Crystal structures of KM(AsF6)3 (M2+ = Mg, Co, Mn, Zn), KCu(SbF6)3 and [Co(HF)2]Sr[Sr(HF)]2[Sr(HF)2]2[AsF6]12

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.

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

2021

Eur J Inorg Chem

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Reaction between NOSbF6 and Cu(SbF6)2 in aHF yielded NOCu(SbF6)3. In the presence of H3OSbF6, single crystals of (H3O)0.2(NO)0.8Cu(SbF6)3 were grown from a saturated aHF solution. Both salts are isotypic and crystallize in the orthorhombic space group Pnma (No. 62) at 200 K. The main feature of their crystal structures are rings of CuF6 octahedra sharing apexes with SbF6 octahedra connected into 3‐D network. Single charged cations are located inside the cavities. Reaction between 0.25NOSbF6, 0.75NO2SbF6 and Cu(SbF6)2 in aHF yielded (NO)0.25(NO2)0.75Cu(SbF6)3 upon the crystallization. It crystallizes in the cubic space group Im3‾ (No. 204) at 200 K. Subsequent experiments with M(SbF6)2 (M=Cu, Zn) showed that, when the NO+ cations are partially or completely replaced by H3O+, the grown crystals of (H3O)0.125(NO)0.125(NO2)0.75Zn(SbF6)3 and (H3O)0.25(NO2)0.75M(SbF6)3 (M=Cu, Zn) are isotypic to (NO)0.25(NO2)0.75Cu(SbF6)3. Crystal structure of the latter demonstrates similar 3‐D structural motif as observed for the NOCu(SbF6)3 salt. The crystal structures of (H3O)0.64(NO2)0.36CuF(SbF6)2 and [Cu(H2O)6](SbF6)2 were also determined. Crystallizations of NOSbF6/O2SbF6 were carried out in aHF in different molar ratios. The crystal structure determinations of grown single crystals showed that they have the composition (NO)x(O2)1‐xSbF6 (x=0.17, 0.55 0.75) indicating that most likely all phases with x=0–1 exist. They are isotypic to NOSbF6.

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Crystal structure determination of Pb2F2(HF)(SbF6)2, PbFSbF6 and Ba(HF)(AF6)2: (A=As, Sb)

Tramšek

Journal of Fluorine Chemistry

et al. 2015

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