MgV8(OF)8 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(7), one O(8), one F(3), and one F(6) atom to form MgO4F2 octahedra that share  a cornercorner with one V(5)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra,  a cornercorner with one V(7)O3F3 octahedra,  a cornercorner with one V(8)O3F3 octahedra, edges with two equivalent V(1)O3F3 octahedra, edges with two equivalent V(2)O3F3 octahedra,  a faceface with one V(5)O3F3 octahedra, and  a faceface with one V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), one O(8), one F(3), one F(4), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent V(7)O3F3 octahedra, corners with two equivalent V(8)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and edges with two equivalent Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 31-63°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(7), one F(3), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(8)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(3)O3F3 octahedra, and edges with two equivalent Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 39-63°. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one F(2), one F(5), and one F(7) atom to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. In the fourth V site, V(4) is bonded to one O(4), one O(5), one O(6), one F(1), one F(4), and one F(8) atom to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 38-55°. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(8), one F(4), one F(6), and one F(8) atom to form distorted VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(2)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(7)O3F3 octahedra,  an edgeedge with one V(8)O3F3 octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. In the sixth V site, V(6) is bonded to one O(3), one O(6), one O(7), one F(1), one F(2), and one F(7) atom to form VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(2)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O3F3 octahedra,  an edgeedge with one V(7)O3F3 octahedra, and  an edgeedge with one V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. In the seventh V site, V(7) is bonded to one O(1), one O(4), one O(5), one F(1), one F(7), and one F(8) atom to form VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 38-63°. In the eighth V site, V(8) is bonded to one O(2), one O(7), one O(8), one F(2), one F(3), and one F(5) atom to form VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(2)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 31-56°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Mg(1), one V(1), one V(5), and one V(7) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(2), one V(5), and one V(8) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(6) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one V(7) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(2), one V(6), and one V(8) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), one V(5), and one V(8) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(4), one V(6), and one V(7) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(3), one V(6), and one V(8) atom. In the third F site, F(3) is bonded to one Mg(1), one V(1), one V(2), and one V(8) atom to form a mixture of distorted corner and edge-sharing FMgV3 trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(8) atom. In the sixth F site, F(6) is bonded to one Mg(1), one V(1), one V(2), and one V(5) atom to form a mixture of corner and edge-sharing FMgV3 trigonal pyramids. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one V(3), one V(6), and one V(7) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one V(4), one V(5), and one V(7) atom.
MgV8(OF)8 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(7), one O(8), one F(3), and one F(6) atom to form MgO4F2 octahedra that share  a cornercorner with one V(5)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra,  a cornercorner with one V(7)O3F3 octahedra,  a cornercorner with one V(8)O3F3 octahedra, edges with two equivalent V(1)O3F3 octahedra, edges with two equivalent V(2)O3F3 octahedra,  a faceface with one V(5)O3F3 octahedra, and  a faceface with one V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Mg(1)-O(1) bond length is 2.12 Å. The Mg(1)-O(2) bond length is 2.00 Å. The Mg(1)-O(7) bond length is 2.11 Å. The Mg(1)-O(8) bond length is 2.04 Å. The Mg(1)-F(3) bond length is 1.96 Å. The Mg(1)-F(6) bond length is 1.97 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), one O(8), one F(3), one F(4), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent V(7)O3F3 octahedra, corners with two equivalent V(8)O3F3 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and edges with two equivalent Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 31-63°. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(5) bond length is 1.89 Å. The V(1)-O(8) bond length is 2.06 Å. The V(1)-F(3) bond length is 2.28 Å. The V(1)-F(4) bond length is 2.03 Å. The V(1)-F(6) bond length is 2.12 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(7), one F(3), one F(5), and one F(6) atom to form VO3F3 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(8)O3F3 octahedra,  an edgeedge with one V(1)O3F3 octahedra,  an edgeedge with one V(3)O3F3 octahedra, and edges with two equivalent Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 39-63°. The V(2)-O(2) bond length is 2.16 Å. The V(2)-O(3) bond length is 2.04 Å. The V(2)-O(7) bond length is 2.14 Å. The V(2)-F(3) bond length is 2.17 Å. The V(2)-F(5) bond length is 2.07 Å. The V(2)-F(6) bond length is 2.28 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one F(2), one F(5), and one F(7) atom to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. The V(3)-O(3) bond length is 1.95 Å. The V(3)-O(4) bond length is 2.03 Å. The V(3)-O(6) bond length is 2.04 Å. The V(3)-F(2) bond length is 2.09 Å. The V(3)-F(5) bond length is 2.11 Å. The V(3)-F(7) bond length is 2.07 Å. In the fourth V site, V(4) is bonded to one O(4), one O(5), one O(6), one F(1), one F(4), and one F(8) atom to form a mixture of corner and edge-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 38-55°. The V(4)-O(4) bond length is 2.00 Å. The V(4)-O(5) bond length is 2.06 Å. The V(4)-O(6) bond length is 1.91 Å. The V(4)-F(1) bond length is 2.10 Å. The V(4)-F(4) bond length is 2.13 Å. The V(4)-F(8) bond length is 2.10 Å. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(8), one F(4), one F(6), and one F(8) atom to form distorted VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(2)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(7)O3F3 octahedra,  an edgeedge with one V(8)O3F3 octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. The V(5)-O(1) bond length is 2.22 Å. The V(5)-O(2) bond length is 2.07 Å. The V(5)-O(8) bond length is 2.08 Å. The V(5)-F(4) bond length is 2.06 Å. The V(5)-F(6) bond length is 2.23 Å. The V(5)-F(8) bond length is 2.09 Å. In the sixth V site, V(6) is bonded to one O(3), one O(6), one O(7), one F(1), one F(2), and one F(7) atom to form VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(2)O3F3 octahedra, corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O3F3 octahedra,  an edgeedge with one V(7)O3F3 octahedra, and  an edgeedge with one V(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-63°. The V(6)-O(3) bond length is 2.00 Å. The V(6)-O(6) bond length is 2.06 Å. The V(6)-O(7) bond length is 1.95 Å. The V(6)-F(1) bond length is 2.16 Å. The V(6)-F(2) bond length is 2.11 Å. The V(6)-F(7) bond length is 2.13 Å. In the seventh V site, V(7) is bonded to one O(1), one O(4), one O(5), one F(1), one F(7), and one F(8) atom to form VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(4)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra, and  an edgeedge with one V(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 38-63°. The V(7)-O(1) bond length is 2.01 Å. The V(7)-O(4) bond length is 1.95 Å. The V(7)-O(5) bond length is 2.07 Å. The V(7)-F(1) bond length is 2.10 Å. The V(7)-F(7) bond length is 2.16 Å. The V(7)-F(8) bond length is 2.09 Å. In the eighth V site, V(8) is bonded to one O(2), one O(7), one O(8), one F(2), one F(3), and one F(5) atom to form VO3F3 octahedra that share  a cornercorner with one Mg(1)O4F2 octahedra, corners with two equivalent V(1)O3F3 octahedra, corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(2)O3F3 octahedra,  an edgeedge with one V(5)O3F3 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 31-56°. The V(8)-O(2) bond length is 1.97 Å. The V(8)-O(7) bond length is 2.10 Å. The V(8)-O(8) bond length is 2.05 Å. The V(8)-F(2) bond length is 2.11 Å. The V(8)-F(3) bond length is 2.22 Å. The V(8)-F(5) bond length is 2.02 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Mg(1), one V(1), one V(5), and one V(7) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(2), one V(5), and one V(8) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(6) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one V(7) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(2), one V(6), and one V(8) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), one V(5), and one V(8) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(4), one V(6), and one V(7) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(3), one V(6), and one V(8) atom. In the third F site, F(3) is bonded to one Mg(1), one V(1), one V(2), and one V(8) atom to form a mixture of distorted corner and edge-sharing FMgV3 trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(8) atom. In the sixth F site, F(6) is bonded to one Mg(1), one V(1), one V(2), and one V(5) atom to form a mixture of corner and edge-sharing FMgV3 trigonal pyramids. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one V(3), one V(6), and one V(7) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one V(4), one V(5), and one V(7) atom.