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 in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(6) atom. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 14°. In the third Li site, Li(3) is bonded to one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 72°. 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  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(3)O5 trigonal bipyramids. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(4) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(5), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Cr(1), and one B(2) atom to form distorted corner-sharing OLi2CrB tetrahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), one Cr(1), and one B(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(1), and one B(1) atom. In the fourth O site, O(4) 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 fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Cr(1), and one B(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Cr(1), and one B(2) atom to form distorted corner-sharing OLi2CrB trigonal pyramids.
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 in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 2.40 Å. The Li(1)-O(4) bond length is 1.87 Å. The Li(1)-O(5) bond length is 2.46 Å. The Li(1)-O(6) bond length is 1.96 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 14°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(2) bond length is 2.32 Å. The Li(2)-O(3) bond length is 2.11 Å. The Li(2)-O(4) bond length is 2.14 Å. The Li(2)-O(5) bond length is 2.04 Å. In the third Li site, Li(3) is bonded to one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 72°. The Li(3)-O(3) bond length is 2.04 Å. The Li(3)-O(5) bond length is 2.01 Å. The Li(3)-O(6) bond length is 2.27 Å. There is one shorter (2.00 Å) and one longer (2.20 Å) Li(3)-O(2) bond length. 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  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(3)O5 trigonal bipyramids. The Cr(1)-O(1) bond length is 2.04 Å. The Cr(1)-O(2) bond length is 2.17 Å. The Cr(1)-O(3) bond length is 2.03 Å. The Cr(1)-O(4) bond length is 1.99 Å. The Cr(1)-O(5) bond length is 2.03 Å. The Cr(1)-O(6) bond length is 1.98 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(4) atom. The B(1)-O(2) bond length is 1.40 Å. The B(1)-O(3) bond length is 1.37 Å. The B(1)-O(4) bond length is 1.39 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(5), and one O(6) atom. The B(2)-O(1) bond length is 1.39 Å. The B(2)-O(5) bond length is 1.40 Å. The B(2)-O(6) bond length is 1.38 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Cr(1), and one B(2) atom to form distorted corner-sharing OLi2CrB tetrahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), one Cr(1), and one B(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(1), and one B(1) atom. In the fourth O site, O(4) 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 fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Cr(1), and one B(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Cr(1), and one B(2) atom to form distorted corner-sharing OLi2CrB trigonal pyramids.