Li(CrS2)2 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with four equivalent Cr(2)S6 octahedra,  an edgeedge with one Cr(2)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 60-72°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form CrS6 octahedra that share corners with four equivalent Cr(2)S6 octahedra, corners with two equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with two equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the second Cr site, Cr(2) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CrS6 octahedra that share corners with four equivalent Cr(1)S6 octahedra, corners with four equivalent Cr(2)S6 octahedra, corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, and  an edgeedge with one Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(1), and two equivalent Cr(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Cr(2), and two equivalent Cr(1) atoms. In the third S site, S(3) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form distorted corner-sharing SLiCr3 tetrahedra.
Li(CrS2)2 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with four equivalent Cr(2)S6 octahedra,  an edgeedge with one Cr(2)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 60-72°. The Li(1)-S(2) bond length is 2.30 Å. The Li(1)-S(3) bond length is 2.27 Å. Both Li(1)-S(1) bond lengths are 2.31 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form CrS6 octahedra that share corners with four equivalent Cr(2)S6 octahedra, corners with two equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with two equivalent Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. Both Cr(1)-S(1) bond lengths are 2.41 Å. Both Cr(1)-S(2) bond lengths are 2.41 Å. Both Cr(1)-S(3) bond lengths are 2.32 Å. In the second Cr site, Cr(2) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CrS6 octahedra that share corners with four equivalent Cr(1)S6 octahedra, corners with four equivalent Cr(2)S6 octahedra, corners with four equivalent Li(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, and  an edgeedge with one Li(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Cr(2)-S(2) bond length is 2.37 Å. The Cr(2)-S(3) bond length is 2.37 Å. There are two shorter (2.38 Å) and two longer (2.51 Å) Cr(2)-S(1) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(1), and two equivalent Cr(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Cr(2), and two equivalent Cr(1) atoms. In the third S site, S(3) is bonded to one Li(1), one Cr(2), and two equivalent Cr(1) atoms to form distorted corner-sharing SLiCr3 tetrahedra.