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

Abstract

The reactions between XeF5SbF6 and M(SbF6)2 (M2+ = Ni, Mg, Zn, Co, Mn, Pd) in anhydrous HF (aHF) in a 1:1 molar ratio yielded XeF5M(SbF6)3 upon crystallization. All six structures were characterized at 150 K by single‐crystal X‐ray diffraction. For Mn, there is a phase transition at around 235 K, and for Pd between 260 and 296 K. Similar attempts to prepare new [XeF5]+/M2+ mixed‐cation salts with M2+ = Ca, Sr, Ba, Cr, Fe, Ag, Cd, and Hg were only successful for Hg, for which (XeF5)3[Hg(HF)]2(SbF6)7 was obtained. The crystal structures of XeF5M(SbF6)3 (M2+ = Mg, Co, Ni, Zn) and the low‐temperature phase α‐XeF5Mn(SbF6)3 are isotypic with the known XeF5Cu(SbF6)3. The main features of the crystal structures of β‐XeF5Mn(SbF6)3 and β‐XeF5Pd(SbF6)3 are similar to those of the other XeF5M(SbF6)3 compounds, that is, a 3D framework consisting of rings of MF6 octahedra that share the apexes with SbF6 octahedra, forming cavities within which the [XeF5]+ cations are located. At 296 K, the disordered [XeF5]+ cations in β‐XeF5Pd(SbF6)3 are ordered in the α‐phase (260 K). The crystal structure of (XeF5)3[Hg(HF)]2(SbF6)7 consists of columns of [Hg(HF)]2+ cations bridged by SbF6 units. The charge balance is maintained by the [XeF5]+ cations, which form secondary contacts with the F atoms of the SbF6 groups.

Crystal Structures of Xenon(VI) Salts: XeF5Ni(AsF6)3, XeF5AF6 (A = Nb, Ta, Ru, Rh, Ir, Pt, Au), and XeF5A2F11 (A = Nb, Ta)

“…Some geometric parameters are listed in Table 5. The crystal structure of XeF 5 Ni(AsF 6 ) 3 is isotypical to the previously reported crystal structures of XeF 5 M(SbF 6 ) 3 (M 2+ = Mg, Mn, Co, Ni, Cu, Zn, Pd) [34,35]. Some geometric parameters are given in Table 6.…”

“…Later, this was extended to HF [32], XeOF 4 [33], and even KrF 2 [32]. Recently, the XeF 5 SbF 6 salt was also found to react with other MSbF 6 and M(SbF 6 ) 2 salts to give XeF 5 M(SbF 6 ) 2 (M = NO 2 + , Rb + , Cs + ) [28,34], XeF 5 M(SbF 6 ) 3 (M 2+ = Mg, Mn, Co, Ni, Cu, Zn, Pd), and (XeF 5 ) 3 [M(HF) 2 ](SbF 6 ) 7 (M = Hg) [34,35] or even more complex salts (H 3 O)(XeF 5 ) 2 M 2 (SbF 6 ) 7 •nHF (M = Ca, Cd) [36] and (O 2 )(XeF 5 ) 2 Sr 4 (SbF 6 ) 11 •8HF [36] with three different cations. In addition, mixed anion salts Cs[XeF 5 ][Bi x Sb 1-x F 6 ] [28] and [XeF 5 ][As 1-x Sb x F 6 ) (x~0.5 and 0.7) [37] have also been reported.…”

Nitrosonium and Nitronium Salts of New Mixed‐Cation Hexafluoridoantimonates(V)

“…, NO + , NH 4 + , K + , Rb + , Cs + ; M=Ni), [12] KM II (AsF 6 ) 3 (M=Mg, Co, Mn, Zn,), [63] KCu (SbF 6 ) 3 , [63] and XeF 5 M II (SbF 6 ) 3 (M=Ni, Mg, Cu, Zn, Co, Mn, Pd) salts. [48,64] This implies that such arrangement is energetically very favorable.…”

Mixed cation [H3O]+/[XeF5]+/M2+ (M=Ca, Cd), [O2]+/[XeF5]+/Sr2+ and [H3O]+/Sr2+ fluoridoantimonate(V) salts

“…In addition, during the photochemical synthesis of [XeF 5 ] + salts with UV‐irradiated elemental fluorine the presence of oxygen can lead to the formation of [O 2 ] + containing impurities [28] . In the attempts to prepare [XeF 5 ] y M y (SbF 6 ) x+y salts (M=Ca, Sr, Cd), some by‐products were obtained unintentionally for which preliminary crystallographic studies indicate that they contain some H 3 O + or O 2 + cations in addition to M 2+ (M=Ca, Cd, Sr) and XeF 5 + cations [25] . Later, we investigated the possibility of growing single crystals of these compounds.…”

“…An example of the former are the [XeF 7 ] − and [XeF 8 ] 2− salts, [6–8] while examples of the latter are various [XeF 5 ] + and [Xe 2 F 11 ] + salts, [9–11] which in most cases are obtained by reaction between XeF 6 and binary fluorides (MF 3 , [12,13] MF 4 , [14–17] MF 5 [18–20] ) or oxyfluorides (OsO 3 F 2 , [21] MOF 4 , M=Cr, [22] Mo, [23] W, [23] ). Recently, more complex mixed cation salts AXeF 5 (SbF 6 ) 2 (A=NO 2 + , [24] Rb + , [13] Cs +[13] ), [XeF 5 ]M(SbF 6 ) 3 (M 2+ =Ni, Mg, Cu, Zn, Co, Mn, Pd) [25] and (XeF 5 ) 3 [Hg(HF)] 2 (SbF 6 ) 7 [25] were described.…”