NiAlF5 crystallizes in the orthorhombic Immm space group. Ni(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NiF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and edges with two equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-55°. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with six equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-55°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Ni(1) and one Al(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Ni(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms. In the fourth F site, F(1) is bonded in a trigonal planar geometry to two equivalent Ni(1) and one Al(1) atom.
NiAlF5 crystallizes in the orthorhombic Immm space group. Ni(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NiF6 octahedra that share corners with six equivalent Al(1)F6 octahedra and edges with two equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-55°. Both Ni(1)-F(2) bond lengths are 1.93 Å. All Ni(1)-F(1) bond lengths are 2.17 Å. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with six equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-55°. Both Al(1)-F(1) bond lengths are 1.85 Å. Both Al(1)-F(2) bond lengths are 1.79 Å. Both Al(1)-F(3) bond lengths are 1.76 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Ni(1) and one Al(1) atom. In the second F site, F(2) is bonded in a linear geometry to one Ni(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms. In the fourth F site, F(1) is bonded in a trigonal planar geometry to two equivalent Ni(1) and one Al(1) atom. Both F(1)-Ni(1) bond lengths are 2.17 Å. The F(1)-Al(1) bond length is 1.85 Å.