LiCuF4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(3), one F(4), and one F(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(12), one F(2), one F(5), and one F(6) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one F(10), one F(11), one F(7), and one F(9) atom. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(3), one F(6), and two equivalent F(7) atoms to form distorted CuF6 octahedra that share  an edgeedge with one Cu(1)F6 octahedra and  an edgeedge with one Cu(2)F5 trigonal bipyramid. In the second Cu site, Cu(2) is bonded to one F(3), one F(4), one F(5), one F(6), and one F(9) atom to form distorted edge-sharing CuF5 trigonal bipyramids. In the third Cu site, Cu(3) is bonded in a 6-coordinate geometry to one F(10), one F(11), one F(12), one F(5), one F(8), and one F(9) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one Cu(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Li(2) and one Cu(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one Cu(2) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Li(2), one Cu(2), and one Cu(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(1), and one Cu(2) atom. In the seventh F site, F(7) is bonded in a distorted single-bond geometry to one Li(3) and two equivalent Cu(1) atoms. In the eighth F site, F(8) is bonded in a linear geometry to one Li(1) and one Cu(3) atom. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(3), one Cu(2), and one Cu(3) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one Li(3) and one Cu(3) atom. In the eleventh F site, F(11) is bonded in a bent 120 degrees geometry to one Li(3) and one Cu(3) atom. In the twelfth F site, F(12) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one Cu(3) atom.
LiCuF4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(3), one F(4), and one F(8) atom. The Li(1)-F(1) bond length is 2.19 Å. The Li(1)-F(3) bond length is 1.70 Å. The Li(1)-F(4) bond length is 2.39 Å. The Li(1)-F(8) bond length is 1.97 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(12), one F(2), one F(5), and one F(6) atom. The Li(2)-F(12) bond length is 1.73 Å. The Li(2)-F(2) bond length is 1.88 Å. The Li(2)-F(5) bond length is 2.39 Å. The Li(2)-F(6) bond length is 2.18 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one F(10), one F(11), one F(7), and one F(9) atom. The Li(3)-F(10) bond length is 2.03 Å. The Li(3)-F(11) bond length is 1.91 Å. The Li(3)-F(7) bond length is 1.40 Å. The Li(3)-F(9) bond length is 2.46 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(1), one F(2), one F(3), one F(6), and two equivalent F(7) atoms to form distorted CuF6 octahedra that share  an edgeedge with one Cu(1)F6 octahedra and  an edgeedge with one Cu(2)F5 trigonal bipyramid. The Cu(1)-F(1) bond length is 2.16 Å. The Cu(1)-F(2) bond length is 1.85 Å. The Cu(1)-F(3) bond length is 2.27 Å. The Cu(1)-F(6) bond length is 1.97 Å. There is one shorter (2.09 Å) and one longer (2.13 Å) Cu(1)-F(7) bond length. In the second Cu site, Cu(2) is bonded to one F(3), one F(4), one F(5), one F(6), and one F(9) atom to form distorted edge-sharing CuF5 trigonal bipyramids. The Cu(2)-F(3) bond length is 2.08 Å. The Cu(2)-F(4) bond length is 2.07 Å. The Cu(2)-F(5) bond length is 2.16 Å. The Cu(2)-F(6) bond length is 2.20 Å. The Cu(2)-F(9) bond length is 1.99 Å. In the third Cu site, Cu(3) is bonded in a 6-coordinate geometry to one F(10), one F(11), one F(12), one F(5), one F(8), and one F(9) atom. The Cu(3)-F(10) bond length is 1.80 Å. The Cu(3)-F(11) bond length is 2.20 Å. The Cu(3)-F(12) bond length is 1.92 Å. The Cu(3)-F(5) bond length is 2.22 Å. The Cu(3)-F(8) bond length is 1.86 Å. The Cu(3)-F(9) bond length is 2.54 Å. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one Cu(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Li(2) and one Cu(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(1) and one Cu(2) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Li(2), one Cu(2), and one Cu(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(1), and one Cu(2) atom. In the seventh F site, F(7) is bonded in a distorted single-bond geometry to one Li(3) and two equivalent Cu(1) atoms. In the eighth F site, F(8) is bonded in a linear geometry to one Li(1) and one Cu(3) atom. In the ninth F site, F(9) is bonded in a 3-coordinate geometry to one Li(3), one Cu(2), and one Cu(3) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one Li(3) and one Cu(3) atom. In the eleventh F site, F(11) is bonded in a bent 120 degrees geometry to one Li(3) and one Cu(3) atom. In the twelfth F site, F(12) is bonded in a distorted bent 120 degrees geometry to one Li(2) and one Cu(3) atom.