ZnBi2O4 crystallizes in the orthorhombic Pnma space group. Zn(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form ZnO5 square pyramids that share corners with six equivalent Bi(1)O5 square pyramids,  an edgeedge with one Bi(1)O5 square pyramid, and edges with two equivalent Zn(1)O5 square pyramids. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted BiO5 square pyramids that share corners with six equivalent Zn(1)O5 square pyramids,  an edgeedge with one Zn(1)O5 square pyramid, and edges with two equivalent Bi(1)O5 square pyramids. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to one O(2) and three equivalent O(1) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to three equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Zn(1), one Bi(2), and two equivalent Bi(1) atoms to form distorted corner-sharing OZnBi3 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Zn(1) and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Zn(1) and one Bi(1) atom.
ZnBi2O4 crystallizes in the orthorhombic Pnma space group. Zn(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form ZnO5 square pyramids that share corners with six equivalent Bi(1)O5 square pyramids,  an edgeedge with one Bi(1)O5 square pyramid, and edges with two equivalent Zn(1)O5 square pyramids. The Zn(1)-O(2) bond length is 2.10 Å. Both Zn(1)-O(3) bond lengths are 2.18 Å. Both Zn(1)-O(4) bond lengths are 2.24 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted BiO5 square pyramids that share corners with six equivalent Zn(1)O5 square pyramids,  an edgeedge with one Zn(1)O5 square pyramid, and edges with two equivalent Bi(1)O5 square pyramids. The Bi(1)-O(4) bond length is 2.18 Å. Both Bi(1)-O(2) bond lengths are 2.30 Å. Both Bi(1)-O(3) bond lengths are 2.57 Å. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to one O(2) and three equivalent O(1) atoms. The Bi(2)-O(2) bond length is 2.33 Å. There are two shorter (2.20 Å) and one longer (2.36 Å) Bi(2)-O(1) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to three equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Zn(1), one Bi(2), and two equivalent Bi(1) atoms to form distorted corner-sharing OZnBi3 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Zn(1) and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Zn(1) and one Bi(1) atom.