MgV4O7F5 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one O(3), one O(5), one O(6), one F(4), and one F(5) atom to form distorted MgO4F2 pentagonal pyramids that share  a cornercorner with one V(1)O4F2 octahedra and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles are 61°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(7), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with three equivalent V(4)O3F3 octahedra and  a cornercorner with one Mg(1)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 18-39°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(7), one F(1), and one F(3) atom. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(6), one F(1), one F(4), and one F(5) atom. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(6), one F(2), one F(4), and one F(5) atom to form VO3F3 octahedra that share corners with three equivalent V(1)O4F2 octahedra and edges with two equivalent Mg(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 18-39°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) 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 V(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mg(1), one V(3), 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 bent 150 degrees geometry to one V(2) 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(4) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Mg(1), one V(3), and one V(4) atom.
MgV4O7F5 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one O(3), one O(5), one O(6), one F(4), and one F(5) atom to form distorted MgO4F2 pentagonal pyramids that share  a cornercorner with one V(1)O4F2 octahedra and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles are 61°. The Mg(1)-O(2) bond length is 2.07 Å. The Mg(1)-O(3) bond length is 2.05 Å. The Mg(1)-O(5) bond length is 2.10 Å. The Mg(1)-O(6) bond length is 2.03 Å. The Mg(1)-F(4) bond length is 2.08 Å. The Mg(1)-F(5) bond length is 2.11 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(7), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with three equivalent V(4)O3F3 octahedra and  a cornercorner with one Mg(1)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 18-39°. The V(1)-O(1) bond length is 1.71 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(4) bond length is 1.97 Å. The V(1)-O(7) bond length is 1.98 Å. The V(1)-F(2) bond length is 2.02 Å. The V(1)-F(3) bond length is 2.04 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(7), one F(1), and one F(3) atom. The V(2)-O(3) bond length is 2.48 Å. The V(2)-O(4) bond length is 1.69 Å. The V(2)-O(5) bond length is 1.79 Å. The V(2)-O(7) bond length is 1.70 Å. The V(2)-F(1) bond length is 2.20 Å. The V(2)-F(3) bond length is 1.98 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(6), one F(1), one F(4), and one F(5) atom. The V(3)-O(3) bond length is 1.68 Å. The V(3)-O(5) bond length is 1.95 Å. The V(3)-O(6) bond length is 1.98 Å. The V(3)-F(1) bond length is 1.91 Å. The V(3)-F(4) bond length is 2.03 Å. The V(3)-F(5) bond length is 2.42 Å. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(6), one F(2), one F(4), and one F(5) atom to form VO3F3 octahedra that share corners with three equivalent V(1)O4F2 octahedra and edges with two equivalent Mg(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 18-39°. The V(4)-O(1) bond length is 1.94 Å. The V(4)-O(2) bond length is 1.81 Å. The V(4)-O(6) bond length is 1.82 Å. The V(4)-F(2) bond length is 1.97 Å. The V(4)-F(4) bond length is 2.24 Å. The V(4)-F(5) bond length is 1.98 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) 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 V(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mg(1), one V(3), 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 bent 150 degrees geometry to one V(2) 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(4) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Mg(1), one V(3), and one V(4) atom.