MgV4(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one F(1), and one F(6) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), one F(3), one F(4), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-45°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one F(2), one F(4), and one F(6) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 27-41°. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one F(1), one F(3), and one F(5) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-45°. In the fourth V site, V(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(2), and one F(6) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 27-41°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(4) 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(3) 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 distorted trigonal planar geometry to one Mg(1), one V(3), and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(2) 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(3) 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 distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one V(4) atom.
MgV4(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one F(1), and one F(6) atom. The Mg(1)-O(2) bond length is 2.20 Å. The Mg(1)-O(3) bond length is 2.19 Å. The Mg(1)-O(4) bond length is 2.02 Å. The Mg(1)-O(5) bond length is 1.99 Å. The Mg(1)-F(1) bond length is 2.00 Å. The Mg(1)-F(6) bond length is 2.26 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), one F(3), one F(4), and one F(5) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-45°. The V(1)-O(1) bond length is 1.69 Å. The V(1)-O(3) bond length is 2.05 Å. The V(1)-O(5) bond length is 2.09 Å. The V(1)-F(3) bond length is 1.97 Å. The V(1)-F(4) bond length is 2.01 Å. The V(1)-F(5) bond length is 1.96 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one F(2), one F(4), and one F(6) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 27-41°. The V(2)-O(2) bond length is 2.14 Å. The V(2)-O(3) bond length is 1.74 Å. The V(2)-O(4) bond length is 1.92 Å. The V(2)-F(2) bond length is 1.93 Å. The V(2)-F(4) bond length is 2.00 Å. The V(2)-F(6) bond length is 1.99 Å. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one F(1), one F(3), and one F(5) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 22-45°. The V(3)-O(1) bond length is 2.14 Å. The V(3)-O(5) bond length is 1.86 Å. The V(3)-O(6) bond length is 1.72 Å. The V(3)-F(1) bond length is 2.12 Å. The V(3)-F(3) bond length is 1.95 Å. The V(3)-F(5) bond length is 1.95 Å. In the fourth V site, V(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(2), and one F(6) atom to form corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 27-41°. The V(4)-O(2) bond length is 1.75 Å. The V(4)-O(4) bond length is 1.95 Å. The V(4)-O(6) bond length is 1.87 Å. The V(4)-F(1) bond length is 2.20 Å. The V(4)-F(2) bond length is 1.95 Å. The V(4)-F(6) bond length is 2.01 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(4) 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(3) 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 distorted trigonal planar geometry to one Mg(1), one V(3), and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(2) 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(3) 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 distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one V(4) atom.