DOE OSTI2020
LiTiCl3 crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a trigonal non-coplanar geometry to three Cl1- atoms. There are two shorter (2.25 Å) and one longer (2.32 Å) Li–Cl bond lengths. In the second Li1+ site, Li1+ is bonded in a trigonal non-coplanar geometry to three Cl1- atoms. There are two shorter (2.34 Å) and one longer (2.37 Å) Li–Cl bond lengths. In the third Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four Cl1- atoms. There are two shorter (2.42 Å) and two longer (2.45 Å) Li–Cl bond lengths. In the fourth Li1+ site, Li1+ is bonded to six Cl1- atoms to form LiCl6 octahedra that share edges with four equivalent TiCl6 octahedra and edges with two TiCl5 trigonal bipyramids. There are a spread of Li–Cl bond distances ranging from 2.53–2.61 Å. There are three inequivalent Ti2+ sites. In the first Ti2+ site, Ti2+ is bonded to five Cl1- atoms to form distorted TiCl5 trigonal bipyramids that share an edgeedge with one LiCl6 octahedra and edges with two equivalent TiCl6 octahedra. There are a spread of Ti–Cl bond distances ranging from 2.36–2.52 Å. In the second Ti2+ site, Ti2+ is bonded to six Cl1- atoms to form distorted TiCl6 octahedra that share edges with two equivalent LiCl6 octahedra, edges with two equivalent TiCl6 octahedra, and edges with two TiCl5 trigonal bipyramids. There are a spread of Ti–Cl bond distances ranging from 2.39–2.82 Å. In the third Ti2+ site, Ti2+ is bonded to five Cl1- atoms to form TiCl5 trigonal bipyramids that share an edgeedge with one LiCl6 octahedra and edges with two equivalent TiCl6 octahedra. There are a spread of Ti–Cl bond distances ranging from 2.34–2.60 Å. There are eight inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted trigonal non-coplanar geometry to two Li1+ and one Ti2+ atom. In the second Cl1- site, Cl1- is bonded in a 4-coordinate geometry to one Li1+ and three Ti2+ atoms. In the third Cl1- site, Cl1- is bonded in an L-shaped geometry to one Li1+ and one Ti2+ atom. In the fourth Cl1- site, Cl1- is bonded to two Li1+ and two equivalent Ti2+ atoms to form distorted edge-sharing ClLi2Ti2 tetrahedra. In the fifth Cl1- site, Cl1- is bonded to two Li1+ and two Ti2+ atoms to form a mixture of distorted edge and corner-sharing ClLi2Ti2 tetrahedra. In the sixth Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to one Li1+ and two Ti2+ atoms. In the seventh Cl1- site, Cl1- is bonded in a distorted T-shaped geometry to one Li1+ and two equivalent Ti2+ atoms. In the eighth Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Ti2+ atoms.