MnP2O7 crystallizes in the hexagonal P6_3/m space group. Mn(1) is bonded to six equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. P(1) is bonded to one O(1) and three equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the second O site, O(1) is bonded in a linear geometry to two equivalent P(1) atoms.
MnP2O7 crystallizes in the hexagonal P6_3/m space group. Mn(1) is bonded to six equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Mn(1)-O(2) bond lengths are 1.88 Å. P(1) is bonded to one O(1) and three equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The P(1)-O(1) bond length is 1.56 Å. All P(1)-O(2) bond lengths are 1.52 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the second O site, O(1) is bonded in a linear geometry to two equivalent P(1) atoms.