MgV2CoO6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(5), one O(6), and two equivalent O(2) atoms to form MgO5 trigonal bipyramids that share  a cornercorner with one V(2)O5 trigonal bipyramid, corners with two equivalent Mg(1)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent V(2)O5 trigonal bipyramids, and edges with two equivalent Co(1)O5 trigonal bipyramids. 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 Co(1)O5 trigonal bipyramid, corners with two equivalent Mg(1)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent V(2)O5 trigonal bipyramids, and edges with two equivalent Co(1)O5 trigonal bipyramids. 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)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, corners with two equivalent Co(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. Co(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, corners with two equivalent Co(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1), one V(2), and one Co(1) atom. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one Co(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Co(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Mg(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), and two equivalent Co(1) atoms.
MgV2CoO6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(5), one O(6), and two equivalent O(2) atoms to form MgO5 trigonal bipyramids that share  a cornercorner with one V(2)O5 trigonal bipyramid, corners with two equivalent Mg(1)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent V(2)O5 trigonal bipyramids, and edges with two equivalent Co(1)O5 trigonal bipyramids. The Mg(1)-O(1) bond length is 2.09 Å. The Mg(1)-O(5) bond length is 1.96 Å. The Mg(1)-O(6) bond length is 2.06 Å. There is one shorter (2.04 Å) and one longer (2.06 Å) Mg(1)-O(2) bond length. 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 Co(1)O5 trigonal bipyramid, corners with two equivalent Mg(1)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent V(2)O5 trigonal bipyramids, and edges with two equivalent Co(1)O5 trigonal bipyramids. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(3) bond length is 1.69 Å. The V(1)-O(6) bond length is 1.89 Å. There is one shorter (2.04 Å) and one longer (2.06 Å) V(1)-O(4) bond length. 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)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, corners with two equivalent Co(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The V(2)-O(2) bond length is 1.89 Å. The V(2)-O(4) bond length is 1.97 Å. The V(2)-O(5) bond length is 1.68 Å. Both V(2)-O(1) bond lengths are 2.06 Å. Co(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form distorted CoO5 trigonal bipyramids that share  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, corners with two equivalent Co(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The Co(1)-O(2) bond length is 2.09 Å. The Co(1)-O(3) bond length is 1.94 Å. The Co(1)-O(4) bond length is 2.12 Å. There is one shorter (2.01 Å) and one longer (2.11 Å) Co(1)-O(6) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1), one V(2), and one Co(1) atom. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one Co(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Co(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Mg(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Mg(1), one V(1), and two equivalent Co(1) atoms.