LiCuPO4 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with four equivalent P(1)O4 tetrahedra and corners with five equivalent Cu(1)O5 trigonal bipyramids. Cu(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted CuO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Cu(1)O5 trigonal bipyramids, corners with five equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one P(1)O4 tetrahedra. 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 three equivalent Cu(1)O5 trigonal bipyramids, corners with four equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. There are four 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 in a trigonal non-coplanar geometry to one Li(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent Cu(1), and one P(1) atom to form distorted corner-sharing OLiCu2P trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one P(1) atom.
LiCuPO4 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 trigonal pyramids that share corners with four equivalent P(1)O4 tetrahedra and corners with five equivalent Cu(1)O5 trigonal bipyramids. The Li(1)-O(1) bond length is 1.92 Å. The Li(1)-O(2) bond length is 2.06 Å. The Li(1)-O(3) bond length is 2.41 Å. The Li(1)-O(4) bond length is 2.44 Å. Cu(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted CuO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Cu(1)O5 trigonal bipyramids, corners with five equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one P(1)O4 tetrahedra. The Cu(1)-O(1) bond length is 2.01 Å. The Cu(1)-O(2) bond length is 1.98 Å. The Cu(1)-O(4) bond length is 2.17 Å. There is one shorter (1.97 Å) and one longer (2.13 Å) Cu(1)-O(3) bond length. 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 three equivalent Cu(1)O5 trigonal bipyramids, corners with four equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.61 Å. The P(1)-O(4) bond length is 1.52 Å. There are four 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 in a trigonal non-coplanar geometry to one Li(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent Cu(1), and one P(1) atom to form distorted corner-sharing OLiCu2P trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Cu(1), and one P(1) atom.