Zn2Bi2O5 crystallizes in the triclinic P1 space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form ZnO4 trigonal pyramids that share corners with two equivalent Zn(1)O4 trigonal pyramids,  an edgeedge with one Zn(2)O4 tetrahedra, and edges with two equivalent Bi(4)O5 trigonal bipyramids. In the second Zn site, Zn(2) is bonded to one O(5), one O(6), and two equivalent O(3) atoms to form distorted ZnO4 tetrahedra that share corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Bi(4)O5 trigonal bipyramids, and  an edgeedge with one Zn(1)O4 trigonal pyramid. In the third Zn site, Zn(3) is bonded to one O(10), one O(8), and two equivalent O(7) atoms to form ZnO4 trigonal pyramids that share corners with two equivalent Bi(4)O5 trigonal bipyramids, corners with two equivalent Zn(3)O4 trigonal pyramids, and  an edgeedge with one Zn(4)O4 trigonal pyramid. In the fourth Zn site, Zn(4) is bonded to one O(10), one O(8), and two equivalent O(2) atoms to form a mixture of corner and edge-sharing ZnO4 trigonal pyramids. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(8) atoms. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(10) atoms. In the third Bi site, Bi(3) is bonded in a 3-coordinate geometry to one O(2), one O(9), and two equivalent O(5) atoms. In the fourth Bi site, Bi(4) is bonded to one O(4), one O(7), one O(9), and two equivalent O(6) atoms to form distorted BiO5 trigonal bipyramids that share corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Bi(4)O5 trigonal bipyramids, corners with two equivalent Zn(3)O4 trigonal pyramids, and edges with two equivalent Zn(1)O4 trigonal pyramids. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Bi(1) and one Bi(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Zn(4), one Bi(2), and one Bi(3) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Zn(2) and one Bi(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Zn(1), one Bi(1), and one Bi(4) atom. In the fifth O site, O(5) is bonded to one Zn(1), one Zn(2), and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OZn2Bi2 tetrahedra. In the sixth O site, O(6) is bonded to one Zn(1), one Zn(2), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OZn2Bi2 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Zn(3) and one Bi(4) atom. In the eighth O site, O(8) is bonded to one Zn(3), one Zn(4), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OZn2Bi2 tetrahedra. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Bi(3) and one Bi(4) atom. In the tenth O site, O(10) is bonded to one Zn(3), one Zn(4), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OZn2Bi2 trigonal pyramids.
Zn2Bi2O5 crystallizes in the triclinic P1 space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form ZnO4 trigonal pyramids that share corners with two equivalent Zn(1)O4 trigonal pyramids,  an edgeedge with one Zn(2)O4 tetrahedra, and edges with two equivalent Bi(4)O5 trigonal bipyramids. The Zn(1)-O(5) bond length is 2.16 Å. The Zn(1)-O(6) bond length is 2.18 Å. There is one shorter (2.00 Å) and one longer (2.01 Å) Zn(1)-O(4) bond length. In the second Zn site, Zn(2) is bonded to one O(5), one O(6), and two equivalent O(3) atoms to form distorted ZnO4 tetrahedra that share corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Bi(4)O5 trigonal bipyramids, and  an edgeedge with one Zn(1)O4 trigonal pyramid. The Zn(2)-O(5) bond length is 2.22 Å. The Zn(2)-O(6) bond length is 2.00 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) Zn(2)-O(3) bond length. In the third Zn site, Zn(3) is bonded to one O(10), one O(8), and two equivalent O(7) atoms to form ZnO4 trigonal pyramids that share corners with two equivalent Bi(4)O5 trigonal bipyramids, corners with two equivalent Zn(3)O4 trigonal pyramids, and  an edgeedge with one Zn(4)O4 trigonal pyramid. The Zn(3)-O(10) bond length is 2.02 Å. The Zn(3)-O(8) bond length is 2.13 Å. There is one shorter (1.93 Å) and one longer (1.94 Å) Zn(3)-O(7) bond length. In the fourth Zn site, Zn(4) is bonded to one O(10), one O(8), and two equivalent O(2) atoms to form a mixture of corner and edge-sharing ZnO4 trigonal pyramids. The Zn(4)-O(10) bond length is 2.15 Å. The Zn(4)-O(8) bond length is 2.07 Å. There is one shorter (1.96 Å) and one longer (1.97 Å) Zn(4)-O(2) bond length. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(8) atoms. The Bi(1)-O(1) bond length is 2.05 Å. The Bi(1)-O(4) bond length is 2.82 Å. There is one shorter (2.21 Å) and one longer (2.23 Å) Bi(1)-O(8) bond length. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(10) atoms. The Bi(2)-O(1) bond length is 2.20 Å. The Bi(2)-O(2) bond length is 2.47 Å. The Bi(2)-O(3) bond length is 2.53 Å. There is one shorter (2.18 Å) and one longer (2.22 Å) Bi(2)-O(10) bond length. In the third Bi site, Bi(3) is bonded in a 3-coordinate geometry to one O(2), one O(9), and two equivalent O(5) atoms. The Bi(3)-O(2) bond length is 2.82 Å. The Bi(3)-O(9) bond length is 2.06 Å. There is one shorter (2.26 Å) and one longer (2.28 Å) Bi(3)-O(5) bond length. In the fourth Bi site, Bi(4) is bonded to one O(4), one O(7), one O(9), and two equivalent O(6) atoms to form distorted BiO5 trigonal bipyramids that share corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Bi(4)O5 trigonal bipyramids, corners with two equivalent Zn(3)O4 trigonal pyramids, and edges with two equivalent Zn(1)O4 trigonal pyramids. The Bi(4)-O(4) bond length is 2.42 Å. The Bi(4)-O(7) bond length is 2.41 Å. The Bi(4)-O(9) bond length is 2.28 Å. There is one shorter (2.20 Å) and one longer (2.25 Å) Bi(4)-O(6) bond length. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Bi(1) and one Bi(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Zn(4), one Bi(2), and one Bi(3) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Zn(2) and one Bi(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Zn(1), one Bi(1), and one Bi(4) atom. In the fifth O site, O(5) is bonded to one Zn(1), one Zn(2), and two equivalent Bi(3) atoms to form a mixture of corner and edge-sharing OZn2Bi2 tetrahedra. In the sixth O site, O(6) is bonded to one Zn(1), one Zn(2), and two equivalent Bi(4) atoms to form a mixture of corner and edge-sharing OZn2Bi2 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Zn(3) and one Bi(4) atom. In the eighth O site, O(8) is bonded to one Zn(3), one Zn(4), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OZn2Bi2 tetrahedra. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Bi(3) and one Bi(4) atom. In the tenth O site, O(10) is bonded to one Zn(3), one Zn(4), and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OZn2Bi2 trigonal pyramids.