VMn2PO7 crystallizes in the monoclinic Cm space group. V(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form distorted VO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-63°. Mn(1) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted MnO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Mn(1)O6 octahedra. P(1) is bonded to one O(1), one O(3), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-60°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to two equivalent Mn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Mn(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Mn(1) and one P(1) atom.
VMn2PO7 crystallizes in the monoclinic Cm space group. V(1) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form distorted VO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-63°. The V(1)-O(2) bond length is 1.73 Å. The V(1)-O(3) bond length is 1.82 Å. Both V(1)-O(4) bond lengths are 1.74 Å. Mn(1) is bonded to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted MnO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Mn(1)O6 octahedra. The Mn(1)-O(1) bond length is 2.29 Å. The Mn(1)-O(2) bond length is 2.13 Å. There is one shorter (2.10 Å) and one longer (2.24 Å) Mn(1)-O(4) bond length. There is one shorter (2.22 Å) and one longer (2.34 Å) Mn(1)-O(5) bond length. P(1) is bonded to one O(1), one O(3), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with six equivalent Mn(1)O6 octahedra and  a cornercorner with one V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-60°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.57 Å. Both P(1)-O(5) bond lengths are 1.55 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to two equivalent Mn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Mn(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Mn(1) and one P(1) atom.