Cu2Zn(BiO4)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(5), one O(6), and one O(7) atom to form distorted CuO5 trigonal bipyramids that share corners with three equivalent Bi(2)O4 trigonal pyramids and edges with two equivalent Zn(1)O6 octahedra. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(4), one O(6), and one O(8) atom. Zn(1) is bonded to one O(1), one O(4), one O(7), one O(8), and two equivalent O(3) atoms to form ZnO6 octahedra that share corners with three equivalent Bi(2)O4 trigonal pyramids,  an edgeedge with one Zn(1)O6 octahedra, and edges with two equivalent Cu(1)O5 trigonal bipyramids. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(6), and one O(7) atom. In the second Bi site, Bi(2) is bonded to one O(3), one O(5), one O(6), and one O(8) atom to form distorted BiO4 trigonal pyramids that share corners with three equivalent Zn(1)O6 octahedra and corners with three equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 57-77°. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a 3-coordinate geometry to one Cu(1), one Zn(1), and one Bi(1) atom. In the second O site, O(8) is bonded in a trigonal non-coplanar geometry to one Cu(2), one Zn(1), and one Bi(2) atom. In the third O site, O(1) is bonded in a trigonal non-coplanar geometry to one Cu(1), one Zn(1), and one Bi(1) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Cu(2) and one Bi(1) atom. In the fifth O site, O(3) is bonded to one Cu(1), two equivalent Zn(1), and one Bi(2) atom to form OZn2CuBi trigonal pyramids that share corners with two equivalent O(6)Cu2Bi2 trigonal pyramids and  an edgeedge with one O(3)Zn2CuBi trigonal pyramid. In the sixth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2), one Zn(1), and one Bi(1) atom. In the seventh O site, O(5) is bonded in a bent 120 degrees geometry to one Cu(1) and one Bi(2) atom. In the eighth O site, O(6) is bonded to one Cu(1), one Cu(2), one Bi(1), and one Bi(2) atom to form distorted corner-sharing OCu2Bi2 trigonal pyramids.
Cu2Zn(BiO4)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(5), one O(6), and one O(7) atom to form distorted CuO5 trigonal bipyramids that share corners with three equivalent Bi(2)O4 trigonal pyramids and edges with two equivalent Zn(1)O6 octahedra. The Cu(1)-O(1) bond length is 1.86 Å. The Cu(1)-O(3) bond length is 1.92 Å. The Cu(1)-O(5) bond length is 1.82 Å. The Cu(1)-O(6) bond length is 1.89 Å. The Cu(1)-O(7) bond length is 2.47 Å. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(4), one O(6), and one O(8) atom. The Cu(2)-O(2) bond length is 1.85 Å. The Cu(2)-O(4) bond length is 1.85 Å. The Cu(2)-O(6) bond length is 1.89 Å. The Cu(2)-O(8) bond length is 1.85 Å. Zn(1) is bonded to one O(1), one O(4), one O(7), one O(8), and two equivalent O(3) atoms to form ZnO6 octahedra that share corners with three equivalent Bi(2)O4 trigonal pyramids,  an edgeedge with one Zn(1)O6 octahedra, and edges with two equivalent Cu(1)O5 trigonal bipyramids. The Zn(1)-O(1) bond length is 2.11 Å. The Zn(1)-O(4) bond length is 2.19 Å. The Zn(1)-O(7) bond length is 2.11 Å. The Zn(1)-O(8) bond length is 1.99 Å. There is one shorter (2.10 Å) and one longer (2.11 Å) Zn(1)-O(3) bond length. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(6), and one O(7) atom. The Bi(1)-O(1) bond length is 2.10 Å. The Bi(1)-O(2) bond length is 2.08 Å. The Bi(1)-O(4) bond length is 2.11 Å. The Bi(1)-O(6) bond length is 2.54 Å. The Bi(1)-O(7) bond length is 2.05 Å. In the second Bi site, Bi(2) is bonded to one O(3), one O(5), one O(6), and one O(8) atom to form distorted BiO4 trigonal pyramids that share corners with three equivalent Zn(1)O6 octahedra and corners with three equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 57-77°. The Bi(2)-O(3) bond length is 2.22 Å. The Bi(2)-O(5) bond length is 2.10 Å. The Bi(2)-O(6) bond length is 2.53 Å. The Bi(2)-O(8) bond length is 2.16 Å. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a 3-coordinate geometry to one Cu(1), one Zn(1), and one Bi(1) atom. In the second O site, O(8) is bonded in a trigonal non-coplanar geometry to one Cu(2), one Zn(1), and one Bi(2) atom. In the third O site, O(1) is bonded in a trigonal non-coplanar geometry to one Cu(1), one Zn(1), and one Bi(1) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Cu(2) and one Bi(1) atom. In the fifth O site, O(3) is bonded to one Cu(1), two equivalent Zn(1), and one Bi(2) atom to form OZn2CuBi trigonal pyramids that share corners with two equivalent O(6)Cu2Bi2 trigonal pyramids and  an edgeedge with one O(3)Zn2CuBi trigonal pyramid. In the sixth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Cu(2), one Zn(1), and one Bi(1) atom. In the seventh O site, O(5) is bonded in a bent 120 degrees geometry to one Cu(1) and one Bi(2) atom. In the eighth O site, O(6) is bonded to one Cu(1), one Cu(2), one Bi(1), and one Bi(2) atom to form distorted corner-sharing OCu2Bi2 trigonal pyramids.