Mn2AlO4 is Ilmenite-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with four equivalent Mn(2)O6 octahedra, corners with two equivalent Al(1)O4 trigonal pyramids, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Al(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-57°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form MnO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with four equivalent Al(1)O4 trigonal pyramids, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Al(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 52-57°. Al(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form AlO4 trigonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-70°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one Al(1) atom. In the second O site, O(2) is bonded to one Mn(2), two equivalent Mn(1), and one Al(1) atom to form distorted corner-sharing OMn3Al trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Al(1) atom.
Mn2AlO4 is Ilmenite-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with four equivalent Mn(2)O6 octahedra, corners with two equivalent Al(1)O4 trigonal pyramids, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Al(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-57°. Both Mn(1)-O(1) bond lengths are 2.10 Å. Both Mn(1)-O(2) bond lengths are 2.18 Å. Both Mn(1)-O(3) bond lengths are 1.98 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form MnO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with four equivalent Al(1)O4 trigonal pyramids, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Al(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 52-57°. The Mn(2)-O(1) bond length is 2.17 Å. The Mn(2)-O(2) bond length is 2.16 Å. There are two shorter (2.17 Å) and two longer (2.41 Å) Mn(2)-O(3) bond lengths. Al(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form AlO4 trigonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-70°. The Al(1)-O(1) bond length is 1.82 Å. The Al(1)-O(2) bond length is 1.73 Å. Both Al(1)-O(3) bond lengths are 1.79 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one Al(1) atom. In the second O site, O(2) is bonded to one Mn(2), two equivalent Mn(1), and one Al(1) atom to form distorted corner-sharing OMn3Al trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Al(1) atom.