[XeF₅]⁺/Metal and [XeF₅]⁺/Non‐Metal Mixed‐Cation Salts of Hexafluoridoantimonate(V)

Abstract

New types of [XeF5]+ salts, i.e., NO2XeF5(SbF6)2 and XeF5[Cu(SbF6)3], are derived from reactions between XeF5SbF6 and NO2SbF6 or Cu(SbF6)2, respectively. The crystal structure of the former consists of [NO2]+ and [XeF5]+ cations and [SbF6]– anions. The main feature of the crystal structure of XeF5[Cu(SbF6)3] are rings of CuF6 octahedra that share apexes with SbF6 octahedra connected into an infinite tridimensional framework. This arrangement leads to the formation of cavities within which [XeF5]+ cations are located. Raman spectra of both [NO2]+/[XeF5]+ and [XeF5]+/Cu2+ mixed‐cation hexafluorido‐antimonates(V) are reported herein.

Influence of the Increasing Size of the M2+ Cation on the Crystal Structures of XeF5M(SbF6)3 (M = Ni, Mg, Cu, Zn, Co, Mn, Pd) and (XeF5)3[Hg(HF)]2(SbF6)7

“…The unit‐cell volumes (all at 150 K) increase (Table ) with increasing size of the M 2+ cations, that is, Ni 2+ < Mg 2+ < Cu 2+ < Zn 2+ < Co 2+ < Mn 2+ (for the coordination number six) . The unit‐cell volume of XeF 5 Cu(SbF 6 ) 3 measured at 150 K is 1710.81(7) Å (see Table S1 in the Supporting Information and ref …”

“…The recently reported XeF 5 Cu(SbF 6 ) 3 can be prepared by the reaction between XeF 5 SbF 6 and Cu(SbF 6 ) 2 in anhydrous hydrogen fluoride, and the corresponding single crystals can be grown from an aHF saturated solution . Single crystals of XeF 5 M(SbF 6 ) 3 (M = Ni, Mg, Zn, Co, Mn, Pd) were obtained as products upon the crystallization of M(SbF 6 ) 2 and XeF 5 SbF 6 mixtures (starting molar ratio 1:1) from aHF solutions.…”

Single-crystal structure determination of NO2SbF6, XeF5SbF6 and XeF5Sb2F11

“…The effect of this treatment was to enable the aHF to be slowly evaporated from the narrower into the wider tube, leaving behind the crystals. Single crystals of NO 2 SbF 6 were grown during the attempt to prepare the (NO 2 )(XeF)(SbF 6 ) 2 compound as in the case of Xe(VI) where NO 2 XeF 5 (SbF6) 2 [21] was synthesized. In a similar attempt to prepare unknown (H 3 O)XeF 5 (SbF 6 ) 2 by a reaction between H 3 OSbF 6 and XeF 5 SbF 6 only single crystals of the latter were found between the powdered material.…”

“…The SbF 5 , NO 2 SbF 6 and XeF 5 SbF 6 were prepared as described previously [21]. Anhydrous HF (Linde, Fluorwasserstoff 3.5) was treated with K 2 NiF 6 (Ozark-Mahoning, 99%) for several hours prior to its use.…”

“…Single crystals of XeF 5 SbF 6 , XeF 5 Sb 2 F 11 and NO 2 SbF 6 were grown during attempts to prepare analog mixed-cation compounds such as NO 2 XeF 5 (SbF 6 ) 2 [21] with other cations. Their crystal structures were determined and are described in the present paper.…”