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The Reactions of Silver, Zirconium, and Hafnium Fluorides with Liquid Ammonia: Syntheses and Crystal Structures of Ag(NH 3 ) 2 F·2NH 3 , [M(NH 3 ) 4 F 4 ]·NH 3 (M = Zr, Hf), and (N 2 H 7 )F
Author(s) -
Kraus Florian,
Baer Sebastian A.,
Fichtl Matthias B.
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200800980
Subject(s) - chemistry , orthorhombic crystal system , ammonia , fluoride , inorganic chemistry , crystallography , liquid ammonia , crystal structure , ternary operation , halide , tetragonal crystal system , zirconium , ammonium , organic chemistry , computer science , programming language
By reaction of the tetrafluorides MF 4 or the ternary silver fluorides Ag 3 M 2 F 14 (M = Zr, Hf) with dry liquid ammonia at –40 °C, the pentaammoniates [M(NH 3 ) 4 F 4 ] · NH 3 ( 1 , M = Zr; 2 , M = Hf) were obtained, and these compounds represent hitherto unknown molecular inorganic Zr and Hf compounds that simultaneously bear nitrogen and fluorine ligands. The compounds crystallize isotypically in the shape of colorless needles in the tetragonal space group P 4/ ncc . As a further product [NH 4 (NH 3 )]F ( 3 ) was isolated in the form of colorless cubes in the orthorhombic space group Pca 2 1 . It is the first ammoniate of ammonium fluoride. Ag(NH 3 ) 2 F · 2NH 3 ( 4 ) can be synthesized either from AgF or AgF 2 in liquid ammonia. The compound crystallizes merohedrally twinned in the orthorhombic space group Pnna and represents the first crystallographically characterized diamine silver(I) halide complex. In the latter two structures, free fluoride anions are encountered. The ammoniates are highly temperature‐sensitive and decompose at temperatures above –30 °C due to their ammonia pressure.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)