Received 15 October 2012
The silver zinc hexadecaphosphide Ag3.73(4)Zn2.27(4)P16 is the first polyphosphide in the ternary system Ag/Zn/P. It was synthesized from stoichiometric mixtures of Ag, Zn and P in the molar ratio 4:2:16, using AgI as a mineralizing agent in a gas-phase-assisted reaction. Ag3.73(4)Zn2.27(4)P16 crystallizes in the Cu5InP16 structure type. The asymmetric unit contains two Ag/Zn sites with mixed occupancies and four P sites. One of the Ag/Zn sites is located on a twofold rotation axis. The polyanionic [P16]-substructure consists of corrugated six-membered rings that are connected into a layer via the 1-, 2-, 4- and 5-positions of the rings by a bridging P atom in each case. The layers extend parallel to the bc plane and are stacked along the a axis. Both Ag/Zn sites are tetrahedrally coordinated by P atoms.
For background to and structures of related polyphosphides, see: Bawohl & Nilges (2009); Dommann et al. (1989); Edmunds & Qurashi (1951); Lange et al. (2008); Möller & Jeitschko (1981); Olofsson (1965); Zanin et al. (2003). For background to the extinction correction, see: Becker & Coppens (1974).
Data collection: X-AREA (Stoe & Cie, 2011); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petricek et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2694 ).
The authors thank the German Science Foundation (DFG) for the kind support of project NI1095/1-2.
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