Li3Cr(BO3)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-82°. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one O(5), and one O(6) atom. In the third Li site, Li(3) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-85°. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CrO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(6) is bonded in a distorted trigonal bipyramidal geometry to one Li(1), one Li(2), one Li(3), one Cr(1), and one B(2) atom. In the second O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one B(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one B(1) atom. In the fourth O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one B(1) atom. In the fifth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Cr(1), and one B(2) atom. In the sixth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Cr(1), and one B(2) atom.
Li3Cr(BO3)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-82°. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-O(3) bond length is 1.88 Å. The Li(1)-O(6) bond length is 2.10 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one O(5), and one O(6) atom. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-O(4) bond length is 1.95 Å. The Li(2)-O(5) bond length is 1.96 Å. The Li(2)-O(6) bond length is 2.17 Å. In the third Li site, Li(3) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-85°. The Li(3)-O(1) bond length is 1.90 Å. The Li(3)-O(4) bond length is 1.99 Å. The Li(3)-O(5) bond length is 1.88 Å. The Li(3)-O(6) bond length is 2.06 Å. Cr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CrO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Cr(1)-O(1) bond length is 2.04 Å. The Cr(1)-O(2) bond length is 2.05 Å. The Cr(1)-O(3) bond length is 1.97 Å. The Cr(1)-O(4) bond length is 2.09 Å. The Cr(1)-O(5) bond length is 2.05 Å. The Cr(1)-O(6) bond length is 2.10 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The B(1)-O(1) bond length is 1.39 Å. The B(1)-O(2) bond length is 1.39 Å. The B(1)-O(3) bond length is 1.39 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. The B(2)-O(4) bond length is 1.37 Å. The B(2)-O(5) bond length is 1.39 Å. The B(2)-O(6) bond length is 1.41 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a distorted trigonal bipyramidal geometry to one Li(1), one Li(2), one Li(3), one Cr(1), and one B(2) atom. In the second O site, O(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one B(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one B(1) atom. In the fourth O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Cr(1), and one B(1) atom. In the fifth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Cr(1), and one B(2) atom. In the sixth O site, O(5) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one Cr(1), and one B(2) atom.