La4MnO8 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to two equivalent O(1), three equivalent O(2), and four equivalent O(3) atoms. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent O(2), three equivalent O(1), and four equivalent O(3) atoms. Mn(1) is bonded in an octahedral geometry to two equivalent O(1) and four equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent La(1), three equivalent La(2), and one Mn(1) atom to form distorted OLa5Mn octahedra that share corners with five equivalent O(1)La5Mn octahedra, corners with twelve equivalent O(3)La4Mn square pyramids, edges with two equivalent O(1)La5Mn octahedra, and faces with four equivalent O(3)La4Mn square pyramids. The corner-sharing octahedral tilt angles range from 0-16°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent La(2) and three equivalent La(1) atoms. In the third O site, O(3) is bonded to two equivalent La(1), two equivalent La(2), and one Mn(1) atom to form distorted OLa4Mn square pyramids that share corners with six equivalent O(1)La5Mn octahedra,  a cornercorner with one O(3)La4Mn square pyramid, edges with four equivalent O(3)La4Mn square pyramids, faces with two equivalent O(1)La5Mn octahedra, and faces with two equivalent O(3)La4Mn square pyramids. The corner-sharing octahedral tilt angles range from 48-52°.
La4MnO8 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to two equivalent O(1), three equivalent O(2), and four equivalent O(3) atoms. Both La(1)-O(1) bond lengths are 2.73 Å. There is one shorter (2.24 Å) and two longer (2.78 Å) La(1)-O(2) bond lengths. All La(1)-O(3) bond lengths are 2.60 Å. In the second La site, La(2) is bonded in a 9-coordinate geometry to two equivalent O(2), three equivalent O(1), and four equivalent O(3) atoms. Both La(2)-O(2) bond lengths are 2.79 Å. There is one shorter (2.60 Å) and two longer (2.72 Å) La(2)-O(1) bond lengths. All La(2)-O(3) bond lengths are 2.52 Å. Mn(1) is bonded in an octahedral geometry to two equivalent O(1) and four equivalent O(3) atoms. Both Mn(1)-O(1) bond lengths are 2.06 Å. All Mn(1)-O(3) bond lengths are 1.86 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent La(1), three equivalent La(2), and one Mn(1) atom to form distorted OLa5Mn octahedra that share corners with five equivalent O(1)La5Mn octahedra, corners with twelve equivalent O(3)La4Mn square pyramids, edges with two equivalent O(1)La5Mn octahedra, and faces with four equivalent O(3)La4Mn square pyramids. The corner-sharing octahedral tilt angles range from 0-16°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent La(2) and three equivalent La(1) atoms. In the third O site, O(3) is bonded to two equivalent La(1), two equivalent La(2), and one Mn(1) atom to form distorted OLa4Mn square pyramids that share corners with six equivalent O(1)La5Mn octahedra,  a cornercorner with one O(3)La4Mn square pyramid, edges with four equivalent O(3)La4Mn square pyramids, faces with two equivalent O(1)La5Mn octahedra, and faces with two equivalent O(3)La4Mn square pyramids. The corner-sharing octahedral tilt angles range from 48-52°.