Fe2Al2Bi2O9 crystallizes in the orthorhombic Pbam space group. Fe(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form FeO4 tetrahedra that share corners with four equivalent Al(1)O6 octahedra and  a cornercorner with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form AlO6 octahedra that share corners with four equivalent Fe(1)O4 tetrahedra and edges with two equivalent Al(1)O6 octahedra. Bi(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(1), one Al(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Al(1) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Fe(1) and two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Fe(1) atoms.
Fe2Al2Bi2O9 crystallizes in the orthorhombic Pbam space group. Fe(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form FeO4 tetrahedra that share corners with four equivalent Al(1)O6 octahedra and  a cornercorner with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. The Fe(1)-O(3) bond length is 1.89 Å. The Fe(1)-O(4) bond length is 1.86 Å. Both Fe(1)-O(1) bond lengths are 1.92 Å. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form AlO6 octahedra that share corners with four equivalent Fe(1)O4 tetrahedra and edges with two equivalent Al(1)O6 octahedra. Both Al(1)-O(1) bond lengths are 1.94 Å. Both Al(1)-O(2) bond lengths are 1.98 Å. Both Al(1)-O(3) bond lengths are 1.90 Å. Bi(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Bi(1)-O(1) bond lengths are 2.15 Å. There is one shorter (2.22 Å) and one longer (2.49 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 Fe(1), one Al(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Al(1) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Fe(1) and two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent Fe(1) atoms.