LiCuPO4F crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Cu(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Cu(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-63°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form CuO4F2 octahedra that share corners with two equivalent Cu(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 47°. In the second Cu site, Cu(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form CuO4F2 octahedra that share corners with two equivalent Cu(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O4F2 octahedra, corners with two equivalent Cu(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 35-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Cu(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Cu(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one Cu(2) atom.
LiCuPO4F crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Cu(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Cu(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-63°. The Li(1)-O(1) bond length is 2.09 Å. The Li(1)-O(2) bond length is 2.10 Å. There is one shorter (2.13 Å) and one longer (2.26 Å) Li(1)-O(4) bond length. The Li(1)-F(1) bond length is 1.86 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form CuO4F2 octahedra that share corners with two equivalent Cu(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 47°. Both Cu(1)-O(1) bond lengths are 1.98 Å. Both Cu(1)-O(4) bond lengths are 2.04 Å. Both Cu(1)-F(1) bond lengths are 1.92 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form CuO4F2 octahedra that share corners with two equivalent Cu(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. Both Cu(2)-O(2) bond lengths are 1.90 Å. Both Cu(2)-O(3) bond lengths are 1.93 Å. Both Cu(2)-F(1) bond lengths are 2.14 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O4F2 octahedra, corners with two equivalent Cu(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 35-53°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Cu(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Cu(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one Cu(2) atom.