Cu5(PO5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form CuO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent Cu(2)O5 trigonal bipyramids, and edges with two equivalent Cu(1)O5 trigonal bipyramids. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(5) atoms to form distorted CuO5 trigonal bipyramids that share corners with four equivalent P(1)O4 tetrahedra, corners with three equivalent Cu(1)O5 trigonal bipyramids, and  an edgeedge with one Cu(2)O5 trigonal bipyramid. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with three equivalent Cu(1)O5 trigonal bipyramids and corners with four equivalent Cu(2)O5 trigonal bipyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Cu(2), one Cu(3), and two equivalent Cu(1) atoms to form a mixture of edge and corner-sharing OCu4 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Cu(3), two equivalent Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Cu(2) and one P(1) atom.
Cu5(PO5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form CuO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent Cu(2)O5 trigonal bipyramids, and edges with two equivalent Cu(1)O5 trigonal bipyramids. The Cu(1)-O(2) bond length is 1.93 Å. Both Cu(1)-O(1) bond lengths are 1.94 Å. There is one shorter (2.13 Å) and one longer (2.26 Å) Cu(1)-O(3) bond length. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(5) atoms to form distorted CuO5 trigonal bipyramids that share corners with four equivalent P(1)O4 tetrahedra, corners with three equivalent Cu(1)O5 trigonal bipyramids, and  an edgeedge with one Cu(2)O5 trigonal bipyramid. The Cu(2)-O(1) bond length is 1.93 Å. The Cu(2)-O(2) bond length is 2.52 Å. The Cu(2)-O(4) bond length is 1.88 Å. There is one shorter (1.94 Å) and one longer (1.98 Å) Cu(2)-O(5) bond length. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Cu(3)-O(1) bond lengths are 1.92 Å. Both Cu(3)-O(3) bond lengths are 2.05 Å. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with three equivalent Cu(1)O5 trigonal bipyramids and corners with four equivalent Cu(2)O5 trigonal bipyramids. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.50 Å. The P(1)-O(5) bond length is 1.55 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Cu(2), one Cu(3), and two equivalent Cu(1) atoms to form a mixture of edge and corner-sharing OCu4 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Cu(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Cu(3), two equivalent Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Cu(2) and one P(1) atom.