Li2Cr2(SO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one S(2)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one S(1)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 57-78°. Cr(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form distorted CrO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form SO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-59°. In the second S site, S(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form SO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra and corners with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-35°. There are six inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Cr(1), and one S(1) atom. In the second O site, O(5) is bonded in a distorted linear geometry to one Cr(1) and one S(2) atom. In the third O site, O(6) is bonded in a bent 150 degrees geometry to one Cr(1) and one S(1) atom. In the fourth O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one S(2) atom. In the fifth O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one S(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one S(1) atom.
Li2Cr2(SO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one S(2)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one S(1)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 57-78°. The Li(1)-O(1) bond length is 2.18 Å. The Li(1)-O(3) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.34 Å. There is one shorter (2.05 Å) and one longer (2.06 Å) Li(1)-O(2) bond length. Cr(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form distorted CrO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Cr(1)-O(1) bond length is 2.08 Å. The Cr(1)-O(3) bond length is 2.09 Å. The Cr(1)-O(5) bond length is 2.23 Å. The Cr(1)-O(6) bond length is 2.08 Å. There is one shorter (2.14 Å) and one longer (2.64 Å) Cr(1)-O(4) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form SO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-59°. The S(1)-O(2) bond length is 1.48 Å. The S(1)-O(3) bond length is 1.50 Å. The S(1)-O(4) bond length is 1.51 Å. The S(1)-O(6) bond length is 1.47 Å. In the second S site, S(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form SO4 tetrahedra that share corners with four equivalent Cr(1)O6 octahedra and corners with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-35°. Both S(2)-O(1) bond lengths are 1.51 Å. Both S(2)-O(5) bond lengths are 1.46 Å. There are six inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Cr(1), and one S(1) atom. In the second O site, O(5) is bonded in a distorted linear geometry to one Cr(1) and one S(2) atom. In the third O site, O(6) is bonded in a bent 150 degrees geometry to one Cr(1) and one S(1) atom. In the fourth O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cr(1), and one S(2) atom. In the fifth O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one S(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Cr(1), and one S(1) atom.