Mn5O8 is beta indium sulfide-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the second Mn site, Mn(2) is bonded to six equivalent O(2) atoms to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing MnO6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Mn(3) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms.
Mn5O8 is beta indium sulfide-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 15°. All Mn(1)-O(2) bond lengths are 2.20 Å. In the second Mn site, Mn(2) is bonded to six equivalent O(2) atoms to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 15°. All Mn(2)-O(2) bond lengths are 2.14 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing MnO6 octahedra. Both Mn(3)-O(1) bond lengths are 1.99 Å. All Mn(3)-O(2) bond lengths are 1.96 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Mn(3) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms.