Bi2(SO4)3 crystallizes in the monoclinic C2/c space group. Bi(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form BiO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form SO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-55°. In the second S site, S(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form SO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-33°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Bi(1) and one S(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Bi(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to one Bi(1) and one S(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Bi(1) and one S(1) atom.
Bi2(SO4)3 crystallizes in the monoclinic C2/c space group. Bi(1) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form BiO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 octahedra. The Bi(1)-O(1) bond length is 2.40 Å. The Bi(1)-O(3) bond length is 2.31 Å. The Bi(1)-O(5) bond length is 2.26 Å. The Bi(1)-O(6) bond length is 2.32 Å. There is one shorter (2.45 Å) and one longer (2.54 Å) Bi(1)-O(4) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form SO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-55°. The S(1)-O(2) bond length is 1.43 Å. The S(1)-O(3) bond length is 1.50 Å. The S(1)-O(4) bond length is 1.56 Å. The S(1)-O(6) bond length is 1.50 Å. In the second S site, S(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form SO4 tetrahedra that share corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-33°. Both S(2)-O(1) bond lengths are 1.48 Å. Both S(2)-O(5) bond lengths are 1.49 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Bi(1) and one S(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Bi(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to one Bi(1) and one S(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Bi(1) and one S(1) atom.