Li3Cr(BO3)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one O(6) atom. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 17°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), and two equivalent O(5) atoms to form distorted LiO5 square pyramids that share corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 56-65°. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form distorted CrO6 octahedra that share corners with three equivalent Li(3)O5 square pyramids,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Cr(1)O6 octahedra, and edges with two equivalent Li(2)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(1), one O(4), and one O(5) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Cr(1), and one B(1) atom to form distorted corner-sharing OLi2CrB tetrahedra. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one B(2) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Cr(1), and one B(2) atom to form distorted OLi2Cr2B square pyramids that share corners with three equivalent O(1)Li2CrB tetrahedra and  an edgeedge with one O(3)Li2Cr2B square pyramid. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), 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), two equivalent Li(3), and one B(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one B(2) atom.
Li3Cr(BO3)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one O(6) atom. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.08 Å. The Li(1)-O(5) bond length is 1.89 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(3), one O(4), one O(5), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Cr(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, and edges with two equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 17°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(3) bond length is 2.20 Å. The Li(2)-O(4) bond length is 2.15 Å. The Li(2)-O(5) bond length is 1.95 Å. The Li(2)-O(6) bond length is 2.33 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), and two equivalent O(5) atoms to form distorted LiO5 square pyramids that share corners with three equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 56-65°. The Li(3)-O(1) bond length is 2.14 Å. The Li(3)-O(2) bond length is 1.94 Å. The Li(3)-O(4) bond length is 2.03 Å. There is one shorter (2.03 Å) and one longer (2.29 Å) Li(3)-O(5) bond length. Cr(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form distorted CrO6 octahedra that share corners with three equivalent Li(3)O5 square pyramids,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Cr(1)O6 octahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The Cr(1)-O(1) bond length is 1.99 Å. The Cr(1)-O(2) bond length is 1.98 Å. The Cr(1)-O(4) bond length is 1.94 Å. The Cr(1)-O(6) bond length is 2.03 Å. There is one shorter (2.19 Å) and one longer (2.21 Å) Cr(1)-O(3) bond length. 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(4), and one O(5) atom. The B(1)-O(1) bond length is 1.41 Å. The B(1)-O(4) bond length is 1.40 Å. The B(1)-O(5) bond length is 1.37 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. The B(2)-O(2) bond length is 1.38 Å. The B(2)-O(3) bond length is 1.44 Å. The B(2)-O(6) bond length is 1.36 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Cr(1), and one B(1) atom to form distorted corner-sharing OLi2CrB tetrahedra. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one B(2) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Cr(1), and one B(2) atom to form distorted OLi2Cr2B square pyramids that share corners with three equivalent O(1)Li2CrB tetrahedra and  an edgeedge with one O(3)Li2Cr2B square pyramid. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), 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), two equivalent Li(3), and one B(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one B(2) atom.