ZnPCl₇: a compositionally and structurally unprecedented metal-phospho-rus halide.

Area of Science:

• Solid-state chemistry
• Inorganic chemistry
• Crystallography

Background:

• Mixed-metal halides represent a diverse class of compounds with varied structural motifs.
• Understanding the synthesis and structure of novel compounds is crucial for expanding chemical knowledge.

Purpose of the Study:

• To report the synthesis and crystal structure of a new compound, zinc phosphorus hepta-chloride (ZnPCl7).
• To characterize the structural features and bonding in ZnPCl7.

Main Methods:

• Single crystal X-ray diffraction was employed to determine the crystal structure.
• The synthesis involved reacting zinc chloride (ZnCl2) with phosphorus pentachloride (PCl5) at elevated temperatures.
• Bond-valence sum calculations were used to support oxidation state assignments.

Main Results:

• A novel compound, formulated as zinc phosphorus hepta-chloride (ZnPCl7) or {[PCl4][ZnCl3]}n, was successfully synthesized.
• ZnPCl7 crystallizes in the orthorhombic space group Ama2, featuring isolated [PCl4]+ tetrahedra and one-dimensional chains of corner-sharing ZnCl4 tetrahedra.
• Specific atomic positions and crystallographic symmetry elements were identified.

Conclusions:

• The study reports an unprecedented compound, ZnPCl7, with a unique extended structure.
• The findings contribute to the understanding of mixed-metal halide chemistry and structural diversity.
• The results highlight the potential for novel structures in reactions between metal chlorides and non-metal chlorides.