Li4TiCo5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Ti(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share edges with six equivalent Co(2)O6 octahedra. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CoO6 octahedra. In the second Co site, Co(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form CoO6 octahedra that share edges with three equivalent Ti(1)O6 octahedra and edges with three equivalent Co(2)O6 octahedra. In the third Co site, Co(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CoO6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Co(2) atoms to form OLi2TiCo2 trigonal bipyramids that share corners with two equivalent O(2)Li2Co3 trigonal bipyramids, corners with three equivalent O(1)Li2TiCo2 trigonal bipyramids,  an edgeedge with one O(2)Li2Co3 trigonal bipyramid, and edges with four equivalent O(1)Li2TiCo2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(3), and two equivalent Co(1) atoms to form OLi2Co3 trigonal bipyramids that share corners with two equivalent O(1)Li2TiCo2 trigonal bipyramids, corners with three equivalent O(2)Li2Co3 trigonal bipyramids,  an edgeedge with one O(1)Li2TiCo2 trigonal bipyramid, and edges with four equivalent O(2)Li2Co3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Co(3) and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Co(2) atoms.
Li4TiCo5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There is one shorter (1.99 Å) and one longer (2.04 Å) Li(1)-O(1) bond length. There is one shorter (2.02 Å) and one longer (2.05 Å) Li(1)-O(2) bond length. Ti(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share edges with six equivalent Co(2)O6 octahedra. Both Ti(1)-O(4) bond lengths are 1.96 Å. All Ti(1)-O(1) bond lengths are 2.00 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CoO6 octahedra. Both Co(1)-O(3) bond lengths are 1.90 Å. There are two shorter (1.92 Å) and two longer (1.94 Å) Co(1)-O(2) bond lengths. In the second Co site, Co(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form CoO6 octahedra that share edges with three equivalent Ti(1)O6 octahedra and edges with three equivalent Co(2)O6 octahedra. Both Co(2)-O(4) bond lengths are 1.92 Å. There are two shorter (1.94 Å) and two longer (1.95 Å) Co(2)-O(1) bond lengths. In the third Co site, Co(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing CoO6 octahedra. Both Co(3)-O(3) bond lengths are 1.88 Å. All Co(3)-O(2) bond lengths are 1.92 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Co(2) atoms to form OLi2TiCo2 trigonal bipyramids that share corners with two equivalent O(2)Li2Co3 trigonal bipyramids, corners with three equivalent O(1)Li2TiCo2 trigonal bipyramids,  an edgeedge with one O(2)Li2Co3 trigonal bipyramid, and edges with four equivalent O(1)Li2TiCo2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(3), and two equivalent Co(1) atoms to form OLi2Co3 trigonal bipyramids that share corners with two equivalent O(1)Li2TiCo2 trigonal bipyramids, corners with three equivalent O(2)Li2Co3 trigonal bipyramids,  an edgeedge with one O(1)Li2TiCo2 trigonal bipyramid, and edges with four equivalent O(2)Li2Co3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Co(3) and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Co(2) atoms.