V3(OF3)2 crystallizes in the monoclinic Pc space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(5), and one F(6) atom to form a mixture of edge and corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. In the second V site, V(2) is bonded to one O(1), one O(2), one F(1), one F(3), one F(4), and one F(5) atom to form a mixture of edge and corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-50°. In the third V site, V(3) is bonded to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(6) atom to form a mixture of edge and corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-52°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. There are six 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(3) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth F site, F(5) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom.
V3(OF3)2 crystallizes in the monoclinic Pc space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(1), one F(2), one F(5), and one F(6) atom to form a mixture of edge and corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. The V(1)-O(1) bond length is 2.09 Å. The V(1)-O(2) bond length is 2.03 Å. The V(1)-F(1) bond length is 1.98 Å. The V(1)-F(2) bond length is 1.98 Å. The V(1)-F(5) bond length is 2.01 Å. The V(1)-F(6) bond length is 1.96 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one F(1), one F(3), one F(4), and one F(5) atom to form a mixture of edge and corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-50°. The V(2)-O(1) bond length is 1.78 Å. The V(2)-O(2) bond length is 1.92 Å. The V(2)-F(1) bond length is 1.97 Å. The V(2)-F(3) bond length is 2.02 Å. The V(2)-F(4) bond length is 1.98 Å. The V(2)-F(5) bond length is 1.95 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(6) atom to form a mixture of edge and corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 35-52°. The V(3)-O(1) bond length is 2.09 Å. The V(3)-O(2) bond length is 1.96 Å. The V(3)-F(2) bond length is 1.98 Å. The V(3)-F(3) bond length is 1.99 Å. The V(3)-F(4) bond length is 2.01 Å. The V(3)-F(6) bond length is 2.00 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. There are six 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(3) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth F site, F(5) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom.