MgV6(OF5)3 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(3), one F(11), one F(13), one F(4), one F(7), and one F(8) atom to form distorted MgOF5 octahedra that share corners with three equivalent V(2)OF5 octahedra, edges with three equivalent V(6)OF5 octahedra, and  a faceface with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(10), one F(12), one F(15), one F(3), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 28-37°. In the second V site, V(2) is bonded to one O(3), one F(13), one F(14), one F(4), one F(5), and one F(9) atom to form VOF5 octahedra that share corners with three equivalent Mg(1)OF5 octahedra, corners with three equivalent V(3)OF5 octahedra, and corners with three equivalent V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-59°. In the third V site, V(3) is bonded to one O(1), one F(1), one F(14), one F(2), one F(5), and one F(9) atom to form distorted corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. In the fourth V site, V(4) is bonded to one O(1), one F(1), one F(10), one F(15), one F(2), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 23-37°. In the fifth V site, V(5) is bonded to one O(2), one F(11), one F(12), one F(3), one F(7), and one F(8) atom to form distorted VOF5 octahedra that share corners with three equivalent V(1)OF5 octahedra, corners with three equivalent V(6)OF5 octahedra, and  a faceface with one Mg(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-37°. In the sixth V site, V(6) is bonded to one O(3), one F(11), one F(13), one F(4), one F(7), and one F(8) atom to form VOF5 octahedra that share corners with three equivalent V(2)OF5 octahedra, corners with three equivalent V(5)OF5 octahedra, and edges with three equivalent Mg(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) 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(6) atom. There are fifteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to 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(3) 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(5) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Mg(1), one V(5), and one V(6) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Mg(1), one V(5), and one V(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one Mg(1), one V(5), and one V(6) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(6) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifteenth F site, F(15) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom.
MgV6(OF5)3 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(3), one F(11), one F(13), one F(4), one F(7), and one F(8) atom to form distorted MgOF5 octahedra that share corners with three equivalent V(2)OF5 octahedra, edges with three equivalent V(6)OF5 octahedra, and  a faceface with one V(5)OF5 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. The Mg(1)-O(3) bond length is 2.02 Å. The Mg(1)-F(11) bond length is 2.06 Å. The Mg(1)-F(13) bond length is 2.05 Å. The Mg(1)-F(4) bond length is 2.03 Å. The Mg(1)-F(7) bond length is 2.09 Å. The Mg(1)-F(8) bond length is 2.07 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(10), one F(12), one F(15), one F(3), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 28-37°. The V(1)-O(2) bond length is 1.84 Å. The V(1)-F(10) bond length is 2.04 Å. The V(1)-F(12) bond length is 2.05 Å. The V(1)-F(15) bond length is 2.01 Å. The V(1)-F(3) bond length is 2.00 Å. The V(1)-F(6) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(3), one F(13), one F(14), one F(4), one F(5), and one F(9) atom to form VOF5 octahedra that share corners with three equivalent Mg(1)OF5 octahedra, corners with three equivalent V(3)OF5 octahedra, and corners with three equivalent V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-59°. The V(2)-O(3) bond length is 1.93 Å. The V(2)-F(13) bond length is 2.15 Å. The V(2)-F(14) bond length is 2.00 Å. The V(2)-F(4) bond length is 2.16 Å. The V(2)-F(5) bond length is 1.98 Å. The V(2)-F(9) bond length is 1.91 Å. In the third V site, V(3) is bonded to one O(1), one F(1), one F(14), one F(2), one F(5), and one F(9) atom to form distorted corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. The V(3)-O(1) bond length is 1.67 Å. The V(3)-F(1) bond length is 1.93 Å. The V(3)-F(14) bond length is 1.99 Å. The V(3)-F(2) bond length is 1.95 Å. The V(3)-F(5) bond length is 2.01 Å. The V(3)-F(9) bond length is 2.15 Å. In the fourth V site, V(4) is bonded to one O(1), one F(1), one F(10), one F(15), one F(2), and one F(6) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 23-37°. The V(4)-O(1) bond length is 2.03 Å. The V(4)-F(1) bond length is 2.02 Å. The V(4)-F(10) bond length is 1.94 Å. The V(4)-F(15) bond length is 1.94 Å. The V(4)-F(2) bond length is 2.02 Å. The V(4)-F(6) bond length is 1.94 Å. In the fifth V site, V(5) is bonded to one O(2), one F(11), one F(12), one F(3), one F(7), and one F(8) atom to form distorted VOF5 octahedra that share corners with three equivalent V(1)OF5 octahedra, corners with three equivalent V(6)OF5 octahedra, and  a faceface with one Mg(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-37°. The V(5)-O(2) bond length is 1.78 Å. The V(5)-F(11) bond length is 2.16 Å. The V(5)-F(12) bond length is 1.92 Å. The V(5)-F(3) bond length is 1.96 Å. The V(5)-F(7) bond length is 2.30 Å. The V(5)-F(8) bond length is 2.21 Å. In the sixth V site, V(6) is bonded to one O(3), one F(11), one F(13), one F(4), one F(7), and one F(8) atom to form VOF5 octahedra that share corners with three equivalent V(2)OF5 octahedra, corners with three equivalent V(5)OF5 octahedra, and edges with three equivalent Mg(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. The V(6)-O(3) bond length is 1.90 Å. The V(6)-F(11) bond length is 2.04 Å. The V(6)-F(13) bond length is 2.10 Å. The V(6)-F(4) bond length is 2.09 Å. The V(6)-F(7) bond length is 1.95 Å. The V(6)-F(8) bond length is 2.02 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) 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(6) atom. There are fifteen inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to 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(3) 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(5) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Mg(1), one V(5), and one V(6) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Mg(1), one V(5), and one V(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the eleventh F site, F(11) is bonded in a T-shaped geometry to one Mg(1), one V(5), and one V(6) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the thirteenth F site, F(13) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(2), and one V(6) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifteenth F site, F(15) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom.