LiTi3O6 is Ilmenite-like structured and crystallizes in the orthorhombic Fddd space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 17-19°. In the second Ti site, Ti(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles are 19°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing OLiTi3 trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(2) and two equivalent Ti(1) atoms.
LiTi3O6 is Ilmenite-like structured and crystallizes in the orthorhombic Fddd space group. Li(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) atoms. All Li(1)-O(1) bond lengths are 1.95 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 17-19°. Both Ti(1)-O(2) bond lengths are 1.97 Å. There are two shorter (1.99 Å) and two longer (2.03 Å) Ti(1)-O(1) bond lengths. In the second Ti site, Ti(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles are 19°. Both Ti(2)-O(2) bond lengths are 2.02 Å. All Ti(2)-O(1) bond lengths are 2.00 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing OLiTi3 trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(2) and two equivalent Ti(1) atoms.