Li3CrF6 is beta indium sulfide-derived structured and crystallizes in the monoclinic Pc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form LiF6 octahedra that share corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Cr(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Cr(1)F6 octahedra, and edges with two equivalent Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-51°. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(5), and one F(6) atom to form distorted LiF4 tetrahedra that share corners with four equivalent Cr(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom 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,  an edgeedge with one Cr(1)F6 octahedra, and edges with two equivalent Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-51°. Cr(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form CrF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one Cr(1) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one Cr(1) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom.
Li3CrF6 is beta indium sulfide-derived structured and crystallizes in the monoclinic Pc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form LiF6 octahedra that share corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Cr(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Cr(1)F6 octahedra, and edges with two equivalent Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-51°. The Li(1)-F(1) bond length is 2.11 Å. The Li(1)-F(2) bond length is 2.09 Å. The Li(1)-F(3) bond length is 1.98 Å. The Li(1)-F(4) bond length is 2.00 Å. The Li(1)-F(5) bond length is 2.14 Å. The Li(1)-F(6) bond length is 2.13 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(5), and one F(6) atom to form distorted LiF4 tetrahedra that share corners with four equivalent Cr(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. The Li(2)-F(1) bond length is 1.86 Å. The Li(2)-F(2) bond length is 1.86 Å. The Li(2)-F(5) bond length is 1.86 Å. The Li(2)-F(6) bond length is 1.86 Å. In the third Li site, Li(3) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom 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,  an edgeedge with one Cr(1)F6 octahedra, and edges with two equivalent Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-51°. The Li(3)-F(1) bond length is 2.11 Å. The Li(3)-F(2) bond length is 2.13 Å. The Li(3)-F(3) bond length is 2.01 Å. The Li(3)-F(4) bond length is 1.98 Å. The Li(3)-F(5) bond length is 2.12 Å. The Li(3)-F(6) bond length is 2.11 Å. Cr(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form CrF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. The Cr(1)-F(1) bond length is 1.95 Å. The Cr(1)-F(2) bond length is 1.95 Å. The Cr(1)-F(3) bond length is 1.95 Å. The Cr(1)-F(4) bond length is 1.94 Å. The Cr(1)-F(5) bond length is 1.95 Å. The Cr(1)-F(6) bond length is 1.94 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one Cr(1) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one Cr(1) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Li(3), and one Cr(1) atom.