K(V5S8)3 crystallizes in the triclinic P-1 space group. K(1) is bonded in a 10-coordinate geometry to two equivalent V(8), two equivalent S(1), two equivalent S(10), two equivalent S(3), and two equivalent S(6) atoms. There are eight inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(11), two equivalent S(2), and two equivalent S(6) atoms to form distorted VS6 octahedra that share corners with two equivalent V(3)S6 octahedra and faces with two equivalent V(6)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 57°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one S(1), one S(10), one S(12), one S(3), one S(7), and one S(8) atom. In the third V site, V(3) is bonded to one S(1), one S(11), one S(5), one S(7), and two equivalent S(3) atoms to form distorted VS6 octahedra that share  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one V(4)S7 pentagonal bipyramid,  an edgeedge with one V(3)S6 octahedra, and  an edgeedge with one V(6)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 57°. In the fourth V site, V(4) is bonded to one S(10), one S(4), one S(5), one S(8), one S(9), and two equivalent S(12) atoms to form distorted VS7 pentagonal bipyramids that share  a cornercorner with one V(3)S6 octahedra,  an edgeedge with one V(4)S7 pentagonal bipyramid,  an edgeedge with one V(6)S7 pentagonal bipyramid, and  a faceface with one V(6)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 49°. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one S(10), one S(2), one S(4), one S(7), and one S(9) atom. In the sixth V site, V(6) is bonded to one S(10), one S(11), one S(12), one S(2), one S(5), one S(6), and one S(8) atom to form VS7 pentagonal bipyramids that share  an edgeedge with one V(3)S6 octahedra,  an edgeedge with one V(4)S7 pentagonal bipyramid,  a faceface with one V(1)S6 octahedra, and  a faceface with one V(4)S7 pentagonal bipyramid. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to one S(11), one S(12), one S(2), one S(7), one S(8), and one S(9) atom. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one K(1), one S(1), one S(11), one S(2), one S(3), one S(6), and one S(7) atom. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one K(1), one V(2), one V(3), and one V(8) atom. In the second S site, S(2) is bonded to one V(1), one V(5), one V(6), one V(7), and one V(8) atom to form distorted corner-sharing SV5 trigonal bipyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one V(2), one V(8), and two equivalent V(3) atoms. In the fourth S site, S(4) is bonded in a distorted linear geometry to one V(4) and one V(5) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one V(6) atom. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one K(1), one V(1), one V(6), and one V(8) atom. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one V(2), one V(3), one V(5), one V(7), and one V(8) atom. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one V(2), one V(4), one V(6), and one V(7) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one V(4), one V(5), and one V(7) atom. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to one K(1), one V(2), one V(4), one V(5), and one V(6) atom. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to one V(1), one V(3), one V(6), one V(7), and one V(8) atom. In the twelfth S site, S(12) is bonded in a 5-coordinate geometry to one V(2), one V(6), one V(7), and two equivalent V(4) atoms.
K(V5S8)3 crystallizes in the triclinic P-1 space group. K(1) is bonded in a 10-coordinate geometry to two equivalent V(8), two equivalent S(1), two equivalent S(10), two equivalent S(3), and two equivalent S(6) atoms. Both K(1)-V(8) bond lengths are 3.09 Å. Both K(1)-S(1) bond lengths are 3.35 Å. Both K(1)-S(10) bond lengths are 3.07 Å. Both K(1)-S(3) bond lengths are 3.11 Å. Both K(1)-S(6) bond lengths are 2.86 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(11), two equivalent S(2), and two equivalent S(6) atoms to form distorted VS6 octahedra that share corners with two equivalent V(3)S6 octahedra and faces with two equivalent V(6)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 57°. Both V(1)-S(11) bond lengths are 2.44 Å. Both V(1)-S(2) bond lengths are 2.47 Å. Both V(1)-S(6) bond lengths are 2.35 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one S(1), one S(10), one S(12), one S(3), one S(7), and one S(8) atom. The V(2)-S(1) bond length is 2.38 Å. The V(2)-S(10) bond length is 2.37 Å. The V(2)-S(12) bond length is 2.46 Å. The V(2)-S(3) bond length is 2.42 Å. The V(2)-S(7) bond length is 2.55 Å. The V(2)-S(8) bond length is 2.62 Å. In the third V site, V(3) is bonded to one S(1), one S(11), one S(5), one S(7), and two equivalent S(3) atoms to form distorted VS6 octahedra that share  a cornercorner with one V(1)S6 octahedra,  a cornercorner with one V(4)S7 pentagonal bipyramid,  an edgeedge with one V(3)S6 octahedra, and  an edgeedge with one V(6)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 57°. The V(3)-S(1) bond length is 2.31 Å. The V(3)-S(11) bond length is 2.44 Å. The V(3)-S(5) bond length is 2.46 Å. The V(3)-S(7) bond length is 2.32 Å. There is one shorter (2.37 Å) and one longer (2.41 Å) V(3)-S(3) bond length. In the fourth V site, V(4) is bonded to one S(10), one S(4), one S(5), one S(8), one S(9), and two equivalent S(12) atoms to form distorted VS7 pentagonal bipyramids that share  a cornercorner with one V(3)S6 octahedra,  an edgeedge with one V(4)S7 pentagonal bipyramid,  an edgeedge with one V(6)S7 pentagonal bipyramid, and  a faceface with one V(6)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 49°. The V(4)-S(10) bond length is 2.49 Å. The V(4)-S(4) bond length is 2.39 Å. The V(4)-S(5) bond length is 2.42 Å. The V(4)-S(8) bond length is 2.42 Å. The V(4)-S(9) bond length is 2.52 Å. There is one shorter (2.43 Å) and one longer (2.54 Å) V(4)-S(12) bond length. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one S(10), one S(2), one S(4), one S(7), and one S(9) atom. The V(5)-S(10) bond length is 2.37 Å. The V(5)-S(2) bond length is 2.55 Å. The V(5)-S(4) bond length is 2.12 Å. The V(5)-S(7) bond length is 2.43 Å. The V(5)-S(9) bond length is 2.28 Å. In the sixth V site, V(6) is bonded to one S(10), one S(11), one S(12), one S(2), one S(5), one S(6), and one S(8) atom to form VS7 pentagonal bipyramids that share  an edgeedge with one V(3)S6 octahedra,  an edgeedge with one V(4)S7 pentagonal bipyramid,  a faceface with one V(1)S6 octahedra, and  a faceface with one V(4)S7 pentagonal bipyramid. The V(6)-S(10) bond length is 2.54 Å. The V(6)-S(11) bond length is 2.48 Å. The V(6)-S(12) bond length is 2.44 Å. The V(6)-S(2) bond length is 2.48 Å. The V(6)-S(5) bond length is 2.39 Å. The V(6)-S(6) bond length is 2.49 Å. The V(6)-S(8) bond length is 2.41 Å. In the seventh V site, V(7) is bonded in a 6-coordinate geometry to one S(11), one S(12), one S(2), one S(7), one S(8), and one S(9) atom. The V(7)-S(11) bond length is 2.41 Å. The V(7)-S(12) bond length is 2.70 Å. The V(7)-S(2) bond length is 2.49 Å. The V(7)-S(7) bond length is 2.36 Å. The V(7)-S(8) bond length is 2.40 Å. The V(7)-S(9) bond length is 2.25 Å. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one K(1), one S(1), one S(11), one S(2), one S(3), one S(6), and one S(7) atom. The V(8)-S(1) bond length is 2.56 Å. The V(8)-S(11) bond length is 2.30 Å. The V(8)-S(2) bond length is 2.45 Å. The V(8)-S(3) bond length is 2.38 Å. The V(8)-S(6) bond length is 2.36 Å. The V(8)-S(7) bond length is 2.79 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one K(1), one V(2), one V(3), and one V(8) atom. In the second S site, S(2) is bonded to one V(1), one V(5), one V(6), one V(7), and one V(8) atom to form distorted corner-sharing SV5 trigonal bipyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one K(1), one V(2), one V(8), and two equivalent V(3) atoms. In the fourth S site, S(4) is bonded in a distorted linear geometry to one V(4) and one V(5) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one V(3), one V(4), and one V(6) atom. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one K(1), one V(1), one V(6), and one V(8) atom. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one V(2), one V(3), one V(5), one V(7), and one V(8) atom. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one V(2), one V(4), one V(6), and one V(7) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one V(4), one V(5), and one V(7) atom. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to one K(1), one V(2), one V(4), one V(5), and one V(6) atom. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to one V(1), one V(3), one V(6), one V(7), and one V(8) atom. In the twelfth S site, S(12) is bonded in a 5-coordinate geometry to one V(2), one V(6), one V(7), and two equivalent V(4) atoms.