ZnBi2O4 is Spinel-like structured and crystallizes in the trigonal R3m space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(3) and three equivalent O(4) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(2)O6 octahedra and corners with nine equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-56°. In the second Zn site, Zn(2) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form ZnO6 octahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Bi(1)O4 tetrahedra, and edges with six equivalent Bi(2)O6 octahedra. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(2) and three equivalent O(1) atoms to form BiO4 tetrahedra that share corners with three equivalent Zn(2)O6 octahedra and corners with nine equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-65°. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form BiO6 octahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Bi(1)O4 tetrahedra, edges with two equivalent Zn(2)O6 octahedra, and edges with four equivalent Bi(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Zn(2), one Bi(1), and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Bi(1) and three equivalent Bi(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Zn(1) and three equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Zn(1), one Zn(2), and two equivalent Bi(2) atoms.
ZnBi2O4 is Spinel-like structured and crystallizes in the trigonal R3m space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(3) and three equivalent O(4) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(2)O6 octahedra and corners with nine equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-56°. The Zn(1)-O(3) bond length is 2.05 Å. All Zn(1)-O(4) bond lengths are 2.13 Å. In the second Zn site, Zn(2) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form ZnO6 octahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Bi(1)O4 tetrahedra, and edges with six equivalent Bi(2)O6 octahedra. All Zn(2)-O(1) bond lengths are 2.16 Å. All Zn(2)-O(4) bond lengths are 2.39 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(2) and three equivalent O(1) atoms to form BiO4 tetrahedra that share corners with three equivalent Zn(2)O6 octahedra and corners with nine equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-65°. The Bi(1)-O(2) bond length is 2.19 Å. All Bi(1)-O(1) bond lengths are 2.31 Å. In the second Bi site, Bi(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form BiO6 octahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Bi(1)O4 tetrahedra, edges with two equivalent Zn(2)O6 octahedra, and edges with four equivalent Bi(2)O6 octahedra. The Bi(2)-O(2) bond length is 2.41 Å. The Bi(2)-O(3) bond length is 2.41 Å. Both Bi(2)-O(1) bond lengths are 2.40 Å. Both Bi(2)-O(4) bond lengths are 2.40 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Zn(2), one Bi(1), and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Bi(1) and three equivalent Bi(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Zn(1) and three equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Zn(1), one Zn(2), and two equivalent Bi(2) atoms.