LiCuPO4 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(5), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent Cu(2)O4 tetrahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form CuO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. In the second Cu site, Cu(2) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form CuO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Cu(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with three equivalent Cu(1)O4 tetrahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cu(1), and one P(2) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Li(2), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Cu(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one Cu(1), and one P(1) atom.
LiCuPO4 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(5), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The Li(1)-O(1) bond length is 1.97 Å. The Li(1)-O(3) bond length is 1.95 Å. The Li(1)-O(5) bond length is 2.02 Å. The Li(1)-O(8) bond length is 2.07 Å. In the second Li site, Li(2) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent Cu(2)O4 tetrahedra. The Li(2)-O(2) bond length is 2.35 Å. The Li(2)-O(4) bond length is 1.96 Å. The Li(2)-O(6) bond length is 1.94 Å. The Li(2)-O(7) bond length is 1.97 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form CuO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The Cu(1)-O(1) bond length is 1.94 Å. The Cu(1)-O(3) bond length is 1.94 Å. The Cu(1)-O(4) bond length is 2.12 Å. The Cu(1)-O(8) bond length is 1.90 Å. In the second Cu site, Cu(2) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form CuO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The Cu(2)-O(2) bond length is 1.98 Å. The Cu(2)-O(5) bond length is 1.91 Å. The Cu(2)-O(6) bond length is 1.98 Å. The Cu(2)-O(7) bond length is 1.97 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Cu(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.55 Å. The P(1)-O(8) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with three equivalent Cu(1)O4 tetrahedra. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cu(1), and one P(2) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Li(2), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one Cu(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one Cu(1), and one P(1) atom.