Zn(CuO2)2 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form CuO6 octahedra that share corners with two equivalent Zn(2)O6 pentagonal pyramids, corners with three equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Cu(2)O6 octahedra,  an edgeedge with one Zn(1)O6 pentagonal pyramid, and  a faceface with one Zn(2)O6 pentagonal pyramid. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CuO6 octahedra that share corners with four equivalent Zn(2)O6 pentagonal pyramids, edges with two equivalent Cu(2)O6 octahedra, edges with four equivalent Cu(1)O6 octahedra, and edges with two equivalent Zn(1)O6 pentagonal pyramids. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted ZnO6 pentagonal pyramids that share corners with six equivalent Cu(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Cu(2)O6 octahedra, and edges with two equivalent Zn(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 4-19°. In the second Zn site, Zn(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Cu(1)O6 octahedra, corners with eight equivalent Cu(2)O6 octahedra, edges with two equivalent Zn(1)O6 pentagonal pyramids, and faces with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Cu(1), two equivalent Cu(2), and one Zn(1) atom. In the second O site, O(2) is bonded to one Cu(1), two equivalent Cu(2), and one Zn(2) atom to form OZnCu3 trigonal pyramids that share corners with four equivalent O(3)Zn2Cu3 trigonal bipyramids, corners with three equivalent O(2)ZnCu3 trigonal pyramids, and edges with four equivalent O(3)Zn2Cu3 trigonal bipyramids. In the third O site, O(3) is bonded to one Cu(2), two equivalent Cu(1), one Zn(1), and one Zn(2) atom to form OZn2Cu3 trigonal bipyramids that share corners with five equivalent O(3)Zn2Cu3 trigonal bipyramids, corners with two equivalent O(2)ZnCu3 trigonal pyramids, edges with four equivalent O(3)Zn2Cu3 trigonal bipyramids, and edges with two equivalent O(2)ZnCu3 trigonal pyramids.
Zn(CuO2)2 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form CuO6 octahedra that share corners with two equivalent Zn(2)O6 pentagonal pyramids, corners with three equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Cu(2)O6 octahedra,  an edgeedge with one Zn(1)O6 pentagonal pyramid, and  a faceface with one Zn(2)O6 pentagonal pyramid. The Cu(1)-O(1) bond length is 1.96 Å. The Cu(1)-O(2) bond length is 1.96 Å. There are two shorter (1.99 Å) and two longer (2.12 Å) Cu(1)-O(3) bond lengths. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CuO6 octahedra that share corners with four equivalent Zn(2)O6 pentagonal pyramids, edges with two equivalent Cu(2)O6 octahedra, edges with four equivalent Cu(1)O6 octahedra, and edges with two equivalent Zn(1)O6 pentagonal pyramids. Both Cu(2)-O(1) bond lengths are 1.92 Å. Both Cu(2)-O(2) bond lengths are 2.02 Å. Both Cu(2)-O(3) bond lengths are 2.06 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted ZnO6 pentagonal pyramids that share corners with six equivalent Cu(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with four equivalent Cu(2)O6 octahedra, and edges with two equivalent Zn(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 4-19°. Both Zn(1)-O(1) bond lengths are 2.09 Å. All Zn(1)-O(3) bond lengths are 2.18 Å. In the second Zn site, Zn(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Cu(1)O6 octahedra, corners with eight equivalent Cu(2)O6 octahedra, edges with two equivalent Zn(1)O6 pentagonal pyramids, and faces with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. Both Zn(2)-O(2) bond lengths are 2.10 Å. All Zn(2)-O(3) bond lengths are 2.18 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Cu(1), two equivalent Cu(2), and one Zn(1) atom. In the second O site, O(2) is bonded to one Cu(1), two equivalent Cu(2), and one Zn(2) atom to form OZnCu3 trigonal pyramids that share corners with four equivalent O(3)Zn2Cu3 trigonal bipyramids, corners with three equivalent O(2)ZnCu3 trigonal pyramids, and edges with four equivalent O(3)Zn2Cu3 trigonal bipyramids. In the third O site, O(3) is bonded to one Cu(2), two equivalent Cu(1), one Zn(1), and one Zn(2) atom to form OZn2Cu3 trigonal bipyramids that share corners with five equivalent O(3)Zn2Cu3 trigonal bipyramids, corners with two equivalent O(2)ZnCu3 trigonal pyramids, edges with four equivalent O(3)Zn2Cu3 trigonal bipyramids, and edges with two equivalent O(2)ZnCu3 trigonal pyramids.