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Synthesis and Crystal Structure of the Partially Oxidized Cyanoplatinates Rb 1.75 [Pt(CN) 4 ]·1.25H 2 O and Cs 1.75 [Pt(CN) 4 ]·0.5H 2 O
Author(s) -
Mühle Claus,
Nuss Jürgen,
Jansen Martin
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200543
Subject(s) - platinum , monoclinic crystal system , chemistry , crystallography , aqueous solution , crystal structure , single crystal , raman spectroscopy , stereochemistry , catalysis , physics , optics , biochemistry
Abstract Crystal structures of partially oxidized cyanoplatinates were determined by single crystal analysis. Rb 1.75 [Pt(CN) 4 ] · 1.25H 2 O crystallizes monoclinic in the space group P 2 1 / c [ a = 1171.4(2) pm, b = 3315.3(6) pm, c = 1054.4(2) pm, β = 114.253(2)°, V = 3733.2(11) · 10 6 pm 3 , Z = 16, N total = 31567, R (F) N = 0.0858]. The compound was obtained by mixing aqueous solutions of Rb 2 [Pt(CN) 4 ] · 1.5H 2 O and Rb 2 [Pt(CN) 4 ]Br 2 . Cs 1.75 [Pt(CN) 4 ] · 0.5H 2 O crystallizes in the space group Ibam [ a = 1266.1(3) pm, b = 1347.5(3) pm, c = 580.4(1) pm, V = 990.2(3) · 10 6 pm 3 , Z = 4, N total = 5997, R (F) N = 0.0807]. Crystals of the latter were grown by slow electrochemical oxidation of Cs 2 [Pt(CN) 4 ] · H 2 O in aqueous solution using platinum wires as electrodes. In both compounds platinum is partially oxidized to Pt +2.25 and the nearly square‐planar tetracyanoplatinate groups are arranged to columns in a staggered conformation. The rubidium compound features a large unit cell with nonlinear chains of platinum atoms and short alternating Pt–Pt distances of 292 and 294 pm, the cesium compound crystallizes more symmetrically with Pt–Pt distances of c /2 = 290 pm. The two compounds were also characterized by differential thermal analysis, thermogravimetry, infrared, and Raman spectroscopy.