New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Abstract

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 ϩ , and nitratometalate anions. N-O distances in the linear NO 2 ϩ cations are in the range of 1.08Ϫ1.13 Å . In both [Fe(NO 3 ) 4 ] Ϫ and [Zr(NO 3 ) 5 ] Ϫ anions, all nitrate groups are coordinated bidentately with average M-O distances 2.134 and Neue Flüchtige Nitrylnitratometallate: NO 2 [Fe(NO 3 ) 4 ] und NO 2 [Zr(NO 3 ) 5 ] ؊ Synthese und Kristallstruktur Inhaltsübersicht. Kristallines NO 2 [Fe(NO 3 ) 4 ] wurde durch Einengen einer Lösung von Fe(NO 3 ) 3 in 100%iger HNO 3 und nachfolgender Sublimation des erhaltenen Feststoffes hergestellt. NO 2 [Zr(NO 3 ) 5 ] wurde durch Reaktion von ZrCl 4 mit N 2 O 5 und anschließender Vakuumsublimation synthetisiert. Die Röntgenein-kristallstrukturanalyse zeigt, dass beide Verbindungen aus Nitrylkationen, NO 2 ϩ , und Nitratometallatanionen bestehen. Die N-OAbstände in den linearen NO 2 ϩ -Kationen liegen im Bereich von 1.08Ϫ1.13 Å . In den [Fe(NO 3 ) 4 ] Ϫ -und [Zr(NO 3 ) 5 ] Ϫ -Anionen sind

On the singularity of scandium

“…The more nitrates bind to the metal, the higher the coordination number can be. Thus, in the [Fe(k 2 -NO 3 ) 4 ] À ion, found in (Ph 4 As)[Fe(NO 3 ) 4 ], 85 and in (NO 2 )[Fe(NO 3 ) 4 ], 86 Fe(III) is eight coordinate. However, nine coordinate scandium is found (NO) 2 [Sc(NO 3 ) 5 ].…”

New iron(III) nitrate hydrates: Fe(NO3)3·xH2O withx= 4, 5 and 6

“…There are examples in the literature of salts with tetranitratoferrate anions, [Fe(NO 3 ) 4 ] À , where the nitrate groups coordinate in a bidentate fashion, resulting in a coordination number of eight for Fe III (Addison & Chapman, 1965;Tikhomirov et al, 2002;Blackwell et al, 1975;Fedorova et al, 2002). However, the pentagonal-bipyramidal coordination of Fe III has only been observed before for metal-organic Fe III complexes (Andjelkovic et al, 2002;Bonardi et al, 1991 Noncoordinated water molecules in Fe(NO 3 ) 3 Á4H 2 O connecting two pentagonal-bipyramidal [Fe(NO 3 ) 2 (H 2 O) 3 ] + units via hydrogen bonds (black lines).…”

Nitronium tetrafluoroborate

“…The N O distances in [ (Tikhomirov et al, 2002). In addition, the B-F distances (see Table 1) are typical for a tetrafluoroborate anion.…”