BBi3O6 crystallizes in the orthorhombic Pnma space group. B(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form BO4 tetrahedra that share corners with four equivalent Bi(2)O6 octahedra and edges with two equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. In the second Bi site, Bi(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted BiO6 octahedra that share corners with two equivalent Bi(2)O6 octahedra, corners with two equivalent B(1)O4 tetrahedra, edges with two equivalent Bi(2)O6 octahedra, and  an edgeedge with one B(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and two equivalent Bi(2) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and two equivalent Bi(2) atoms.
BBi3O6 crystallizes in the orthorhombic Pnma space group. B(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form BO4 tetrahedra that share corners with four equivalent Bi(2)O6 octahedra and edges with two equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-61°. The B(1)-O(2) bond length is 1.56 Å. The B(1)-O(4) bond length is 1.45 Å. Both B(1)-O(3) bond lengths are 1.52 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. The Bi(1)-O(2) bond length is 2.41 Å. The Bi(1)-O(4) bond length is 2.79 Å. Both Bi(1)-O(1) bond lengths are 2.14 Å. Both Bi(1)-O(3) bond lengths are 2.78 Å. In the second Bi site, Bi(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted BiO6 octahedra that share corners with two equivalent Bi(2)O6 octahedra, corners with two equivalent B(1)O4 tetrahedra, edges with two equivalent Bi(2)O6 octahedra, and  an edgeedge with one B(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. The Bi(2)-O(2) bond length is 2.49 Å. The Bi(2)-O(4) bond length is 2.52 Å. There is one shorter (2.28 Å) and one longer (2.38 Å) Bi(2)-O(1) bond length. There is one shorter (2.33 Å) and one longer (2.38 Å) Bi(2)-O(3) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and two equivalent Bi(2) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and two equivalent Bi(2) atoms.