Li2Cu(PO3)4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(5), and one O(6) atom. Cu(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, 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  a cornercorner with one Cu(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 36°. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-40°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Li(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cu(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Li(1), one Cu(1), and one P(2) atom.
Li2Cu(PO3)4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(5), and one O(6) atom. The Li(1)-O(2) bond length is 2.25 Å. The Li(1)-O(3) bond length is 1.84 Å. The Li(1)-O(5) bond length is 2.01 Å. The Li(1)-O(6) bond length is 2.57 Å. Cu(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Cu(1)-O(2) bond lengths are 2.46 Å. Both Cu(1)-O(5) bond lengths are 1.95 Å. Both Cu(1)-O(6) bond lengths are 1.97 Å. There are two inequivalent P sites. In the first P site, 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  a cornercorner with one Cu(1)O6 octahedra and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 36°. The P(1)-O(1) bond length is 1.63 Å. The P(1)-O(2) bond length is 1.50 Å. The P(1)-O(3) bond length is 1.48 Å. The P(1)-O(4) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-40°. The P(2)-O(1) bond length is 1.58 Å. The P(2)-O(4) bond length is 1.59 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.49 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Cu(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Li(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Cu(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Li(1), one Cu(1), and one P(2) atom.