Cu3(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form CuO5 trigonal bipyramids that share corners with five equivalent P(1)O4 tetrahedra and  an edgeedge with one Cu(1)O5 trigonal bipyramid. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent O(3) 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 five equivalent Cu(1)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Cu(1) and one P(1) atom. In the second O site, O(2) is bonded in a 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 distorted trigonal planar geometry to one Cu(1), one Cu(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(1) atom.
Cu3(PO4)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form CuO5 trigonal bipyramids that share corners with five equivalent P(1)O4 tetrahedra and  an edgeedge with one Cu(1)O5 trigonal bipyramid. The Cu(1)-O(2) bond length is 1.94 Å. The Cu(1)-O(3) bond length is 2.36 Å. The Cu(1)-O(4) bond length is 1.94 Å. There is one shorter (1.94 Å) and one longer (2.01 Å) Cu(1)-O(1) bond length. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Cu(2)-O(2) bond lengths are 1.92 Å. Both Cu(2)-O(3) bond lengths are 1.98 Å. 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 five equivalent Cu(1)O5 trigonal bipyramids. 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 1.53 Å. The P(1)-O(4) bond length is 1.51 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Cu(1) and one P(1) atom. In the second O site, O(2) is bonded in a 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 distorted trigonal planar geometry to one Cu(1), one Cu(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(1) atom.