VH6(OF)3 crystallizes in the monoclinic Cm space group. There are four inequivalent V sites. In the first V site, V(1) is bonded in an octahedral geometry to one O(7), two equivalent O(2), one F(6), and two equivalent F(3) atoms. In the second V site, V(2) is bonded in an octahedral geometry to one O(8), two equivalent O(3), one F(7), and two equivalent F(4) atoms. In the third V site, V(3) is bonded in an octahedral geometry to one O(5), two equivalent O(4), one F(8), and two equivalent F(1) atoms. In the fourth V site, V(4) is bonded in an octahedral geometry to one O(6), two equivalent O(1), one F(5), and two equivalent F(2) atoms. There are eleven inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(5) and one F(1) atom. In the second H site, H(2,4) is bonded in a distorted single-bond geometry to one O(6) and one F(2) atom. In the third H site, H(3) is bonded in a distorted single-bond geometry to one O(7) and one F(3) atom. In the fourth H site, H(5) is bonded in a distorted single-bond geometry to one O(1) and one F(5) atom. In the fifth H site, H(6) is bonded in a distorted single-bond geometry to one O(2) and one F(6) atom. In the sixth H site, H(7) is bonded in a distorted single-bond geometry to one O(3) and one F(7) atom. In the seventh H site, H(8) is bonded in a distorted linear geometry to one O(4) and one F(8) atom. In the eighth H site, H(9) is bonded in a distorted single-bond geometry to one O(1) and one F(1) atom. In the ninth H site, H(10) is bonded in a distorted linear geometry to one O(2) and one F(2) atom. In the tenth H site, H(11) is bonded in a distorted single-bond geometry to one O(3) and one F(3) atom. In the eleventh H site, H(12) is bonded in a distorted linear geometry to one O(4) and one F(4) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(4), one H(5), and one H(9) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one H(10), and one H(6) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one H(11), and one H(7) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3), one H(12), and one H(8) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent H(1) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(4) and two equivalent H(2,4) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent H(3) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent H(2,4) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(3), one H(1), and one H(9) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one V(4); one H(10); and one H(2,4) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one V(1), one H(11), and one H(3) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(2); one H(12); and one H(2,4) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one V(4) and two equivalent H(5) atoms. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one V(1) and two equivalent H(6) atoms. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one V(2) and two equivalent H(7) atoms. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one V(3) and two equivalent H(8) atoms.
VH6(OF)3 crystallizes in the monoclinic Cm space group. There are four inequivalent V sites. In the first V site, V(1) is bonded in an octahedral geometry to one O(7), two equivalent O(2), one F(6), and two equivalent F(3) atoms. The V(1)-O(7) bond length is 2.04 Å. Both V(1)-O(2) bond lengths are 2.04 Å. The V(1)-F(6) bond length is 1.98 Å. Both V(1)-F(3) bond lengths are 1.98 Å. In the second V site, V(2) is bonded in an octahedral geometry to one O(8), two equivalent O(3), one F(7), and two equivalent F(4) atoms. The V(2)-O(8) bond length is 2.04 Å. Both V(2)-O(3) bond lengths are 2.04 Å. The V(2)-F(7) bond length is 1.98 Å. Both V(2)-F(4) bond lengths are 1.98 Å. In the third V site, V(3) is bonded in an octahedral geometry to one O(5), two equivalent O(4), one F(8), and two equivalent F(1) atoms. The V(3)-O(5) bond length is 2.04 Å. Both V(3)-O(4) bond lengths are 2.04 Å. The V(3)-F(8) bond length is 1.98 Å. Both V(3)-F(1) bond lengths are 1.98 Å. In the fourth V site, V(4) is bonded in an octahedral geometry to one O(6), two equivalent O(1), one F(5), and two equivalent F(2) atoms. The V(4)-O(6) bond length is 2.04 Å. Both V(4)-O(1) bond lengths are 2.04 Å. The V(4)-F(5) bond length is 1.98 Å. Both V(4)-F(2) bond lengths are 1.98 Å. There are eleven inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one O(5) and one F(1) atom. The H(1)-O(5) bond length is 1.00 Å. The H(1)-F(1) bond length is 1.60 Å. In the second H site, H(2,4) is bonded in a distorted single-bond geometry to one O(6) and one F(2) atom. The H(2,4)-O(6) bond length is 1.00 Å. The H(2,4)-F(2) bond length is 1.60 Å. In the third H site, H(3) is bonded in a distorted single-bond geometry to one O(7) and one F(3) atom. The H(3)-O(7) bond length is 1.00 Å. The H(3)-F(3) bond length is 1.60 Å. In the fourth H site, H(5) is bonded in a distorted single-bond geometry to one O(1) and one F(5) atom. The H(5)-O(1) bond length is 1.00 Å. The H(5)-F(5) bond length is 1.60 Å. In the fifth H site, H(6) is bonded in a distorted single-bond geometry to one O(2) and one F(6) atom. The H(6)-O(2) bond length is 1.00 Å. The H(6)-F(6) bond length is 1.60 Å. In the sixth H site, H(7) is bonded in a distorted single-bond geometry to one O(3) and one F(7) atom. The H(7)-O(3) bond length is 1.00 Å. The H(7)-F(7) bond length is 1.60 Å. In the seventh H site, H(8) is bonded in a distorted linear geometry to one O(4) and one F(8) atom. The H(8)-O(4) bond length is 1.00 Å. The H(8)-F(8) bond length is 1.60 Å. In the eighth H site, H(9) is bonded in a distorted single-bond geometry to one O(1) and one F(1) atom. The H(9)-O(1) bond length is 1.00 Å. The H(9)-F(1) bond length is 1.61 Å. In the ninth H site, H(10) is bonded in a distorted linear geometry to one O(2) and one F(2) atom. The H(10)-O(2) bond length is 1.00 Å. The H(10)-F(2) bond length is 1.59 Å. In the tenth H site, H(11) is bonded in a distorted single-bond geometry to one O(3) and one F(3) atom. The H(11)-O(3) bond length is 1.00 Å. The H(11)-F(3) bond length is 1.61 Å. In the eleventh H site, H(12) is bonded in a distorted linear geometry to one O(4) and one F(4) atom. The H(12)-O(4) bond length is 1.00 Å. The H(12)-F(4) bond length is 1.59 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(4), one H(5), and one H(9) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one H(10), and one H(6) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one H(11), and one H(7) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3), one H(12), and one H(8) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent H(1) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(4) and two equivalent H(2,4) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent H(3) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent H(2,4) atoms. Both O(8)-H(2,4) bond lengths are 1.00 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(3), one H(1), and one H(9) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one V(4); one H(10); and one H(2,4) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one V(1), one H(11), and one H(3) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(2); one H(12); and one H(2,4) atom. The F(4)-H(2,4) bond length is 1.60 Å. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one V(4) and two equivalent H(5) atoms. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one V(1) and two equivalent H(6) atoms. In the seventh F site, F(7) is bonded in a trigonal planar geometry to one V(2) and two equivalent H(7) atoms. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one V(3) and two equivalent H(8) atoms.