Li3Ti(PO4)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with five equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, corners with three equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and corners with six equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 76°. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with five equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 37-61°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Ti(1), and one P(1) atom to form distorted OLi2TiP trigonal pyramids that share corners with five equivalent O(3)Li3P tetrahedra and corners with two equivalent O(1)Li2TiP trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Ti(1), and one P(1) atom. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(3)Li3P tetrahedra and corners with five equivalent O(1)Li2TiP trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one P(1) atom.
Li3Ti(PO4)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with five equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, corners with three equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. The Li(1)-O(1) bond length is 2.37 Å. The Li(1)-O(2) bond length is 2.37 Å. The Li(1)-O(4) bond length is 2.03 Å. There is one shorter (2.07 Å) and one longer (2.27 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and corners with six equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 76°. Both Li(2)-O(1) bond lengths are 2.04 Å. Both Li(2)-O(3) bond lengths are 2.03 Å. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. Both Ti(1)-O(1) bond lengths are 2.15 Å. Both Ti(1)-O(2) bond lengths are 2.00 Å. Both Ti(1)-O(4) bond lengths are 2.04 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with five equivalent Li(1)O5 trigonal bipyramids, and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 37-61°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Ti(1), and one P(1) atom to form distorted OLi2TiP trigonal pyramids that share corners with five equivalent O(3)Li3P tetrahedra and corners with two equivalent O(1)Li2TiP trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Ti(1), and one P(1) atom. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with three equivalent O(3)Li3P tetrahedra and corners with five equivalent O(1)Li2TiP trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one P(1) atom.