ZnBi2O4 crystallizes in the orthorhombic Cmcm space group. Zn(1) is bonded in a distorted water-like geometry to two equivalent O(2) and four equivalent O(1) atoms. Bi(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-76°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Zn(1) and three equivalent Bi(1) atoms. In the second O site, O(2) is bonded to two equivalent Zn(1) and two equivalent Bi(1) atoms to form corner-sharing OZn2Bi2 tetrahedra. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent Bi(1) atoms.
ZnBi2O4 crystallizes in the orthorhombic Cmcm space group. Zn(1) is bonded in a distorted water-like geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Zn(1)-O(2) bond lengths are 2.02 Å. All Zn(1)-O(1) bond lengths are 2.59 Å. Bi(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-76°. The Bi(1)-O(2) bond length is 2.47 Å. Both Bi(1)-O(3) bond lengths are 2.40 Å. All Bi(1)-O(1) bond lengths are 2.39 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Zn(1) and three equivalent Bi(1) atoms. In the second O site, O(2) is bonded to two equivalent Zn(1) and two equivalent Bi(1) atoms to form corner-sharing OZn2Bi2 tetrahedra. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent Bi(1) atoms.