MgV(TeO3)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(10), one O(11), one O(3), one O(7), and one O(8) atom to form MgO6 octahedra that share  an edgeedge with one Te(2)O6 octahedra and edges with two equivalent V(1)O6 octahedra. V(1) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra and edges with two equivalent Te(2)O6 octahedra. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom. In the second Te site, Te(2) is bonded to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom to form TeO6 octahedra that share  an edgeedge with one Mg(1)O6 octahedra and edges with two equivalent V(1)O6 octahedra. In the third Te site, Te(3) is bonded in a 4-coordinate geometry to one O(12), one O(2), one O(4), and one O(9) atom. In the fourth Te site, Te(4) is bonded in a 3-coordinate geometry to one O(3), one O(5), and one O(6) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one V(1), and one Te(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Te(1) and one Te(3) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Mg(1), one Te(1), and one Te(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Te(2), and one Te(3) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Te(1) and one Te(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Te(2) and one Te(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one V(1), and one Te(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Te(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(1), one Te(2), and one Te(3) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one Mg(1) and one Te(1) atom. In the eleventh O site, O(11) is bonded in a trigonal non-coplanar geometry to one Mg(1), one V(1), and one Te(1) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Te(2) and one Te(3) atom.
MgV(TeO3)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(10), one O(11), one O(3), one O(7), and one O(8) atom to form MgO6 octahedra that share  an edgeedge with one Te(2)O6 octahedra and edges with two equivalent V(1)O6 octahedra. The Mg(1)-O(1) bond length is 2.17 Å. The Mg(1)-O(10) bond length is 2.04 Å. The Mg(1)-O(11) bond length is 2.09 Å. The Mg(1)-O(3) bond length is 2.06 Å. The Mg(1)-O(7) bond length is 2.23 Å. The Mg(1)-O(8) bond length is 2.13 Å. V(1) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra and edges with two equivalent Te(2)O6 octahedra. The V(1)-O(1) bond length is 2.01 Å. The V(1)-O(11) bond length is 2.01 Å. The V(1)-O(4) bond length is 2.06 Å. The V(1)-O(7) bond length is 2.02 Å. The V(1)-O(8) bond length is 1.75 Å. The V(1)-O(9) bond length is 2.16 Å. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom. The Te(1)-O(10) bond length is 1.88 Å. The Te(1)-O(11) bond length is 1.99 Å. The Te(1)-O(2) bond length is 2.71 Å. The Te(1)-O(3) bond length is 2.65 Å. The Te(1)-O(5) bond length is 2.04 Å. The Te(1)-O(8) bond length is 2.39 Å. In the second Te site, Te(2) is bonded to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom to form TeO6 octahedra that share  an edgeedge with one Mg(1)O6 octahedra and edges with two equivalent V(1)O6 octahedra. The Te(2)-O(1) bond length is 2.00 Å. The Te(2)-O(12) bond length is 1.96 Å. The Te(2)-O(4) bond length is 2.06 Å. The Te(2)-O(6) bond length is 1.93 Å. The Te(2)-O(7) bond length is 1.96 Å. The Te(2)-O(9) bond length is 1.94 Å. In the third Te site, Te(3) is bonded in a 4-coordinate geometry to one O(12), one O(2), one O(4), and one O(9) atom. The Te(3)-O(12) bond length is 2.00 Å. The Te(3)-O(2) bond length is 1.82 Å. The Te(3)-O(4) bond length is 2.12 Å. The Te(3)-O(9) bond length is 2.45 Å. In the fourth Te site, Te(4) is bonded in a 3-coordinate geometry to one O(3), one O(5), and one O(6) atom. The Te(4)-O(3) bond length is 1.87 Å. The Te(4)-O(5) bond length is 1.92 Å. The Te(4)-O(6) bond length is 2.01 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one V(1), and one Te(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Te(1) and one Te(3) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Mg(1), one Te(1), and one Te(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one Te(2), and one Te(3) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Te(1) and one Te(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Te(2) and one Te(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one V(1), and one Te(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Te(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(1), one Te(2), and one Te(3) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one Mg(1) and one Te(1) atom. In the eleventh O site, O(11) is bonded in a trigonal non-coplanar geometry to one Mg(1), one V(1), and one Te(1) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Te(2) and one Te(3) atom.