Li3(VS2)4 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one S(1), one S(2), one S(3), and one S(4) atom. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one S(1), one S(5), and two equivalent S(4) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one S(2), one S(5), two equivalent S(3), and two equivalent S(4) atoms to form edge-sharing VS6 octahedra. In the second V site, V(2) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form distorted edge-sharing VS6 octahedra. In the third V site, V(3) is bonded to one S(1), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form distorted edge-sharing VS6 octahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one V(3), and two equivalent V(2) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Li(1), one V(1), and two equivalent V(2) atoms. In the third S site, S(3) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted corner-sharing SLiV3 trigonal pyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom. In the fifth S site, S(5) is bonded to one Li(2), one V(1), and two equivalent V(2) atoms to form distorted corner-sharing SLiV3 trigonal pyramids. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one V(3) and two equivalent V(2) atoms.
Li3(VS2)4 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Li(1)-S(1) bond length is 2.43 Å. The Li(1)-S(2) bond length is 2.44 Å. The Li(1)-S(3) bond length is 2.39 Å. The Li(1)-S(4) bond length is 2.44 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one S(1), one S(5), and two equivalent S(4) atoms. The Li(2)-S(1) bond length is 2.43 Å. The Li(2)-S(5) bond length is 2.39 Å. Both Li(2)-S(4) bond lengths are 2.43 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one S(2), one S(5), two equivalent S(3), and two equivalent S(4) atoms to form edge-sharing VS6 octahedra. The V(1)-S(2) bond length is 2.46 Å. The V(1)-S(5) bond length is 2.32 Å. Both V(1)-S(3) bond lengths are 2.33 Å. Both V(1)-S(4) bond lengths are 2.45 Å. In the second V site, V(2) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form distorted edge-sharing VS6 octahedra. The V(2)-S(1) bond length is 2.56 Å. The V(2)-S(2) bond length is 2.34 Å. The V(2)-S(3) bond length is 2.47 Å. The V(2)-S(4) bond length is 2.34 Å. The V(2)-S(5) bond length is 2.46 Å. The V(2)-S(6) bond length is 2.29 Å. In the third V site, V(3) is bonded to one S(1), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form distorted edge-sharing VS6 octahedra. The V(3)-S(1) bond length is 2.56 Å. The V(3)-S(6) bond length is 2.30 Å. Both V(3)-S(3) bond lengths are 2.46 Å. Both V(3)-S(4) bond lengths are 2.34 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one V(3), and two equivalent V(2) atoms. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Li(1), one V(1), and two equivalent V(2) atoms. In the third S site, S(3) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted corner-sharing SLiV3 trigonal pyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one V(1), one V(2), and one V(3) atom. In the fifth S site, S(5) is bonded to one Li(2), one V(1), and two equivalent V(2) atoms to form distorted corner-sharing SLiV3 trigonal pyramids. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one V(3) and two equivalent V(2) atoms.