MgV4(OF2)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one F(1), one F(3), one F(6), and one F(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), one F(2), one F(4), one F(5), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-40°. In the second V site, V(2) is bonded to one O(1), one O(3), one F(1), one F(4), one F(6), and one F(7) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. In the third V site, V(3) is bonded to one O(2), one O(3), one F(1), one F(3), one F(6), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. In the fourth V site, V(4) is bonded to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. There are four 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(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar 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(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar 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 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(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(3) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom.
MgV4(OF2)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one F(1), one F(3), one F(6), and one F(8) atom. The Mg(1)-O(2) bond length is 2.09 Å. The Mg(1)-O(3) bond length is 2.01 Å. The Mg(1)-F(1) bond length is 2.03 Å. The Mg(1)-F(3) bond length is 2.20 Å. The Mg(1)-F(6) bond length is 2.04 Å. The Mg(1)-F(8) 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(4), one F(2), one F(4), one F(5), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-40°. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.96 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(4) bond length is 1.96 Å. The V(1)-F(5) bond length is 1.95 Å. The V(1)-F(7) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one F(1), one F(4), one F(6), and one F(7) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. The V(2)-O(1) bond length is 1.70 Å. The V(2)-O(3) bond length is 1.86 Å. The V(2)-F(1) bond length is 2.27 Å. The V(2)-F(4) bond length is 2.03 Å. The V(2)-F(6) bond length is 2.11 Å. The V(2)-F(7) bond length is 1.94 Å. In the third V site, V(3) is bonded to one O(2), one O(3), one F(1), one F(3), one F(6), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. The V(3)-O(2) bond length is 1.90 Å. The V(3)-O(3) bond length is 1.99 Å. The V(3)-F(1) bond length is 2.11 Å. The V(3)-F(3) bond length is 1.99 Å. The V(3)-F(6) bond length is 2.15 Å. The V(3)-F(8) bond length is 2.05 Å. In the fourth V site, V(4) is bonded to one O(2), one O(4), one F(2), one F(3), one F(5), and one F(8) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. The V(4)-O(2) bond length is 1.86 Å. The V(4)-O(4) bond length is 1.69 Å. The V(4)-F(2) bond length is 1.93 Å. The V(4)-F(3) bond length is 2.08 Å. The V(4)-F(5) bond length is 2.00 Å. The V(4)-F(8) bond length is 2.24 Å. There are four 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(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom. In the third O site, O(3) is bonded in a distorted trigonal planar 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(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar 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 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(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(3) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(4) atom.