Mn2O4H 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 distorted edge-sharing MnO6 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form edge-sharing MnO6 octahedra. H(1) is bonded in a single-bond geometry to one O(1) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one H(1) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1) and two equivalent Mn(2) atoms.
Mn2O4H 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 distorted edge-sharing MnO6 octahedra. Both Mn(1)-O(1) bond lengths are 2.23 Å. Both Mn(1)-O(2) bond lengths are 1.93 Å. Both Mn(1)-O(3) bond lengths are 1.94 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 edge-sharing MnO6 octahedra. The Mn(2)-O(1) bond length is 1.91 Å. The Mn(2)-O(2) bond length is 1.91 Å. There are two shorter (1.89 Å) and two longer (1.91 Å) Mn(2)-O(3) bond lengths. H(1) is bonded in a single-bond geometry to one O(1) atom. The H(1)-O(1) bond length is 0.98 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one H(1) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1) and two equivalent Mn(2) atoms.