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(2)O2F4 octahedra, corners with two equivalent Hf(3)O4F2 octahedra, and corners with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-49°. In the second Hf site, Hf(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form HfO2F4 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra, corners with two equivalent Hf(3)O4F2 octahedra, and corners with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-57°. In the third Hf site, Hf(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(3) atoms to form HfO4F2 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra, corners with two equivalent Hf(2)O2F4 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra, corners with two equivalent Hf(2)O2F4 octahedra, and edges with two equivalent Hf(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-57°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Hf(2), one Hf(3), and one Ni(1) atom. In the second O site, O(2) is bonded in a water-like geometry to one Hf(3) and one Ni(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Hf(1) and one Ni(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Hf(1) and one Hf(2) atom. In the second F site, F(2) is bonded in a single-bond geometry to one Hf(2) atom. In the third F site, F(3) is bonded in a bent 150 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(2)O2F4 octahedra, corners with two equivalent Hf(3)O4F2 octahedra, and corners with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-49°. Both Hf(1)-O(3) bond lengths are 1.98 Å. Both Hf(1)-F(1) bond lengths are 2.09 Å. Both Hf(1)-F(3) bond lengths are 2.07 Å. In the second Hf site, Hf(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form HfO2F4 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra, corners with two equivalent Hf(3)O4F2 octahedra, and corners with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-57°. Both Hf(2)-O(1) bond lengths are 2.13 Å. Both Hf(2)-F(1) bond lengths are 2.10 Å. Both Hf(2)-F(2) bond lengths are 1.95 Å. In the third Hf site, Hf(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(3) atoms to form HfO4F2 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra, corners with two equivalent Hf(2)O2F4 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. Both Hf(3)-O(1) bond lengths are 2.09 Å. Both Hf(3)-O(2) bond lengths are 2.02 Å. Both Hf(3)-F(3) bond lengths are 2.10 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Hf(1)O2F4 octahedra, corners with two equivalent Hf(2)O2F4 octahedra, and edges with two equivalent Hf(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-57°. Both Ni(1)-O(1) bond lengths are 1.91 Å. Both Ni(1)-O(2) bond lengths are 1.84 Å. Both Ni(1)-O(3) bond lengths are 1.84 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Hf(2), one Hf(3), and one Ni(1) atom. In the second O site, O(2) is bonded in a water-like geometry to one Hf(3) and one Ni(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Hf(1) and one Ni(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Hf(1) and one Hf(2) atom. In the second F site, F(2) is bonded in a single-bond geometry to one Hf(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Hf(1) and one Hf(3) atom.