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Azidoaurates of the Alkali Metals
Author(s) -
Afyon Semih,
Höhn Peter,
Armbrüster Marc,
Baranov Alexey,
Wagner Frank R.,
Somer Mehmet,
Kniep Rüdiger
Publication year - 2006
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.200600062
Subject(s) - raman spectroscopy , monoclinic crystal system , ternary operation , alkali metal , chemistry , crystal structure , crystallography , aqueous solution , x ray crystallography , inorganic chemistry , analytical chemistry (journal) , diffraction , organic chemistry , programming language , physics , computer science , optics
Synthesis, crystal structure as well as IR‐ and Raman‐spectroscopic properties of the new ternary azidoaurates(III) A [Au(N 3 ) 4 ] ( A = K, Rb, Cs) are reported. The translucent orange‐red compounds were prepared by reaction of the respective binary azides with HAuCl 4 in aqueous solutions at room temperature. The crystal structures determined by single crystal X‐ray diffraction methods are monoclinic ( C 2/ c (No. 15), K/Rb/Cs[Au(N 3 ) 4 ]: a = 1049.30(9) pm / 1033.93(10) pm / 1011.9(8) pm, b = 1047.52(8) pm / 1064.20(11) pm / 1093.8(8) pm, c = 776.97(7) pm / 809.79(8) pm / 858.4(6) pm, β = 91.220(5)° / 90.322(5)° / 92.72(5)°) and provide the first examples for azidoaurates with mono‐atomic cations. The unusual reduction of the lattice parameter a with increasing cation size in the isotypic series is discussed in detail. IR‐ and Raman‐spectroscopic measurements show strongly covalent gold‐nitrogen contacts, a bonding situation which is further supported by quantum chemical calculations and ELF‐analyses.