Li2Cu5(PO4)4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 7-coordinate geometry to one O(1), one O(4), one O(6), two equivalent O(3), and two equivalent O(5) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(7) atom to form distorted CuO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Cu(3)O5 trigonal bipyramid,  an edgeedge with one Cu(2)O6 octahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cu(1)O5 trigonal bipyramids. In the third Cu site, Cu(3) is bonded to one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form distorted CuO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Cu(1)O5 trigonal bipyramid, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(1)O5 trigonal bipyramids, and corners with three equivalent Cu(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 56°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cu(2)O6 octahedra, corners with two equivalent Cu(3)O5 trigonal bipyramids, and corners with three equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 40-47°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Cu(1), one Cu(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1), one Cu(1), one Cu(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Cu(1), one Cu(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), 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 Cu(1), one Cu(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cu(3) and one P(1) atom.
Li2Cu5(PO4)4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 7-coordinate geometry to one O(1), one O(4), one O(6), two equivalent O(3), and two equivalent O(5) atoms. The Li(1)-O(1) bond length is 2.43 Å. The Li(1)-O(4) bond length is 2.02 Å. The Li(1)-O(6) bond length is 2.21 Å. There is one shorter (2.56 Å) and one longer (2.65 Å) Li(1)-O(3) bond length. There is one shorter (2.58 Å) and one longer (2.64 Å) Li(1)-O(5) bond length. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(7) atom to form distorted CuO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Cu(3)O5 trigonal bipyramid,  an edgeedge with one Cu(2)O6 octahedra, and  an edgeedge with one Cu(3)O5 trigonal bipyramid. The Cu(1)-O(1) bond length is 2.11 Å. The Cu(1)-O(2) bond length is 1.94 Å. The Cu(1)-O(3) bond length is 2.08 Å. The Cu(1)-O(5) bond length is 2.02 Å. The Cu(1)-O(7) bond length is 2.04 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cu(1)O5 trigonal bipyramids. Both Cu(2)-O(1) bond lengths are 2.28 Å. Both Cu(2)-O(3) bond lengths are 2.09 Å. Both Cu(2)-O(6) bond lengths are 1.98 Å. In the third Cu site, Cu(3) is bonded to one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form distorted CuO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a cornercorner with one Cu(1)O5 trigonal bipyramid, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. The Cu(3)-O(2) bond length is 2.15 Å. The Cu(3)-O(4) bond length is 1.99 Å. The Cu(3)-O(5) bond length is 2.24 Å. The Cu(3)-O(7) bond length is 1.99 Å. The Cu(3)-O(8) bond length is 1.93 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cu(2)O6 octahedra, corners with two equivalent Cu(1)O5 trigonal bipyramids, and corners with three equivalent Cu(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 56°. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.58 Å. The P(1)-O(8) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Cu(2)O6 octahedra, corners with two equivalent Cu(3)O5 trigonal bipyramids, and corners with three equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 40-47°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.57 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Cu(1), one Cu(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1), one Cu(1), one Cu(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Cu(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Cu(1), one Cu(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), 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 Cu(1), one Cu(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Cu(3) and one P(1) atom.