Li3ThF7 crystallizes in the tetragonal P4/ncc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent F(3) atoms to form corner-sharing LiF4 tetrahedra. In the second Li site, Li(2) is bonded to two equivalent F(3) and three equivalent F(1) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent Li(1)F4 tetrahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. Th(1) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to three equivalent Li(2) atoms. In the second F site, F(2) is bonded in a single-bond geometry to one Th(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Th(1) atom.
Li3ThF7 crystallizes in the tetragonal P4/ncc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent F(3) atoms to form corner-sharing LiF4 tetrahedra. All Li(1)-F(3) bond lengths are 1.89 Å. In the second Li site, Li(2) is bonded to two equivalent F(3) and three equivalent F(1) atoms to form distorted LiF5 trigonal bipyramids that share corners with two equivalent Li(1)F4 tetrahedra, corners with four equivalent Li(2)F5 trigonal bipyramids, and  an edgeedge with one Li(2)F5 trigonal bipyramid. Both Li(2)-F(3) bond lengths are 2.09 Å. There are two shorter (1.99 Å) and one longer (2.11 Å) Li(2)-F(1) bond length. Th(1) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. The Th(1)-F(2) bond length is 2.15 Å. All Th(1)-F(3) bond lengths are 2.25 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to three equivalent Li(2) atoms. In the second F site, F(2) is bonded in a single-bond geometry to one Th(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one Th(1) atom.