one K(4), one Mn(1), one H(11), and one H(12) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Mn(2) and one S(4) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one K(3), one K(4), and one S(4) atom. In the eighteenth O site, O(18) is bonded in a single-bond geometry to one S(3) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one K(2), one K(3), and one S(4) atom. In the twentieth O site, O(20) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one S(3) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one S(3) atom. In the twenty-second O site, O(22) is bonded in a single-bond geometry to one K(4) and one S(4) atom. In the twenty-third O site, O(23) is bonded in a distorted water-like geometry to one Mn(1), one H(16), and one H(2) atom.