Zn2Bi3O8 is beta indium sulfide-derived structured and crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra, corners with three equivalent Zn(2)O4 trigonal pyramids, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the second Zn site, Zn(2) is bonded to one O(4) and three equivalent O(2) atoms to form ZnO4 trigonal pyramids that share corners with three equivalent Zn(1)O6 octahedra and corners with nine equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-66°. Bi(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form BiO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with three equivalent Zn(2)O4 trigonal pyramids,  an edgeedge with one Zn(1)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Zn(1), one Zn(2), and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to one Zn(2) and three equivalent Bi(1) atoms.
Zn2Bi3O8 is beta indium sulfide-derived structured and crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra, corners with three equivalent Zn(2)O4 trigonal pyramids, and edges with three equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. All Zn(1)-O(1) bond lengths are 2.09 Å. All Zn(1)-O(2) bond lengths are 2.36 Å. In the second Zn site, Zn(2) is bonded to one O(4) and three equivalent O(2) atoms to form ZnO4 trigonal pyramids that share corners with three equivalent Zn(1)O6 octahedra and corners with nine equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-66°. The Zn(2)-O(4) bond length is 2.02 Å. All Zn(2)-O(2) bond lengths are 2.12 Å. Bi(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form BiO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with three equivalent Zn(2)O4 trigonal pyramids,  an edgeedge with one Zn(1)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The Bi(1)-O(3) bond length is 2.23 Å. The Bi(1)-O(4) bond length is 2.33 Å. Both Bi(1)-O(1) bond lengths are 2.23 Å. Both Bi(1)-O(2) bond lengths are 2.31 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Zn(1), one Zn(2), and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to one Zn(2) and three equivalent Bi(1) atoms.