Starting generally with a 4:6:3 molar ratio of Pt, Sn, and (where = La-Sm), with or without the application of a NaCl flux, seven ternary compounds were obtained as single crystals. The platinides PtSnR ( = La-Nd) crystallize with the PtGePr type of structure (52, , = 27.6-27.8 Å, = 4.59-4.64 Å, = 9.33-9.40 Å). With = Pr, PtSnPr (52, , = 7.2863(3) Å, = 4.4909(2) Å, = 35.114(1) Å) is also obtained, which might be considered a high-temperature polymorph with disorder on the Sn- and Pr-sites. For = Nd and Sm, a structurally related isostructural series with a slightly different composition PtSn (52, 2, = 4.50-4.51 Å, = 26.14-26.30 Å, ≈ 7.29 Å) has been observed, together with PtSnSm (42, 2, = 4.3289(5) Å, = 28.798(4) Å, = 7.2534(9) Å) under the same conditions. The latter exhibits the rare ZrPdP-type structure, linking polar intermetallics to metal phosphides, in accord with PPdZr≡PtSnSm. All structures may be described in terms of either negative Pt/Sn networks encapsulating positive atoms, or {PtSn} clusters ( = 5, 6, or rarely 7) sharing vertices and edges with in the second coordination sphere and with considerable heterometallic Pt- bonding contributions.
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| http://dx.doi.org/10.1021/acs.inorgchem.0c00884 | DOI Listing |
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