LiTi4O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(3) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), and three equivalent O(4) atoms. In the second Ti site, Ti(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles are 26°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one Ti(1), and one Ti(2) atom. In the fourth O site, O(4) is bonded to one Ti(2) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OTi4 trigonal pyramids.
LiTi4O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(3) atoms. All Li(1)-O(3) bond lengths are 2.39 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), and three equivalent O(4) atoms. The Ti(1)-O(1) bond length is 1.95 Å. The Ti(1)-O(2) bond length is 2.04 Å. The Ti(1)-O(3) bond length is 1.82 Å. There are two shorter (1.96 Å) and one longer (2.36 Å) Ti(1)-O(4) bond length. In the second Ti site, Ti(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles are 26°. The Ti(2)-O(3) bond length is 1.95 Å. The Ti(2)-O(4) bond length is 2.14 Å. There is one shorter (1.90 Å) and one longer (2.10 Å) Ti(2)-O(1) bond length. Both Ti(2)-O(2) bond lengths are 1.95 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one Ti(1), and one Ti(2) atom. In the fourth O site, O(4) is bonded to one Ti(2) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OTi4 trigonal pyramids.