MgV2P2(O4F)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(4), one O(5), one O(6), and one F(2) atom to form distorted MgO4F trigonal bipyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-56°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(6), one O(8), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 47°. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), one O(7), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 47°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 37-51°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra, and  a cornercorner with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-47°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom.
MgV2P2(O4F)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(4), one O(5), one O(6), and one F(2) atom to form distorted MgO4F trigonal bipyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-56°. The Mg(1)-O(1) bond length is 2.11 Å. The Mg(1)-O(4) bond length is 2.07 Å. The Mg(1)-O(5) bond length is 2.09 Å. The Mg(1)-O(6) bond length is 2.12 Å. The Mg(1)-F(2) bond length is 1.95 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(6), one O(8), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 47°. The V(1)-O(1) bond length is 2.12 Å. The V(1)-O(3) bond length is 1.94 Å. The V(1)-O(6) bond length is 2.08 Å. The V(1)-O(8) bond length is 1.93 Å. The V(1)-F(1) bond length is 1.98 Å. The V(1)-F(2) bond length is 2.11 Å. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), one O(7), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 47°. The V(2)-O(2) bond length is 2.00 Å. The V(2)-O(4) bond length is 2.06 Å. The V(2)-O(5) bond length is 2.09 Å. The V(2)-O(7) bond length is 1.95 Å. The V(2)-F(1) bond length is 1.96 Å. The V(2)-F(2) bond length is 2.11 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Mg(1)O4F trigonal bipyramid, and  an edgeedge with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 37-51°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra, and  a cornercorner with one Mg(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-47°. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.58 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.53 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom.