MgV4O8 crystallizes in the trigonal R-3m space group. Mg(1) is bonded to six equivalent O(1) atoms to form MgO6 octahedra that share corners with six equivalent V(2)O6 octahedra and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent Mg(1)O6 octahedra and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(1) atoms.
MgV4O8 crystallizes in the trigonal R-3m space group. Mg(1) is bonded to six equivalent O(1) atoms to form MgO6 octahedra that share corners with six equivalent V(2)O6 octahedra and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. All Mg(1)-O(1) bond lengths are 2.18 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Both V(1)-O(2) bond lengths are 1.97 Å. All V(1)-O(1) bond lengths are 2.00 Å. In the second V site, V(2) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent Mg(1)O6 octahedra and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. All V(2)-O(1) bond lengths are 2.07 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(2), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(1) atoms.