Li2MoF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Mo(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Mo(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. Mo(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form MoF6 octahedra that share corners with eight equivalent Li(1)F6 octahedra and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mo(1) atom. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mo(1) atom.
Li2MoF6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Mo(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Mo(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. Both Li(1)-F(1) bond lengths are 2.02 Å. There are two shorter (1.96 Å) and two longer (2.05 Å) Li(1)-F(2) bond lengths. Mo(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form MoF6 octahedra that share corners with eight equivalent Li(1)F6 octahedra and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. Both Mo(1)-F(1) bond lengths are 1.94 Å. All Mo(1)-F(2) bond lengths are 1.98 Å. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mo(1) atom. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Mo(1) atom.