LiCuF3 is Sylvanite-like structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(11), one F(12), one F(2), one F(4), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, edges with two equivalent Cu(3)F6 octahedra, edges with two equivalent Cu(4)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-45°. In the second Li site, Li(2) is bonded to one F(1), one F(11), one F(12), one F(2), one F(4), and one F(9) atom to form distorted LiF6 octahedra that share corners with four equivalent Cu(3)F6 octahedra, corners with four equivalent Cu(4)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. In the third Li site, Li(3) is bonded to one F(10), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share corners with four equivalent Cu(1)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra,  an edgeedge with one Cu(3)F6 octahedra,  an edgeedge with one Cu(4)F6 octahedra, and faces with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. In the fourth Li site, Li(4) is bonded to one F(10), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share corners with two equivalent Cu(3)F6 octahedra, corners with two equivalent Cu(4)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, edges with two equivalent Cu(2)F6 octahedra, and faces with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-47°. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(10), one F(11), one F(2), one F(3), one F(6), and one F(7) atom to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Cu(3)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and edges with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. In the second Cu site, Cu(2) is bonded to one F(1), one F(10), one F(12), one F(3), one F(5), and one F(8) atom to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Cu(4)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra, and edges with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the third Cu site, Cu(3) is bonded to one F(11), one F(2), one F(4), one F(6), one F(7), and one F(9) atom to form CuF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Cu(4)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the fourth Cu site, Cu(4) is bonded to one F(1), one F(12), one F(4), one F(5), one F(8), and one F(9) atom to form CuF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Cu(3)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(2), and one Cu(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(1), and one Cu(3) atom. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Li(3), one Li(4), one Cu(1), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cu(3), and one Cu(4) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Cu(2), and one Cu(4) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Cu(1), and one Cu(3) atom. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Cu(1), and one Cu(3) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Cu(2), and one Cu(4) atom. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cu(3), and one Cu(4) atom. In the tenth F site, F(10) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Cu(1), and one Cu(2) atom. In the eleventh F site, F(11) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(1), and one Cu(3) atom. In the twelfth F site, F(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(2), and one Cu(4) atom.
LiCuF3 is Sylvanite-like structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(11), one F(12), one F(2), one F(4), and one F(9) atom to form LiF6 octahedra that share corners with two equivalent Cu(1)F6 octahedra, corners with two equivalent Cu(2)F6 octahedra, edges with two equivalent Cu(3)F6 octahedra, edges with two equivalent Cu(4)F6 octahedra, and faces with two equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-45°. The Li(1)-F(1) bond length is 2.00 Å. The Li(1)-F(11) bond length is 2.23 Å. The Li(1)-F(12) bond length is 2.01 Å. The Li(1)-F(2) bond length is 2.19 Å. The Li(1)-F(4) bond length is 1.94 Å. The Li(1)-F(9) bond length is 1.94 Å. In the second Li site, Li(2) is bonded to one F(1), one F(11), one F(12), one F(2), one F(4), and one F(9) atom to form distorted LiF6 octahedra that share corners with four equivalent Cu(3)F6 octahedra, corners with four equivalent Cu(4)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and faces with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. The Li(2)-F(1) bond length is 1.94 Å. The Li(2)-F(11) bond length is 1.92 Å. The Li(2)-F(12) bond length is 1.94 Å. The Li(2)-F(2) bond length is 1.93 Å. The Li(2)-F(4) bond length is 2.35 Å. The Li(2)-F(9) bond length is 2.32 Å. In the third Li site, Li(3) is bonded to one F(10), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share corners with four equivalent Cu(1)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra,  an edgeedge with one Cu(3)F6 octahedra,  an edgeedge with one Cu(4)F6 octahedra, and faces with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. The Li(3)-F(10) bond length is 2.45 Å. The Li(3)-F(3) bond length is 2.23 Å. The Li(3)-F(5) bond length is 1.92 Å. The Li(3)-F(6) bond length is 1.95 Å. The Li(3)-F(7) bond length is 1.97 Å. The Li(3)-F(8) bond length is 1.93 Å. In the fourth Li site, Li(4) is bonded to one F(10), one F(3), one F(5), one F(6), one F(7), and one F(8) atom to form distorted LiF6 octahedra that share corners with two equivalent Cu(3)F6 octahedra, corners with two equivalent Cu(4)F6 octahedra, edges with two equivalent Cu(1)F6 octahedra, edges with two equivalent Cu(2)F6 octahedra, and faces with two equivalent Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-47°. The Li(4)-F(10) bond length is 1.93 Å. The Li(4)-F(3) bond length is 1.95 Å. The Li(4)-F(5) bond length is 2.28 Å. The Li(4)-F(6) bond length is 1.96 Å. The Li(4)-F(7) bond length is 1.97 Å. The Li(4)-F(8) bond length is 2.31 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one F(10), one F(11), one F(2), one F(3), one F(6), and one F(7) atom to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Cu(3)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Cu(2)F6 octahedra, and edges with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Cu(1)-F(10) bond length is 1.98 Å. The Cu(1)-F(11) bond length is 1.93 Å. The Cu(1)-F(2) bond length is 1.92 Å. The Cu(1)-F(3) bond length is 2.00 Å. The Cu(1)-F(6) bond length is 2.35 Å. The Cu(1)-F(7) bond length is 2.35 Å. In the second Cu site, Cu(2) is bonded to one F(1), one F(10), one F(12), one F(3), one F(5), and one F(8) atom to form CuF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Li(3)F6 octahedra, corners with four equivalent Cu(4)F6 octahedra,  an edgeedge with one Li(2)F6 octahedra,  an edgeedge with one Cu(1)F6 octahedra, and edges with two equivalent Li(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Cu(2)-F(1) bond length is 1.93 Å. The Cu(2)-F(10) bond length is 1.99 Å. The Cu(2)-F(12) bond length is 1.94 Å. The Cu(2)-F(3) bond length is 2.01 Å. The Cu(2)-F(5) bond length is 2.33 Å. The Cu(2)-F(8) bond length is 2.33 Å. In the third Cu site, Cu(3) is bonded to one F(11), one F(2), one F(4), one F(6), one F(7), and one F(9) atom to form CuF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Cu(1)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Cu(4)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The Cu(3)-F(11) bond length is 2.33 Å. The Cu(3)-F(2) bond length is 2.34 Å. The Cu(3)-F(4) bond length is 1.99 Å. The Cu(3)-F(6) bond length is 1.93 Å. The Cu(3)-F(7) bond length is 1.93 Å. The Cu(3)-F(9) bond length is 1.99 Å. In the fourth Cu site, Cu(4) is bonded to one F(1), one F(12), one F(4), one F(5), one F(8), and one F(9) atom to form CuF6 octahedra that share corners with two equivalent Li(4)F6 octahedra, corners with four equivalent Li(2)F6 octahedra, corners with four equivalent Cu(2)F6 octahedra,  an edgeedge with one Li(3)F6 octahedra,  an edgeedge with one Cu(3)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The Cu(4)-F(1) bond length is 2.37 Å. The Cu(4)-F(12) bond length is 2.34 Å. The Cu(4)-F(4) bond length is 2.00 Å. The Cu(4)-F(5) bond length is 1.92 Å. The Cu(4)-F(8) bond length is 1.92 Å. The Cu(4)-F(9) bond length is 2.00 Å. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(2), and one Cu(4) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(1), and one Cu(3) atom. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Li(3), one Li(4), one Cu(1), and one Cu(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cu(3), and one Cu(4) atom. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Cu(2), and one Cu(4) atom. In the sixth F site, F(6) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Cu(1), and one Cu(3) atom. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one Cu(1), and one Cu(3) atom. In the eighth F site, F(8) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Cu(2), and one Cu(4) atom. In the ninth F site, F(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Cu(3), and one Cu(4) atom. In the tenth F site, F(10) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Cu(1), and one Cu(2) atom. In the eleventh F site, F(11) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(1), and one Cu(3) atom. In the twelfth F site, F(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Cu(2), and one Cu(4) atom.