MgVMoO5 crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form MgO5 trigonal bipyramids that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mg(1)O5 trigonal bipyramids, edges with two equivalent Mo(1)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-55°. V(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted VO6 octahedra that share  a cornercorner with one Mo(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with three equivalent Mo(1)O6 octahedra, and edges with three equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-24°. Mo(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form MoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mg(1)O5 trigonal bipyramids, edges with three equivalent V(1)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-30°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to one V(1) and one Mo(1) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Mg(1), two equivalent V(1), and one Mo(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Mg(1), one V(1), and one Mo(1) atom. In the fourth O site, O(4) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one Mo(1) atom. In the fifth O site, O(5) is bonded to one Mg(1), one V(1), and two equivalent Mo(1) atoms to form corner-sharing OMgVMo2 trigonal pyramids.
MgVMoO5 crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form MgO5 trigonal bipyramids that share corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mg(1)O5 trigonal bipyramids, edges with two equivalent Mo(1)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-55°. The Mg(1)-O(2) bond length is 2.04 Å. The Mg(1)-O(4) bond length is 1.98 Å. The Mg(1)-O(5) bond length is 2.06 Å. Both Mg(1)-O(3) bond lengths are 2.05 Å. V(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted VO6 octahedra that share  a cornercorner with one Mo(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with three equivalent Mo(1)O6 octahedra, and edges with three equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-24°. The V(1)-O(1) bond length is 1.74 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(4) bond length is 2.09 Å. The V(1)-O(5) bond length is 2.13 Å. Both V(1)-O(2) bond lengths are 2.03 Å. Mo(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form MoO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Mo(1)O6 octahedra, corners with two equivalent Mg(1)O5 trigonal bipyramids, edges with three equivalent V(1)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-30°. The Mo(1)-O(1) bond length is 2.09 Å. The Mo(1)-O(2) bond length is 2.21 Å. The Mo(1)-O(3) bond length is 2.22 Å. The Mo(1)-O(4) bond length is 1.91 Å. Both Mo(1)-O(5) bond lengths are 2.06 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to one V(1) and one Mo(1) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Mg(1), two equivalent V(1), and one Mo(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Mg(1), one V(1), and one Mo(1) atom. In the fourth O site, O(4) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one Mo(1) atom. In the fifth O site, O(5) is bonded to one Mg(1), one V(1), and two equivalent Mo(1) atoms to form corner-sharing OMgVMo2 trigonal pyramids.