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The layered polyphosphide Ag3.73(4)Zn2.27(4)P16.

Marianne Köpf¹, Oliver Osters, Melanie Bawohl

¹Technische Universität München, Department Chemie, Lichtenbergstrasse 4, 85747 Garching bei München, Germany.

Acta Crystallographica. Section E, Structure Reports Online

|March 8, 2013

Summary

Researchers synthesized the novel silver zinc hexa-deca-phosphide (Ag3.73(4)Zn2.27(4)P16), the first polyphosphide in the Ag/Zn/P system. This compound features a unique layered [P16] substructure with mixed silver-zinc occupancies.

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Area of Science:

Solid-state chemistry
Inorganic materials science
Crystallography

Background:

The ternary system Ag/Zn/P is underexplored for novel phosphide compounds.
Polyphosphides offer unique structural motifs and potential electronic properties.

Purpose of the Study:

To synthesize and characterize a new polyphosphide in the Ag/Zn/P ternary system.
To elucidate the crystal structure and bonding of the novel compound.

Main Methods:

Synthesis via gas-phase-assisted reaction using AgI as a mineralizing agent.
Stoichiometric mixtures of silver (Ag), zinc (Zn), and phosphorus (P) in a 4:2:16 molar ratio.
Single-crystal X-ray diffraction for structural determination.

Main Results:

The first polyphosphide, Ag3.73(4)Zn2.27(4)P16, was successfully synthesized.
The compound crystallizes in the Cu5InP16 structure type.
A polyanionic [P16] substructure with corrugated six-membered rings arranged in layers parallel to the bc plane was identified.
Two Ag/Zn sites with mixed occupancies and tetrahedral coordination by phosphorus atoms were observed.

Conclusions:

Ag3.73(4)Zn2.27(4)P16 represents a new structural type in ternary silver-zinc phosphides.
The layered [P16] substructure highlights the diversity of polyphosphide frameworks.
The mixed occupancy of Ag/Zn sites provides insights into cation distribution in these materials.