LiCuPO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Cu(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 71-78°. Cu(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with six equivalent Cu(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-51°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent Cu(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLiCu2P tetrahedra.
LiCuPO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Cu(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 71-78°. Both Li(1)-O(1) bond lengths are 1.98 Å. Both Li(1)-O(2) bond lengths are 2.09 Å. Cu(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. Both Cu(1)-O(1) bond lengths are 1.96 Å. All Cu(1)-O(2) bond lengths are 2.22 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with six equivalent Cu(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-51°. Both P(1)-O(1) bond lengths are 1.54 Å. Both P(1)-O(2) bond lengths are 1.57 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent Cu(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLiCu2P tetrahedra.