LiCuF3 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent F(1), two equivalent F(3), and two equivalent F(6) atoms. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with eight equivalent Cu(2)F6 octahedra and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-51°. In the third Li site, Li(3) is bonded to one F(5) and four equivalent F(2) atoms to form LiF5 square pyramids that share corners with six equivalent Cu(1)F6 octahedra and edges with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(3), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form CuF6 octahedra that share corners with four equivalent Cu(2)F6 octahedra, corners with three equivalent Li(3)F5 square pyramids,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. In the second Cu site, Cu(2) is bonded to one F(3), one F(6), two equivalent F(1), and two equivalent F(2) atoms to form distorted CuF6 octahedra that share corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and  an edgeedge with one Li(3)F5 square pyramid. The corner-sharing octahedral tilt angles range from 35-56°. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and two equivalent Cu(2) atoms to form a mixture of distorted corner and edge-sharing FLi3Cu2 trigonal bipyramids. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(3), one Cu(1), and one Cu(2) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cu(1), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to two equivalent Cu(1) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Cu(1) atoms. In the sixth F site, F(6) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cu(1), and one Cu(2) atom.
LiCuF3 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent F(1), two equivalent F(3), and two equivalent F(6) atoms. Both Li(1)-F(1) bond lengths are 1.92 Å. Both Li(1)-F(3) bond lengths are 2.04 Å. Both Li(1)-F(6) bond lengths are 2.49 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(6) atoms to form LiF6 octahedra that share corners with eight equivalent Cu(2)F6 octahedra and edges with two equivalent Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-51°. Both Li(2)-F(1) bond lengths are 2.18 Å. Both Li(2)-F(3) bond lengths are 1.96 Å. Both Li(2)-F(6) bond lengths are 1.88 Å. In the third Li site, Li(3) is bonded to one F(5) and four equivalent F(2) atoms to form LiF5 square pyramids that share corners with six equivalent Cu(1)F6 octahedra and edges with two equivalent Cu(2)F6 octahedra. The corner-sharing octahedral tilt angles are 48°. The Li(3)-F(5) bond length is 2.16 Å. All Li(3)-F(2) bond lengths are 2.02 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(3), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form CuF6 octahedra that share corners with four equivalent Cu(2)F6 octahedra, corners with three equivalent Li(3)F5 square pyramids,  an edgeedge with one Li(2)F6 octahedra, and  an edgeedge with one Cu(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The Cu(1)-F(3) bond length is 2.12 Å. The Cu(1)-F(4) bond length is 1.93 Å. The Cu(1)-F(5) bond length is 1.99 Å. The Cu(1)-F(6) bond length is 2.01 Å. Both Cu(1)-F(2) bond lengths are 2.13 Å. In the second Cu site, Cu(2) is bonded to one F(3), one F(6), two equivalent F(1), and two equivalent F(2) atoms to form distorted CuF6 octahedra that share corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and  an edgeedge with one Li(3)F5 square pyramid. The corner-sharing octahedral tilt angles range from 35-56°. The Cu(2)-F(3) bond length is 2.45 Å. The Cu(2)-F(6) bond length is 2.26 Å. Both Cu(2)-F(1) bond lengths are 2.08 Å. Both Cu(2)-F(2) bond lengths are 1.88 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and two equivalent Cu(2) atoms to form a mixture of distorted corner and edge-sharing FLi3Cu2 trigonal bipyramids. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(3), one Cu(1), and one Cu(2) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cu(1), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to two equivalent Cu(1) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3) and two equivalent Cu(1) atoms. In the sixth F site, F(6) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cu(1), and one Cu(2) atom.