MgV2CoO6 crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form distorted MgO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra,  a cornercorner with one V(1)O5 trigonal bipyramid,  a cornercorner with one V(2)O5 trigonal bipyramid,  an edgeedge with one V(2)O5 trigonal bipyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 32°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(6), and two equivalent O(4) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), and two equivalent O(1) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with two equivalent V(2)O5 trigonal bipyramids,  an edgeedge with one Mg(1)O6 octahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 37°. Co(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(5) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded to one V(1), two equivalent V(2), and one Co(1) atom to form distorted OV3Co trigonal pyramids that share corners with two equivalent O(6)Mg2VCo trigonal pyramids, corners with two equivalent O(1)V3Co trigonal pyramids, edges with two equivalent O(4)MgV3 trigonal pyramids, and edges with two equivalent O(5)MgVCo2 trigonal pyramids. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one Co(1) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one Co(1) atom. In the fourth O site, O(4) is bonded to one Mg(1), one V(2), and two equivalent V(1) atoms to form distorted OMgV3 trigonal pyramids that share corners with two equivalent O(4)MgV3 trigonal pyramids, corners with two equivalent O(5)MgVCo2 trigonal pyramids, edges with two equivalent O(6)Mg2VCo trigonal pyramids, and edges with two equivalent O(1)V3Co trigonal pyramids. In the fifth O site, O(5) is bonded to one Mg(1), one V(2), and two equivalent Co(1) atoms to form OMgVCo2 trigonal pyramids that share corners with two equivalent O(4)MgV3 trigonal pyramids, corners with two equivalent O(5)MgVCo2 trigonal pyramids, edges with two equivalent O(6)Mg2VCo trigonal pyramids, and edges with two equivalent O(1)V3Co trigonal pyramids. In the sixth O site, O(6) is bonded to two equivalent Mg(1), one V(1), and one Co(1) atom to form distorted OMg2VCo trigonal pyramids that share corners with two equivalent O(6)Mg2VCo trigonal pyramids, corners with two equivalent O(1)V3Co trigonal pyramids, edges with two equivalent O(4)MgV3 trigonal pyramids, and edges with two equivalent O(5)MgVCo2 trigonal pyramids.
MgV2CoO6 crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form distorted MgO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra,  a cornercorner with one V(1)O5 trigonal bipyramid,  a cornercorner with one V(2)O5 trigonal bipyramid,  an edgeedge with one V(2)O5 trigonal bipyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 32°. The Mg(1)-O(2) bond length is 2.30 Å. The Mg(1)-O(3) bond length is 2.02 Å. The Mg(1)-O(4) bond length is 2.31 Å. The Mg(1)-O(5) bond length is 2.22 Å. Both Mg(1)-O(6) bond lengths are 1.99 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(6), and two equivalent O(4) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°. The V(1)-O(1) bond length is 1.96 Å. The V(1)-O(3) bond length is 1.73 Å. The V(1)-O(6) bond length is 1.87 Å. Both V(1)-O(4) bond lengths are 2.00 Å. In the second V site, V(2) is bonded to one O(2), one O(4), one O(5), and two equivalent O(1) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with two equivalent V(2)O5 trigonal bipyramids,  an edgeedge with one Mg(1)O6 octahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 37°. The V(2)-O(2) bond length is 1.72 Å. The V(2)-O(4) bond length is 1.98 Å. The V(2)-O(5) bond length is 1.89 Å. Both V(2)-O(1) bond lengths are 2.00 Å. Co(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(5) atoms. The Co(1)-O(1) bond length is 2.44 Å. The Co(1)-O(2) bond length is 2.03 Å. The Co(1)-O(3) bond length is 2.16 Å. The Co(1)-O(6) bond length is 2.29 Å. Both Co(1)-O(5) bond lengths are 2.02 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one V(1), two equivalent V(2), and one Co(1) atom to form distorted OV3Co trigonal pyramids that share corners with two equivalent O(6)Mg2VCo trigonal pyramids, corners with two equivalent O(1)V3Co trigonal pyramids, edges with two equivalent O(4)MgV3 trigonal pyramids, and edges with two equivalent O(5)MgVCo2 trigonal pyramids. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one Co(1) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one Co(1) atom. In the fourth O site, O(4) is bonded to one Mg(1), one V(2), and two equivalent V(1) atoms to form distorted OMgV3 trigonal pyramids that share corners with two equivalent O(4)MgV3 trigonal pyramids, corners with two equivalent O(5)MgVCo2 trigonal pyramids, edges with two equivalent O(6)Mg2VCo trigonal pyramids, and edges with two equivalent O(1)V3Co trigonal pyramids. In the fifth O site, O(5) is bonded to one Mg(1), one V(2), and two equivalent Co(1) atoms to form OMgVCo2 trigonal pyramids that share corners with two equivalent O(4)MgV3 trigonal pyramids, corners with two equivalent O(5)MgVCo2 trigonal pyramids, edges with two equivalent O(6)Mg2VCo trigonal pyramids, and edges with two equivalent O(1)V3Co trigonal pyramids. In the sixth O site, O(6) is bonded to two equivalent Mg(1), one V(1), and one Co(1) atom to form distorted OMg2VCo trigonal pyramids that share corners with two equivalent O(6)Mg2VCo trigonal pyramids, corners with two equivalent O(1)V3Co trigonal pyramids, edges with two equivalent O(4)MgV3 trigonal pyramids, and edges with two equivalent O(5)MgVCo2 trigonal pyramids.