MgV4O7F5 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(4), one F(1), one F(3), and one F(5) atom to form distorted MgO3F3 pentagonal pyramids that share  a cornercorner with one V(2)O4F2 octahedra and  an edgeedge with one V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 56°. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), one O(4), one O(7), one F(2), and one F(5) atom. In the second V site, V(2) is bonded to one O(2), one O(5), one O(6), one O(7), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(4)O4F2 octahedra and  a cornercorner with one Mg(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 24-27°. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(5) atom. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(5), one O(6), one F(3), and one F(4) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(2)O4F2 octahedra and  an edgeedge with one Mg(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 24-27°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one V(1), and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Mg(1) and one V(3) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(3) atom.
MgV4O7F5 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(4), one F(1), one F(3), and one F(5) atom to form distorted MgO3F3 pentagonal pyramids that share  a cornercorner with one V(2)O4F2 octahedra and  an edgeedge with one V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 56°. The Mg(1)-O(1) bond length is 2.12 Å. The Mg(1)-O(2) bond length is 2.04 Å. The Mg(1)-O(4) bond length is 2.05 Å. The Mg(1)-F(1) bond length is 2.01 Å. The Mg(1)-F(3) bond length is 2.20 Å. The Mg(1)-F(5) bond length is 2.09 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), one O(4), one O(7), one F(2), and one F(5) atom. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(4) bond length is 1.90 Å. The V(1)-O(7) bond length is 1.68 Å. The V(1)-F(2) bond length is 1.94 Å. The V(1)-F(5) bond length is 2.00 Å. In the second V site, V(2) is bonded to one O(2), one O(5), one O(6), one O(7), one F(2), and one F(4) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(4)O4F2 octahedra and  a cornercorner with one Mg(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 24-27°. The V(2)-O(2) bond length is 1.80 Å. The V(2)-O(5) bond length is 1.71 Å. The V(2)-O(6) bond length is 1.74 Å. The V(2)-O(7) bond length is 2.05 Å. The V(2)-F(2) bond length is 2.17 Å. The V(2)-F(4) bond length is 2.05 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one F(1), one F(3), and one F(5) atom. The V(3)-O(1) bond length is 1.72 Å. The V(3)-O(3) bond length is 1.95 Å. The V(3)-O(4) bond length is 1.88 Å. The V(3)-F(1) bond length is 1.95 Å. The V(3)-F(3) bond length is 1.99 Å. The V(3)-F(5) bond length is 2.40 Å. In the fourth V site, V(4) is bonded to one O(1), one O(3), one O(5), one O(6), one F(3), and one F(4) atom to form distorted VO4F2 octahedra that share corners with three equivalent V(2)O4F2 octahedra and  an edgeedge with one Mg(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 24-27°. The V(4)-O(1) bond length is 2.13 Å. The V(4)-O(3) bond length is 1.71 Å. The V(4)-O(5) bond length is 1.92 Å. The V(4)-O(6) bond length is 1.91 Å. The V(4)-F(3) bond length is 2.15 Å. The V(4)-F(4) bond length is 1.98 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one V(1), and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Mg(1) and one V(3) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(3) atom.