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Intermediates in Ammonothermal GaN Crystal Growth under Ammonoacidic Conditions
Author(s) -
Zhang Shiyu,
Hintze Frauke,
Schnick Wolfgang,
Niewa Rainer
Publication year - 2013
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.201300958
Subject(s) - chemistry , gallium , crystallography , crystal structure , ammonia , raman spectroscopy , deamination , ion , x ray crystallography , infrared spectroscopy , hydrogen bond , fluoride , inorganic chemistry , molecule , diffraction , biochemistry , physics , enzyme , organic chemistry , optics
Crystals of two new hexammoniates, namely, [Ga(NH 3 ) 6 ]I 3 · NH 3 and [Ga(NH 3 ) 6 ]Br 3 · NH 3 , were grown from liquid ammonia solutions of GaI 3 and GaBr 3 in a wide temperature range. The known compound [Ga(NH 3 ) 5 Cl]Cl 2 and the new triammoniate of gallium fluoride Ga(NH 3 ) 3 F 3 were obtained ammonothermally during the synthesis of GaN from NH 4 Cl and NH 4 F, respectively. The compounds are characterized by crystallographic parameters derived from their X‐ray diffraction data. The crystal structures of all the ammoniates feature octahedrally coordinated Ga atoms in complex ions of the general form [Ga(NH 3 ) 6– n X n ] (3– n )+ ( n = 0, 1, 2, 4; X = F, Cl, Br, I). The extensive N–H ··· X hydrogen bonding networks in these compounds are analyzed. The IR and Raman spectroscopy data for [Ga(NH 3 ) 6 ]X 3 · NH 3 (X = Br, I) and Ga(NH 3 ) 2 F 3 are provided, and the IR spectrum of Ga(NH 3 ) 3 F 3 is compared with those published for the monoammoniate Ga(NH 3 )F 3 and the diammoniate Ga(NH 3 ) 2 F 3 . Finally, the thermal deamination features of [Ga(NH 3 ) 6 ]X 3 · NH 3 (X = Br, I) and Ga(NH 3 ) 3 F 3 are also discussed.