MgV4(O2F)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(5), one O(7), one F(2), and one F(4) atom to form distorted MgO4F2 octahedra that share corners with three equivalent V(4)O4F2 octahedra and edges with three equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 54-64°. 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 O(7), one F(2), and one F(4) atom to form VO4F2 octahedra that share corners with three equivalent V(4)O4F2 octahedra and edges with three equivalent Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 38-45°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one F(1), and one F(4) atom. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one O(8), one F(1), and one F(3) atom to form distorted corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 19-38°. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(7), one O(8), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with three equivalent Mg(1)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, and corners with three equivalent V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 19-64°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 3-coordinate 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 bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mg(1), 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(2) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. There are four 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 distorted trigonal planar geometry to one Mg(1), 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 distorted water-like geometry to one Mg(1), one V(1), and one V(2) atom.
MgV4(O2F)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(5), one O(7), one F(2), and one F(4) atom to form distorted MgO4F2 octahedra that share corners with three equivalent V(4)O4F2 octahedra and edges with three equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 54-64°. The Mg(1)-O(1) bond length is 2.07 Å. The Mg(1)-O(2) bond length is 2.14 Å. The Mg(1)-O(5) bond length is 2.06 Å. The Mg(1)-O(7) bond length is 2.07 Å. The Mg(1)-F(2) bond length is 2.04 Å. The Mg(1)-F(4) bond length is 2.08 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 O(7), one F(2), and one F(4) atom to form VO4F2 octahedra that share corners with three equivalent V(4)O4F2 octahedra and edges with three equivalent Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 38-45°. The V(1)-O(1) bond length is 1.96 Å. The V(1)-O(2) bond length is 1.71 Å. The V(1)-O(5) bond length is 2.01 Å. The V(1)-O(7) bond length is 2.06 Å. The V(1)-F(2) bond length is 2.18 Å. The V(1)-F(4) bond length is 1.92 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one F(1), and one F(4) atom. The V(2)-O(1) bond length is 1.78 Å. The V(2)-O(2) bond length is 2.29 Å. The V(2)-O(4) bond length is 1.68 Å. The V(2)-O(6) bond length is 1.73 Å. The V(2)-F(1) bond length is 1.90 Å. The V(2)-F(4) bond length is 2.51 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one O(8), one F(1), and one F(3) atom to form distorted corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 19-38°. The V(3)-O(3) bond length is 1.69 Å. The V(3)-O(4) bond length is 2.06 Å. The V(3)-O(6) bond length is 1.87 Å. The V(3)-O(8) bond length is 1.70 Å. The V(3)-F(1) bond length is 2.17 Å. The V(3)-F(3) bond length is 2.04 Å. In the fourth V site, V(4) is bonded to one O(3), one O(5), one O(7), one O(8), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with three equivalent Mg(1)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, and corners with three equivalent V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 19-64°. The V(4)-O(3) bond length is 2.08 Å. The V(4)-O(5) bond length is 1.86 Å. The V(4)-O(7) bond length is 1.79 Å. The V(4)-O(8) bond length is 2.00 Å. The V(4)-F(2) bond length is 2.09 Å. The V(4)-F(3) bond length is 1.96 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a 3-coordinate 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 bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mg(1), 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(2) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. There are four 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 distorted trigonal planar geometry to one Mg(1), 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 distorted water-like geometry to one Mg(1), one V(1), and one V(2) atom.