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New Volatile Nitronium Nitratometalates: NO 2 [Fe(NO 3 ) 4 ] and NO 2 [Zr(NO 3 ) 5 ] — Synthesis and Crystal Structure
Author(s) -
Tikhomirov G.,
Morozov I.,
Znamenkov K.,
Kemnitz E.,
Troyanov S.
Publication year - 2002
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 - 10.1002/1521-3749(200205)628:4<872::aid-zaac872>3.0.co;2-i
Subject(s) - sublimation (psychology) , chemistry , crystal structure , zirconium , crystallography , inorganic chemistry , trigonal crystal system , psychology , psychotherapist
Crystalline NO 2 [Fe(NO 3 ) 4 ] was obtained by dehydration of a solution of Fe(NO 3 ) 3 in 100 % HNO 3 and subsequent sublimation. NO 2 [Zr(NO 3 ) 5 ] was synthesized by reaction of ZrCl 4 with N 2 O 5 followed by sublimation in vacuum. X‐ray single crystal structure determination showed both compounds to consist of nitronium cations, NO 2 + , and nitratometalate anions. N‐O distances in the linear NO 2 + cations are in the range of 1.08—1.13Å. In both [Fe(NO 3 ) 4 ] − and [Zr(NO 3 ) 5 ] − anions, all nitrate groups are coordinated bidentately with average M‐O distances 2.134 and 2.293Å, respectively. Taking into account the position of N atoms around the M atoms, the arrangement of nitrate groups can be described as tetrahedral for the Fe complex and trigonal‐bipyramidal for the Zr complex. There are four shortest N(nitronium)····O(nitrate group) contacts with average distances of 2.705 and 2.726Å in NO 2 [Fe(NO 3 ) 4 ] and 2.749Å in NO 2 [Zr(NO 3 ) 5 ]. Nitronium pentanitratohafnate is isotypic to the zirconium complex.