MgV8Ge4(O2F)8 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(6), one F(2), and one F(6) atom. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(4), one O(5), one F(1), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(6)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(2)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-39°. In the second V site, V(2) is bonded to one O(1), one O(11), one O(16), one O(5), one F(4), and one F(8) atom to form VO4F2 octahedra that share corners with two equivalent V(7)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(3)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-40°. In the third V site, V(3) is bonded to one O(12), one O(14), one O(15), one O(3), one F(2), and one F(6) atom to form VO4F2 octahedra that share corners with two equivalent V(5)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(4)O4 tetrahedra,  an edgeedge with one V(4)O4F2 octahedra, and  an edgeedge with one V(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-37°. In the fourth V site, V(4) is bonded to one O(12), one O(3), one O(7), one O(8), one F(3), and one F(7) atom to form VO4F2 octahedra that share corners with two equivalent V(8)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(1)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. In the fifth V site, V(5) is bonded to one O(10), one O(13), one O(4), one O(6), one F(2), and one F(6) atom to form VO4F2 octahedra that share corners with two equivalent V(3)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-37°. In the sixth V site, V(6) is bonded to one O(14), one O(15), one O(2), one O(9), one F(1), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(4)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-39°. In the seventh V site, V(7) is bonded to one O(2), one O(7), one O(8), one O(9), one F(4), and one F(8) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(1)O4 tetrahedra,  an edgeedge with one V(4)O4F2 octahedra, and  an edgeedge with one V(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-40°. In the eighth V site, V(8) is bonded to one O(11), one O(13), one O(16), one O(6), one F(3), and one F(7) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(3)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(10), one O(2), one O(3), and one O(8) atom to form GeO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O4F2 octahedra,  a cornercorner with one V(6)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, and corners with two equivalent V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. In the second Ge site, Ge(2) is bonded to one O(1), one O(13), one O(4), and one O(7) atom to form GeO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one V(4)O4F2 octahedra,  a cornercorner with one V(7)O4F2 octahedra,  a cornercorner with one V(8)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra, and corners with two equivalent V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. In the third Ge site, Ge(3) is bonded to one O(11), one O(15), one O(5), and one O(6) atom to form distorted GeO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O4F2 octahedra,  a cornercorner with one V(6)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra, and corners with two equivalent V(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-63°. In the fourth Ge site, Ge(4) is bonded to one O(12), one O(14), one O(16), and one O(9) atom to form GeO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one V(4)O4F2 octahedra,  a cornercorner with one V(7)O4F2 octahedra,  a cornercorner with one V(8)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, and corners with two equivalent V(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-57°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Ge(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(6), one V(7), and one Ge(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one Ge(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one Ge(2) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Ge(3) atom. In the sixth O site, O(6) is bonded in a distorted square co-planar geometry to one Mg(1), one V(5), one V(8), and one Ge(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(4), one V(7), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(4), one V(7), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(6), one V(7), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one Ge(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(2), one V(8), and one Ge(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one Ge(4) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(5), one V(8), and one Ge(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(3), one V(6), and one Ge(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Mg(1), one V(3), one V(6), and one Ge(3) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one V(2), one V(8), and one Ge(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(6) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(5) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(4) and one V(8) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(6) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(5) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(4) and one V(8) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom.
MgV8Ge4(O2F)8 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(6), one F(2), and one F(6) atom. The Mg(1)-O(11) bond length is 2.22 Å. The Mg(1)-O(13) bond length is 1.93 Å. The Mg(1)-O(15) bond length is 2.40 Å. The Mg(1)-O(6) bond length is 2.10 Å. The Mg(1)-F(2) bond length is 1.99 Å. The Mg(1)-F(6) bond length is 1.98 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(4), one O(5), one F(1), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(6)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(2)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-39°. The V(1)-O(1) bond length is 2.13 Å. The V(1)-O(10) bond length is 2.04 Å. The V(1)-O(4) bond length is 2.02 Å. The V(1)-O(5) bond length is 2.03 Å. The V(1)-F(1) bond length is 2.03 Å. The V(1)-F(5) bond length is 2.01 Å. In the second V site, V(2) is bonded to one O(1), one O(11), one O(16), one O(5), one F(4), and one F(8) atom to form VO4F2 octahedra that share corners with two equivalent V(7)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(3)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-40°. The V(2)-O(1) bond length is 2.01 Å. The V(2)-O(11) bond length is 2.09 Å. The V(2)-O(16) bond length is 2.06 Å. The V(2)-O(5) bond length is 2.10 Å. The V(2)-F(4) bond length is 2.00 Å. The V(2)-F(8) bond length is 2.00 Å. In the third V site, V(3) is bonded to one O(12), one O(14), one O(15), one O(3), one F(2), and one F(6) atom to form VO4F2 octahedra that share corners with two equivalent V(5)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(4)O4 tetrahedra,  an edgeedge with one V(4)O4F2 octahedra, and  an edgeedge with one V(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-37°. The V(3)-O(12) bond length is 1.98 Å. The V(3)-O(14) bond length is 1.95 Å. The V(3)-O(15) bond length is 2.20 Å. The V(3)-O(3) bond length is 2.04 Å. The V(3)-F(2) bond length is 2.03 Å. The V(3)-F(6) bond length is 2.07 Å. In the fourth V site, V(4) is bonded to one O(12), one O(3), one O(7), one O(8), one F(3), and one F(7) atom to form VO4F2 octahedra that share corners with two equivalent V(8)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(1)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. The V(4)-O(12) bond length is 2.14 Å. The V(4)-O(3) bond length is 2.05 Å. The V(4)-O(7) bond length is 2.06 Å. The V(4)-O(8) bond length is 2.05 Å. The V(4)-F(3) bond length is 1.94 Å. The V(4)-F(7) bond length is 1.92 Å. In the fifth V site, V(5) is bonded to one O(10), one O(13), one O(4), one O(6), one F(2), and one F(6) atom to form VO4F2 octahedra that share corners with two equivalent V(3)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-37°. The V(5)-O(10) bond length is 2.08 Å. The V(5)-O(13) bond length is 2.15 Å. The V(5)-O(4) bond length is 2.08 Å. The V(5)-O(6) bond length is 2.21 Å. The V(5)-F(2) bond length is 2.08 Å. The V(5)-F(6) bond length is 2.11 Å. In the sixth V site, V(6) is bonded to one O(14), one O(15), one O(2), one O(9), one F(1), and one F(5) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, corners with two equivalent Ge(4)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra, and  an edgeedge with one V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-39°. The V(6)-O(14) bond length is 2.09 Å. The V(6)-O(15) bond length is 2.09 Å. The V(6)-O(2) bond length is 2.08 Å. The V(6)-O(9) bond length is 2.00 Å. The V(6)-F(1) bond length is 1.95 Å. The V(6)-F(5) bond length is 1.97 Å. In the seventh V site, V(7) is bonded to one O(2), one O(7), one O(8), one O(9), one F(4), and one F(8) atom to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(1)O4 tetrahedra,  an edgeedge with one V(4)O4F2 octahedra, and  an edgeedge with one V(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-40°. The V(7)-O(2) bond length is 2.01 Å. The V(7)-O(7) bond length is 2.05 Å. The V(7)-O(8) bond length is 2.05 Å. The V(7)-O(9) bond length is 2.09 Å. The V(7)-F(4) bond length is 1.98 Å. The V(7)-F(8) bond length is 1.97 Å. In the eighth V site, V(8) is bonded to one O(11), one O(13), one O(16), one O(6), one F(3), and one F(7) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O4F2 octahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one Ge(4)O4 tetrahedra, corners with two equivalent Ge(3)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. The V(8)-O(11) bond length is 2.25 Å. The V(8)-O(13) bond length is 2.21 Å. The V(8)-O(16) bond length is 2.09 Å. The V(8)-O(6) bond length is 2.25 Å. The V(8)-F(3) bond length is 2.05 Å. The V(8)-F(7) bond length is 2.01 Å. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(10), one O(2), one O(3), and one O(8) atom to form GeO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O4F2 octahedra,  a cornercorner with one V(6)O4F2 octahedra, corners with two equivalent V(4)O4F2 octahedra, and corners with two equivalent V(7)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. The Ge(1)-O(10) bond length is 1.78 Å. The Ge(1)-O(2) bond length is 1.79 Å. The Ge(1)-O(3) bond length is 1.81 Å. The Ge(1)-O(8) bond length is 1.80 Å. In the second Ge site, Ge(2) is bonded to one O(1), one O(13), one O(4), and one O(7) atom to form GeO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one V(4)O4F2 octahedra,  a cornercorner with one V(7)O4F2 octahedra,  a cornercorner with one V(8)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra, and corners with two equivalent V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. The Ge(2)-O(1) bond length is 1.78 Å. The Ge(2)-O(13) bond length is 1.81 Å. The Ge(2)-O(4) bond length is 1.77 Å. The Ge(2)-O(7) bond length is 1.77 Å. In the third Ge site, Ge(3) is bonded to one O(11), one O(15), one O(5), and one O(6) atom to form distorted GeO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one V(5)O4F2 octahedra,  a cornercorner with one V(6)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra, and corners with two equivalent V(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-63°. The Ge(3)-O(11) bond length is 1.83 Å. The Ge(3)-O(15) bond length is 1.82 Å. The Ge(3)-O(5) bond length is 1.72 Å. The Ge(3)-O(6) bond length is 1.81 Å. In the fourth Ge site, Ge(4) is bonded to one O(12), one O(14), one O(16), and one O(9) atom to form GeO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one V(4)O4F2 octahedra,  a cornercorner with one V(7)O4F2 octahedra,  a cornercorner with one V(8)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra, and corners with two equivalent V(6)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-57°. The Ge(4)-O(12) bond length is 1.80 Å. The Ge(4)-O(14) bond length is 1.82 Å. The Ge(4)-O(16) bond length is 1.77 Å. The Ge(4)-O(9) bond length is 1.78 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Ge(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(6), one V(7), and one Ge(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one Ge(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one Ge(2) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Ge(3) atom. In the sixth O site, O(6) is bonded in a distorted square co-planar geometry to one Mg(1), one V(5), one V(8), and one Ge(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(4), one V(7), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(4), one V(7), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(6), one V(7), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(5), and one Ge(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(2), one V(8), and one Ge(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one Ge(4) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(5), one V(8), and one Ge(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(3), one V(6), and one Ge(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one Mg(1), one V(3), one V(6), and one Ge(3) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one V(2), one V(8), and one Ge(4) atom. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(6) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(5) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(4) and one V(8) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(6) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Mg(1), one V(3), and one V(5) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(4) and one V(8) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(7) atom.