Single-crystal structure determination of NO2SbF6, XeF5SbF6 and XeF5Sb2F11

2016

Eur J Inorg Chem

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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.

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

2016

Eur J Inorg Chem

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“…Reactions between ASbF 6 (A = Rb, Cs) and [XeF 5 ][SbF 6 ], in anhydrous HF in 1:1 molar ratios yielded isotypic A[XeF 5 ][SbF 6 ] 2 (A = Rb, Cs) upon crystallization [Equation ]. Traces of starting materials were also observed.

normalA normalS normalb F_{6} (normalA = normalR normalb, normalC normals) + [normalX normale F_{5}] [normalS normalb F_{6}] \overset{+0.611em0.278em.15em normala normalH normalF, 298 normalK}{\to} normalA [normalX normale F_{5}] {[normalS normalb F_{6}]}_{2}

…”

Section: Resultsmentioning

confidence: 99%

“…In 1964, Gard and Cady reported that by varying the proportions of the reactants SbF 5 and XeF 6 , it is possible to prepare each of the crystalline solids: 2XeF 6 · SbF 5 , XeF 6 · SbF 5 , and XeF 6 · 2SbF 5 . The crystal structures of the latter two have been recently determined, and they are both [XeF 5 ] + salts; that is, [XeF 5 ][SbF 6 ] and [XeF 5 ][Sb 2 F 11 ] . No structural data have been reported so far for the 2XeF 6 · SbF 5 compound.…”

Section: Resultsmentioning

confidence: 99%

“…The KF (Ventron, 99.9 %), RbF (Aldrich, 99 %), CsF (Aldrich, 99.9 %), and BF 3 (Union Carbide Austria, 99.5 %) were used as supplied. The H 3 OSbF 6 , [XeF 5 ][AsF 6 ], [XeF 5 ][SbF 6 ], and Cs 2 MnF 6 were synthesized as described previously. The PF 5 , AsF 5 , SbF 5 , BiF 5 were prepared by high‐pressure fluorination of P 2 O 5 , As 2 O 3 , SbF 3 , or BiF 3 , respectively, by elemental fluorine at elevated temperature.…”

Section: Methodsmentioning

confidence: 99%

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Crystal Growth and Characterization of the Mixed‐Cation Rb⁺/[XeF₅]⁺ and Cs⁺/[XeF₅]⁺ Salts

2017

Eur J Inorg Chem

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Reactions between ASbF6 (A = Rb, Cs) and [XeF5][SbF6] in anhydrous HF in 1:1 molar ratios yielded isotypic A[XeF5][SbF6]2 compounds upon crystallization. The A[XeF5][SbF6]2 (A = Rb, Cs) salts crystallize in two crystal modifications at low (α phase, 150 K) and ambient (β phase, 296 K) temperatures. Similar reactions between CsBiF6 and [XeF5][SbF6] (1:1) yielded mixed‐cation/mixed‐anion compounds Cs[XeF5][BixSb1–xF6]2 (x = 0.37–0.39). One of the two crystallographic positions of the pnictogen atoms is randomly occupied with both Bi (ca. 40 %) and Sb (ca. 60 %) atoms. The simultaneous presence of both [SbF6]– and [BiF6]– has been confirmed by Raman spectroscopy. The low‐ and high‐temperature phases of Bi/Sb mixed‐anion compounds are isotypic with the corresponding A[XeF5][SbF6]2 (A = Rb, Cs) phases. No reactions were observed in the AAsF6 (A = Rb, Cs)/[XeF5][AsF6], ASbF6 (A = K, [H3O]+)/[XeF5][SbF6], and KBF4/[XeF5][SbF6] systems. In the CsBF4/[XeF5][SbF6] system, a metathetical reaction occurred, leading to [XeF5][BF4] (orthorhombic at 150 K, Pbca space group) and CsSbF6. The latter reacted further with [XeF5][SbF6], yielding Cs[XeF5][SbF6]2. A double‐displacement reaction also proceeded between Cs2MnF6 and [XeF5][SbF6] to give [XeF5]2[MnF6] and CsSbF6. The reaction between CsPF6 and [XeF5][SbF6] proceeded with the displacement of the weaker Lewis acid, PF5, with the stronger one, SbF5, resulting in [Xe2F11][SbF6] and CsSbF6, which reacted with [XeF5][SbF6] to yield Cs[XeF5][SbF6]2.

ChemInform Abstract: Single‐Crystal Structure Determination of NO₂SbF₆, XeF₅SbF₆ and XeF₅Sb₂F₁₁.

2015

ChemInform

Single-Crystal Structure Determination of NO 2SbF6, XeF5SbF6 and XeF5Sb2F11. -The title compounds are prepared according to the literature and used for single crystal growth in a T-shaped fluoroethylene-hexafluoropropylene crystallization apparatus. Anhydrous HF is condensed on the solids at 77 K prior to being warmed up to 25 C for slow HF evaporation (2 months). NO 2SbF6 crystallizes in the orthorhombic space group Cmmm (Z = 2, single crystal XRD, 150 K) and exhibits a different packing of the [NO 2] + and [SbF6]ions than that in NO2AsF6. The XeF5SbF6 compound crystallizes in the orthorhombic space group Pnma (Z = 4, 150 K) and is isotypic with the known XeF5MF6 structures (M: Nb, Ru, Pt). XeF5Sb2F11 is triclinic (space group P1, Z = 2, 200 K) with each [XeF 5] + cation having four interactions with the three [Sb2F11]anions. -(MAZEJ*, Z.; GORESHNIK, E. A.; J. Fluorine Chem. 175 (2015) 47-50, http://dx.