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PdF3 crystallizes in the trigonal R-3c space group. The structure is three-dimensional. Pd is bonded to six equivalent F atoms to form corner-sharing PdF6 octahedra. The corner-sharing octahedral tilt angles are 42°. All Pd–F bond lengths are 2.05 Å. F is bonded in a bent 150 degrees geometry to two equivalent Pd atoms.
PdF3 crystallizes in the trigonal P321 space group. The structure is three-dimensional. there are two inequivalent Pd sites. In the first Pd site, Pd is bonded to six F atoms to form corner-sharing PdF6 octahedra. The corner-sharing octahedra tilt angles range from 26–35°. There are three shorter (1.99 Å) and three longer (2.04 Å) Pd–F bond lengths. In the second Pd site, Pd is bonded to six equivalent F atoms to form distorted corner-sharing PdF6 octahedra. The corner-sharing octahedral tilt angles are 26°. All Pd–F bond lengths are 2.10 Å. There are two inequivalent F sites. In the first F site, F is bonded in a bent 150 degrees geometry to two Pd atoms. In the second F site, F is bonded in a bent 150 degrees geometry to two equivalent Pd atoms.