MgV8(OF)8 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(5), one O(6), one F(1), and one F(6) atom. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(4), one O(5), one O(7), one F(2), one F(4), and one F(7) atom to form VO3F3 octahedra that share corners with two equivalent V(7)O2F4 octahedra, corners with two equivalent V(8)O2F4 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 38-54°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(7), one O(8), one F(4), and one F(5) atom to form VO4F2 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)O2F4 octahedra, and  an edgeedge with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(3), one O(6), one O(8), one F(3), one F(5), and one F(6) atom. In the fourth V site, V(4) is bonded to one O(3), one O(4), one O(5), one O(6), one F(1), and one F(8) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(7)O2F4 octahedra, and  an edgeedge with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 24-58°. In the fifth V site, V(5) is bonded to one O(1), one O(4), one O(7), one F(2), one F(7), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(7)O2F4 octahedra, and  an edgeedge with one V(8)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. In the sixth V site, V(6) is bonded to one O(2), one O(6), one O(8), one F(1), one F(3), and one F(6) atom to form distorted VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra,  an edgeedge with one V(7)O2F4 octahedra, and  an edgeedge with one V(8)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 24-59°. In the seventh V site, V(7) is bonded to one O(3), one O(5), one F(1), one F(2), one F(6), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent V(4)O4F2 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 45-58°. In the eighth V site, V(8) is bonded to one O(1), one O(8), one F(3), one F(4), one F(5), and one F(7) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent V(2)O4F2 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 45-53°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(8) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mg(1), one V(2), and one V(6) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(3), one V(4), and one V(7) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Mg(1), one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the eighth O site, O(8) is bonded to one V(2), one V(3), one V(6), and one V(8) atom to form distorted OV4 trigonal pyramids that share  a cornercorner with one F(1)MgV3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(1) is bonded to one Mg(1), one V(4), one V(6), and one V(7) atom to form distorted FMgV3 trigonal pyramids that share  a cornercorner with one O(8)V4 trigonal pyramid. In the second F site, F(2) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(7) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one V(3), one V(6), and one V(8) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(8) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(8) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Mg(1), one V(3), one V(6), and one V(7) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one V(8) 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 in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one F(1), and one F(6) atom. The Mg(1)-O(2) bond length is 2.04 Å. The Mg(1)-O(3) bond length is 2.04 Å. The Mg(1)-O(5) bond length is 2.42 Å. The Mg(1)-O(6) bond length is 2.04 Å. The Mg(1)-F(1) bond length is 1.97 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(4), one O(5), one O(7), one F(2), one F(4), and one F(7) atom to form VO3F3 octahedra that share corners with two equivalent V(7)O2F4 octahedra, corners with two equivalent V(8)O2F4 octahedra, corners with four equivalent V(5)O3F3 octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 38-54°. The V(1)-O(4) bond length is 2.03 Å. The V(1)-O(5) bond length is 1.99 Å. The V(1)-O(7) bond length is 2.00 Å. The V(1)-F(2) bond length is 2.11 Å. The V(1)-F(4) bond length is 2.09 Å. The V(1)-F(7) bond length is 2.08 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(7), one O(8), one F(4), and one F(5) atom to form VO4F2 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)O2F4 octahedra, and  an edgeedge with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(2) bond length is 2.06 Å. The V(2)-O(7) bond length is 2.05 Å. The V(2)-O(8) bond length is 2.12 Å. The V(2)-F(4) bond length is 2.07 Å. The V(2)-F(5) bond length is 2.03 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(3), one O(6), one O(8), one F(3), one F(5), and one F(6) atom. The V(3)-O(3) bond length is 2.47 Å. The V(3)-O(6) bond length is 2.01 Å. The V(3)-O(8) bond length is 2.25 Å. The V(3)-F(3) bond length is 2.05 Å. The V(3)-F(5) bond length is 2.13 Å. The V(3)-F(6) bond length is 2.71 Å. In the fourth V site, V(4) is bonded to one O(3), one O(4), one O(5), one O(6), one F(1), and one F(8) atom to form distorted VO4F2 octahedra that share corners with two equivalent V(5)O3F3 octahedra, corners with two equivalent V(6)O3F3 octahedra, corners with four equivalent V(7)O2F4 octahedra, and  an edgeedge with one V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 24-58°. The V(4)-O(3) bond length is 2.03 Å. The V(4)-O(4) bond length is 1.93 Å. The V(4)-O(5) bond length is 2.20 Å. The V(4)-O(6) bond length is 1.98 Å. The V(4)-F(1) bond length is 2.38 Å. The V(4)-F(8) bond length is 2.08 Å. In the fifth V site, V(5) is bonded to one O(1), one O(4), one O(7), one F(2), one F(7), and one F(8) atom to form VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, corners with four equivalent V(1)O3F3 octahedra,  an edgeedge with one V(7)O2F4 octahedra, and  an edgeedge with one V(8)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. The V(5)-O(1) bond length is 1.88 Å. The V(5)-O(4) bond length is 2.08 Å. The V(5)-O(7) bond length is 2.03 Å. The V(5)-F(2) bond length is 2.12 Å. The V(5)-F(7) bond length is 2.12 Å. The V(5)-F(8) bond length is 2.21 Å. In the sixth V site, V(6) is bonded to one O(2), one O(6), one O(8), one F(1), one F(3), and one F(6) atom to form distorted VO3F3 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra,  an edgeedge with one V(7)O2F4 octahedra, and  an edgeedge with one V(8)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 24-59°. The V(6)-O(2) bond length is 1.90 Å. The V(6)-O(6) bond length is 2.02 Å. The V(6)-O(8) bond length is 1.93 Å. The V(6)-F(1) bond length is 2.41 Å. The V(6)-F(3) bond length is 2.07 Å. The V(6)-F(6) bond length is 2.20 Å. In the seventh V site, V(7) is bonded to one O(3), one O(5), one F(1), one F(2), one F(6), and one F(8) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent V(4)O4F2 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 45-58°. The V(7)-O(3) bond length is 2.02 Å. The V(7)-O(5) bond length is 1.96 Å. The V(7)-F(1) bond length is 2.08 Å. The V(7)-F(2) bond length is 2.07 Å. The V(7)-F(6) bond length is 2.10 Å. The V(7)-F(8) bond length is 2.04 Å. In the eighth V site, V(8) is bonded to one O(1), one O(8), one F(3), one F(4), one F(5), and one F(7) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent V(2)O4F2 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 45-53°. The V(8)-O(1) bond length is 2.13 Å. The V(8)-O(8) bond length is 2.21 Å. The V(8)-F(3) bond length is 2.11 Å. The V(8)-F(4) bond length is 2.05 Å. The V(8)-F(5) bond length is 2.05 Å. The V(8)-F(7) bond length is 2.11 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(8) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mg(1), one V(2), and one V(6) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(3), one V(4), and one V(7) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one V(7) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Mg(1), one V(3), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the eighth O site, O(8) is bonded to one V(2), one V(3), one V(6), and one V(8) atom to form distorted OV4 trigonal pyramids that share  a cornercorner with one F(1)MgV3 trigonal pyramid. There are eight inequivalent F sites. In the first F site, F(1) is bonded to one Mg(1), one V(4), one V(6), and one V(7) atom to form distorted FMgV3 trigonal pyramids that share  a cornercorner with one O(8)V4 trigonal pyramid. In the second F site, F(2) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(7) atom. In the third F site, F(3) is bonded in a trigonal non-coplanar geometry to one V(3), one V(6), and one V(8) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(8) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(8) atom. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Mg(1), one V(3), one V(6), and one V(7) atom. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one V(8) 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.