Hf3Ni(OF)6 crystallizes in the triclinic P-1 space group. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(3) atoms to form HfO2F4 octahedra that share corners with two equivalent Hf(3)O2F4 octahedra and corners with two equivalent Hf(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-67°. In the second Hf site, Hf(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(2) atoms to form corner-sharing HfO4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-64°. In the third Hf site, Hf(3) is bonded to two equivalent O(2), two equivalent F(2), and two equivalent F(3) atoms to form HfO2F4 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra and corners with two equivalent Hf(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. Ni(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Hf(2) and one Ni(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Hf(3), one Ni(1), and one O(3) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Hf(1), one Hf(2), and one O(2) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one Hf(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Hf(2) and one Hf(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Hf(1) and one Hf(3) atom.
Hf3Ni(OF)6 crystallizes in the triclinic P-1 space group. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(3) atoms to form HfO2F4 octahedra that share corners with two equivalent Hf(3)O2F4 octahedra and corners with two equivalent Hf(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-67°. Both Hf(1)-O(3) bond lengths are 2.17 Å. Both Hf(1)-F(1) bond lengths are 1.92 Å. Both Hf(1)-F(3) bond lengths are 2.11 Å. In the second Hf site, Hf(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(2) atoms to form corner-sharing HfO4F2 octahedra. The corner-sharing octahedral tilt angles range from 36-64°. Both Hf(2)-O(1) bond lengths are 1.94 Å. Both Hf(2)-O(3) bond lengths are 2.26 Å. Both Hf(2)-F(2) bond lengths are 2.15 Å. In the third Hf site, Hf(3) is bonded to two equivalent O(2), two equivalent F(2), and two equivalent F(3) atoms to form HfO2F4 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra and corners with two equivalent Hf(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. Both Hf(3)-O(2) bond lengths are 2.09 Å. Both Hf(3)-F(2) bond lengths are 2.04 Å. Both Hf(3)-F(3) bond lengths are 2.10 Å. Ni(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Ni(1)-O(1) bond lengths are 1.83 Å. Both Ni(1)-O(2) bond lengths are 2.17 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Hf(2) and one Ni(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Hf(3), one Ni(1), and one O(3) atom. The O(2)-O(3) bond length is 1.51 Å. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Hf(1), one Hf(2), and one O(2) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one Hf(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Hf(2) and one Hf(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Hf(1) and one Hf(3) atom.