BiO2 is Hydrophilite-like structured and crystallizes in the orthorhombic Pmc2_1 space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(5), one O(8), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the second Bi site, Bi(2) is bonded to one O(6), one O(7), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. In the third Bi site, Bi(3) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(8) atoms to form a mixture of distorted corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the fourth Bi site, Bi(4) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Bi(4) and two equivalent Bi(3) atoms. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Bi(3) and two equivalent Bi(4) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Bi(4) and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Bi(3) and two equivalent Bi(1) atoms. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Bi(2) and two equivalent Bi(4) atoms. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Bi(1) and two equivalent Bi(3) atoms.
BiO2 is Hydrophilite-like structured and crystallizes in the orthorhombic Pmc2_1 space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(5), one O(8), two equivalent O(4), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Bi(1)-O(5) bond length is 2.16 Å. The Bi(1)-O(8) bond length is 2.09 Å. Both Bi(1)-O(4) bond lengths are 2.21 Å. Both Bi(1)-O(6) bond lengths are 2.24 Å. In the second Bi site, Bi(2) is bonded to one O(6), one O(7), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. The Bi(2)-O(6) bond length is 2.30 Å. The Bi(2)-O(7) bond length is 2.56 Å. Both Bi(2)-O(3) bond lengths are 2.34 Å. Both Bi(2)-O(5) bond lengths are 2.33 Å. In the third Bi site, Bi(3) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(8) atoms to form a mixture of distorted corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Bi(3)-O(2) bond length is 2.31 Å. The Bi(3)-O(4) bond length is 2.56 Å. Both Bi(3)-O(1) bond lengths are 2.31 Å. Both Bi(3)-O(8) bond lengths are 2.35 Å. In the fourth Bi site, Bi(4) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 47-57°. The Bi(4)-O(1) bond length is 2.15 Å. The Bi(4)-O(3) bond length is 2.10 Å. Both Bi(4)-O(2) bond lengths are 2.23 Å. Both Bi(4)-O(7) bond lengths are 2.21 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Bi(4) and two equivalent Bi(3) atoms. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Bi(3) and two equivalent Bi(4) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Bi(4) and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Bi(3) and two equivalent Bi(1) atoms. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Bi(2) and two equivalent Bi(4) atoms. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Bi(1) and two equivalent Bi(3) atoms.