ZnBi2O6 crystallizes in the orthorhombic Pmn2_1 space group. Zn(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form distorted ZnO4 trigonal pyramids that share corners with eight equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-81°. 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 six equivalent Bi(1)O6 octahedra and corners with four equivalent Zn(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 41-50°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Zn(1) and two equivalent Bi(1) atoms.
ZnBi2O6 crystallizes in the orthorhombic Pmn2_1 space group. Zn(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form distorted ZnO4 trigonal pyramids that share corners with eight equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-81°. The Zn(1)-O(3) bond length is 2.06 Å. The Zn(1)-O(4) bond length is 2.06 Å. Both Zn(1)-O(1) bond lengths are 2.06 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 six equivalent Bi(1)O6 octahedra and corners with four equivalent Zn(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 41-50°. The Bi(1)-O(3) bond length is 2.20 Å. The Bi(1)-O(4) bond length is 2.17 Å. There is one shorter (2.15 Å) and one longer (2.19 Å) Bi(1)-O(1) bond length. There is one shorter (2.11 Å) and one longer (2.15 Å) Bi(1)-O(2) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Zn(1) and two equivalent Bi(1) atoms.