MgV4(O3F2)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MgO6 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(1)O3F2 trigonal bipyramids, edges with two equivalent V(1)O3F2 trigonal bipyramids, and faces with two equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles are 40°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), one F(1), and one F(2) atom to form distorted VO3F2 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with five equivalent V(2)O4F2 octahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one V(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-57°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), one F(1), and one F(2) atom to form distorted VO4F2 octahedra that share  a cornercorner with one Mg(1)O6 octahedra, corners with five equivalent V(1)O3F2 trigonal bipyramids,  an edgeedge with one V(2)O4F2 octahedra, and  a faceface with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles are 40°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OMgV3 trigonal pyramids. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom.
MgV4(O3F2)2 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MgO6 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent V(1)O3F2 trigonal bipyramids, edges with two equivalent V(1)O3F2 trigonal bipyramids, and faces with two equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles are 40°. Both Mg(1)-O(1) bond lengths are 2.05 Å. Both Mg(1)-O(2) bond lengths are 2.03 Å. Both Mg(1)-O(3) bond lengths are 2.08 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), one F(1), and one F(2) atom to form distorted VO3F2 trigonal bipyramids that share  a cornercorner with one Mg(1)O6 octahedra, corners with five equivalent V(2)O4F2 octahedra,  an edgeedge with one Mg(1)O6 octahedra, and  an edgeedge with one V(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-57°. The V(1)-O(3) bond length is 1.71 Å. There is one shorter (1.90 Å) and one longer (2.05 Å) V(1)-O(1) bond length. The V(1)-F(1) bond length is 1.97 Å. The V(1)-F(2) bond length is 1.92 Å. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), one F(1), and one F(2) atom to form distorted VO4F2 octahedra that share  a cornercorner with one Mg(1)O6 octahedra, corners with five equivalent V(1)O3F2 trigonal bipyramids,  an edgeedge with one V(2)O4F2 octahedra, and  a faceface with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles are 40°. The V(2)-O(1) bond length is 2.29 Å. The V(2)-O(3) bond length is 2.24 Å. There is one shorter (1.88 Å) and one longer (1.97 Å) V(2)-O(2) bond length. The V(2)-F(1) bond length is 2.02 Å. The V(2)-F(2) bond length is 2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OMgV3 trigonal pyramids. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom.