MgNb2V2O10 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted MgO5 trigonal bipyramids that share  a cornercorner with one Nb(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Nb(2)O6 octahedra, and  a faceface with one Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(10), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form distorted NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, and  a faceface with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 20°. In the second Nb site, Nb(2) is bonded to one O(1), one O(5), one O(7), one O(9), and two equivalent O(8) atoms to form distorted NbO6 octahedra that share corners with two equivalent Nb(2)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 12°. There are two 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(5) atom to form VO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-42°. In the second V site, V(2) is bonded to one O(10), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-42°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Nb(2) and one V(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Nb(1) and one V(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1) and two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one Nb(1), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Mg(1), one Nb(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one Nb(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Mg(1), one Nb(2), and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to two equivalent Nb(2) atoms. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Nb(2) and one V(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Nb(1) and one V(2) atom.
MgNb2V2O10 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted MgO5 trigonal bipyramids that share  a cornercorner with one Nb(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Nb(2)O6 octahedra, and  a faceface with one Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 62°. The Mg(1)-O(3) bond length is 2.16 Å. The Mg(1)-O(4) bond length is 2.03 Å. The Mg(1)-O(5) bond length is 2.02 Å. The Mg(1)-O(6) bond length is 2.02 Å. The Mg(1)-O(7) bond length is 2.03 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(10), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form distorted NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, and  a faceface with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 20°. The Nb(1)-O(10) bond length is 1.91 Å. The Nb(1)-O(2) bond length is 1.91 Å. The Nb(1)-O(4) bond length is 2.14 Å. The Nb(1)-O(6) bond length is 2.15 Å. There is one shorter (1.86 Å) and one longer (2.32 Å) Nb(1)-O(3) bond length. In the second Nb site, Nb(2) is bonded to one O(1), one O(5), one O(7), one O(9), and two equivalent O(8) atoms to form distorted NbO6 octahedra that share corners with two equivalent Nb(2)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 12°. The Nb(2)-O(1) bond length is 1.93 Å. The Nb(2)-O(5) bond length is 2.17 Å. The Nb(2)-O(7) bond length is 2.15 Å. The Nb(2)-O(9) bond length is 1.93 Å. There is one shorter (1.85 Å) and one longer (2.29 Å) Nb(2)-O(8) bond length. There are two 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(5) atom to form VO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-42°. The V(1)-O(1) bond length is 1.83 Å. The V(1)-O(2) bond length is 1.82 Å. The V(1)-O(4) bond length is 1.81 Å. The V(1)-O(5) bond length is 1.81 Å. In the second V site, V(2) is bonded to one O(10), one O(6), one O(7), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-42°. The V(2)-O(10) bond length is 1.83 Å. The V(2)-O(6) bond length is 1.81 Å. The V(2)-O(7) bond length is 1.81 Å. The V(2)-O(9) bond length is 1.82 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Nb(2) and one V(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Nb(1) and one V(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mg(1) and two equivalent Nb(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), one Nb(1), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Mg(1), one Nb(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mg(1), one Nb(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Mg(1), one Nb(2), and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to two equivalent Nb(2) atoms. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Nb(2) and one V(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Nb(1) and one V(2) atom.