Syntheses and characterization of ANi(AsF6)3 (A=H3O+, O2+, NO+, NH4+, K+, Rb+, and Cs+) compounds

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 M–F (M = Ni, Mg, Zn, Co, Mn) bond lengths (Table ) are comparable to those found in other M 2+ salts in which the M 2+ cations are located in an octahedral coordination of six fluorine atoms, for example, KNi(AsF 6 ) 3 and KM(AsF 6 ) 3 (M = Mg, Zn, Co, Mn). As expected, all the Sb–F bridging bonds are slightly elongated [1.892(4)–1.937(4) Å] in comparison with the Sb–F terminal bonds [1.831(4)–1.885(5) Å].…”

“…with respect to the Mg and Zn compounds ( Table 1). This is caused by the fact that the two crystallographically distinct M 2+ (M = Mg, Co, Ni, Zn, Mn) cations in the corresponding XeF 5 M(SbF 6 ) 3 compounds are located in an almost regular octahedral coordination of six fluorine atoms ( Table 2) are comparable to those found in other M 2+ salts in which the M 2+ cations are located in an octahedral coordination of six fluorine atoms, for example, KNi(AsF 6 ) 3 [15] and KM(AsF 6 ) 3 [16] (M = Mg, 3 were also collected at 100 and 296 K. The determined crystal structures were the same as that reported at 150 K. [2] For Co and Mn, additional measurements were made at 296 K. In contrast to XeF 5 Co(SbF 6 ) 3 , which crystallizes in the same crystal structure at 150 and 296 K, a phase transition was observed for XeF 5 Mn(SbF 6 ) 3 . For this reason, more detailed investigations were carried out (see the Exp.…”

“…The three‐dimensional frameworks of [M(XF 6 ) 3 ] – (M = Ni, Cu, Fe, Zn, Co, Mn; X = As, Sb) constructed of rings of MF 6 octahedra that share apexes with XF 6 octahedra have already been shown to be a very common structural motif in many compounds. This arrangement leads to the formation of cavities within which various singly charged cations are located (H 3 O + , O 2 + , NO + , NH 4 + , K + , Rb, Cs + ) , , , . The latest example was the crystal structure of XeF 5 Cu(SbF 6 ) 3 , for which it was observed for the first time that even larger cations such as [XeF 5 ] + can be accommodated inside such cavities.…”

“…This arrangement leads to the formation of cavities within which various singly charged cations are located (H 3 O + , O 2 + , NO + , NH 4 + , K + , Rb, Cs + ). [15,16,19,20] The latest example was the crystal structure of XeF 5 Cu(SbF 6 ) 3 , [2] for which it was observed for the first time that even larger cations such as [XeF 5 ] + can be accommodated inside such cavities. It seems that this framework is energetically very favorable and stable.…”

Oxonium Ions Substituting Cesium Ions in the Structure of the New High‐Pressure Borate HP‐Cs1−x(H3O)xB3O5 (x=0.5–0.7)

“…Instead, at least half of the cesium atoms must be substituted by oxonium ions (see Figures 3 and 4). The size of the oxonium ion is comparable to that of the K + ion, [35] which perfectly fits into the structure, as shown in HP-KB 3 O 5 .…”