V3(OF3)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of corner and edge-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-49°. In the second V site, V(2) is bonded to two equivalent O(1), one F(1), one F(2), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 36-50°. O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.
V3(OF3)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of corner and edge-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-49°. Both V(1)-O(1) bond lengths are 2.06 Å. Both V(1)-F(1) bond lengths are 1.96 Å. Both V(1)-F(2) bond lengths are 1.98 Å. In the second V site, V(2) is bonded to two equivalent O(1), one F(1), one F(2), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 36-50°. There is one shorter (1.85 Å) and one longer (1.99 Å) V(2)-O(1) bond length. The V(2)-F(1) bond length is 1.98 Å. The V(2)-F(2) bond length is 1.97 Å. There is one shorter (1.98 Å) and one longer (2.02 Å) V(2)-F(3) bond length. O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.