MgV4(NiO6)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a distorted see-saw-like geometry to one O(11), one O(6), one O(8), and one O(9) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one V(4)O5 trigonal bipyramid, and corners with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-63°. In the second V site, V(2) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-45°. In the third V site, V(3) is bonded to one O(10), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one V(2)O5 trigonal bipyramid, and corners with two equivalent V(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-63°. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(2), one O(7), and one O(9) atom to form VO5 trigonal bipyramids that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-44°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(5) atom to form distorted NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra,  an edgeedge with one V(2)O5 trigonal bipyramid, and  an edgeedge with one V(4)O5 trigonal bipyramid. In the second Ni site, Ni(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(3), and one O(8) atom to form NiO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O5 trigonal bipyramids, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with two equivalent Ni(1)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one Ni(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one V(2), one Ni(1), and one Ni(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one Ni(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one Ni(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(3), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(3), one Ni(1), and one Ni(2) atom. In the eleventh O site, O(11) is bonded in a T-shaped geometry to one Mg(1), one V(4), and one Ni(2) atom. In the twelfth O site, O(12) is bonded in a trigonal non-coplanar geometry to one V(4), one Ni(1), and one Ni(2) atom.
MgV4(NiO6)2 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a distorted see-saw-like geometry to one O(11), one O(6), one O(8), and one O(9) atom. The Mg(1)-O(11) bond length is 2.03 Å. The Mg(1)-O(6) bond length is 1.99 Å. The Mg(1)-O(8) bond length is 2.03 Å. The Mg(1)-O(9) bond length is 2.00 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one V(4)O5 trigonal bipyramid, and corners with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-63°. The V(1)-O(1) bond length is 1.72 Å. The V(1)-O(2) bond length is 1.76 Å. The V(1)-O(4) bond length is 1.71 Å. The V(1)-O(6) bond length is 1.81 Å. In the second V site, V(2) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-45°. The V(2)-O(3) bond length is 1.77 Å. The V(2)-O(4) bond length is 2.00 Å. The V(2)-O(5) bond length is 2.09 Å. The V(2)-O(6) bond length is 1.98 Å. The V(2)-O(8) bond length is 1.78 Å. In the third V site, V(3) is bonded to one O(10), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one V(2)O5 trigonal bipyramid, and corners with two equivalent V(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-63°. The V(3)-O(10) bond length is 1.72 Å. The V(3)-O(5) bond length is 1.76 Å. The V(3)-O(7) bond length is 1.72 Å. The V(3)-O(9) bond length is 1.81 Å. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(2), one O(7), and one O(9) atom to form VO5 trigonal bipyramids that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-44°. The V(4)-O(11) bond length is 1.78 Å. The V(4)-O(12) bond length is 1.76 Å. The V(4)-O(2) bond length is 2.08 Å. The V(4)-O(7) bond length is 2.02 Å. The V(4)-O(9) bond length is 1.98 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(5) atom to form distorted NiO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, edges with two equivalent Ni(2)O6 octahedra,  an edgeedge with one V(2)O5 trigonal bipyramid, and  an edgeedge with one V(4)O5 trigonal bipyramid. The Ni(1)-O(1) bond length is 2.14 Å. The Ni(1)-O(10) bond length is 2.14 Å. The Ni(1)-O(12) bond length is 2.01 Å. The Ni(1)-O(2) bond length is 2.26 Å. The Ni(1)-O(3) bond length is 2.00 Å. The Ni(1)-O(5) bond length is 2.27 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(3), and one O(8) atom to form NiO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O5 trigonal bipyramids, corners with two equivalent V(4)O5 trigonal bipyramids, and edges with two equivalent Ni(1)O6 octahedra. The Ni(2)-O(1) bond length is 2.12 Å. The Ni(2)-O(10) bond length is 2.12 Å. The Ni(2)-O(11) bond length is 2.08 Å. The Ni(2)-O(12) bond length is 2.02 Å. The Ni(2)-O(3) bond length is 2.02 Å. The Ni(2)-O(8) bond length is 2.08 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one Ni(1), and one Ni(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one V(1), one V(4), and one Ni(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one V(2), one Ni(1), and one Ni(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one Ni(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Mg(1), one V(2), and one Ni(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mg(1), one V(3), and one V(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(3), one Ni(1), and one Ni(2) atom. In the eleventh O site, O(11) is bonded in a T-shaped geometry to one Mg(1), one V(4), and one Ni(2) atom. In the twelfth O site, O(12) is bonded in a trigonal non-coplanar geometry to one V(4), one Ni(1), and one Ni(2) atom.