Cu5(PO6)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted CuO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. 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 distorted CuO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. In the third Cu site, Cu(3) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(6) atoms. In the fourth Cu site, Cu(4) is bonded in a distorted square co-planar geometry to one O(3), one O(6), and two equivalent O(5) atoms. 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 two equivalent Cu(1)O6 octahedra and corners with two equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-74°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Cu(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(4) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2), one Cu(3), and one Cu(4) atom.
Cu5(PO6)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted CuO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. Both Cu(1)-O(2) bond lengths are 1.88 Å. Both Cu(1)-O(4) bond lengths are 2.52 Å. Both Cu(1)-O(5) bond lengths are 1.96 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 distorted CuO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. Both Cu(2)-O(1) bond lengths are 2.34 Å. Both Cu(2)-O(3) bond lengths are 1.99 Å. Both Cu(2)-O(6) bond lengths are 1.87 Å. In the third Cu site, Cu(3) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(6) atoms. Both Cu(3)-O(1) bond lengths are 1.87 Å. Both Cu(3)-O(6) bond lengths are 1.86 Å. In the fourth Cu site, Cu(4) is bonded in a distorted square co-planar geometry to one O(3), one O(6), and two equivalent O(5) atoms. The Cu(4)-O(3) bond length is 1.90 Å. The Cu(4)-O(6) bond length is 1.91 Å. There is one shorter (1.86 Å) and one longer (1.88 Å) Cu(4)-O(5) 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 two equivalent Cu(1)O6 octahedra and corners with two equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-74°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.61 Å. The P(1)-O(4) bond length is 1.51 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(2), one Cu(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Cu(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(4) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2), one Cu(3), and one Cu(4) atom.