Li2CrF6 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Cr(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. Cr(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CrF6 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 44-47°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cr(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Cr(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cr(1) atom.
Li2CrF6 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Cr(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Cr(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. There is one shorter (1.98 Å) and one longer (2.04 Å) Li(1)-F(1) bond length. Both Li(1)-F(2) bond lengths are 2.01 Å. There is one shorter (1.94 Å) and one longer (1.99 Å) Li(1)-F(3) bond length. Cr(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CrF6 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 44-47°. Both Cr(1)-F(1) bond lengths are 1.83 Å. Both Cr(1)-F(2) bond lengths are 1.82 Å. Both Cr(1)-F(3) bond lengths are 1.85 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cr(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one Cr(1) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Cr(1) atom.