CaCu3P3O13 crystallizes in the monoclinic P2_1/m space group. Ca(1) is bonded to one O(9), two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form distorted CaO7 pentagonal bipyramids that share corners with two equivalent Cu(3)O6 octahedra, corners with three equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(2)O5 square pyramids, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-59°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(5), one O(6), one O(9), and two equivalent O(8) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(3)O6 octahedra, corners with three equivalent Ca(1)O7 pentagonal bipyramids,  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. In the second Cu site, Cu(2) is bonded to one O(1), one O(3), one O(7), and two equivalent O(2) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Ca(1)O7 pentagonal bipyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. In the third Cu site, Cu(3) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Ca(1)O7 pentagonal bipyramids, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra, corners with three equivalent Cu(2)O5 square pyramids, and  an edgeedge with one Ca(1)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 45°. In the second P site, P(2) is bonded to one O(10), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(3)O6 octahedra,  a cornercorner with one Cu(2)O5 square pyramid, and  an edgeedge with one Ca(1)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 46-55°. In the third P site, P(3) is bonded to one O(1), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(3)O6 octahedra, corners with three equivalent Ca(1)O7 pentagonal bipyramids,  a cornercorner with one Cu(2)O5 square pyramid, and  an edgeedge with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are ten inequivalent O sites. In the first O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Cu(3) and one P(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(3) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(2), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(2) atom. In the fifth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(1), one Cu(3), and one P(3) atom. In the sixth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a trigonal planar geometry to one Cu(1) and two equivalent Cu(3) atoms. In the eighth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cu(2) and one P(1) atom. In the ninth O site, O(8) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one P(2) atom. In the tenth O site, O(9) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one P(3) atom.
CaCu3P3O13 crystallizes in the monoclinic P2_1/m space group. Ca(1) is bonded to one O(9), two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form distorted CaO7 pentagonal bipyramids that share corners with two equivalent Cu(3)O6 octahedra, corners with three equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(2)O5 square pyramids, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-59°. The Ca(1)-O(9) bond length is 2.40 Å. Both Ca(1)-O(2) bond lengths are 2.51 Å. Both Ca(1)-O(4) bond lengths are 2.38 Å. Both Ca(1)-O(8) bond lengths are 2.48 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(5), one O(6), one O(9), and two equivalent O(8) atoms to form distorted CuO6 octahedra that share corners with two equivalent Cu(3)O6 octahedra, corners with three equivalent Ca(1)O7 pentagonal bipyramids,  a cornercorner with one Cu(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. The Cu(1)-O(1) bond length is 2.13 Å. The Cu(1)-O(5) bond length is 1.97 Å. The Cu(1)-O(6) bond length is 1.91 Å. The Cu(1)-O(9) bond length is 2.24 Å. Both Cu(1)-O(8) bond lengths are 1.95 Å. In the second Cu site, Cu(2) is bonded to one O(1), one O(3), one O(7), and two equivalent O(2) atoms to form CuO5 square pyramids that share  a cornercorner with one Cu(1)O6 octahedra, corners with two equivalent Ca(1)O7 pentagonal bipyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The Cu(2)-O(1) bond length is 1.92 Å. The Cu(2)-O(3) bond length is 1.92 Å. The Cu(2)-O(7) bond length is 2.07 Å. Both Cu(2)-O(2) bond lengths are 1.95 Å. In the third Cu site, Cu(3) is bonded to two equivalent O(10), two equivalent O(4), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Ca(1)O7 pentagonal bipyramids, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and edges with two equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. Both Cu(3)-O(10) bond lengths are 2.09 Å. Both Cu(3)-O(4) bond lengths are 2.01 Å. Both Cu(3)-O(6) bond lengths are 1.96 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Cu(1)O6 octahedra, corners with three equivalent Cu(2)O5 square pyramids, and  an edgeedge with one Ca(1)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 45°. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.52 Å. Both P(1)-O(2) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(10), one O(3), and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with two equivalent Cu(3)O6 octahedra,  a cornercorner with one Cu(2)O5 square pyramid, and  an edgeedge with one Ca(1)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 46-55°. The P(2)-O(10) bond length is 1.57 Å. The P(2)-O(3) bond length is 1.52 Å. Both P(2)-O(8) bond lengths are 1.55 Å. In the third P site, P(3) is bonded to one O(1), one O(9), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(3)O6 octahedra, corners with three equivalent Ca(1)O7 pentagonal bipyramids,  a cornercorner with one Cu(2)O5 square pyramid, and  an edgeedge with one Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The P(3)-O(1) bond length is 1.58 Å. The P(3)-O(9) bond length is 1.54 Å. Both P(3)-O(4) bond lengths are 1.54 Å. There are ten inequivalent O sites. In the first O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Cu(3) and one P(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(3) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(2), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(2) and one P(2) atom. In the fifth O site, O(4) is bonded in a distorted trigonal planar geometry to one Ca(1), one Cu(3), and one P(3) atom. In the sixth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a trigonal planar geometry to one Cu(1) and two equivalent Cu(3) atoms. In the eighth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cu(2) and one P(1) atom. In the ninth O site, O(8) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one P(2) atom. In the tenth O site, O(9) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one P(3) atom.