Al2(BiO3)3 crystallizes in the monoclinic Cc space group. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form distorted AlO6 octahedra that share corners with three equivalent Al(2)O6 octahedra,  a cornercorner with one Bi(3)O6 pentagonal pyramid,  an edgeedge with one Bi(3)O6 pentagonal pyramid, and edges with two equivalent Bi(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 31-40°. In the second Al site, Al(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form AlO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, corners with two equivalent Bi(1)O6 pentagonal pyramids, edges with two equivalent Bi(3)O6 pentagonal pyramids, and  a faceface with one Bi(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 31-40°. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(3), one O(4), one O(6), one O(8), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share corners with two equivalent Al(2)O6 octahedra, corners with three equivalent Bi(3)O6 pentagonal pyramids, edges with two equivalent Al(1)O6 octahedra, and  a faceface with one Al(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(9) atom. In the third Bi site, Bi(3) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted BiO6 pentagonal pyramids that share  a cornercorner with one Al(1)O6 octahedra, corners with three equivalent Bi(1)O6 pentagonal pyramids,  an edgeedge with one Al(1)O6 octahedra, and edges with two equivalent Al(2)O6 octahedra. The corner-sharing octahedral tilt angles are 59°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Al(1), one Al(2), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Al(1), one Bi(2), and one Bi(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Al(2), one Bi(1), and one Bi(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Al(1), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Al(2), one Bi(2), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Al(1), one Al(2), one Bi(1), and one Bi(3) atom. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one Al(1), one Bi(2), and one Bi(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Al(2), one Bi(1), and one Bi(3) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Al(1), one Al(2), one Bi(1), and one Bi(2) atom.
Al2(BiO3)3 crystallizes in the monoclinic Cc space group. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form distorted AlO6 octahedra that share corners with three equivalent Al(2)O6 octahedra,  a cornercorner with one Bi(3)O6 pentagonal pyramid,  an edgeedge with one Bi(3)O6 pentagonal pyramid, and edges with two equivalent Bi(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 31-40°. The Al(1)-O(1) bond length is 1.93 Å. The Al(1)-O(2) bond length is 1.95 Å. The Al(1)-O(4) bond length is 1.93 Å. The Al(1)-O(6) bond length is 1.95 Å. The Al(1)-O(7) bond length is 1.88 Å. The Al(1)-O(9) bond length is 2.24 Å. In the second Al site, Al(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form AlO6 octahedra that share corners with three equivalent Al(1)O6 octahedra, corners with two equivalent Bi(1)O6 pentagonal pyramids, edges with two equivalent Bi(3)O6 pentagonal pyramids, and  a faceface with one Bi(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 31-40°. The Al(2)-O(1) bond length is 2.07 Å. The Al(2)-O(3) bond length is 1.88 Å. The Al(2)-O(5) bond length is 1.87 Å. The Al(2)-O(6) bond length is 2.02 Å. The Al(2)-O(8) bond length is 1.98 Å. The Al(2)-O(9) bond length is 1.92 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(3), one O(4), one O(6), one O(8), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share corners with two equivalent Al(2)O6 octahedra, corners with three equivalent Bi(3)O6 pentagonal pyramids, edges with two equivalent Al(1)O6 octahedra, and  a faceface with one Al(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. The Bi(1)-O(1) bond length is 2.26 Å. The Bi(1)-O(3) bond length is 2.13 Å. The Bi(1)-O(4) bond length is 2.10 Å. The Bi(1)-O(6) bond length is 2.31 Å. The Bi(1)-O(8) bond length is 2.16 Å. The Bi(1)-O(9) bond length is 2.14 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(9) atom. The Bi(2)-O(1) bond length is 2.54 Å. The Bi(2)-O(2) bond length is 2.22 Å. The Bi(2)-O(4) bond length is 2.39 Å. The Bi(2)-O(5) bond length is 2.34 Å. The Bi(2)-O(7) bond length is 2.30 Å. The Bi(2)-O(9) bond length is 2.59 Å. In the third Bi site, Bi(3) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted BiO6 pentagonal pyramids that share  a cornercorner with one Al(1)O6 octahedra, corners with three equivalent Bi(1)O6 pentagonal pyramids,  an edgeedge with one Al(1)O6 octahedra, and edges with two equivalent Al(2)O6 octahedra. The corner-sharing octahedral tilt angles are 59°. The Bi(3)-O(2) bond length is 2.25 Å. The Bi(3)-O(3) bond length is 2.35 Å. The Bi(3)-O(5) bond length is 2.21 Å. The Bi(3)-O(6) bond length is 2.47 Å. The Bi(3)-O(7) bond length is 2.23 Å. The Bi(3)-O(8) bond length is 2.32 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Al(1), one Al(2), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Al(1), one Bi(2), and one Bi(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Al(2), one Bi(1), and one Bi(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Al(1), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Al(2), one Bi(2), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Al(1), one Al(2), one Bi(1), and one Bi(3) atom. In the seventh O site, O(7) is bonded in a trigonal non-coplanar geometry to one Al(1), one Bi(2), and one Bi(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Al(2), one Bi(1), and one Bi(3) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Al(1), one Al(2), one Bi(1), and one Bi(2) atom.