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

Abstract

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.

Photochemistry with ClF3 – An Access to [ClOF2]+ Salts

“…The M−F distances of those bridging to Cl atoms are in the range from 1.936(6) to 1.951(6) Å ( Sn2 ) and 2.001(3) to 2.040(4) Å ( Pb ). The Sn−F bond lengths agree with those in [ClO 2 ]SnF 5 (1.9047(13) to 2.0627(13) Å at 100 K) [23] and are comparable to those in [O 2 ][Sn 2 F 9 ] (1.898(2) to 2.0374(4) Å at 200 K), [O 2 ][Sn 2 F 9 ] ⋅ 0.9HF (1.880(4) to 2.095(4) Å at 150 K), and (XeF 5 ) 4 [Sn 5 F 24 ] (1.879(6) to 2.101(5) Å at 150 K), [55,56] in which both terminally bound and bridging F atoms are present.…”

Nitrosonium tetrafluoridoborate, NOBF4

“…It is noteworthy that the orientational cationic disorder in the salt NOBF 4 was studied previously by heat capacity measurements from 10 to 304 K (Callanan et al, 1981). The N-O bond length of 1.0216 (10) A ˚in NOBF 4 is similar to the values reported for other nitrosonium fluoride salts, for instance: 1.052 (6) A ˚in NOUF 6 at 100 K (Scheibe et al, 2016) and 1.012 (6) A ˚in NOSbF 6 at 150 K (Mazej & Goreshnik, 2021), with both salts also exhibiting disordered NO + groups. Each anion is surrounded by seven cations and vice versa, with fourteen (N/O)Á Á ÁF contacts shorter than 3.0 A ˚; the shortest contacts [2.6211 (6), 2.6222 (6), and 2.6560 (6) A ˚] involve atom F3.…”

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

“…Numerous examples of [M x + (XeF 2 ) n ][A À ] x salts are known in which XeF 2 is directly coordinated to a metal center (M = M + or M 2 + ; A = BF 4 , AsF 6 , SbF 6 , etc.). [29,30] Our attempt to prepare such a salt with an additional oxonium cation, i. e., [H 3 O] x [Sr(XeF 2 ) n ] y -[SbF 6 ] x + 2y failed. Only a few single crystals of (H 3 O)[Sr-(HF) 2 ] 3 (SbF 6 ) 6 (Sb 2 F 11 ) were found adjacent to powdered material.…”

“…[5] Xenon hexafluoride (XeF 6 ) can act as a fluoride ion acceptor or donor. An example of the former are the [XeF 7 ] À and [XeF 8 ] 2À salts, [6][7][8] while examples of the latter are various [XeF 5 ] + and [Xe 2 F 11 ] + salts, [9][10][11] which in most cases are obtained by reaction between XeF 6 and binary fluorides (MF 3 , [12,13] MF 4 , [14][15][16][17] MF 5 [18][19][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.…”

“…An example of the former are the [XeF 7 ] À and [XeF 8 ] 2À salts, [6][7][8] while examples of the latter are various [XeF 5 ] + and [Xe 2 F 11 ] + salts, [9][10][11] which in most cases are obtained by reaction between XeF 6 and binary fluorides (MF 3 , [12,13] MF 4 , [14][15][16][17] MF 5 [18][19][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. One of the major problems in the synthesis and growth of M(SbF 6 ) 2 (M = metal in the + 2 oxidation state) single crystals and other fluoridoantimonate(V) salts is the presence of trace amounts of moisture or other source of oxygen, that can be protonated in the superacid HF-SbF 5 , resulting in [H 3 O] + impurities.…”