CuZn3P2O9 crystallizes in the monoclinic C2/m space group. Cu(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted CuO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, and edges with two equivalent Zn(1)O5 trigonal bipyramids. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(3), one O(5), one O(6), and one O(7) atom to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent Zn(2)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Zn(1)O5 trigonal bipyramid,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. In the second Zn site, Zn(2) is bonded to one O(2), one O(7), and two equivalent O(1) atoms to form ZnO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with six equivalent Zn(1)O5 trigonal bipyramids, and  an edgeedge with one Zn(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with four equivalent Cu(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-54°. In the second P site, P(2) is bonded to one O(5), one O(7), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and corners with six equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 62°. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Cu(1) and one P(1) atom. In the second O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Zn(1) and one P(2) atom. In the third O site, O(6) is bonded in a 3-coordinate geometry to one Cu(1), one Zn(1), and one P(2) atom. In the fourth O site, O(7) is bonded to one Zn(2), two equivalent Zn(1), and one P(2) atom to form corner-sharing OZn3P tetrahedra. In the fifth O site, O(1) is bonded to two equivalent Zn(1) and two equivalent Zn(2) atoms to form OZn4 tetrahedra that share corners with four equivalent O(7)Zn3P tetrahedra and  an edgeedge with one O(1)Zn4 tetrahedra. In the sixth O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(1) atom. In the seventh O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(1), one Zn(1), and one P(1) atom.
CuZn3P2O9 crystallizes in the monoclinic C2/m space group. Cu(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted CuO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, and edges with two equivalent Zn(1)O5 trigonal bipyramids. Both Cu(1)-O(3) bond lengths are 2.03 Å. Both Cu(1)-O(4) bond lengths are 2.07 Å. Both Cu(1)-O(6) bond lengths are 2.50 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(3), one O(5), one O(6), and one O(7) atom to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent Zn(2)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a cornercorner with one Zn(1)O5 trigonal bipyramid,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The Zn(1)-O(1) bond length is 1.99 Å. The Zn(1)-O(3) bond length is 2.16 Å. The Zn(1)-O(5) bond length is 2.04 Å. The Zn(1)-O(6) bond length is 1.99 Å. The Zn(1)-O(7) bond length is 2.24 Å. In the second Zn site, Zn(2) is bonded to one O(2), one O(7), and two equivalent O(1) atoms to form ZnO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with six equivalent Zn(1)O5 trigonal bipyramids, and  an edgeedge with one Zn(2)O4 tetrahedra. The Zn(2)-O(2) bond length is 1.89 Å. The Zn(2)-O(7) bond length is 1.99 Å. Both Zn(2)-O(1) bond lengths are 2.00 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with four equivalent Cu(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and corners with two equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-54°. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.57 Å. Both P(1)-O(3) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(5), one O(7), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Cu(1)O6 octahedra,  a cornercorner with one Zn(2)O4 tetrahedra, and corners with six equivalent Zn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 62°. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.60 Å. Both P(2)-O(6) bond lengths are 1.53 Å. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Cu(1) and one P(1) atom. In the second O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Zn(1) and one P(2) atom. In the third O site, O(6) is bonded in a 3-coordinate geometry to one Cu(1), one Zn(1), and one P(2) atom. In the fourth O site, O(7) is bonded to one Zn(2), two equivalent Zn(1), and one P(2) atom to form corner-sharing OZn3P tetrahedra. In the fifth O site, O(1) is bonded to two equivalent Zn(1) and two equivalent Zn(2) atoms to form OZn4 tetrahedra that share corners with four equivalent O(7)Zn3P tetrahedra and  an edgeedge with one O(1)Zn4 tetrahedra. In the sixth O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(1) atom. In the seventh O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(1), one Zn(1), and one P(1) atom.