K2LiVS4 crystallizes in the monoclinic Cc space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to one S(1), one S(2), one S(5), one S(6), one S(7), and two equivalent S(3) atoms to form distorted KS7 pentagonal bipyramids that share corners with two equivalent K(1)S7 pentagonal bipyramids,  a cornercorner with one V(1)S4 tetrahedra, corners with two equivalent V(2)S4 tetrahedra,  a cornercorner with one Li(1)S5 trigonal bipyramid,  a cornercorner with one Li(2)S5 trigonal bipyramid,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one V(2)S4 tetrahedra,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  an edgeedge with one Li(2)S5 trigonal bipyramid. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(1), one S(3), one S(4), one S(5), one S(6), and one S(8) atom. In the third K site, K(3) is bonded in a 5-coordinate geometry to one S(3), one S(4), one S(5), one S(6), and one S(7) atom. In the fourth K site, K(4) is bonded in a 7-coordinate geometry to one S(2), one S(3), one S(4), one S(7), one S(8), and two equivalent S(6) atoms. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(4), one S(5), one S(7), and one S(8) atom to form LiS5 trigonal bipyramids that share  a cornercorner with one K(1)S7 pentagonal bipyramid,  a cornercorner with one V(2)S4 tetrahedra, corners with two equivalent Li(2)S5 trigonal bipyramids,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one V(2)S4 tetrahedra, and  an edgeedge with one Li(2)S5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one S(1), one S(2), one S(4), one S(5), and one S(8) atom to form LiS5 trigonal bipyramids that share  a cornercorner with one K(1)S7 pentagonal bipyramid,  a cornercorner with one V(1)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one V(2)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form VS4 tetrahedra that share  a cornercorner with one K(1)S7 pentagonal bipyramid,  a cornercorner with one Li(2)S5 trigonal bipyramid,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  an edgeedge with one Li(2)S5 trigonal bipyramid. In the second V site, V(2) is bonded to one S(3), one S(5), one S(7), and one S(8) atom to form VS4 tetrahedra that share corners with two equivalent K(1)S7 pentagonal bipyramids,  a cornercorner with one Li(1)S5 trigonal bipyramid,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  an edgeedge with one Li(2)S5 trigonal bipyramid. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Li(1), one Li(2), and one V(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one K(1), one K(4), one Li(2), and one V(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one K(2), one K(3), one K(4), two equivalent K(1), and one V(2) atom. In the fourth S site, S(4) is bonded to one K(2), one K(3), one K(4), one Li(1), one Li(2), and one V(1) atom to form a mixture of distorted face and corner-sharing SK3Li2V octahedra. The corner-sharing octahedral tilt angles are 8°. In the fifth S site, S(5) is bonded to one K(1), one K(2), one K(3), one Li(1), one Li(2), and one V(2) atom to form a mixture of distorted face and corner-sharing SK3Li2V octahedra. The corner-sharing octahedral tilt angles are 8°. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one K(1), one K(2), one K(3), two equivalent K(4), and one V(1) atom. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one K(1), one K(3), one K(4), one Li(1), and one V(2) atom. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one K(2), one K(4), one Li(1), one Li(2), and one V(2) atom.
K2LiVS4 crystallizes in the monoclinic Cc space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to one S(1), one S(2), one S(5), one S(6), one S(7), and two equivalent S(3) atoms to form distorted KS7 pentagonal bipyramids that share corners with two equivalent K(1)S7 pentagonal bipyramids,  a cornercorner with one V(1)S4 tetrahedra, corners with two equivalent V(2)S4 tetrahedra,  a cornercorner with one Li(1)S5 trigonal bipyramid,  a cornercorner with one Li(2)S5 trigonal bipyramid,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one V(2)S4 tetrahedra,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  an edgeedge with one Li(2)S5 trigonal bipyramid. The K(1)-S(1) bond length is 3.27 Å. The K(1)-S(2) bond length is 3.49 Å. The K(1)-S(5) bond length is 3.21 Å. The K(1)-S(6) bond length is 3.35 Å. The K(1)-S(7) bond length is 3.40 Å. There is one shorter (3.38 Å) and one longer (3.48 Å) K(1)-S(3) bond length. In the second K site, K(2) is bonded in a 6-coordinate geometry to one S(1), one S(3), one S(4), one S(5), one S(6), and one S(8) atom. The K(2)-S(1) bond length is 3.29 Å. The K(2)-S(3) bond length is 3.44 Å. The K(2)-S(4) bond length is 3.35 Å. The K(2)-S(5) bond length is 3.35 Å. The K(2)-S(6) bond length is 3.44 Å. The K(2)-S(8) bond length is 3.29 Å. In the third K site, K(3) is bonded in a 5-coordinate geometry to one S(3), one S(4), one S(5), one S(6), and one S(7) atom. The K(3)-S(3) bond length is 3.09 Å. The K(3)-S(4) bond length is 3.17 Å. The K(3)-S(5) bond length is 3.22 Å. The K(3)-S(6) bond length is 3.12 Å. The K(3)-S(7) bond length is 3.51 Å. In the fourth K site, K(4) is bonded in a 7-coordinate geometry to one S(2), one S(3), one S(4), one S(7), one S(8), and two equivalent S(6) atoms. The K(4)-S(2) bond length is 3.40 Å. The K(4)-S(3) bond length is 3.35 Å. The K(4)-S(4) bond length is 3.20 Å. The K(4)-S(7) bond length is 3.50 Å. The K(4)-S(8) bond length is 3.27 Å. There is one shorter (3.34 Å) and one longer (3.51 Å) K(4)-S(6) bond length. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(4), one S(5), one S(7), and one S(8) atom to form LiS5 trigonal bipyramids that share  a cornercorner with one K(1)S7 pentagonal bipyramid,  a cornercorner with one V(2)S4 tetrahedra, corners with two equivalent Li(2)S5 trigonal bipyramids,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one V(2)S4 tetrahedra, and  an edgeedge with one Li(2)S5 trigonal bipyramid. The Li(1)-S(1) bond length is 2.56 Å. The Li(1)-S(4) bond length is 2.71 Å. The Li(1)-S(5) bond length is 2.56 Å. The Li(1)-S(7) bond length is 2.68 Å. The Li(1)-S(8) bond length is 2.54 Å. In the second Li site, Li(2) is bonded to one S(1), one S(2), one S(4), one S(5), and one S(8) atom to form LiS5 trigonal bipyramids that share  a cornercorner with one K(1)S7 pentagonal bipyramid,  a cornercorner with one V(1)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one V(1)S4 tetrahedra,  an edgeedge with one V(2)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. The Li(2)-S(1) bond length is 2.53 Å. The Li(2)-S(2) bond length is 2.68 Å. The Li(2)-S(4) bond length is 2.56 Å. The Li(2)-S(5) bond length is 2.74 Å. The Li(2)-S(8) bond length is 2.55 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form VS4 tetrahedra that share  a cornercorner with one K(1)S7 pentagonal bipyramid,  a cornercorner with one Li(2)S5 trigonal bipyramid,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  an edgeedge with one Li(2)S5 trigonal bipyramid. The V(1)-S(1) bond length is 2.17 Å. The V(1)-S(2) bond length is 2.14 Å. The V(1)-S(4) bond length is 2.18 Å. The V(1)-S(6) bond length is 2.15 Å. In the second V site, V(2) is bonded to one S(3), one S(5), one S(7), and one S(8) atom to form VS4 tetrahedra that share corners with two equivalent K(1)S7 pentagonal bipyramids,  a cornercorner with one Li(1)S5 trigonal bipyramid,  an edgeedge with one K(1)S7 pentagonal bipyramid,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  an edgeedge with one Li(2)S5 trigonal bipyramid. The V(2)-S(3) bond length is 2.15 Å. The V(2)-S(5) bond length is 2.18 Å. The V(2)-S(7) bond length is 2.14 Å. The V(2)-S(8) bond length is 2.17 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Li(1), one Li(2), and one V(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one K(1), one K(4), one Li(2), and one V(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one K(2), one K(3), one K(4), two equivalent K(1), and one V(2) atom. In the fourth S site, S(4) is bonded to one K(2), one K(3), one K(4), one Li(1), one Li(2), and one V(1) atom to form a mixture of distorted face and corner-sharing SK3Li2V octahedra. The corner-sharing octahedral tilt angles are 8°. In the fifth S site, S(5) is bonded to one K(1), one K(2), one K(3), one Li(1), one Li(2), and one V(2) atom to form a mixture of distorted face and corner-sharing SK3Li2V octahedra. The corner-sharing octahedral tilt angles are 8°. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one K(1), one K(2), one K(3), two equivalent K(4), and one V(1) atom. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one K(1), one K(3), one K(4), one Li(1), and one V(2) atom. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one K(2), one K(4), one Li(1), one Li(2), and one V(2) atom.