CsNiF3 crystallizes in the hexagonal P6_3/mmc space group. Cs(1) is bonded to twelve equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Ni(1)F6 octahedra, faces with eight equivalent Cs(1)F12 cuboctahedra, and faces with six equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 12°. Ni(1) is bonded to six equivalent F(1) atoms to form NiF6 octahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, and faces with two equivalent Ni(1)F6 octahedra. F(1) is bonded in a 2-coordinate geometry to four equivalent Cs(1) and two equivalent Ni(1) atoms.
CsNiF3 crystallizes in the hexagonal P6_3/mmc space group. Cs(1) is bonded to twelve equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Ni(1)F6 octahedra, faces with eight equivalent Cs(1)F12 cuboctahedra, and faces with six equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles are 12°. There are six shorter (3.11 Å) and six longer (3.30 Å) Cs(1)-F(1) bond lengths. Ni(1) is bonded to six equivalent F(1) atoms to form NiF6 octahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, and faces with two equivalent Ni(1)F6 octahedra. All Ni(1)-F(1) bond lengths are 2.01 Å. F(1) is bonded in a 2-coordinate geometry to four equivalent Cs(1) and two equivalent Ni(1) atoms.