Fe2Al2Bi2O9 crystallizes in the orthorhombic Pbam space group. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with four equivalent Al(1)O4 tetrahedra and edges with two equivalent Fe(1)O6 octahedra. Al(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form AlO4 tetrahedra that share corners with four equivalent Fe(1)O6 octahedra and  a cornercorner with one Al(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-58°. Bi(1) is bonded in a 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 distorted trigonal planar geometry to one Fe(1), one Al(1), and one Bi(1) atom. In the second O site, O(2) is bonded to two equivalent Fe(1) and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OFe2Bi2 tetrahedra. In the third O site, O(3) is bonded in a linear geometry to two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent Fe(1) and one Al(1) atom.
Fe2Al2Bi2O9 crystallizes in the orthorhombic Pbam space group. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with four equivalent Al(1)O4 tetrahedra and edges with two equivalent Fe(1)O6 octahedra. Both Fe(1)-O(1) bond lengths are 2.09 Å. Both Fe(1)-O(2) bond lengths are 2.05 Å. Both Fe(1)-O(4) bond lengths are 1.98 Å. Al(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form AlO4 tetrahedra that share corners with four equivalent Fe(1)O6 octahedra and  a cornercorner with one Al(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-58°. The Al(1)-O(3) bond length is 1.75 Å. The Al(1)-O(4) bond length is 1.78 Å. Both Al(1)-O(1) bond lengths are 1.82 Å. Bi(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Bi(1)-O(1) bond lengths are 2.18 Å. There is one shorter (2.21 Å) and one longer (2.40 Å) Bi(1)-O(2) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Fe(1), one Al(1), and one Bi(1) atom. In the second O site, O(2) is bonded to two equivalent Fe(1) and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OFe2Bi2 tetrahedra. In the third O site, O(3) is bonded in a linear geometry to two equivalent Al(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent Fe(1) and one Al(1) atom.