MgV4(OF)6 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(5), and one F(6) atom to form distorted MgO3F3 pentagonal pyramids that share corners with three equivalent V(1)O3F3 octahedra, edges with three equivalent V(2)O3F3 octahedra, and  a faceface with one V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 57-64°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), one F(2), one F(4), and one F(6) atom to form VO3F3 octahedra that share corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra, and corners with three equivalent Mg(1)O3F3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 22-43°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one F(1), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with three equivalent V(1)O3F3 octahedra, corners with three equivalent V(3)O3F3 octahedra, and edges with three equivalent Mg(1)O3F3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 22-43°. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one F(1), one F(3), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra, and  a faceface with one Mg(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 22-35°. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(6), one F(2), one F(3), and one F(4) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-37°. There are six 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 V(2) 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(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 T-shaped geometry to one Mg(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Mg(1), 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(3) and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom.
MgV4(OF)6 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(5), and one F(6) atom to form distorted MgO3F3 pentagonal pyramids that share corners with three equivalent V(1)O3F3 octahedra, edges with three equivalent V(2)O3F3 octahedra, and  a faceface with one V(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 57-64°. The Mg(1)-O(1) bond length is 2.03 Å. The Mg(1)-O(2) bond length is 2.07 Å. The Mg(1)-O(4) bond length is 2.14 Å. The Mg(1)-F(1) bond length is 2.09 Å. The Mg(1)-F(5) bond length is 2.15 Å. The Mg(1)-F(6) bond length is 2.05 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(5), one F(2), one F(4), and one F(6) atom to form VO3F3 octahedra that share corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra, and corners with three equivalent Mg(1)O3F3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 22-43°. The V(1)-O(1) bond length is 1.88 Å. The V(1)-O(2) bond length is 2.03 Å. The V(1)-O(5) bond length is 1.75 Å. The V(1)-F(2) bond length is 1.99 Å. The V(1)-F(4) bond length is 2.01 Å. The V(1)-F(6) bond length is 2.12 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one F(1), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with three equivalent V(1)O3F3 octahedra, corners with three equivalent V(3)O3F3 octahedra, and edges with three equivalent Mg(1)O3F3 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 22-43°. The V(2)-O(1) bond length is 1.96 Å. The V(2)-O(2) bond length is 1.83 Å. The V(2)-O(4) bond length is 1.81 Å. The V(2)-F(1) bond length is 2.04 Å. The V(2)-F(5) bond length is 2.03 Å. The V(2)-F(6) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one F(1), one F(3), and one F(5) atom to form distorted VO3F3 octahedra that share corners with three equivalent V(2)O3F3 octahedra, corners with three equivalent V(4)O3F3 octahedra, and  a faceface with one Mg(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 22-35°. The V(3)-O(3) bond length is 1.94 Å. The V(3)-O(4) bond length is 1.95 Å. The V(3)-O(6) bond length is 1.67 Å. The V(3)-F(1) bond length is 2.27 Å. The V(3)-F(3) bond length is 1.93 Å. The V(3)-F(5) bond length is 2.06 Å. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(6), one F(2), one F(3), and one F(4) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-37°. The V(4)-O(3) bond length is 1.70 Å. The V(4)-O(5) bond length is 1.91 Å. The V(4)-O(6) bond length is 2.02 Å. The V(4)-F(2) bond length is 1.98 Å. The V(4)-F(3) bond length is 2.00 Å. The V(4)-F(4) bond length is 2.02 Å. There are six 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 V(2) 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(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 T-shaped geometry to one Mg(1), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Mg(1), 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(3) and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fifth F site, F(5) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom.