MgV8(OF)8 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(7), one O(8), one F(3), one F(5), and one F(6) atom to form MgO2F3 trigonal bipyramids that share  a cornercorner with one V(3)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, and  an edgeedge with one V(1)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 11-60°. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), one F(3), one F(4), and one F(6) atom to form distorted VO2F3 square pyramids that share corners with two equivalent V(7)O3F3 octahedra, corners with three equivalent V(5)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 52-57°. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(7), one F(3), and one F(5) atom. 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 VO3F3 octahedra that share corners with two equivalent V(7)O3F3 octahedra, corners with four equivalent V(6)O3F3 octahedra,  a cornercorner with one Mg(1)O2F3 trigonal bipyramid, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-57°. 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 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(7)O3F3 octahedra,  an edgeedge with one V(3)O3F3 octahedra, and  an edgeedge with one V(1)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 42-51°. 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 VO3F3 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with three equivalent V(1)O2F3 square pyramids, corners with two equivalent Mg(1)O2F3 trigonal bipyramids, and  an edgeedge with one V(7)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-43°. 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 corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O3F3 octahedra,  a cornercorner with one Mg(1)O2F3 trigonal bipyramid, and  an edgeedge with one V(7)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. 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 corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(4)O3F3 octahedra, corners with two equivalent V(1)O2F3 square pyramids,  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 47-57°. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(7), one O(8), one F(2), and one F(5) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(7) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one V(2), one V(5), and one V(8) atom. In the third O site, O(3) 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 O(7)MgV3 trigonal pyramid,  a cornercorner with one F(5)MgV3 trigonal pyramid,  an edgeedge with one O(7)MgV3 trigonal pyramid, and  an edgeedge with one F(5)MgV3 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted trigonal planar 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 to one Mg(1), one V(2), one V(6), and one V(8) atom to form distorted OMgV3 trigonal pyramids that share  a cornercorner with one O(3)V4 trigonal pyramid,  a cornercorner with one F(5)MgV3 trigonal pyramid,  an edgeedge with one O(3)V4 trigonal pyramid, and  an edgeedge with one F(5)MgV3 trigonal pyramid. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Mg(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 distorted 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 3-coordinate geometry to one V(3), one V(6), and one V(8) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(2) atom. 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 to one Mg(1), one V(2), one V(3), and one V(8) atom to form distorted FMgV3 trigonal pyramids that share  a cornercorner with one O(7)MgV3 trigonal pyramid,  a cornercorner with one O(3)V4 trigonal pyramid,  an edgeedge with one O(7)MgV3 trigonal pyramid, and  an edgeedge with one O(3)V4 trigonal pyramid. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(5) atom. In the seventh F site, F(7) is bonded in a distorted 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 T-shaped 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(7), one O(8), one F(3), one F(5), and one F(6) atom to form MgO2F3 trigonal bipyramids that share  a cornercorner with one V(3)O3F3 octahedra,  a cornercorner with one V(6)O3F3 octahedra, corners with two equivalent V(5)O3F3 octahedra, and  an edgeedge with one V(1)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 11-60°. The Mg(1)-O(7) bond length is 1.98 Å. The Mg(1)-O(8) bond length is 1.91 Å. The Mg(1)-F(3) bond length is 2.00 Å. The Mg(1)-F(5) bond length is 2.10 Å. The Mg(1)-F(6) bond length is 2.05 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), one F(3), one F(4), and one F(6) atom to form distorted VO2F3 square pyramids that share corners with two equivalent V(7)O3F3 octahedra, corners with three equivalent V(5)O3F3 octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 52-57°. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(5) bond length is 2.05 Å. The V(1)-F(3) bond length is 2.42 Å. The V(1)-F(4) bond length is 2.08 Å. The V(1)-F(6) bond length is 2.11 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(7), one F(3), and one F(5) atom. The V(2)-O(2) bond length is 1.87 Å. The V(2)-O(3) bond length is 1.97 Å. The V(2)-O(7) bond length is 1.98 Å. The V(2)-F(3) bond length is 2.10 Å. The V(2)-F(5) bond length is 2.29 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 VO3F3 octahedra that share corners with two equivalent V(7)O3F3 octahedra, corners with four equivalent V(6)O3F3 octahedra,  a cornercorner with one Mg(1)O2F3 trigonal bipyramid, and  an edgeedge with one V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-57°. The V(3)-O(3) bond length is 2.04 Å. The V(3)-O(4) bond length is 1.90 Å. The V(3)-O(6) bond length is 1.96 Å. The V(3)-F(2) bond length is 2.14 Å. The V(3)-F(5) bond length is 2.15 Å. The V(3)-F(7) bond length is 2.21 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 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(7)O3F3 octahedra,  an edgeedge with one V(3)O3F3 octahedra, and  an edgeedge with one V(1)O2F3 square pyramid. The corner-sharing octahedral tilt angles range from 42-51°. The V(4)-O(4) bond length is 2.00 Å. The V(4)-O(5) bond length is 1.93 Å. The V(4)-O(6) bond length is 2.05 Å. The V(4)-F(1) bond length is 2.19 Å. The V(4)-F(4) bond length is 2.13 Å. The V(4)-F(8) bond length is 2.12 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 VO3F3 octahedra that share corners with two equivalent V(4)O3F3 octahedra, corners with three equivalent V(1)O2F3 square pyramids, corners with two equivalent Mg(1)O2F3 trigonal bipyramids, and  an edgeedge with one V(7)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 42-43°. The V(5)-O(1) bond length is 1.98 Å. The V(5)-O(2) bond length is 2.00 Å. The V(5)-O(8) bond length is 1.95 Å. The V(5)-F(4) bond length is 2.01 Å. The V(5)-F(6) bond length is 2.06 Å. The V(5)-F(8) bond length is 2.25 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 corners with two equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O3F3 octahedra,  a cornercorner with one Mg(1)O2F3 trigonal bipyramid, and  an edgeedge with one V(7)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. The V(6)-O(3) bond length is 2.08 Å. The V(6)-O(6) bond length is 1.92 Å. The V(6)-O(7) bond length is 2.03 Å. The V(6)-F(1) bond length is 2.09 Å. The V(6)-F(2) bond length is 2.09 Å. The V(6)-F(7) bond length is 2.15 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 corners with two equivalent V(3)O3F3 octahedra, corners with four equivalent V(4)O3F3 octahedra, corners with two equivalent V(1)O2F3 square pyramids,  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 47-57°. The V(7)-O(1) bond length is 1.90 Å. The V(7)-O(4) bond length is 2.05 Å. The V(7)-O(5) bond length is 1.99 Å. The V(7)-F(1) bond length is 2.21 Å. The V(7)-F(7) bond length is 2.17 Å. The V(7)-F(8) bond length is 2.17 Å. In the eighth V site, V(8) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(7), one O(8), one F(2), and one F(5) atom. The V(8)-O(2) bond length is 1.98 Å. The V(8)-O(3) bond length is 2.17 Å. The V(8)-O(7) bond length is 2.13 Å. The V(8)-O(8) bond length is 2.11 Å. The V(8)-F(2) bond length is 2.62 Å. The V(8)-F(5) bond length is 2.18 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(5), and one V(7) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one V(2), one V(5), and one V(8) atom. In the third O site, O(3) 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 O(7)MgV3 trigonal pyramid,  a cornercorner with one F(5)MgV3 trigonal pyramid,  an edgeedge with one O(7)MgV3 trigonal pyramid, and  an edgeedge with one F(5)MgV3 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted trigonal planar 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 to one Mg(1), one V(2), one V(6), and one V(8) atom to form distorted OMgV3 trigonal pyramids that share  a cornercorner with one O(3)V4 trigonal pyramid,  a cornercorner with one F(5)MgV3 trigonal pyramid,  an edgeedge with one O(3)V4 trigonal pyramid, and  an edgeedge with one F(5)MgV3 trigonal pyramid. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Mg(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 distorted 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 3-coordinate geometry to one V(3), one V(6), and one V(8) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(2) atom. 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 to one Mg(1), one V(2), one V(3), and one V(8) atom to form distorted FMgV3 trigonal pyramids that share  a cornercorner with one O(7)MgV3 trigonal pyramid,  a cornercorner with one O(3)V4 trigonal pyramid,  an edgeedge with one O(7)MgV3 trigonal pyramid, and  an edgeedge with one O(3)V4 trigonal pyramid. In the sixth F site, F(6) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(5) atom. In the seventh F site, F(7) is bonded in a distorted 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 T-shaped geometry to one V(4), one V(5), and one V(7) atom.