MgV2(PO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted MgO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and faces 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 corners with four equivalent P(1)O4 tetrahedra and  a faceface with one Mg(1)O6 octahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) 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 47-52°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one P(1) atom. 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 3-coordinate geometry to one Mg(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in an L-shaped geometry to one Mg(1) and one V(1) atom.
MgV2(PO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted MgO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra and faces with two equivalent V(1)O5 trigonal bipyramids. Both Mg(1)-O(2) bond lengths are 2.08 Å. Both Mg(1)-O(4) bond lengths are 2.07 Å. Both Mg(1)-O(5) bond lengths are 2.20 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 corners with four equivalent P(1)O4 tetrahedra and  a faceface with one Mg(1)O6 octahedra. The V(1)-O(1) bond length is 1.92 Å. The V(1)-O(2) bond length is 2.08 Å. The V(1)-O(3) bond length is 1.92 Å. The V(1)-O(4) bond length is 2.07 Å. The V(1)-O(5) bond length is 1.66 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) 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 47-52°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.56 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one P(1) atom. 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 3-coordinate geometry to one Mg(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in an L-shaped geometry to one Mg(1) and one V(1) atom.