MgV2(OF3)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form MgOF5 octahedra that share corners with two equivalent V(1)O2F4 octahedra, corners with four equivalent V(2)O2F4 octahedra, and  a faceface with one V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 29-56°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(4), and one F(6) atom to form distorted VO2F4 octahedra that share corners with two equivalent Mg(1)OF5 octahedra, edges with two equivalent V(2)O2F4 octahedra, and  a faceface with one Mg(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. In the second V site, V(2) is bonded to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with four equivalent Mg(1)OF5 octahedra and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 29-47°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in an L-shaped geometry to one Mg(1) and one V(1) 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(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(1) atom.
MgV2(OF3)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form MgOF5 octahedra that share corners with two equivalent V(1)O2F4 octahedra, corners with four equivalent V(2)O2F4 octahedra, and  a faceface with one V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 29-56°. The Mg(1)-O(2) bond length is 2.14 Å. The Mg(1)-F(1) bond length is 2.07 Å. The Mg(1)-F(2) bond length is 2.07 Å. The Mg(1)-F(3) bond length is 1.93 Å. The Mg(1)-F(4) bond length is 2.16 Å. The Mg(1)-F(6) bond length is 1.98 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(4), and one F(6) atom to form distorted VO2F4 octahedra that share corners with two equivalent Mg(1)OF5 octahedra, edges with two equivalent V(2)O2F4 octahedra, and  a faceface with one Mg(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-56°. The V(1)-O(1) bond length is 1.77 Å. The V(1)-O(2) bond length is 1.86 Å. The V(1)-F(1) bond length is 1.88 Å. The V(1)-F(2) bond length is 2.21 Å. The V(1)-F(4) bond length is 2.22 Å. The V(1)-F(6) bond length is 1.89 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with four equivalent Mg(1)OF5 octahedra and edges with two equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 29-47°. The V(2)-O(1) bond length is 1.89 Å. The V(2)-O(2) bond length is 1.90 Å. The V(2)-F(2) bond length is 2.02 Å. The V(2)-F(3) bond length is 1.98 Å. The V(2)-F(4) bond length is 2.00 Å. The V(2)-F(5) bond length is 1.77 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in an L-shaped geometry to one Mg(1) and one V(1) 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(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(1) atom.