MgV4(GeO4)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(4) atom to form MgO6 octahedra that share corners with two equivalent Ge(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Ge(2)O6 octahedra, edges with two equivalent Ge(3)O6 octahedra, and faces with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(16), one O(2), one O(4), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Ge(3)O6 octahedra, corners with four equivalent Mg(1)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra,  an edgeedge with one Ge(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. In the second V site, V(2) is bonded to one O(11), one O(14), one O(3), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(1)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra,  an edgeedge with one Ge(3)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the third V site, V(3) is bonded to one O(12), one O(14), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(4)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra,  an edgeedge with one Ge(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(4) atom to form VO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra,  an edgeedge with one Ge(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and faces with two equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(12), one O(14), one O(16), one O(6), one O(7), and one O(8) atom to form GeO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. In the second Ge site, Ge(2) is bonded to one O(12), one O(15), one O(16), one O(4), one O(6), and one O(7) atom to form GeO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. In the third Ge site, Ge(3) is bonded to one O(1), one O(10), one O(11), one O(13), one O(2), and one O(5) atom to form GeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the fourth Ge site, Ge(4) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(9) atom to form GeO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(4), one Ge(3), and one Ge(4) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(4) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(4), one Ge(3), and one Ge(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom.
MgV4(GeO4)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(4) atom to form MgO6 octahedra that share corners with two equivalent Ge(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Ge(2)O6 octahedra, edges with two equivalent Ge(3)O6 octahedra, and faces with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. The Mg(1)-O(1) bond length is 2.05 Å. The Mg(1)-O(10) bond length is 2.08 Å. The Mg(1)-O(13) bond length is 1.94 Å. The Mg(1)-O(15) bond length is 2.00 Å. The Mg(1)-O(2) bond length is 1.95 Å. The Mg(1)-O(4) bond length is 1.99 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(15), one O(16), one O(2), one O(4), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Ge(3)O6 octahedra, corners with four equivalent Mg(1)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra,  an edgeedge with one Ge(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-56°. The V(1)-O(13) bond length is 2.13 Å. The V(1)-O(15) bond length is 2.04 Å. The V(1)-O(16) bond length is 2.02 Å. The V(1)-O(2) bond length is 2.13 Å. The V(1)-O(4) bond length is 2.02 Å. The V(1)-O(7) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(11), one O(14), one O(3), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(1)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra,  an edgeedge with one Ge(3)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(2)-O(11) bond length is 1.94 Å. The V(2)-O(14) bond length is 2.02 Å. The V(2)-O(3) bond length is 1.91 Å. The V(2)-O(5) bond length is 1.94 Å. The V(2)-O(8) bond length is 2.03 Å. The V(2)-O(9) bond length is 1.92 Å. In the third V site, V(3) is bonded to one O(12), one O(14), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ge(4)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra,  an edgeedge with one Ge(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The V(3)-O(12) bond length is 1.90 Å. The V(3)-O(14) bond length is 1.93 Å. The V(3)-O(3) bond length is 2.08 Å. The V(3)-O(6) bond length is 1.90 Å. The V(3)-O(8) bond length is 1.92 Å. The V(3)-O(9) bond length is 2.07 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(13), one O(15), one O(2), and one O(4) atom to form VO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra,  an edgeedge with one Ge(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and faces with two equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The V(4)-O(1) bond length is 2.00 Å. The V(4)-O(10) bond length is 2.02 Å. The V(4)-O(13) bond length is 2.03 Å. The V(4)-O(15) bond length is 2.02 Å. The V(4)-O(2) bond length is 1.99 Å. The V(4)-O(4) bond length is 2.07 Å. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(12), one O(14), one O(16), one O(6), one O(7), and one O(8) atom to form GeO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(3)O6 octahedra, corners with four equivalent Ge(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. The Ge(1)-O(12) bond length is 2.03 Å. The Ge(1)-O(14) bond length is 1.96 Å. The Ge(1)-O(16) bond length is 1.91 Å. The Ge(1)-O(6) bond length is 2.03 Å. The Ge(1)-O(7) bond length is 1.95 Å. The Ge(1)-O(8) bond length is 1.97 Å. In the second Ge site, Ge(2) is bonded to one O(12), one O(15), one O(16), one O(4), one O(6), and one O(7) atom to form GeO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. The Ge(2)-O(12) bond length is 1.94 Å. The Ge(2)-O(15) bond length is 1.95 Å. The Ge(2)-O(16) bond length is 1.96 Å. The Ge(2)-O(4) bond length is 1.93 Å. The Ge(2)-O(6) bond length is 1.94 Å. The Ge(2)-O(7) bond length is 2.05 Å. In the third Ge site, Ge(3) is bonded to one O(1), one O(10), one O(11), one O(13), one O(2), and one O(5) atom to form GeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra, corners with four equivalent Ge(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Ge(3)-O(1) bond length is 2.02 Å. The Ge(3)-O(10) bond length is 1.96 Å. The Ge(3)-O(11) bond length is 1.92 Å. The Ge(3)-O(13) bond length is 1.95 Å. The Ge(3)-O(2) bond length is 1.92 Å. The Ge(3)-O(5) bond length is 1.93 Å. In the fourth Ge site, Ge(4) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(9) atom to form GeO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with four equivalent Ge(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Ge(4)-O(1) bond length is 2.02 Å. The Ge(4)-O(10) bond length is 2.01 Å. The Ge(4)-O(11) bond length is 2.02 Å. The Ge(4)-O(3) bond length is 1.92 Å. The Ge(4)-O(5) bond length is 2.02 Å. The Ge(4)-O(9) bond length is 1.91 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(4), one Ge(3), and one Ge(4) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(3) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(4) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Ge(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(4), one Ge(3), and one Ge(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(2), one Ge(3), and one Ge(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(3), one Ge(1), and one Ge(2) atom. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(4), and one Ge(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one V(1), one Ge(1), and one Ge(2) atom.