Li3Ti(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(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Ti(1)O5 trigonal bipyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(6) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Ti(1)O5 trigonal bipyramids. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(3) atoms. Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form TiO5 trigonal bipyramids that share corners with three equivalent Li(1)O4 tetrahedra 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(2), one O(3), and one O(6) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Ti(1), and one B(2) atom to form distorted OLi2TiB tetrahedra that share corners with three equivalent O(5)Li2TiB tetrahedra, corners with two equivalent O(3)Li4B trigonal bipyramids, and  an edgeedge with one O(2)Li2TiB trigonal pyramid. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Ti(1), and one B(1) atom to form distorted OLi2TiB trigonal pyramids that share corners with three equivalent O(5)Li2TiB tetrahedra, corners with two equivalent O(3)Li4B trigonal bipyramids,  an edgeedge with one O(1)Li2TiB tetrahedra, and  an edgeedge with one O(3)Li4B trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one B(1) atom to form distorted OLi4B trigonal bipyramids that share corners with two equivalent O(1)Li2TiB tetrahedra, corners with three equivalent O(5)Li2TiB tetrahedra, corners with two equivalent O(2)Li2TiB trigonal pyramids,  an edgeedge with one O(3)Li4B trigonal bipyramid, and  an edgeedge with one O(2)Li2TiB trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Ti(1), and one B(2) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Ti(1), and one B(2) atom to form distorted OLi2TiB tetrahedra that share corners with three equivalent O(1)Li2TiB tetrahedra, corners with three equivalent O(3)Li4B trigonal bipyramids, and corners with three equivalent O(2)Li2TiB trigonal pyramids. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Ti(1), and one B(1) atom.
Li3Ti(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(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Ti(1)O5 trigonal bipyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The Li(1)-O(1) bond length is 2.05 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 1.93 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(5), and one O(6) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Ti(1)O5 trigonal bipyramids. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(2) bond length is 2.15 Å. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(5) bond length is 2.04 Å. The Li(2)-O(6) bond length is 2.35 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(3) atoms. The Li(3)-O(2) bond length is 1.96 Å. The Li(3)-O(5) bond length is 1.96 Å. There is one shorter (1.94 Å) and one longer (2.21 Å) Li(3)-O(3) bond length. Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form TiO5 trigonal bipyramids that share corners with three equivalent Li(1)O4 tetrahedra and edges with two equivalent Li(2)O5 trigonal bipyramids. The Ti(1)-O(1) bond length is 2.10 Å. The Ti(1)-O(2) bond length is 2.02 Å. The Ti(1)-O(4) bond length is 1.90 Å. The Ti(1)-O(5) bond length is 2.12 Å. The Ti(1)-O(6) bond length is 2.02 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(6) atom. The B(1)-O(2) bond length is 1.40 Å. The B(1)-O(3) bond length is 1.38 Å. The B(1)-O(6) bond length is 1.40 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. The B(2)-O(1) bond length is 1.39 Å. The B(2)-O(4) bond length is 1.40 Å. The B(2)-O(5) 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 Ti(1), and one B(2) atom to form distorted OLi2TiB tetrahedra that share corners with three equivalent O(5)Li2TiB tetrahedra, corners with two equivalent O(3)Li4B trigonal bipyramids, and  an edgeedge with one O(2)Li2TiB trigonal pyramid. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Ti(1), and one B(1) atom to form distorted OLi2TiB trigonal pyramids that share corners with three equivalent O(5)Li2TiB tetrahedra, corners with two equivalent O(3)Li4B trigonal bipyramids,  an edgeedge with one O(1)Li2TiB tetrahedra, and  an edgeedge with one O(3)Li4B trigonal bipyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one B(1) atom to form distorted OLi4B trigonal bipyramids that share corners with two equivalent O(1)Li2TiB tetrahedra, corners with three equivalent O(5)Li2TiB tetrahedra, corners with two equivalent O(2)Li2TiB trigonal pyramids,  an edgeedge with one O(3)Li4B trigonal bipyramid, and  an edgeedge with one O(2)Li2TiB trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Ti(1), and one B(2) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Ti(1), and one B(2) atom to form distorted OLi2TiB tetrahedra that share corners with three equivalent O(1)Li2TiB tetrahedra, corners with three equivalent O(3)Li4B trigonal bipyramids, and corners with three equivalent O(2)Li2TiB trigonal pyramids. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Ti(1), and one B(1) atom.