K(V5S8)2 crystallizes in the monoclinic P2/c space group. K(1) is bonded in a distorted q6 geometry to two equivalent S(1), two equivalent S(3), two equivalent S(4), two equivalent S(7), and two equivalent S(8) atoms. There are six inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(4), one S(5), one S(6), and two equivalent S(3) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the second V site, V(2) is bonded to one S(2), one S(3), one S(5), one S(6), and two equivalent S(4) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 43-54°. In the third V site, V(3) is bonded to one S(1), one S(6), one S(7), one S(8), and two equivalent S(5) atoms to form a mixture of distorted face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the fourth V site, V(4) is bonded to one S(2), one S(5), one S(7), one S(8), and two equivalent S(6) atoms to form a mixture of distorted face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the fifth V site, V(5) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(7) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. In the sixth V site, V(6) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(8) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 43-50°. There are eight inequivalent S sites. In the first S site, S(5) is bonded in a 5-coordinate geometry to one V(1), one V(2), one V(4), and two equivalent V(3) atoms. In the second S site, S(6) is bonded in a 5-coordinate geometry to one V(1), one V(2), one V(3), and two equivalent V(4) atoms. In the third S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(3), one V(4), and one V(5) atom. In the fourth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(3), one V(4), and one V(6) atom. In the fifth S site, S(1) is bonded in a 5-coordinate geometry to one K(1), one V(1), one V(3), one V(5), and one V(6) atom. In the sixth S site, S(2) is bonded to one V(2), one V(4), one V(5), and one V(6) atom to form distorted edge-sharing SV4 trigonal pyramids. In the seventh S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(2), and two equivalent V(1) atoms. In the eighth S site, S(4) is bonded in a 4-coordinate geometry to one K(1), one V(1), and two equivalent V(2) atoms.
K(V5S8)2 crystallizes in the monoclinic P2/c space group. K(1) is bonded in a distorted q6 geometry to two equivalent S(1), two equivalent S(3), two equivalent S(4), two equivalent S(7), and two equivalent S(8) atoms. Both K(1)-S(1) bond lengths are 3.32 Å. Both K(1)-S(3) bond lengths are 3.27 Å. Both K(1)-S(4) bond lengths are 3.23 Å. Both K(1)-S(7) bond lengths are 3.18 Å. Both K(1)-S(8) bond lengths are 3.16 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(4), one S(5), one S(6), and two equivalent S(3) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. The V(1)-S(1) bond length is 2.54 Å. The V(1)-S(4) bond length is 2.29 Å. The V(1)-S(5) bond length is 2.50 Å. The V(1)-S(6) bond length is 2.49 Å. There is one shorter (2.27 Å) and one longer (2.37 Å) V(1)-S(3) bond length. In the second V site, V(2) is bonded to one S(2), one S(3), one S(5), one S(6), and two equivalent S(4) atoms to form a mixture of face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 43-54°. The V(2)-S(2) bond length is 2.45 Å. The V(2)-S(3) bond length is 2.29 Å. The V(2)-S(5) bond length is 2.51 Å. The V(2)-S(6) bond length is 2.50 Å. There is one shorter (2.27 Å) and one longer (2.34 Å) V(2)-S(4) bond length. In the third V site, V(3) is bonded to one S(1), one S(6), one S(7), one S(8), and two equivalent S(5) atoms to form a mixture of distorted face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. The V(3)-S(1) bond length is 2.25 Å. The V(3)-S(6) bond length is 2.50 Å. The V(3)-S(7) bond length is 2.33 Å. The V(3)-S(8) bond length is 2.33 Å. There is one shorter (2.44 Å) and one longer (2.61 Å) V(3)-S(5) bond length. In the fourth V site, V(4) is bonded to one S(2), one S(5), one S(7), one S(8), and two equivalent S(6) atoms to form a mixture of distorted face, corner, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. The V(4)-S(2) bond length is 2.27 Å. The V(4)-S(5) bond length is 2.50 Å. The V(4)-S(7) bond length is 2.29 Å. The V(4)-S(8) bond length is 2.30 Å. There is one shorter (2.44 Å) and one longer (2.61 Å) V(4)-S(6) bond length. In the fifth V site, V(5) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(7) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. Both V(5)-S(1) bond lengths are 2.49 Å. Both V(5)-S(2) bond lengths are 2.31 Å. Both V(5)-S(7) bond lengths are 2.40 Å. In the sixth V site, V(6) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(8) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 43-50°. Both V(6)-S(1) bond lengths are 2.42 Å. Both V(6)-S(2) bond lengths are 2.31 Å. Both V(6)-S(8) bond lengths are 2.40 Å. There are eight inequivalent S sites. In the first S site, S(5) is bonded in a 5-coordinate geometry to one V(1), one V(2), one V(4), and two equivalent V(3) atoms. In the second S site, S(6) is bonded in a 5-coordinate geometry to one V(1), one V(2), one V(3), and two equivalent V(4) atoms. In the third S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(3), one V(4), and one V(5) atom. In the fourth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(3), one V(4), and one V(6) atom. In the fifth S site, S(1) is bonded in a 5-coordinate geometry to one K(1), one V(1), one V(3), one V(5), and one V(6) atom. In the sixth S site, S(2) is bonded to one V(2), one V(4), one V(5), and one V(6) atom to form distorted edge-sharing SV4 trigonal pyramids. In the seventh S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(2), and two equivalent V(1) atoms. In the eighth S site, S(4) is bonded in a 4-coordinate geometry to one K(1), one V(1), and two equivalent V(2) atoms.