MgV2(PO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MgO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-56°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Mg(1) and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom.
MgV2(PO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MgO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. Both Mg(1)-O(1) bond lengths are 2.09 Å. Both Mg(1)-O(2) bond lengths are 2.09 Å. Both Mg(1)-O(3) bond lengths are 2.10 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles are 48°. The V(1)-O(1) bond length is 1.65 Å. The V(1)-O(2) bond length is 2.06 Å. The V(1)-O(3) bond length is 2.06 Å. The V(1)-O(4) bond length is 1.95 Å. The V(1)-O(5) bond length is 1.95 Å. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-56°. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.53 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Mg(1) and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom.