MgV2(MoO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(3) and four O(1,1) atoms to form distorted MgO6 octahedra that share corners with four equivalent Mo(1)O4 tetrahedra and faces with two equivalent V(1)O5 trigonal bipyramids. V(1) is bonded to one O(3); two O(1,1); and two O(2,2) atoms to form distorted VO5 trigonal bipyramids that share corners with four equivalent Mo(1)O4 tetrahedra and  a faceface with one Mg(1)O6 octahedra. Mo(1) is bonded to two O(1,1) and two O(2,2) atoms to form MoO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 50°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Mo(1) atom. In the second O site, O(2) is bonded in a linear geometry to one V(1) and one Mo(1) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Mo(1) atom. In the fourth O site, O(2) is bonded in a linear geometry to one V(1) and one Mo(1) atom. In the fifth O site, O(3) is bonded in an L-shaped geometry to one Mg(1) and one V(1) atom.
MgV2(MoO5)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(3) and four O(1,1) atoms to form distorted MgO6 octahedra that share corners with four equivalent Mo(1)O4 tetrahedra and faces with two equivalent V(1)O5 trigonal bipyramids. Both Mg(1)-O(3) bond lengths are 2.21 Å. There are two shorter (2.07 Å) and two longer (2.08 Å) Mg(1)-O(1,1) bond lengths. V(1) is bonded to one O(3); two O(1,1); and two O(2,2) atoms to form distorted VO5 trigonal bipyramids that share corners with four equivalent Mo(1)O4 tetrahedra and  a faceface with one Mg(1)O6 octahedra. The V(1)-O(3) bond length is 1.68 Å. Both V(1)-O(1,1) bond lengths are 2.05 Å. Both V(1)-O(2,2) bond lengths are 1.91 Å. Mo(1) is bonded to two O(1,1) and two O(2,2) atoms to form MoO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 50°. Both Mo(1)-O(1,1) bond lengths are 1.87 Å. Both Mo(1)-O(2,2) bond lengths are 1.84 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Mo(1) atom. In the second O site, O(2) is bonded in a linear geometry to one V(1) and one Mo(1) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one Mo(1) atom. In the fourth O site, O(2) is bonded in a linear geometry to one V(1) and one Mo(1) atom. In the fifth O site, O(3) is bonded in an L-shaped geometry to one Mg(1) and one V(1) atom.