K(VS2)2 crystallizes in the monoclinic Pm space group. K(1) is bonded in a 6-coordinate geometry to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form edge-sharing VS6 octahedra. In the second V site, V(2) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form edge-sharing VS6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent K(1), one V(1), and two equivalent V(2) atoms. In the second S site, S(2) is bonded to one K(1), one V(2), and two equivalent V(1) atoms to form distorted SKV3 trigonal pyramids that share corners with two equivalent S(3)K2V3 square pyramids, corners with two equivalent S(2)KV3 trigonal pyramids, and edges with two equivalent S(3)K2V3 square pyramids. In the third S site, S(3) is bonded to two equivalent K(1), one V(1), and two equivalent V(2) atoms to form distorted SK2V3 square pyramids that share corners with two equivalent S(2)KV3 trigonal pyramids, edges with two equivalent S(3)K2V3 square pyramids, and edges with two equivalent S(2)KV3 trigonal pyramids. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(2), and two equivalent V(1) atoms.
K(VS2)2 crystallizes in the monoclinic Pm space group. K(1) is bonded in a 6-coordinate geometry to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms. The K(1)-S(2) bond length is 3.28 Å. The K(1)-S(4) bond length is 3.20 Å. Both K(1)-S(1) bond lengths are 3.17 Å. Both K(1)-S(3) bond lengths are 3.15 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(3), two equivalent S(2), and two equivalent S(4) atoms to form edge-sharing VS6 octahedra. The V(1)-S(1) bond length is 2.33 Å. The V(1)-S(3) bond length is 2.47 Å. Both V(1)-S(2) bond lengths are 2.41 Å. Both V(1)-S(4) bond lengths are 2.41 Å. In the second V site, V(2) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form edge-sharing VS6 octahedra. The V(2)-S(2) bond length is 2.48 Å. The V(2)-S(4) bond length is 2.32 Å. Both V(2)-S(1) bond lengths are 2.41 Å. Both V(2)-S(3) bond lengths are 2.41 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent K(1), one V(1), and two equivalent V(2) atoms. In the second S site, S(2) is bonded to one K(1), one V(2), and two equivalent V(1) atoms to form distorted SKV3 trigonal pyramids that share corners with two equivalent S(3)K2V3 square pyramids, corners with two equivalent S(2)KV3 trigonal pyramids, and edges with two equivalent S(3)K2V3 square pyramids. In the third S site, S(3) is bonded to two equivalent K(1), one V(1), and two equivalent V(2) atoms to form distorted SK2V3 square pyramids that share corners with two equivalent S(2)KV3 trigonal pyramids, edges with two equivalent S(3)K2V3 square pyramids, and edges with two equivalent S(2)KV3 trigonal pyramids. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one V(2), and two equivalent V(1) atoms.