KV5S8 crystallizes in the monoclinic C2/m space group. K(1) is bonded in a 10-coordinate geometry to two equivalent S(1), four equivalent S(2), and four equivalent S(3) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles are 48°. In the second V site, V(2) is bonded to one S(1), two equivalent S(2), and three equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. In the third V site, V(3) is bonded to one S(1), two equivalent S(4), and three equivalent S(3) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one K(1), one V(2), one V(3), and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent K(1), one V(1), and two equivalent V(2) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent K(1) and three equivalent V(3) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent V(3) and three equivalent V(2) atoms.
KV5S8 crystallizes in the monoclinic C2/m space group. K(1) is bonded in a 10-coordinate geometry to two equivalent S(1), four equivalent S(2), and four equivalent S(3) atoms. Both K(1)-S(1) bond lengths are 3.47 Å. All K(1)-S(2) bond lengths are 3.26 Å. All K(1)-S(3) bond lengths are 3.34 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form a mixture of corner and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles are 48°. Both V(1)-S(2) bond lengths are 2.42 Å. All V(1)-S(1) bond lengths are 2.38 Å. In the second V site, V(2) is bonded to one S(1), two equivalent S(2), and three equivalent S(4) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. The V(2)-S(1) bond length is 2.27 Å. Both V(2)-S(2) bond lengths are 2.32 Å. There are two shorter (2.51 Å) and one longer (2.55 Å) V(2)-S(4) bond length. In the third V site, V(3) is bonded to one S(1), two equivalent S(4), and three equivalent S(3) atoms to form a mixture of corner, face, and edge-sharing VS6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(3)-S(1) bond length is 2.43 Å. Both V(3)-S(4) bond lengths are 2.47 Å. There is one shorter (2.37 Å) and two longer (2.40 Å) V(3)-S(3) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one K(1), one V(2), one V(3), and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent K(1), one V(1), and two equivalent V(2) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent K(1) and three equivalent V(3) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent V(3) and three equivalent V(2) atoms.