ZnBi2O4 crystallizes in the triclinic P-1 space group. Zn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(1), and three equivalent O(3) atoms. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to two equivalent O(2) and three equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded to one Zn(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted corner-sharing OZnBi3 tetrahedra. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Zn(1) and three equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Zn(1) and three equivalent Bi(2) atoms.
ZnBi2O4 crystallizes in the triclinic P-1 space group. Zn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. The Zn(1)-O(1) bond length is 2.05 Å. The Zn(1)-O(2) bond length is 1.99 Å. The Zn(1)-O(4) bond length is 2.34 Å. There is one shorter (2.17 Å) and one longer (2.26 Å) Zn(1)-O(3) bond length. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(1), and three equivalent O(3) atoms. The Bi(1)-O(2) bond length is 2.61 Å. There is one shorter (2.23 Å) and one longer (2.24 Å) Bi(1)-O(1) bond length. There are a spread of Bi(1)-O(3) bond distances ranging from 2.21-2.76 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to two equivalent O(2) and three equivalent O(4) atoms. There is one shorter (2.30 Å) and one longer (2.32 Å) Bi(2)-O(2) bond length. There is one shorter (2.15 Å) and two longer (2.47 Å) Bi(2)-O(4) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded to one Zn(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted corner-sharing OZnBi3 tetrahedra. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Zn(1) and three equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Zn(1) and three equivalent Bi(2) atoms.