MnAlBiO5 crystallizes in the orthorhombic Pbam space group. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with four equivalent Al(1)O5 trigonal bipyramids and edges with two equivalent Mn(1)O6 octahedra. Al(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted AlO5 trigonal bipyramids that share corners with four equivalent Mn(1)O6 octahedra and  an edgeedge with one Al(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 48-51°. Bi(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(4), and four equivalent O(3) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Mn(1) and one Al(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 4-coordinate geometry to one Mn(1), one Al(1), and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Mn(1) and two equivalent Bi(1) atoms.
MnAlBiO5 crystallizes in the orthorhombic Pbam space group. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with four equivalent Al(1)O5 trigonal bipyramids and edges with two equivalent Mn(1)O6 octahedra. Both Mn(1)-O(1) bond lengths are 1.93 Å. Both Mn(1)-O(3) bond lengths are 1.94 Å. Both Mn(1)-O(4) bond lengths are 1.94 Å. Al(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted AlO5 trigonal bipyramids that share corners with four equivalent Mn(1)O6 octahedra and  an edgeedge with one Al(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 48-51°. The Al(1)-O(1) bond length is 1.84 Å. Both Al(1)-O(2) bond lengths are 1.90 Å. Both Al(1)-O(3) bond lengths are 1.90 Å. Bi(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(4), and four equivalent O(3) atoms. Both Bi(1)-O(2) bond lengths are 2.43 Å. There is one shorter (2.40 Å) and one longer (2.41 Å) Bi(1)-O(4) bond length. There are two shorter (2.42 Å) and two longer (2.63 Å) Bi(1)-O(3) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Mn(1) and one Al(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 4-coordinate geometry to one Mn(1), one Al(1), and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Mn(1) and two equivalent Bi(1) atoms.