MgCo2(VO4)2 crystallizes in the orthorhombic Amm2 space group. Mg(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted MgO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-68°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra and corners with two equivalent Mg(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. In the second V site, V(2) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra and  an edgeedge with one Mg(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-56°. Co(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Mg(1)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mg(1), one V(1), and one Co(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the third O site, O(3) is bonded to one Mg(1), one V(2), and two equivalent Co(1) atoms to form distorted edge-sharing OMgVCo2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(2) and one Co(1) atom.
MgCo2(VO4)2 crystallizes in the orthorhombic Amm2 space group. Mg(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted MgO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-68°. Both Mg(1)-O(1) bond lengths are 1.96 Å. Both Mg(1)-O(3) bond lengths are 2.09 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra and corners with two equivalent Mg(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. Both V(1)-O(1) bond lengths are 1.76 Å. Both V(1)-O(2) bond lengths are 1.75 Å. In the second V site, V(2) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with six equivalent Co(1)O6 octahedra and  an edgeedge with one Mg(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-56°. Both V(2)-O(3) bond lengths are 1.83 Å. Both V(2)-O(4) bond lengths are 1.68 Å. Co(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Mg(1)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. The Co(1)-O(1) bond length is 2.13 Å. The Co(1)-O(4) bond length is 2.02 Å. Both Co(1)-O(2) bond lengths are 2.12 Å. Both Co(1)-O(3) bond lengths are 2.21 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mg(1), one V(1), and one Co(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Co(1) atoms. In the third O site, O(3) is bonded to one Mg(1), one V(2), and two equivalent Co(1) atoms to form distorted edge-sharing OMgVCo2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(2) and one Co(1) atom.