Li(CrS2)2 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form LiS5 trigonal bipyramids that share corners with six equivalent Cr(1)S6 octahedra, corners with three equivalent Cr(2)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids, and  an edgeedge with one Cr(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-43°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(3) and four equivalent S(1) atoms to form distorted CrS6 octahedra that share  a cornercorner with one Cr(2)S4 tetrahedra, corners with six equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Cr(2)S4 tetrahedra, faces with two equivalent Cr(1)S6 octahedra, and  a faceface with one Cr(2)S4 tetrahedra. In the second Cr site, Cr(2) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted CrS4 tetrahedra that share  a cornercorner with one Cr(1)S6 octahedra, corners with three equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Cr(1)S6 octahedra,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Li(1), one Cr(2), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Cr(2) atom. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), and two equivalent Cr(1) atoms.
Li(CrS2)2 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form LiS5 trigonal bipyramids that share corners with six equivalent Cr(1)S6 octahedra, corners with three equivalent Cr(2)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids, and  an edgeedge with one Cr(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-43°. The Li(1)-S(3) bond length is 2.55 Å. Both Li(1)-S(1) bond lengths are 2.60 Å. There is one shorter (2.67 Å) and one longer (2.77 Å) Li(1)-S(2) bond length. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(3) and four equivalent S(1) atoms to form distorted CrS6 octahedra that share  a cornercorner with one Cr(2)S4 tetrahedra, corners with six equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Cr(2)S4 tetrahedra, faces with two equivalent Cr(1)S6 octahedra, and  a faceface with one Cr(2)S4 tetrahedra. There is one shorter (2.28 Å) and one longer (2.60 Å) Cr(1)-S(3) bond length. There are two shorter (2.29 Å) and two longer (2.42 Å) Cr(1)-S(1) bond lengths. In the second Cr site, Cr(2) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted CrS4 tetrahedra that share  a cornercorner with one Cr(1)S6 octahedra, corners with three equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Cr(1)S6 octahedra,  an edgeedge with one Li(1)S5 trigonal bipyramid, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles are 46°. The Cr(2)-S(2) bond length is 2.09 Å. The Cr(2)-S(3) bond length is 2.15 Å. Both Cr(2)-S(1) bond lengths are 2.18 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Li(1), one Cr(2), and two equivalent Cr(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Cr(2) atom. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Cr(2), and two equivalent Cr(1) atoms.