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Synthesis and Crystal Structure of the Partially Oxidized Cyanoplatinates Rb1.75[Pt(CN)4]•1.25H2O and Cs1.75[Pt(CN)4]•0.5H2O

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Mühle,  C.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;
Department Quantum Materials (Hidenori Takagi), Max Planck Institute for Solid State Research, Max Planck Society;

/persons/resource/persons280350

Nuss,  J.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;
Department Quantum Materials (Hidenori Takagi), Max Planck Institute for Solid State Research, Max Planck Society;

/persons/resource/persons280091

Jansen,  M.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;

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Citation

Mühle, C., Nuss, J., & Jansen, M. (2013). Synthesis and Crystal Structure of the Partially Oxidized Cyanoplatinates Rb1.75[Pt(CN)4]•1.25H2O and Cs1.75[Pt(CN)4]•0.5H2O. Zeitschrift für anorganische und allgemeine Chemie, 639(3-4), 479-484.


Cite as: https://hdl.handle.net/21.11116/0000-000E-C587-B
Abstract
Crystal structures of partially oxidized cyanoplatinates were determined by single crystal analysis. Rb1.75[Pt(CN)4]center dot 1.25H2O crystallizes monoclinic in the space group P21/c [a = 1171.4(2) pm, b = 3315.3(6) pm, c = 1054.4(2) pm, = 114.253(2)degrees, V = 3733.2(11)center dot 106 pm3, Z = 16, Ntotal = 31567, R(F)N = 0.0858]. The compound was obtained by mixing aqueous solutions of Rb2[Pt(CN)4]center dot 1.5H2O and Rb2[Pt(CN)4]Br2. Cs1.75[Pt(CN)4]center dot 0.5H2O 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)center dot 106 pm3, Z = 4, Ntotal = 5997, R(F)N = 0.0807]. Crystals of the latter were grown by slow electrochemical oxidation of Cs2[Pt(CN)4]center dot H2O 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 PtPt distances of 292 and 294 pm, the cesium compound crystallizes more symmetrically with PtPt distances of c/2 = 290 pm. The two compounds were also characterized by differential thermal analysis, thermogravimetry, infrared, and Raman spectroscopy.