Protonated deca­fluoro­benzo­phenone and the deca­fluoro­benzo­phenone–arsenic penta­fluoride adduct

Uran, E.; Lozinšek, M.

doi:10.1107/S2053229625007697

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 81| Part 10| October 2025| Pages 577-583

https://doi.org/10.1107/S2053229625007697

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Protonated decafluorobenzophenone and the decafluorobenzophenone–arsenic pentafluoride adduct

Erik Uran ^a,^b and Matic Lozinšek ^a,^b ^*

^aExtreme Conditions Chemistry Laboratory (ECCL K2), Jožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia, and ^bJožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia
^*Correspondence e-mail: [email protected]

Edited by R. I. Cooper, University of Oxford, United Kingdom (Received 28 July 2025; accepted 28 August 2025; online 23 September 2025)

The reaction of decafluorobenzophenone [perfluorobenzophenone, (C₆F₅)₂CO] with AsF₅ in anhydrous HF yields the protonated salt [bis(2,3,4,5,6-pentafluorophenyl)methylidene]oxidanium hexafluoridoarsenate, (C₆F₅)₂COH⁺[AsF₆]⁻, whereas its reaction with AsF₅ in SO₂ affords the Lewis acid–base adduct decafluorobenzophenone–arsenic pentafluoride, (C₆F₅)₂CO·AsF₅. In both compounds, the decafluorobenzophenone moiety exhibits an elongated C=O bond [1.274 (2) and 1.2526 (15) Å in the salt and adduct, respectively]. The crystal structure of (C₆F₅)₂COH⁺[AsF₆]⁻ features a short O—H⋯F hydrogen bond between the cation and the anion, and the crystal structure of (C₆F₅)₂CO·AsF₅ represents a rare example of a ketone coordinated to the strong Lewis acid AsF₅.

Keywords: superacid medium; protonation; decafluorobenzophenone; AsF₅ adduct; crystal structure; protonated ketone.

CCDC references: 2483527; 2483526; 2483525; 2483524

1. Introduction

Protonation of small molecules plays an important role in investigating and elucidating the reaction mechanisms of acid-catalysed organic reactions. These reactive cations are typically generated in superacidic media (Olah et al., 2009 ) and a wide range of compounds has been shown to undergo protonation under such conditions. Examples include nitriles (Haiges et al., 2016 ; Goetz et al., 2016 ), organic azides (Saal et al., 2020 ), carboxylic acids (Saal et al., 2023 ; Hollenwäger et al., 2024 ), acyl halides (Steiner et al., 2024a ), amides (Axhausen et al., 2013 ; Saal et al., 2023), esters (Hollenwäger et al., 2025 ) and amino sulfonic acids (Bockmair et al., 2024 ).

The protonation of aldehydes and ketones in solution has been studied in detail by low-temperature NMR spectroscopy. For example, the protonation of aliphatic aldehydes (Olah et al., 1967b ) and aliphatic ketones (Olah et al., 1967a ) was studied in the superacidic media HSO₃F–SbF₅–SO₂, protonated alicyclic ketones in HSO₃F–SbF₅–SO₂ and HSO₃F–SO₂ (Olah & Calin, 1968 ), protonated acetophenones in HSO₃F (Birchall & Gillespie, 1965 ) and benzophenones in HSO₃F–SbF₅ (Sekuur & Kranenburg, 1966 ; van der Linde et al., 1968 ). The reaction of hexafluoroacetone in an HF–SbF₅ mixture, however, results in HF addition to the ketone, followed by protonation, yielding a rare example of a protonated alcohol (Minkwitz & Reinemann, 1999 ).

Several crystallographically characterized examples of protonated ketones (Childs et al., 1982 , 1990 ; Chadda et al., 1986 ; Stuart et al., 2017 ; Schickinger et al., 2018 ) and protonated aldehydes (Hwang et al., 2010 ; Heo et al., 2011 ; Hayatifar et al., 2014 ; Stuart et al., 2017) have been reported. The crystal structure of protonated benzophenone has been reported in the form of [HCB₁₁H₅Cl₆]⁻ carborane (Stasko et al., 2002 ) and [TaF₆]⁻ salts (Marchetti et al., 2007 ), both featuring a hydrogen-bonded dimer, [(C₆H₅)₂C=O—H⋯O=C(C₆H₅)₂]⁺.

The protonation of decafluorobenzophenone, (C₆F₅)₂CO, in solution was previously studied in H₂SO₄ and HSO₃F (Chambers & Spring, 1969 ), and in HF–SbF₅–SO₂ClF mixtures (Olah & Mo, 1973 ) by NMR spectroscopy. Research on Lewis acid–base adducts of AsF₅ with ketones remains scarce (Stuart et al., 2019 ) and no crystal structures containing a C₂CO–AsF₅ fragment have been reported in the Cambridge Structural Database (CSD, Version 6.00, April 2025; Groom et al., 2016 ).

In this work, the synthesis and structural characterization of the protonated decafluorobenzophenone (perfluorobenzophenone) salt (C₆F₅)₂C=OH⁺[AsF₆]⁻ and a Lewis acid–base adduct of arsenic pentafluoride and decafluorobenzophenone, i.e. (C₆F₅)₂CO·AsF₅, are reported.

2. Experimental

2.1. Synthesis and crystallization

A fluorinated ethylene propylene (FEP) vessel (outer diameter: 6 mm; inner diameter: 4.6 mm), equipped with an aluminium-encased polychlorotrifluoroethylene (PCTFE) valve, was passivated with fluorine overnight prior to use. In a nitrogen-filled glovebox (Vigor SG1200/750E–SG1500/750E; H₂O < 0.02 ppm, O₂ < 2 ppm), the vessel was loaded with (C₆F₅)₂CO (23 mg, 0.064 mmol; Thermo Scientific, 97%). Anhydrous HF (0.2 ml; Linde, 99.995%; stored over K₂NiF₆) was then condensed into it using a vacuum line designed for handling elemental fluorine, resulting in a suspension of (C₆F₅)₂CO at room temperature. Upon addition of AsF₅ (0.137 mmol), synthesized as described previously (Mazej & Žemva, 2005 ), a yellow precipitate formed that dissolved completely upon warming to room temperature. Slow cooling to −30 °C yielded canary-yellow crystals of (C₆F₅)₂COH⁺[AsF₆]⁻. The solvent aHF was removed under dynamic vacuum at −78 °C, leaving a yellow crystalline solid. Another synthesis was performed on a slightly larger scale [113 mg, 0.312 mmol (C₆F₅)₂CO; 0.4 ml aHF; 0.936 mmol AsF₅] (Figs. 1–3 ).

Figure 1
Synthesis of the (C₆F₅)₂COH⁺[AsF₆]⁻ salt and the (C₆F₅)₂CO·AsF₅ adduct.

Figure 2
The low-temperature Raman spectra of (C₆F₅)₂CO (top), (C₆F₅)₂COH⁺[AsF₆]⁻ (middle) and (C₆F₅)₂CO·AsF₅ (bottom) measured at −90, −90 and −93 °C, respectively.

Figure 3
Canary-yellow crystals of (C₆F₅)₂COH⁺[AsF₆]⁻ that formed upon cooling a solution of (C₆F₅)₂CO and AsF₅ in anhydrous HF to about −10 °C using an ethanol bath. The outer diameter of the FEP tube is 6 mm.

For the synthesis of (C₆F₅)₂CO·AsF₅, (C₆F₅)₂CO (14 mg, 0.039 mmol) was dissolved in dry SO₂ (0.3 ml; Ruše, stored over CaH₂ in a glass bulb) at room temperature. AsF₅ (0.168 mmol) was added at −196 °C. Upon thawing of the SO₂–AsF₅ mixture, a yellow coloration appeared immediately. The vessel was then stored at −78 °C under a nitrogen overpressure (∼1000 Torr). Large yellow crystals of (C₆F₅)₂CO·AsF₅ formed over a period of ten days. Volatiles, SO₂ and excess AsF₅ were removed under dynamic vacuum between −78 and −50 °C, yielding a yellow solid (Figs. 1 and 2).

A crystalline sample was quickly deposited from the FEP reaction vessel into an aluminium trough of the low-temperature crystal-mounting apparatus, designed and employed for mounting highly reactive moisture-sensitive noble-gas compounds (Lozinšek et al., 2021 ; Motaln et al., 2024 ), which was cooled using a stream of cold nitrogen to temperatures ranging from −80 to −100 °C. Suitable crystals were selected under a stereomicroscope and mounted on the tip of a MiTeGen loop using Fomblin oil (Z25, SynQuest) (Motaln et al., 2025 ). The loop assembly was picked up with cryo-pin tongs cooled to −196 °C and quickly transferred to the magnetic holder on the goniometer head, where the crystal was protected by a cold nitrogen stream at 100 K.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The position of the H atom in the crystal structure of (C₆F₅)₂COH⁺[AsF₆]⁻ was located in a difference electron-density map and refined freely, including its isotropic displacement parameter (Cooper et al., 2010 ).

Table 1
Experimental details

Experiments were carried out at 100 K using a Rigaku OD XtaLAB Synergy-S Dualflex diffractometer with an Eiger2 R CdTe 1M detector. The absorption correction was Gaussian (CrysAlis PRO; Rigaku OD, 2025 ).

	(C₆F₅)₂CO	(C₆F₅)₂COH⁺[AsF₆]⁻	(C₆F₅)₂CO·AsF₅
Crystal data
Chemical formula	C₁₃F₁₀O	C₁₃HF₁₀O⁺AsF₆⁻	C₁₃AsF₁₅O
M_r	362.13	552.06	532.05
Crystal system, space group	Monoclinic, C2	Monoclinic, P2₁/n	Orthorhombic, Pbca
a, b, c (Å)	20.1460 (4), 5.39987 (10), 5.47058 (14)	8.19207 (7), 21.17409 (18), 9.28475 (9)	12.39109 (18), 12.04038 (17), 20.8754 (3)
α, β, γ (°)	90, 95.912 (2), 90	90, 98.2086 (8), 90	90, 90, 90
V (Å³)	591.96 (2)	1594.03 (2)	3114.47 (8)
Z	2	4	8
Radiation type	Cu Kα	Cu Kα	Ag Kα, λ = 0.56087 Å
μ (mm⁻¹)	2.18	4.70	1.25
Crystal size (mm)	0.43 × 0.1 × 0.07	0.09 × 0.05 × 0.03	0.58 × 0.29 × 0.22

Data collection
T_min, T_max	0.491, 1.000	0.842, 1.000	0.290, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10783, 1212, 1193	26147, 3336, 3134	97292, 8537, 7132
R_int	0.056	0.032	0.033
(sin θ/λ)_max (Å⁻¹)	0.629	0.630	0.914

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.095, 1.11	0.025, 0.066, 1.05	0.031, 0.081, 1.09
No. of reflections	1212	3336	8537
No. of parameters	110	285	271
No. of restraints	1	0	0
H-atom treatment	–	All H-atom parameters refined	–
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.24	0.30, −0.49	0.53, −0.64
Absolute structure	Flack x determined using 514 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 )	–	–
Absolute structure parameter	0.05 (10)	–	–
Computer programs: CrysAlis PRO (Rigaku OD, 2025), olex2.solve (Bourhis et al., 2015 ), SHELXL (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2022 ) and OLEX2 (Dolomanov et al., 2009 ).

2.3. Raman spectroscopy

Raman spectroscopy was performed using either a Horiba Jobin Yvon LabRAM HR spectrometer coupled with an Olympus BXFM-ILHS microscope or a Bruker Senterra II confocal Raman microscope equipped with a Linkam LTS420 low-temperature stage. Red (633 and 785 nm) and green (532 nm) lasers were tested, with the laser power adjusted to the sample. The Raman spectra of (C₆F₅)₂COH⁺[AsF₆]⁻ and (C₆F₅)₂CO·AsF₅ exhibited fluorescence regardless of the excitation wavelength used. The low-temperature (−90 °C) spectrum of solid (C₆F₅)₂CO (Fig. 2), which is in good agreement with the previously published Raman spectrum (Anandhi & Umapathy, 2000 ), was recorded using the Bruker spectrometer with a 785 nm red laser at 1.5 cm⁻¹ resolution. Low-temperature Raman spectra of the (C₆F₅)₂COH⁺[AsF₆]⁻ salt and the (C₆F₅)₂CO·AsF₅ adduct (Fig. 2) were acquired on the Horiba system using a 633 nm red laser at 4 cm⁻¹ resolution from crystalline material protected by a cold nitrogen stream of the crystal-mounting apparatus. Background subtraction from the spectra was performed using the Bruker OPUS8.7 software suite, with 15 iterations of concave rubber-band correction and 50 baseline points.

3. Results and discussion

To facilitate a comparison of structural changes in the decafluorobenzophenone moiety upon protonation and coordination to AsF₅, the crystal structure of (C₆F₅)₂CO was redetermined at 100 K (Table 1; Figs. S1 and S2 in the supporting information). The current structural parameters [C=O = 1.197 (4) Å; C—CO = 1.498 (3) Å; C—C = 1.373 (3)–1.392 (3) Å; C—F = 1.331 (3)–1.341 (3) Å] are in excellent agreement with the previously reported crystal structure measured at 153 K [C=O = 1.201 (8) Å; C—CO = 1.489 (6) Å; C—C = 1.361 (6)–1.403 (5) Å; C—F = 1.329 (5)–1.351 (4) Å; Schwarzer et al., 2004 ]. Decafluorobenzophenone crystallizes in the Sohncke space group C2 and the molecule exhibits axial chirality owing to sterically hindered rotation of the C₆F₅ rings about the C_aryl—C(O)—C_aryl bonds (Farmer & Walker, 1967 ). Similarly, chiral crystallization has also been reported for achiral benzophenone (Matsumoto et al., 2016 ).

The synthetic procedure for the preparation of (C₆F₅)₂COH⁺[AsF₆]⁻ and (C₆F₅)₂CO·AsF₅ involved the reaction of (C₆F₅)₂CO with AsF₅ in anhydrous HF (aHF) and in liquid SO₂ solvent, respectively (Fig. 1). Although decafluorobenzophenone was poorly soluble in aHF, the addition of AsF₅ resulted in its dissolution at room temperature, accompanied by the development of a yellow coloration. Upon cooling the reaction mixture, canary-yellow plank-shaped crystals began to form (Fig. 3). Slow removal of the aHF solvent yielded a crystalline canary-yellow solid, identified as (C₆F₅)₂COH⁺[AsF₆]⁻.

The protonated salt (C₆F₅)₂COH⁺[AsF₆]⁻ crystallizes in the monoclinic space group P2₁/n and contains one (C₆F₅)₂COH⁺ cation and one [AsF₆]⁻ anion in the asymmetric unit (Table 1 and Figs. 4 and S3).

Figure 4
The asymmetric unit with the atom-labelling scheme in the crystal structure of (C₆F₅)₂COH⁺[AsF₆]⁻. The O—H⋯F hydrogen bond is shown as an orange dashed line. Displacement ellipsoids are depicted at the 50% probability level.

In (C₆F₅)₂COH⁺[AsF₆]⁻ (Fig. 4), the C=O bond length [1.274 (2) Å] is elongated compared to that in (C₆F₅)₂CO [1.197 (4) Å], and is comparable to values observed in the protonated ketones: acetone, C₃H₆OH⁺ [1.271 (3) and 1.273 (3) Å]; adamantan-2-one, C₁₀H₁₄OH⁺ [1.274 (2) Å]; and cyclopentanone, C₅H₈OH⁺ [1.266 (3) and 1.267 (2) Å] (Stuart et al., 2017). Similar C=O bond lengths have been reported for the crystal structures of the hemiprotonated benzophenone salts [(C₆H₅)₂CO]₂H⁺[CHB₁₁H₅Cl₆]⁻ [1.274 (4) Å; Stasko et al., 2002] and [(C₆H₅)₂CO]₂H⁺[TaF₆]⁻ [1.259 (3) Å; Marchetti et al., 2007]. The C—C(=O) bonds in (C₆F₅)₂COH⁺ [1.443 (2) and 1.455 (2) Å] are shorter than the corresponding bonds in (C₆F₅)₂CO [1.498 (3) Å]. The remaining C—F and C—C bonds in the (C₆F₅)₂COH⁺ cation [C—C = 1.370 (2)–1.406 (2) Å; C—F = 1.322 (2)–1.334 (2) Å] remain within the range of those observed in the crystal structure of (C₆F₅)₂CO. The angle between the plane normals of the two arene rings [76.58 (6)°] is very similar to that in (C₆F₅)₂CO [77.22 (9)°]. The angles between the arene-ring-plane normals and the plane normal of the carbonyl-bond-containing C₂C=O fragment [36.93 (7) and 44.90 (7)°] are smaller than the corresponding value observed in the crystal structure of (C₆F₅)₂CO [47.97 (7)°].

The crystal structure exhibits a short hydrogen bond between the (C₆F₅)₂COH⁺ cation and the [AsF₆]⁻ anion (Table 2). The H atom lies only slightly out of the C₂C=O plane [0.14 (3) Å]. The O⋯F hydrogen-bond distance [2.5279 (16) Å] is shorter than those observed in the crystal structures of [PnF₆]⁻ (Pn = As or Sb) salts of protonated ketones – acetone, cyclopentanone and adamantan-2-one [2.560 (3)–2.6233 (16) Å; Stuart et al., 2017] – due to the greater Brønsted acidity of the perfluorinated conjugate acid (C₆F₅)₂COH⁺. The hydrogen-bonded As—F bond is elongated [As—F(H) = 1.7853 (10) Å; As—F = 1.6943 (10)–1.7237 (11) Å], resulting in a distortion of the [AsF₆]⁻ anion from idealized octahedral geometry. Interestingly, similar As—F_bridging bond lengths have been observed in metal complexes where the [AsF₆]⁻ anion is coordinated to a metal centre, for example, in [Mg(KrF₂)₄(AsF₆)₂] [1.7856 (14) and 1.7965 (13) Å] (Lozinšek et al., 2017 ).

Table 2
Hydrogen-bond geometry (Å, °) for (C₆F₅)₂COH⁺[AsF₆]⁻

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯F16	0.90 (3)	1.63 (3)	2.5279 (16)	178 (3)

The supporting information includes an additional crystal structure determination of (C₆F₅)₂COH⁺[AsF₆]⁻ employing Ag Kα radiation, providing results essentially similar to those presented in the text.

The reaction of decafluorobenzophenone with an excess of AsF₅ in SO₂ at low temperature (Fig. 1) resulted in the formation of a yellow solution, from which large yellow plate-like crystals of the Lewis acid–base adduct (C₆F₅)₂CO·AsF₅ crystallized at −78 °C over a period of ten days. The compound crystallizes in the orthorhombic space group Pbca (Table 1) and represents a rare crystallographically characterized example of a ketone coordinated to AsF₅ (Figs. 5 and S4).

Figure 5
The asymmetric unit with the atom-labelling scheme in the crystal structure of adduct (C₆F₅)₂CO·AsF₅. Displacement ellipsoids are depicted at the 50% probability level.

The C=O bond length [1.2526 (15) Å] in the crystal structure of the adduct is elongated compared to that in (C₆F₅)₂CO [1.197 (4) Å], although to a lesser extent than in the protonated salt [1.274 (2) Å]. A similar C=O bond length was observed in the benzophenone adduct with TaCl₅ [1.265 (3) Å; Marchetti et al., 2007], in the adducts of BF₃ with ethylene carbonate [1.2486 (14) Å], dimethyl carbonate [1.2559 (14) Å], diethyl carbonate [1.2562 (18) Å] and γ-butyrolactone [1.2541 (16) Å] (Bodin et al., 2023 ), and in the amide moiety of capsaicin [1.2459 (19) Å; Lozinšek, 2025 ]. The elongation of the C=O bond is accompanied by a significant shortening of the anti-C—C(=O) bond [1.4549 (16) Å], whereas the syn-C—C(=O) bond length remains virtually unchanged [1.4879 (16) Å] compared to the corresponding distance observed in (C₆F₅)₂CO [1.498 (3) Å]. All other bond lengths in the (C₆F₅)₂CO moiety within (C₆F₅)₂CO·AsF₅ [C—C = 1.3788 (17)–1.4133 (15) Å; C—F = 1.3162 (13)–1.3359 (15) Å] are similar to those observed in (C₆F₅)₂COH⁺[AsF₆]⁻ and (C₆F₅)₂CO. The angle between the plane normals of the two arene rings [81.57 (4)°] differs from those in the crystal structures of (C₆F₅)₂CO and (C₆F₅)₂COH⁺[AsF₆]⁻. Of the two rings, one is almost coplanar with the plane formed by the C₂C=O moiety [9.44 (5)°], while the other is nearly perpendicular [75.63 (5)°].

The O—As bond [1.9897 (10) Å] in the crystal structure of (C₆F₅)₂CO·AsF₅ is substantially longer than that reported for the adduct of Roesky's ketone, S₂N₂CO·AsF₅ [1.879 (7) Å; Gieren et al., 1980 ], and shorter than the O—As bond lengths (Table 3) observed in the limited number of crystal structures of compounds featuring a C=O—AsF₅ linkage, involving acyl fluorides (Bayer et al., 2021 ; Steiner et al., 2024b ). The As atom resides slightly out of the C₂C=O plane [0.417 (2) Å]. The C=O—As bond angle [133.83 (8)°] is comparable to those in other compounds where a C=O group acts as a ligand to AsF₅ (Table 3). The As—F_ax (ax is axial) bond trans to As—O is somewhat shorter [1.6890 (8) Å] than the As—F_eq (eq is equatorial) bonds in the AsF₅ moiety [1.6960 (10)–1.7018 (9) Å]. The O—As—F_ax angle [176.30 (5)°] is close to linear. The acute O—As—F_eq angles [83.84 (5)–89.06 (5)°], the obtuse F_ax—As—F_eq angles [92.94 (5)–94.16 (5)°] and the trans-F_eq—As—F_eq angles deviating from linearity [171.85 (5) and 172.89 (5)°] reflect the smaller bond domain (Gillespie, 2008 ) and lower bond order (Stuart et al., 2019) of the As—O bond compared to the As—F bonds.

Table 3
Selected geometric parameters (Å, °) for crystallographically characterized compounds featuring AsF₅ coordinated to a carbonyl group

S₂N₂CO = 5-oxo-1,3λ⁴,2,4-dithiadiazole, C₄H₂F₂O₂ = fumaryl fluoride, CH₂ClCFO = chloroacetyl fluoride and CH₂FCFO = fluoroacetyl fluoride.

Compound (moiety)	C=O	O—As	As—F_ax	C—O—As	Reference
(C₆F₅)₂CO·AsF₅	1.2526 (15)	1.9897 (10)	1.6890 (8)	133.83 (8)	This work
S₂N₂CO·AsF₅	1.279 (4)	1.879 (7)	1.695 (6)	127.3 (1)	Gieren et al. (1980)
C₄H₂F₂O₂·4(C₄H₂F₂O₂·AsF₅)·(C₄H₂F₂O₂·2AsF₅)					Bayer et al. (2021)
(C₄H₂F₂O₂·AsF₅)	1.221 (2)	2.0367 (15)	1.6840 (14)	132.33 (15)
(C₄H₂F₂O₂·AsF₅)	1.220 (2)	2.0472 (14)	1.6835 (13)	130.67 (14)
(C₄H₂F₂O₂·2AsF₅)	1.215 (3)	2.0444 (14)	1.6926 (13)	130.83 (14)
CH₂ClCFO·AsF₅	1.213 (3)	2.0418 (16)	1.6854 (14)	128.96 (17)	Steiner et al. (2024b)
CH₂FCFO·AsF₅	1.210 (3)	2.0306 (15)	1.6835 (13)	130.49 (15)	Steiner et al. (2024b)

In all three crystal structures, i.e. (C₆F₅)₂CO, (C₆F₅)₂COH⁺[AsF₆]⁻ and (C₆F₅)₂CO·AsF₅, the dominant intermolecular contacts are F⋯F (Figs. 6 and S5), which involve contributions of 56.8, 69.6 and 72.8%, respectively, whereas the C⋯F contacts (Fig. S6) cover 30.7, 23.7 and 25.2% of the surface area, respectively. The similarity in the intermolecular interactions between (C₆F₅)₂COH⁺[AsF₆]⁻ and (C₆F₅)₂CO·AsF₅ is evident from a comparison of their Hirshfeld fingerprint plots (Figs. 6 and S5–S7) (Spackman & McKinnon, 2002 ; Spackman et al., 2021 ). In the crystal structure of (C₆F₅)₂CO, O⋯F contacts (Fig. S7) also contribute to the packing, accounting for 8.5% of the surface area. However, in the crystal structures of (C₆F₅)₂COH⁺[AsF₆]⁻ and (C₆F₅)₂CO·AsF₅, this contribution is reduced to 4.4 and 1.9%, respectively, as the O atom is bonded to hydrogen and arsenic, respectively. In the protonated salt, F⋯H contacts involve 2.3% of the surface area (Fig. S8).

Figure 6
Hirshfeld fingerprint plots of (a) (C₆F₅)₂CO (56.8%), (b) (C₆F₅)₂COH⁺[AsF₆]⁻ (69.6%) and (c) (C₆F₅)₂CO·AsF₅ (72.8%), showing the prevalent F⋯F intermolecular contacts.

4. Conclusion

In this work, the syntheses, crystal structure determination and Raman spectra of a protonated decafluorobenzophenone salt, (C₆F₅)₂COH⁺[AsF₆]⁻, and a Lewis acid–base adduct, (C₆F₅)₂CO·AsF₅, are reported. The crystal structure of (C₆F₅)₂CO was also redetermined at 100 K. These crystal structures represent rare examples of a protonated perfluorinated aromatic ketone and a ketone–arsenic pentafluoride adduct.

Supporting information

CCDC references: 2483527; 2483526; 2483525; 2483524

Crystal structure: contains datablocks pfbp_1, pfbphas_1, pfbpasf5_1_1, pfpah_asf6_3_1, global. DOI: https://doi.org/10.1107/S2053229625007697/op3037sup1.cif

Structure factors: contains datablock pfbp_1. DOI: https://doi.org/10.1107/S2053229625007697/op3037pfbp_1sup2.hkl

Structure factors: contains datablock pfbphas_1. DOI: https://doi.org/10.1107/S2053229625007697/op3037pfbphas_1sup3.hkl

Structure factors: contains datablock pfbpasf5_1_1. DOI: https://doi.org/10.1107/S2053229625007697/op3037pfbpasf5_1_1sup4.hkl

Structure factors: contains datablock pfpah_asf6_3_1. DOI: https://doi.org/10.1107/S2053229625007697/op3037pfpah_asf6_3_1sup5.hkl

Additional figures. DOI: https://doi.org/10.1107/S2053229625007697/op3037sup6.pdf

Computing details top

Bis(2,3,4,5,6-pentafluorophenyl)methanone (pfbp_1) top

Crystal data top

C₁₃F₁₀O	F(000) = 352
M_r = 362.13	D_x = 2.032 Mg m⁻³
Monoclinic, C2	Cu Kα radiation, λ = 1.54184 Å
a = 20.1460 (4) Å	Cell parameters from 8190 reflections
b = 5.39987 (10) Å	θ = 4.4–75.7°
c = 5.47058 (14) Å	µ = 2.18 mm⁻¹
β = 95.912 (2)°	T = 100 K
V = 591.96 (2) Å³	Plank, clear colourless
Z = 2	0.43 × 0.1 × 0.07 mm

Data collection top

Rigaku OD XtaLAB Synergy-S Dualflex diffractometer with an Eiger2 R CdTe 1M detector	1212 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1193 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.056
Detector resolution: 13.3333 pixels mm^-1	θ_max = 75.8°, θ_min = 4.4°
ω scans	h = −24→25
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2025)	k = −6→6
T_min = 0.491, T_max = 1.000	l = −6→6
10783 measured reflections

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0725P)² + 0.0709P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.034	(Δ/σ)_max < 0.001
wR(F²) = 0.095	Δρ_max = 0.28 e Å⁻³
S = 1.11	Δρ_min = −0.24 e Å⁻³
1212 reflections	Absolute structure: Flack x determined using 514 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
110 parameters	Absolute structure parameter: 0.05 (10)
1 restraint

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.500000	0.5279 (6)	0.000000	0.0254 (6)
F1	0.55011 (6)	0.9228 (3)	0.3092 (2)	0.0297 (3)
O1	0.500000	0.3063 (5)	0.000000	0.0363 (6)
C2	0.56145 (10)	0.6731 (4)	−0.0384 (4)	0.0248 (5)
F2	0.65871 (7)	1.1917 (3)	0.2293 (3)	0.0386 (4)
C3	0.58311 (10)	0.8685 (4)	0.1153 (4)	0.0245 (5)
F3	0.72843 (7)	1.0815 (4)	−0.1543 (3)	0.0393 (4)
C4	0.63891 (11)	1.0062 (4)	0.0784 (4)	0.0287 (5)
F4	0.69032 (7)	0.6982 (3)	−0.4572 (3)	0.0399 (4)
C5	0.67484 (11)	0.9486 (4)	−0.1160 (4)	0.0288 (5)
F5	0.58043 (7)	0.4335 (3)	−0.3865 (3)	0.0379 (4)
C6	0.65533 (11)	0.7512 (5)	−0.2692 (4)	0.0294 (5)
C7	0.59954 (11)	0.6169 (4)	−0.2295 (4)	0.0279 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0312 (15)	0.0190 (14)	0.0261 (15)	0.000	0.0031 (11)	0.000
F1	0.0328 (6)	0.0324 (7)	0.0249 (6)	0.0001 (6)	0.0080 (5)	−0.0056 (6)
O1	0.0367 (12)	0.0214 (11)	0.0519 (15)	0.000	0.0095 (10)	0.000
C2	0.0275 (10)	0.0215 (10)	0.0252 (10)	0.0037 (8)	0.0017 (8)	0.0011 (8)
F2	0.0376 (7)	0.0349 (8)	0.0433 (9)	−0.0090 (6)	0.0052 (6)	−0.0128 (7)
C3	0.0267 (9)	0.0247 (11)	0.0225 (10)	0.0031 (8)	0.0043 (8)	0.0017 (7)
F3	0.0287 (7)	0.0438 (8)	0.0466 (9)	−0.0078 (6)	0.0097 (6)	0.0009 (7)
C4	0.0305 (11)	0.0263 (11)	0.0288 (12)	0.0003 (9)	0.0005 (9)	−0.0021 (10)
F4	0.0345 (7)	0.0559 (10)	0.0311 (8)	0.0034 (7)	0.0130 (6)	−0.0047 (8)
C5	0.0240 (10)	0.0308 (12)	0.0317 (11)	−0.0003 (9)	0.0035 (8)	0.0043 (10)
F5	0.0401 (7)	0.0378 (8)	0.0368 (8)	−0.0026 (7)	0.0089 (6)	−0.0160 (7)
C6	0.0280 (10)	0.0360 (13)	0.0244 (10)	0.0069 (9)	0.0048 (8)	0.0009 (9)
C7	0.0295 (10)	0.0260 (10)	0.0281 (11)	0.0033 (9)	0.0018 (8)	−0.0037 (9)

Geometric parameters (Å, º) top

C1—O1	1.197 (4)	C3—C4	1.380 (3)
C1—C2ⁱ	1.498 (3)	F3—C5	1.331 (3)
C1—C2	1.498 (3)	C4—C5	1.382 (3)
F1—C3	1.341 (2)	F4—C6	1.336 (3)
C2—C3	1.391 (3)	C5—C6	1.388 (3)
C2—C7	1.392 (3)	F5—C7	1.341 (3)
F2—C4	1.332 (3)	C6—C7	1.373 (3)

O1—C1—C2ⁱ	121.54 (13)	C3—C4—C5	119.4 (2)
O1—C1—C2	121.54 (13)	F3—C5—C4	119.8 (2)
C2ⁱ—C1—C2	116.9 (3)	F3—C5—C6	120.2 (2)
C3—C2—C1	121.61 (18)	C4—C5—C6	119.96 (19)
C3—C2—C7	117.1 (2)	F4—C6—C5	119.4 (2)
C7—C2—C1	121.2 (2)	F4—C6—C7	120.9 (2)
F1—C3—C2	119.60 (18)	C7—C6—C5	119.7 (2)
F1—C3—C4	118.4 (2)	F5—C7—C2	119.8 (2)
C4—C3—C2	122.0 (2)	F5—C7—C6	118.3 (2)
F2—C4—C3	120.7 (2)	C6—C7—C2	121.8 (2)
F2—C4—C5	119.9 (2)

C1—C2—C3—F1	2.9 (3)	C3—C2—C7—F5	−178.74 (19)
C1—C2—C3—C4	−178.70 (18)	C3—C2—C7—C6	−1.4 (3)
C1—C2—C7—F5	1.6 (3)	C3—C4—C5—F3	179.50 (19)
C1—C2—C7—C6	178.88 (19)	C3—C4—C5—C6	−1.1 (3)
F1—C3—C4—F2	−1.2 (3)	F3—C5—C6—F4	−0.9 (3)
F1—C3—C4—C5	178.09 (18)	F3—C5—C6—C7	−179.3 (2)
O1—C1—C2—C3	−131.84 (16)	C4—C5—C6—F4	179.7 (2)
O1—C1—C2—C7	47.8 (2)	C4—C5—C6—C7	1.3 (3)
C2ⁱ—C1—C2—C3	48.16 (16)	F4—C6—C7—C2	−178.4 (2)
C2ⁱ—C1—C2—C7	−132.2 (2)	F4—C6—C7—F5	−1.0 (3)
C2—C3—C4—F2	−179.69 (19)	C5—C6—C7—C2	0.0 (3)
C2—C3—C4—C5	−0.4 (3)	C5—C6—C7—F5	177.4 (2)
F2—C4—C5—F3	−1.2 (3)	C7—C2—C3—F1	−176.83 (17)
F2—C4—C5—C6	178.2 (2)	C7—C2—C3—C4	1.6 (3)

Symmetry code: (i) −x+1, y, −z.

[Bis(2,3,4,5,6-pentafluorophenyl)methylidene]oxidanium hexafluoridoarsenate (pfbphas_1) top

Crystal data top

C₁₃HF₁₀O⁺·AsF₆⁻	F(000) = 1056
M_r = 552.06	D_x = 2.300 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 8.19207 (7) Å	Cell parameters from 17949 reflections
b = 21.17409 (18) Å	θ = 4.2–75.8°
c = 9.28475 (9) Å	µ = 4.70 mm⁻¹
β = 98.2086 (8)°	T = 100 K
V = 1594.03 (2) Å³	Irregular, clear yellow
Z = 4	0.09 × 0.05 × 0.03 mm

Data collection top

Rigaku OD XtaLAB Synergy-S Dualflex diffractometer with an Eiger2 R CdTe 1M detector	3336 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3134 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.032
Detector resolution: 13.3333 pixels mm^-1	θ_max = 76.2°, θ_min = 4.2°
ω scans	h = −10→10
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2025)	k = −26→26
T_min = 0.842, T_max = 1.000	l = −11→11
26147 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0365P)² + 1.1067P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.066	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.30 e Å⁻³
3336 reflections	Δρ_min = −0.49 e Å⁻³
285 parameters	Extinction correction: SHELXL2019 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00062 (9)
Primary atom site location: iterative

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
As1	−0.04788 (2)	0.36662 (2)	0.08141 (2)	0.01629 (8)
C1	0.0308 (2)	0.24086 (8)	0.45829 (18)	0.0173 (3)
F1	0.08742 (14)	0.22108 (5)	0.76315 (11)	0.0250 (2)
O1	0.08150 (15)	0.23385 (6)	0.33572 (13)	0.0206 (3)
H1	0.095 (4)	0.2690 (14)	0.285 (3)	0.047 (8)*
C2	−0.0159 (2)	0.18363 (8)	0.52632 (18)	0.0169 (3)
F2	0.04697 (14)	0.10757 (6)	0.88119 (13)	0.0316 (3)
C3	0.0209 (2)	0.17462 (8)	0.67751 (19)	0.0192 (3)
F3	−0.09505 (16)	0.01254 (5)	0.71399 (15)	0.0365 (3)
C4	−0.0006 (2)	0.11675 (9)	0.7396 (2)	0.0226 (4)
F4	−0.18184 (14)	0.02812 (5)	0.42358 (14)	0.0330 (3)
C5	−0.0702 (2)	0.06760 (8)	0.6537 (2)	0.0254 (4)
F5	−0.12336 (14)	0.13815 (5)	0.29942 (12)	0.0257 (2)
C6	−0.1127 (2)	0.07546 (8)	0.5054 (2)	0.0236 (4)
F6	0.28339 (14)	0.33217 (6)	0.46949 (13)	0.0354 (3)
C7	−0.0819 (2)	0.13200 (8)	0.4428 (2)	0.0198 (3)
F7	0.2469 (2)	0.45084 (6)	0.56574 (17)	0.0600 (5)
C8	0.0198 (2)	0.30331 (8)	0.52164 (18)	0.0206 (3)
F8	−0.0351 (3)	0.48440 (6)	0.66527 (16)	0.0652 (6)
C9	0.1433 (3)	0.34851 (10)	0.5171 (2)	0.0285 (4)
F9	−0.2831 (2)	0.39958 (7)	0.67083 (14)	0.0508 (4)
C10	0.1259 (3)	0.40887 (10)	0.5671 (2)	0.0402 (6)
F10	−0.24547 (15)	0.28072 (5)	0.58219 (13)	0.0294 (2)
C11	−0.0181 (4)	0.42584 (9)	0.6190 (2)	0.0435 (6)
F11	0.05490 (13)	0.43629 (5)	0.09411 (13)	0.0284 (2)
C12	−0.1439 (3)	0.38265 (10)	0.6241 (2)	0.0352 (5)
F12	−0.21720 (13)	0.39793 (6)	−0.02074 (12)	0.0289 (2)
C13	−0.1225 (3)	0.32160 (9)	0.57846 (19)	0.0246 (4)
F13	0.03949 (14)	0.34708 (6)	−0.06940 (11)	0.0312 (3)
F14	−0.12650 (14)	0.38246 (6)	0.23962 (12)	0.0298 (2)
F15	−0.13957 (14)	0.29328 (5)	0.07867 (14)	0.0305 (3)
F16	0.12598 (12)	0.33179 (5)	0.19056 (11)	0.0226 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.01455 (12)	0.01742 (12)	0.01641 (12)	−0.00053 (6)	0.00052 (7)	0.00166 (6)
C1	0.0135 (7)	0.0208 (8)	0.0168 (7)	0.0006 (6)	−0.0011 (6)	0.0017 (6)
F1	0.0323 (6)	0.0247 (5)	0.0169 (5)	0.0007 (4)	−0.0001 (4)	−0.0010 (4)
O1	0.0224 (6)	0.0214 (6)	0.0187 (6)	0.0009 (5)	0.0055 (5)	0.0037 (5)
C2	0.0141 (7)	0.0175 (7)	0.0191 (8)	0.0020 (6)	0.0024 (6)	0.0016 (6)
F2	0.0332 (6)	0.0380 (6)	0.0248 (5)	0.0101 (5)	0.0084 (4)	0.0153 (5)
C3	0.0170 (8)	0.0204 (8)	0.0205 (8)	0.0029 (6)	0.0040 (6)	0.0003 (6)
F3	0.0364 (6)	0.0202 (5)	0.0567 (8)	0.0023 (5)	0.0192 (6)	0.0163 (5)
C4	0.0188 (8)	0.0267 (9)	0.0236 (9)	0.0070 (7)	0.0074 (7)	0.0088 (7)
F4	0.0297 (6)	0.0196 (5)	0.0513 (7)	−0.0072 (4)	0.0120 (5)	−0.0097 (5)
C5	0.0194 (8)	0.0180 (8)	0.0415 (11)	0.0046 (7)	0.0133 (8)	0.0091 (7)
F5	0.0260 (6)	0.0290 (6)	0.0210 (5)	−0.0039 (4)	−0.0007 (4)	−0.0045 (4)
C6	0.0164 (8)	0.0182 (8)	0.0377 (10)	0.0002 (6)	0.0085 (7)	−0.0034 (7)
F6	0.0287 (6)	0.0374 (7)	0.0366 (6)	−0.0143 (5)	−0.0072 (5)	0.0131 (5)
C7	0.0161 (8)	0.0200 (8)	0.0234 (9)	0.0018 (6)	0.0033 (7)	−0.0011 (6)
F7	0.0829 (11)	0.0277 (7)	0.0563 (9)	−0.0295 (7)	−0.0355 (8)	0.0150 (6)
C8	0.0289 (9)	0.0173 (8)	0.0142 (7)	−0.0010 (7)	−0.0022 (6)	0.0019 (6)
F8	0.1303 (16)	0.0168 (6)	0.0379 (8)	0.0131 (8)	−0.0242 (9)	−0.0088 (5)
C9	0.0358 (11)	0.0243 (9)	0.0211 (9)	−0.0069 (8)	−0.0106 (8)	0.0069 (7)
F9	0.0868 (11)	0.0415 (8)	0.0255 (6)	0.0362 (8)	0.0124 (7)	−0.0008 (5)
C10	0.0623 (15)	0.0200 (9)	0.0293 (10)	−0.0127 (10)	−0.0240 (10)	0.0073 (8)
F10	0.0339 (6)	0.0272 (6)	0.0304 (6)	0.0071 (5)	0.0156 (5)	0.0044 (4)
C11	0.0855 (19)	0.0155 (9)	0.0215 (9)	0.0079 (10)	−0.0190 (11)	−0.0016 (7)
F11	0.0230 (5)	0.0196 (5)	0.0431 (7)	−0.0029 (4)	0.0059 (5)	0.0021 (4)
C12	0.0640 (15)	0.0247 (10)	0.0151 (8)	0.0176 (10)	−0.0009 (9)	−0.0013 (7)
F12	0.0208 (5)	0.0323 (6)	0.0317 (6)	0.0036 (4)	−0.0028 (4)	0.0089 (5)
C13	0.0381 (10)	0.0203 (8)	0.0148 (8)	0.0056 (8)	0.0017 (7)	0.0016 (6)
F13	0.0311 (6)	0.0432 (7)	0.0194 (5)	0.0059 (5)	0.0036 (4)	−0.0032 (5)
F14	0.0222 (5)	0.0440 (7)	0.0240 (5)	−0.0001 (5)	0.0066 (4)	−0.0015 (5)
F15	0.0223 (5)	0.0211 (5)	0.0455 (7)	−0.0043 (4)	−0.0042 (5)	0.0014 (5)
F16	0.0162 (5)	0.0265 (5)	0.0242 (5)	−0.0014 (4)	−0.0003 (4)	0.0074 (4)

Geometric parameters (Å, º) top

As1—F11	1.6943 (10)	C4—C5	1.383 (3)
As1—F12	1.6992 (10)	F4—C6	1.334 (2)
As1—F13	1.7118 (11)	C5—C6	1.382 (3)
As1—F14	1.7191 (11)	F5—C7	1.332 (2)
As1—F15	1.7237 (11)	C6—C7	1.370 (2)
As1—F16	1.7853 (10)	F6—C9	1.333 (3)
C1—O1	1.274 (2)	F7—C10	1.333 (3)
C1—C2	1.443 (2)	C8—C9	1.397 (3)
C1—C8	1.455 (2)	C8—C13	1.401 (3)
F1—C3	1.332 (2)	F8—C11	1.326 (2)
O1—H1	0.90 (3)	C9—C10	1.374 (3)
C2—C3	1.406 (2)	F9—C12	1.326 (3)
C2—C7	1.403 (2)	C10—C11	1.385 (4)
F2—C4	1.331 (2)	F10—C13	1.333 (2)
C3—C4	1.376 (2)	C11—C12	1.383 (4)
F3—C5	1.322 (2)	C12—C13	1.379 (3)

F11—As1—F12	93.28 (5)	F3—C5—C4	119.70 (18)
F11—As1—F13	90.33 (6)	F3—C5—C6	119.75 (18)
F11—As1—F14	90.79 (6)	C6—C5—C4	120.54 (16)
F11—As1—F15	175.30 (5)	F4—C6—C5	120.19 (17)
F11—As1—F16	88.39 (5)	F4—C6—C7	120.29 (18)
F12—As1—F13	92.35 (6)	C7—C6—C5	119.52 (17)
F12—As1—F14	91.45 (6)	F5—C7—C2	119.96 (15)
F12—As1—F15	91.38 (5)	F5—C7—C6	118.23 (16)
F12—As1—F16	178.18 (5)	C6—C7—C2	121.73 (17)
F13—As1—F14	175.97 (6)	C9—C8—C1	121.55 (18)
F13—As1—F15	90.14 (6)	C9—C8—C13	117.82 (17)
F13—As1—F16	88.38 (5)	C13—C8—C1	120.42 (16)
F14—As1—F15	88.43 (6)	F6—C9—C8	119.55 (18)
F14—As1—F16	87.79 (5)	F6—C9—C10	119.3 (2)
F15—As1—F16	86.95 (5)	C10—C9—C8	121.1 (2)
O1—C1—C2	115.69 (15)	F7—C10—C9	120.3 (3)
O1—C1—C8	120.91 (15)	F7—C10—C11	120.2 (2)
C2—C1—C8	123.39 (15)	C9—C10—C11	119.6 (2)
C1—O1—H1	117.0 (19)	F8—C11—C10	119.3 (2)
C3—C2—C1	121.21 (15)	F8—C11—C12	119.6 (3)
C7—C2—C1	121.16 (15)	C12—C11—C10	121.07 (19)
C7—C2—C3	117.20 (15)	F9—C12—C11	120.8 (2)
F1—C3—C2	120.48 (15)	F9—C12—C13	120.5 (2)
F1—C3—C4	118.27 (16)	C13—C12—C11	118.8 (2)
C4—C3—C2	121.12 (16)	F10—C13—C8	120.21 (16)
F2—C4—C3	120.45 (18)	F10—C13—C12	118.09 (19)
F2—C4—C5	119.84 (17)	C12—C13—C8	121.6 (2)
C3—C4—C5	119.70 (17)

C1—C2—C3—F1	5.8 (2)	F4—C6—C7—C2	177.19 (16)
C1—C2—C3—C4	−169.91 (16)	F4—C6—C7—F5	0.3 (3)
C1—C2—C7—F5	−9.2 (2)	C5—C6—C7—C2	−3.5 (3)
C1—C2—C7—C6	173.94 (16)	C5—C6—C7—F5	179.64 (15)
C1—C8—C9—F6	−8.1 (2)	F6—C9—C10—F7	1.1 (3)
C1—C8—C9—C10	174.91 (17)	F6—C9—C10—C11	−178.91 (17)
C1—C8—C13—F10	3.7 (2)	C7—C2—C3—F1	178.40 (15)
C1—C8—C13—C12	−172.58 (16)	C7—C2—C3—C4	2.6 (2)
F1—C3—C4—F2	−1.2 (2)	F7—C10—C11—F8	1.0 (3)
F1—C3—C4—C5	179.64 (15)	F7—C10—C11—C12	−178.71 (17)
O1—C1—C2—C3	141.13 (16)	C8—C1—C2—C3	−39.8 (2)
O1—C1—C2—C7	−31.1 (2)	C8—C1—C2—C7	147.93 (17)
O1—C1—C8—C9	−41.8 (2)	C8—C9—C10—F7	178.10 (16)
O1—C1—C8—C13	132.82 (17)	C8—C9—C10—C11	−1.9 (3)
C2—C1—C8—C9	139.21 (17)	F8—C11—C12—F9	1.9 (3)
C2—C1—C8—C13	−46.2 (2)	F8—C11—C12—C13	−178.59 (17)
C2—C3—C4—F2	174.68 (15)	C9—C8—C13—F10	178.48 (15)
C2—C3—C4—C5	−4.5 (3)	C9—C8—C13—C12	2.2 (3)
F2—C4—C5—F3	2.7 (3)	C9—C10—C11—F8	−179.08 (17)
F2—C4—C5—C6	−176.82 (16)	C9—C10—C11—C12	1.3 (3)
C3—C2—C7—F5	178.22 (15)	F9—C12—C13—C8	176.69 (16)
C3—C2—C7—C6	1.4 (3)	F9—C12—C13—F10	0.4 (3)
C3—C4—C5—F3	−178.10 (16)	C10—C11—C12—F9	−178.45 (18)
C3—C4—C5—C6	2.4 (3)	C10—C11—C12—C13	1.1 (3)
F3—C5—C6—F4	1.4 (3)	C11—C12—C13—C8	−2.8 (3)
F3—C5—C6—C7	−177.95 (16)	C11—C12—C13—F10	−179.17 (17)
C4—C5—C6—F4	−179.09 (16)	C13—C8—C9—F6	177.20 (15)
C4—C5—C6—C7	1.6 (3)	C13—C8—C9—C10	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···F16	0.90 (3)	1.63 (3)	2.5279 (16)	178 (3)

[Bis(2,3,4,5,6-pentafluorophenyl)methylidene]\ (pentafluoro-λ⁶-arsanyl)oxidanium (pfbpasf5_1_1) top

Crystal data top

C₁₃AsF₁₅O	D_x = 2.269 Mg m⁻³
M_r = 532.05	Ag Kα radiation, λ = 0.56087 Å
Orthorhombic, Pbca	Cell parameters from 47122 reflections
a = 12.39109 (18) Å	θ = 2.0–30.5°
b = 12.04038 (17) Å	µ = 1.25 mm⁻¹
c = 20.8754 (3) Å	T = 100 K
V = 3114.47 (8) Å³	Block, clear yellow
Z = 8	0.58 × 0.29 × 0.22 mm
F(000) = 2032

Data collection top

Rigaku OD XtaLAB Synergy-S Dualflex diffractometer with an Eiger2 R CdTe 1M detector	8537 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Ag) X-ray Source	7132 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.033
Detector resolution: 13.3333 pixels mm^-1	θ_max = 30.9°, θ_min = 2.0°
ω scans	h = −22→20
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2025)	k = −19→20
T_min = 0.290, T_max = 1.000	l = −33→34
97292 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: iterative
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0274P)² + 2.135P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.081	(Δ/σ)_max = 0.002
S = 1.09	Δρ_max = 0.53 e Å⁻³
8537 reflections	Δρ_min = −0.64 e Å⁻³
271 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
As1	0.50792 (2)	0.40911 (2)	0.64848 (2)	0.02257 (3)
C5	0.28261 (10)	0.19309 (10)	0.92493 (6)	0.02246 (19)
C4	0.24222 (10)	0.12768 (11)	0.87612 (6)	0.0234 (2)
C3	0.27171 (10)	0.14865 (10)	0.81359 (6)	0.02212 (19)
C2	0.34450 (9)	0.23460 (9)	0.79776 (5)	0.01867 (17)
C7	0.38522 (9)	0.29831 (9)	0.84923 (5)	0.01876 (17)
C6	0.35415 (9)	0.27853 (10)	0.91164 (5)	0.02070 (18)
C1	0.37817 (9)	0.25751 (10)	0.73232 (5)	0.02101 (18)
C8	0.32579 (9)	0.20170 (10)	0.67684 (5)	0.02081 (18)
C9	0.22534 (10)	0.23470 (12)	0.65449 (6)	0.0252 (2)
C10	0.18101 (10)	0.18654 (12)	0.60053 (6)	0.0253 (2)
C11	0.23673 (11)	0.10312 (11)	0.56902 (6)	0.0242 (2)
C12	0.33583 (12)	0.06706 (10)	0.59150 (6)	0.0256 (2)
C13	0.37967 (11)	0.11747 (10)	0.64512 (6)	0.0240 (2)
F11	0.55613 (8)	0.48758 (8)	0.58783 (4)	0.03464 (19)
F12	0.48259 (10)	0.52132 (9)	0.69524 (5)	0.0447 (3)
F13	0.63035 (8)	0.39401 (10)	0.68384 (5)	0.0445 (3)
F15	0.52715 (9)	0.28689 (8)	0.60916 (5)	0.0378 (2)
F14	0.37842 (8)	0.41244 (8)	0.62149 (5)	0.0356 (2)
F5	0.45393 (7)	0.37995 (6)	0.83950 (4)	0.02408 (14)
F4	0.39370 (7)	0.33967 (7)	0.95905 (4)	0.02815 (16)
F3	0.25376 (8)	0.17360 (7)	0.98480 (4)	0.03145 (17)
F2	0.17660 (8)	0.04381 (8)	0.89019 (4)	0.03378 (19)
F1	0.22986 (8)	0.08292 (8)	0.76879 (4)	0.03288 (19)
F6	0.17231 (7)	0.31596 (10)	0.68461 (5)	0.0414 (2)
F7	0.08585 (7)	0.22050 (10)	0.57809 (5)	0.0386 (2)
F8	0.19484 (8)	0.05827 (8)	0.51654 (4)	0.03254 (18)
F9	0.38834 (9)	−0.01392 (8)	0.56135 (5)	0.0397 (2)
F10	0.47526 (8)	0.08443 (8)	0.66693 (5)	0.0355 (2)
O1	0.45443 (8)	0.32420 (9)	0.72383 (4)	0.0294 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.02273 (6)	0.02432 (6)	0.02067 (6)	−0.00182 (4)	0.00199 (4)	0.00121 (4)
C5	0.0242 (5)	0.0227 (5)	0.0205 (5)	−0.0004 (4)	0.0030 (4)	0.0015 (4)
C4	0.0226 (5)	0.0228 (5)	0.0249 (5)	−0.0053 (4)	−0.0008 (4)	0.0033 (4)
C3	0.0223 (5)	0.0223 (5)	0.0218 (5)	−0.0040 (4)	−0.0031 (4)	0.0007 (4)
C2	0.0180 (4)	0.0192 (4)	0.0188 (4)	−0.0007 (3)	−0.0008 (3)	0.0004 (3)
C7	0.0181 (4)	0.0170 (4)	0.0212 (4)	−0.0003 (3)	0.0014 (3)	−0.0007 (3)
C6	0.0218 (4)	0.0200 (4)	0.0202 (4)	−0.0008 (4)	0.0016 (3)	−0.0028 (3)
C1	0.0204 (4)	0.0225 (5)	0.0201 (4)	0.0000 (4)	−0.0017 (3)	0.0011 (3)
C8	0.0209 (4)	0.0228 (5)	0.0187 (4)	−0.0005 (4)	−0.0020 (3)	−0.0003 (3)
C9	0.0192 (4)	0.0353 (6)	0.0211 (5)	0.0026 (4)	−0.0004 (3)	−0.0052 (4)
C10	0.0195 (4)	0.0353 (6)	0.0211 (5)	−0.0010 (4)	−0.0022 (4)	−0.0014 (4)
C11	0.0284 (5)	0.0254 (5)	0.0188 (4)	−0.0050 (4)	−0.0026 (4)	−0.0006 (4)
C12	0.0323 (6)	0.0195 (5)	0.0251 (5)	0.0020 (4)	−0.0029 (4)	−0.0020 (4)
C13	0.0261 (5)	0.0194 (4)	0.0265 (5)	0.0029 (4)	−0.0054 (4)	0.0005 (4)
F11	0.0407 (5)	0.0354 (4)	0.0278 (4)	−0.0089 (4)	0.0053 (3)	0.0073 (3)
F12	0.0583 (7)	0.0336 (5)	0.0421 (5)	−0.0139 (5)	0.0196 (5)	−0.0138 (4)
F13	0.0248 (4)	0.0637 (7)	0.0450 (5)	−0.0123 (4)	−0.0074 (4)	0.0217 (5)
F15	0.0465 (5)	0.0276 (4)	0.0393 (5)	0.0008 (4)	0.0153 (4)	−0.0043 (4)
F14	0.0271 (4)	0.0348 (4)	0.0450 (5)	−0.0006 (3)	−0.0076 (4)	0.0128 (4)
F5	0.0261 (3)	0.0209 (3)	0.0252 (3)	−0.0068 (3)	0.0045 (3)	−0.0034 (3)
F4	0.0343 (4)	0.0287 (4)	0.0215 (3)	−0.0061 (3)	0.0031 (3)	−0.0079 (3)
F3	0.0401 (5)	0.0327 (4)	0.0215 (3)	−0.0072 (3)	0.0075 (3)	0.0021 (3)
F2	0.0369 (4)	0.0331 (4)	0.0313 (4)	−0.0178 (4)	−0.0015 (3)	0.0063 (3)
F1	0.0398 (5)	0.0345 (4)	0.0243 (4)	−0.0176 (4)	−0.0072 (3)	−0.0001 (3)
F6	0.0254 (4)	0.0632 (7)	0.0356 (5)	0.0168 (4)	−0.0046 (3)	−0.0227 (4)
F7	0.0220 (4)	0.0611 (6)	0.0327 (4)	0.0062 (4)	−0.0084 (3)	−0.0100 (4)
F8	0.0385 (5)	0.0358 (4)	0.0234 (4)	−0.0070 (4)	−0.0066 (3)	−0.0059 (3)
F9	0.0515 (6)	0.0266 (4)	0.0410 (5)	0.0127 (4)	−0.0099 (4)	−0.0134 (4)
F10	0.0359 (4)	0.0278 (4)	0.0429 (5)	0.0139 (3)	−0.0153 (4)	−0.0052 (3)
O1	0.0285 (4)	0.0392 (5)	0.0205 (4)	−0.0126 (4)	−0.0014 (3)	0.0035 (3)

Geometric parameters (Å, º) top

As1—F11	1.6890 (8)	C7—F5	1.3162 (13)
As1—F12	1.6960 (10)	C6—F4	1.3271 (14)
As1—F13	1.6967 (10)	C1—C8	1.4879 (16)
As1—F15	1.7018 (9)	C1—O1	1.2526 (15)
As1—F14	1.7012 (9)	C8—C9	1.3874 (17)
As1—O1	1.9897 (10)	C8—C13	1.3830 (17)
C5—C4	1.3817 (18)	C9—C10	1.3808 (17)
C5—C6	1.3861 (17)	C9—F6	1.3359 (15)
C5—F3	1.3209 (14)	C10—C11	1.3850 (19)
C4—C3	1.3788 (17)	C10—F7	1.3331 (15)
C4—F2	1.3293 (14)	C11—C12	1.3844 (19)
C3—C2	1.4120 (16)	C11—F8	1.3270 (14)
C3—F1	1.3303 (14)	C12—C13	1.3844 (18)
C2—C7	1.4133 (15)	C12—F9	1.3304 (15)
C2—C1	1.4549 (16)	C13—F10	1.3300 (15)
C7—C6	1.3792 (16)

F11—As1—F12	92.94 (5)	F5—C7—C2	121.25 (10)
F11—As1—F13	94.01 (5)	F5—C7—C6	117.09 (10)
F11—As1—F15	94.16 (5)	C7—C6—C5	119.72 (11)
F11—As1—F14	94.14 (5)	F4—C6—C5	119.91 (10)
F11—As1—O1	176.30 (5)	F4—C6—C7	120.37 (10)
F12—As1—F13	90.03 (6)	C2—C1—C8	121.34 (10)
F12—As1—F15	172.89 (5)	O1—C1—C2	118.07 (10)
F12—As1—F14	89.84 (6)	O1—C1—C8	120.57 (11)
F12—As1—O1	83.84 (5)	C9—C8—C1	121.59 (11)
F13—As1—F15	89.54 (6)	C13—C8—C1	119.55 (11)
F13—As1—F14	171.85 (5)	C13—C8—C9	118.82 (11)
F13—As1—O1	84.20 (5)	C10—C9—C8	120.73 (12)
F15—As1—O1	89.06 (5)	F6—C9—C8	119.52 (11)
F14—As1—F15	89.58 (5)	F6—C9—C10	119.73 (11)
F14—As1—O1	87.69 (4)	C9—C10—C11	119.59 (11)
C4—C5—C6	120.47 (11)	F7—C10—C9	120.65 (12)
F3—C5—C4	119.90 (11)	F7—C10—C11	119.76 (11)
F3—C5—C6	119.62 (11)	C12—C11—C10	120.57 (11)
C3—C4—C5	119.86 (11)	F8—C11—C10	119.49 (12)
F2—C4—C5	119.44 (11)	F8—C11—C12	119.94 (12)
F2—C4—C3	120.69 (11)	C13—C12—C11	118.99 (12)
C4—C3—C2	121.67 (11)	F9—C12—C11	120.22 (12)
F1—C3—C4	116.95 (11)	F9—C12—C13	120.79 (12)
F1—C3—C2	121.38 (11)	C8—C13—C12	121.28 (12)
C3—C2—C7	116.61 (10)	F10—C13—C8	119.04 (11)
C3—C2—C1	122.81 (10)	F10—C13—C12	119.68 (12)
C7—C2—C1	120.58 (10)	C1—O1—As1	133.83 (8)
C6—C7—C2	121.66 (10)

C5—C4—C3—C2	1.28 (19)	C9—C8—C13—F10	−179.02 (12)
C5—C4—C3—F1	−179.82 (12)	C9—C10—C11—C12	0.6 (2)
C4—C5—C6—C7	−0.01 (18)	C9—C10—C11—F8	−178.84 (12)
C4—C5—C6—F4	−178.94 (11)	C10—C11—C12—C13	−1.5 (2)
C4—C3—C2—C7	−0.25 (17)	C10—C11—C12—F9	179.28 (13)
C4—C3—C2—C1	179.10 (12)	C11—C12—C13—C8	0.8 (2)
C3—C2—C7—C6	−0.93 (16)	C11—C12—C13—F10	−179.39 (12)
C3—C2—C7—F5	179.67 (10)	C13—C8—C9—C10	−1.7 (2)
C3—C2—C1—C8	8.79 (17)	C13—C8—C9—F6	−179.98 (13)
C3—C2—C1—O1	−169.78 (12)	F5—C7—C6—C5	−179.50 (11)
C2—C7—C6—C5	1.07 (18)	F5—C7—C6—F4	−0.58 (17)
C2—C7—C6—F4	180.00 (11)	F3—C5—C4—C3	179.49 (12)
C2—C1—C8—C9	77.33 (16)	F3—C5—C4—F2	−1.65 (19)
C2—C1—C8—C13	−105.02 (14)	F3—C5—C6—C7	179.35 (11)
C2—C1—O1—As1	−163.21 (9)	F3—C5—C6—F4	0.42 (18)
C7—C2—C1—C8	−171.88 (11)	F2—C4—C3—C2	−177.56 (12)
C7—C2—C1—O1	9.55 (17)	F2—C4—C3—F1	1.33 (19)
C6—C5—C4—C3	−1.15 (19)	F1—C3—C2—C7	−179.10 (11)
C6—C5—C4—F2	177.71 (12)	F1—C3—C2—C1	0.26 (18)
C1—C2—C7—C6	179.70 (11)	F6—C9—C10—C11	179.32 (13)
C1—C2—C7—F5	0.30 (17)	F6—C9—C10—F7	0.2 (2)
C1—C8—C9—C10	175.95 (12)	F7—C10—C11—C12	179.77 (12)
C1—C8—C9—F6	−2.32 (19)	F7—C10—C11—F8	0.33 (19)
C1—C8—C13—C12	−176.95 (12)	F8—C11—C12—C13	177.92 (12)
C1—C8—C13—F10	3.27 (18)	F8—C11—C12—F9	−1.3 (2)
C8—C1—O1—As1	18.2 (2)	F9—C12—C13—C8	−179.97 (12)
C8—C9—C10—C11	1.0 (2)	F9—C12—C13—F10	−0.2 (2)
C8—C9—C10—F7	−178.12 (12)	O1—C1—C8—C9	−104.14 (15)
C9—C8—C13—C12	0.76 (19)	O1—C1—C8—C13	73.51 (16)

[Bis(2,3,4,5,6-pentafluorophenyl)methylidene]oxidanium hexafluoridoarsenate (pfpah_asf6_3_1) top

Crystal data top

C₁₃HF₁₀O⁺·AsF₆⁻	F(000) = 1056
M_r = 552.06	D_x = 2.302 Mg m⁻³
Monoclinic, P2₁/n	Ag Kα radiation, λ = 0.56087 Å
a = 8.18723 (9) Å	Cell parameters from 57924 reflections
b = 21.1810 (3) Å	θ = 1.9–30.9°
c = 9.28084 (11) Å	µ = 1.23 mm⁻¹
β = 98.1450 (11)°	T = 100 K
V = 1593.19 (3) Å³	Plank, clear yellow
Z = 4	0.79 × 0.3 × 0.24 mm

Data collection top

Rigaku OD XtaLAB Synergy-S Dualflex diffractometer with an Eiger2 R CdTe 1M detector	7721 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Ag) X-ray Source	6714 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.061
Detector resolution: 13.3333 pixels mm^-1	θ_max = 27.9°, θ_min = 2.3°
ω scans	h = −12→13
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2025)	k = −35→35
T_min = 0.184, T_max = 1.000	l = −15→15
111309 measured reflections

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	All H-atom parameters refined
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0409P)² + 0.4919P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
7721 reflections	Δρ_max = 0.66 e Å⁻³
284 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
As1	0.54834 (2)	0.13336 (2)	0.41865 (2)	0.01973 (4)
C1	0.46962 (13)	0.25916 (5)	0.04191 (11)	0.02022 (16)
F1	0.41347 (10)	0.27895 (4)	−0.26302 (8)	0.02849 (14)
O1	0.41878 (11)	0.26616 (4)	0.16450 (9)	0.02390 (15)
H1	0.406 (3)	0.2335 (10)	0.208 (2)	0.037 (5)*
C2	0.51636 (13)	0.31646 (5)	−0.02621 (11)	0.02003 (16)
F2	0.45354 (11)	0.39248 (5)	−0.38122 (10)	0.03437 (18)
C3	0.47961 (13)	0.32522 (5)	−0.17732 (12)	0.02224 (18)
F3	0.59551 (12)	0.48756 (4)	−0.21390 (12)	0.0392 (2)
C4	0.50127 (14)	0.38327 (6)	−0.23956 (14)	0.0258 (2)
F4	0.68203 (11)	0.47191 (4)	0.07670 (11)	0.03656 (19)
C5	0.57042 (15)	0.43260 (6)	−0.15354 (16)	0.0283 (2)
F5	0.62363 (11)	0.36183 (4)	0.20083 (9)	0.02891 (15)
C6	0.61357 (14)	0.42482 (5)	−0.00478 (15)	0.0263 (2)
F6	0.21692 (11)	0.16787 (5)	0.03032 (10)	0.0380 (2)
C7	0.58212 (14)	0.36794 (5)	0.05826 (13)	0.02212 (18)
F7	0.25325 (18)	0.04921 (5)	−0.06609 (14)	0.0610 (4)
C8	0.48102 (15)	0.19681 (5)	−0.02156 (12)	0.02330 (18)
F8	0.5357 (2)	0.01558 (5)	−0.16518 (13)	0.0678 (4)
C9	0.35678 (18)	0.15161 (6)	−0.01683 (14)	0.0312 (2)
F9	0.78382 (17)	0.10049 (5)	−0.17057 (10)	0.0528 (3)
C10	0.3746 (2)	0.09099 (7)	−0.06737 (17)	0.0422 (4)
F10	0.74618 (11)	0.21943 (4)	−0.08188 (10)	0.03250 (16)
C11	0.5179 (3)	0.07409 (6)	−0.11909 (16)	0.0460 (4)
F11	0.44533 (10)	0.06363 (4)	0.40625 (10)	0.03148 (16)
C12	0.6446 (2)	0.11726 (7)	−0.12362 (14)	0.0380 (3)
F12	0.71773 (10)	0.10213 (4)	0.52117 (9)	0.03215 (16)
C13	0.62350 (18)	0.17847 (6)	−0.07816 (13)	0.0275 (2)
F13	0.46089 (11)	0.15294 (5)	0.56951 (9)	0.03438 (18)
F14	0.62696 (10)	0.11747 (5)	0.26024 (9)	0.03248 (16)
F15	0.64003 (10)	0.20678 (4)	0.42139 (11)	0.03370 (17)
F16	0.37452 (9)	0.16812 (4)	0.30944 (8)	0.02551 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.01778 (5)	0.02108 (6)	0.02005 (5)	−0.00054 (3)	0.00171 (4)	0.00169 (3)
C1	0.0193 (4)	0.0212 (4)	0.0197 (4)	0.0002 (3)	0.0012 (3)	0.0017 (3)
F1	0.0355 (4)	0.0284 (3)	0.0207 (3)	0.0004 (3)	0.0012 (3)	−0.0009 (3)
O1	0.0261 (4)	0.0244 (4)	0.0222 (3)	0.0013 (3)	0.0065 (3)	0.0030 (3)
C2	0.0192 (4)	0.0197 (4)	0.0212 (4)	0.0004 (3)	0.0031 (3)	0.0012 (3)
F2	0.0351 (4)	0.0400 (5)	0.0293 (4)	0.0094 (3)	0.0090 (3)	0.0141 (3)
C3	0.0215 (4)	0.0233 (4)	0.0223 (4)	0.0022 (3)	0.0046 (3)	0.0023 (3)
F3	0.0389 (4)	0.0247 (4)	0.0576 (6)	0.0025 (3)	0.0198 (4)	0.0162 (4)
C4	0.0233 (4)	0.0280 (5)	0.0272 (5)	0.0053 (4)	0.0078 (4)	0.0085 (4)
F4	0.0334 (4)	0.0239 (3)	0.0547 (5)	−0.0075 (3)	0.0141 (4)	−0.0096 (3)
C5	0.0239 (5)	0.0220 (5)	0.0413 (6)	0.0036 (4)	0.0130 (4)	0.0090 (4)
F5	0.0292 (4)	0.0321 (4)	0.0245 (3)	−0.0040 (3)	0.0004 (3)	−0.0045 (3)
C6	0.0219 (4)	0.0201 (4)	0.0384 (6)	−0.0008 (3)	0.0093 (4)	−0.0016 (4)
F6	0.0305 (4)	0.0405 (5)	0.0400 (4)	−0.0137 (3)	−0.0056 (3)	0.0129 (4)
C7	0.0198 (4)	0.0209 (4)	0.0259 (5)	−0.0001 (3)	0.0039 (3)	−0.0012 (3)
F7	0.0822 (8)	0.0301 (5)	0.0585 (7)	−0.0272 (5)	−0.0321 (6)	0.0133 (4)
C8	0.0301 (5)	0.0192 (4)	0.0194 (4)	−0.0013 (4)	−0.0003 (4)	0.0013 (3)
F8	0.1302 (13)	0.0209 (4)	0.0418 (5)	0.0122 (6)	−0.0241 (7)	−0.0088 (4)
C9	0.0378 (6)	0.0255 (5)	0.0264 (5)	−0.0085 (5)	−0.0084 (4)	0.0061 (4)
F9	0.0854 (8)	0.0455 (6)	0.0290 (4)	0.0349 (6)	0.0136 (5)	−0.0016 (4)
C10	0.0640 (10)	0.0219 (5)	0.0328 (6)	−0.0111 (6)	−0.0211 (6)	0.0056 (5)
F10	0.0361 (4)	0.0304 (4)	0.0343 (4)	0.0063 (3)	0.0160 (3)	0.0040 (3)
C11	0.0862 (13)	0.0192 (5)	0.0253 (5)	0.0066 (6)	−0.0176 (7)	−0.0022 (4)
F11	0.0264 (3)	0.0225 (3)	0.0460 (5)	−0.0034 (3)	0.0066 (3)	0.0022 (3)
C12	0.0659 (10)	0.0265 (5)	0.0200 (5)	0.0165 (6)	0.0002 (5)	−0.0016 (4)
F12	0.0243 (3)	0.0358 (4)	0.0345 (4)	0.0039 (3)	−0.0023 (3)	0.0088 (3)
C13	0.0405 (6)	0.0232 (5)	0.0189 (4)	0.0057 (4)	0.0038 (4)	0.0012 (4)
F13	0.0339 (4)	0.0464 (5)	0.0233 (3)	0.0060 (3)	0.0056 (3)	−0.0037 (3)
F14	0.0249 (3)	0.0477 (5)	0.0261 (3)	0.0003 (3)	0.0082 (3)	−0.0018 (3)
F15	0.0251 (3)	0.0240 (3)	0.0497 (5)	−0.0052 (3)	−0.0026 (3)	0.0015 (3)
F16	0.0195 (3)	0.0287 (3)	0.0275 (3)	−0.0008 (2)	0.0008 (2)	0.0076 (3)

Geometric parameters (Å, º) top

As1—F11	1.6965 (8)	C4—C5	1.386 (2)
As1—F12	1.7006 (8)	F4—C6	1.3270 (15)
As1—F13	1.7115 (8)	C5—C6	1.386 (2)
As1—F14	1.7196 (8)	F5—C7	1.3250 (14)
As1—F15	1.7254 (8)	C6—C7	1.3793 (16)
As1—F16	1.7849 (7)	F6—C9	1.3279 (19)
C1—O1	1.2743 (13)	F7—C10	1.3316 (19)
C1—C2	1.4448 (15)	C8—C9	1.4021 (17)
C1—C8	1.4545 (16)	C8—C13	1.4004 (18)
F1—C3	1.3282 (14)	F8—C11	1.3258 (17)
O1—H1	0.82 (2)	C9—C10	1.382 (2)
C2—C3	1.4044 (15)	F9—C12	1.325 (2)
C2—C7	1.4049 (15)	C10—C11	1.376 (3)
F2—C4	1.3317 (15)	F10—C13	1.3313 (17)
C3—C4	1.3806 (16)	C11—C12	1.388 (3)
F3—C5	1.3206 (14)	C12—C13	1.3820 (18)

F11—As1—F12	93.29 (4)	F3—C5—C4	119.71 (13)
F11—As1—F13	90.28 (5)	F3—C5—C6	119.64 (13)
F11—As1—F14	90.82 (5)	C6—C5—C4	120.66 (11)
F11—As1—F15	175.32 (4)	F4—C6—C5	120.39 (11)
F11—As1—F16	88.39 (4)	F4—C6—C7	120.26 (12)
F12—As1—F13	92.24 (4)	C7—C6—C5	119.34 (11)
F12—As1—F14	91.60 (4)	F5—C7—C2	120.34 (10)
F12—As1—F15	91.36 (4)	F5—C7—C6	118.16 (10)
F12—As1—F16	178.19 (4)	C6—C7—C2	121.40 (11)
F13—As1—F14	175.95 (4)	C9—C8—C1	121.26 (12)
F13—As1—F15	90.06 (5)	C13—C8—C1	120.55 (11)
F13—As1—F16	88.41 (4)	C13—C8—C9	117.97 (12)
F14—As1—F15	88.52 (5)	F6—C9—C8	119.77 (12)
F14—As1—F16	87.72 (4)	F6—C9—C10	119.36 (14)
F15—As1—F16	86.95 (4)	C10—C9—C8	120.80 (15)
O1—C1—C2	115.67 (10)	F7—C10—C9	119.99 (19)
O1—C1—C8	121.00 (10)	F7—C10—C11	120.26 (15)
C2—C1—C8	123.32 (10)	C11—C10—C9	119.75 (15)
C1—O1—H1	115.1 (15)	F8—C11—C10	119.60 (18)
C3—C2—C1	121.02 (10)	F8—C11—C12	119.3 (2)
C3—C2—C7	117.75 (10)	C10—C11—C12	121.13 (13)
C7—C2—C1	120.81 (10)	F9—C12—C11	120.99 (14)
F1—C3—C2	120.80 (10)	F9—C12—C13	120.17 (17)
F1—C3—C4	118.18 (10)	C13—C12—C11	118.84 (16)
C4—C3—C2	120.89 (11)	F10—C13—C8	120.05 (10)
F2—C4—C3	120.42 (12)	F10—C13—C12	118.42 (13)
F2—C4—C5	119.80 (11)	C12—C13—C8	121.44 (14)
C3—C4—C5	119.77 (11)

C1—C2—C3—F1	−5.76 (16)	F4—C6—C7—C2	−177.21 (10)
C1—C2—C3—C4	170.02 (10)	F4—C6—C7—F5	−0.68 (17)
C1—C2—C7—F5	9.38 (16)	C5—C6—C7—C2	3.87 (17)
C1—C2—C7—C6	−174.16 (10)	C5—C6—C7—F5	−179.59 (10)
C1—C8—C9—F6	8.22 (17)	F6—C9—C10—F7	−1.18 (19)
C1—C8—C9—C10	−174.99 (11)	F6—C9—C10—C11	178.73 (12)
C1—C8—C13—F10	−3.88 (16)	C7—C2—C3—F1	−178.36 (10)
C1—C8—C13—C12	172.49 (11)	C7—C2—C3—C4	−2.58 (16)
F1—C3—C4—F2	1.38 (16)	F7—C10—C11—F8	−1.2 (2)
F1—C3—C4—C5	−179.79 (10)	F7—C10—C11—C12	178.90 (12)
O1—C1—C2—C3	−141.22 (11)	C8—C1—C2—C3	39.75 (15)
O1—C1—C2—C7	31.15 (15)	C8—C1—C2—C7	−147.89 (11)
O1—C1—C8—C9	41.84 (16)	C8—C9—C10—F7	−177.98 (11)
O1—C1—C8—C13	−132.65 (12)	C8—C9—C10—C11	1.93 (19)
C2—C1—C8—C9	−139.18 (11)	F8—C11—C12—F9	−1.3 (2)
C2—C1—C8—C13	46.33 (15)	F8—C11—C12—C13	178.68 (12)
C2—C3—C4—F2	−174.51 (10)	C9—C8—C13—F10	−178.55 (11)
C2—C3—C4—C5	4.32 (17)	C9—C8—C13—C12	−2.18 (17)
F2—C4—C5—F3	−3.13 (17)	C9—C10—C11—F8	178.84 (12)
F2—C4—C5—C6	176.89 (10)	C9—C10—C11—C12	−1.0 (2)
C3—C2—C7—F5	−178.01 (10)	F9—C12—C13—C8	−176.93 (11)
C3—C2—C7—C6	−1.55 (16)	F9—C12—C13—F10	−0.50 (18)
C3—C4—C5—F3	178.03 (10)	C10—C11—C12—F9	178.55 (13)
C3—C4—C5—C6	−1.95 (17)	C10—C11—C12—C13	−1.5 (2)
F3—C5—C6—F4	−1.01 (17)	C11—C12—C13—C8	3.08 (18)
F3—C5—C6—C7	177.91 (11)	C11—C12—C13—F10	179.51 (12)
C4—C5—C6—F4	178.98 (11)	C13—C8—C9—F6	−177.15 (11)
C4—C5—C6—C7	−2.11 (17)	C13—C8—C9—C10	−0.36 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···F16	0.82 (2)	1.71 (2)	2.5280 (11)	176 (2)

Selected geometric parameters (Å, °) for crystallographically characterized compounds featuring AsF₅ coordinated to a carbonyl group top

S₂N₂CO = 5-oxo-1,3,2,4-dithiadiazole, C₄H₂F₂O₂ = fumaryl fluoride, CH₂ClCFO = chloroacetyl fluoride and CH₂FCFO = fluoroacetyl fluoride.

Compound (moiety)	C═O	O—As	As—F_axial	C—O—As	Reference
(C₆F₅)₂CO.AsF₅	1.2526 (15)	1.9897 (10)	1.6890 (8)	133.83 (8)	This work
S₂N₂CO.AsF₅	1.279 (4)	1.879 (7)	1.695 (6)	127.3 (1)	Gieren et al. (1980)
\ C₄H₂F₂O₂·4(C₄H₂F₂O₂·AsF₅)\ ·(C₄H₂F₂O₂·2AsF₅)		Bayer et al. (2021)
(C₄H₂F₂O₂.AsF₅)	1.221 (2)	2.0367 (15)	1.6840 (14)	132.33 (15)
(C₄H₂F₂O₂.AsF₅)	1.220 (2)	2.0472 (14)	1.6835 (13)	130.67 (14)
(C₄H₂F₂O₂.2AsF₅)	1.215 (3)	2.0444 (14)	1.6926 (13)	130.83 (14)
CH₂ClCFO.AsF₅	1.213 (3)	2.0418 (16)	1.6854 (14)	128.96 (17)	Steiner et al. (2024b)
CH₂FCFO.AsF₅	1.210 (3)	2.0306 (15)	1.6835 (13)	130.49 (15)	Steiner et al., (2024b)

Funding information

Funding for this research was provided by: European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (Starting Grant No. 950625); Jožef Stefan Institute Director's Fund.

References

Anandhi, R. & Umapathy, S. (2000). J. Raman Spectrosc. 31, 331–338. CrossRef Google Scholar
Axhausen, J., Ritter, C., Lux, K. & Kornath, A. (2013). Z. Anorg. Allg. Chem. 639, 65–72. CSD CrossRef Google Scholar
Bayer, M. C., Jessen, C. & Kornath, A. J. (2021). Z. Anorg. Allg. Chem. 647, 258–265. CSD CrossRef Google Scholar
Birchall, T. & Gillespie, R. J. (1965). Can. J. Chem. 43, 1045–1051. CrossRef Google Scholar
Bockmair, V., Klöck, A., Hollenwäger, D. & Kornath, A. J. (2024). Acta Cryst. C80, 781–786. CSD CrossRef IUCr Journals Google Scholar
Bodin, C., Forero Saboya, J., Jankowski, P., Radan, K., Foix, D., Courrèges, C., Yousef, I., Dedryvère, R., Davoisne, C., Lozinšek, M. & Ponrouch, A. (2023). Batteries Supercaps 6, e202200433. Web of Science CSD CrossRef Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2022). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Chadda, S. K., Childs, R. F., Faggiani, R. & Lock, C. J. L. (1986). J. Am. Chem. Soc. 108, 1694–1695. CSD CrossRef Google Scholar
Chambers, R. D. & Spring, D. J. (1969). Tetrahedron 25, 565–572. CrossRef Google Scholar
Childs, R. F., Kostyk, M. D., Lock, C. J. L. & Mahendran, M. (1990). J. Am. Chem. Soc. 112, 8912–8920. CSD CrossRef Google Scholar
Childs, R. F., Varadarajan, A., Lock, C. J. L., Faggiani, R., Fyfe, C. A. & Wasylishen, R. E. (1982). J. Am. Chem. Soc. 104, 2452–2456. CSD CrossRef Google Scholar
Cooper, R. I., Thompson, A. L. & Watkin, D. J. (2010). J. Appl. Cryst. 43, 1100–1107. Web of Science CrossRef CAS IUCr Journals Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farmer, D. B. & Walker, S. (1967). Trans. Faraday Soc. 63, 966–973. CrossRef Google Scholar
Gieren, A., Dederer, B., Martin, R., Schanda, F., Roesky, H. W. & Eiser, M. (1980). Chem. Ber. 113, 3904–3909. CSD CrossRef Google Scholar
Gillespie, R. J. (2008). Coord. Chem. Rev. 252, 1315–1327. Web of Science CrossRef CAS Google Scholar
Goetz, N. R., Axhausen, J. A. H., Soltner, T., Rotter, C. & Kornath, A. J. (2016). ChemistrySelect 1, 5517–5520. CSD CrossRef ICSD Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Haiges, R., Baxter, A. F., Goetz, N. R., Axhausen, J. A., Soltner, T., Kornath, A. & Christe, K. O. (2016). Dalton Trans. 45, 8494–8499. Web of Science CSD CrossRef CAS PubMed Google Scholar
Hayatifar, M., Marchetti, F., Pampaloni, G. & Zacchini, S. (2014). Polyhedron 70, 6–10. CSD CrossRef Google Scholar
Heo, S. W., Hwang, I.-C., Chun, Y., Lee, J. W., Singh, N. J., Kim, S. B. & Kim, K. S. (2011). Chem. Asian J. 6, 2055–2061. Web of Science CSD CrossRef CAS PubMed Google Scholar
Hollenwäger, D., Bockmair, V. & Kornath, A. J. (2025). Acta Cryst. C81, 31–37. CSD CrossRef IUCr Journals Google Scholar
Hollenwäger, D., Thamm, S., Bockmair, V., Nitzer, A. & Kornath, A. J. (2024). J. Org. Chem. 89, 11421–11428. PubMed Google Scholar
Hwang, I.-C., Heo, S. W., Singh, N. J., Lee, J. W., Chun, Y., Baek, S. B., Jin, K. S., Ree, M., Lee, H. C., Kim, S. B. & Kim, K. S. (2010). J. Phys. Chem. B 114, 7216–7221. CSD CrossRef PubMed Google Scholar
Lozinšek, M. (2025). Acta Cryst. C81, 188–192. CSD CrossRef IUCr Journals Google Scholar
Lozinšek, M., Mercier, H. P. A., Brock, D. S., Žemva, B. & Schrobilgen, G. J. (2017). Angew. Chem. Int. Ed. 56, 6251–6254. Google Scholar
Lozinšek, M., Mercier, H. P. A. & Schrobilgen, G. J. (2021). Angew. Chem. Int. Ed. 60, 8149–8156. Google Scholar
Marchetti, F., Pampaloni, G. & Zacchini, S. (2007). Dalton Trans. pp. 4343–4351. CSD CrossRef Google Scholar
Matsumoto, A., Tsuchiya, S., Hagiwara, Y., Ishikawa, K., Koshima, H., Asahi, T. & Soai, K. (2016). Chem. Lett. 45, 526–528. CSD CrossRef Google Scholar
Mazej, Z. & Žemva, B. (2005). J. Fluorine Chem. 126, 1432–1434. CrossRef Google Scholar
Minkwitz, R. & Reinemann, S. (1999). Z. Anorg. Allg. Chem. 625, 121–125. CrossRef Google Scholar
Motaln, K., Gurung, K., Brázda, P., Kokalj, A., Radan, K., Dragomir, M., Žemva, B., Palatinus, L. & Lozinšek, M. (2024). ACS Cent. Sci. 10, 1733–1741. Web of Science CrossRef ICSD CAS PubMed Google Scholar
Motaln, K., Uran, E., Giordano, N., Parsons, S. & Lozinšek, M. (2025). J. Appl. Cryst. 58, 221–226. Web of Science CrossRef CAS IUCr Journals Google Scholar
Olah, G. A. & Calin, M. (1968). J. Am. Chem. Soc. 90, 938–943. CrossRef Google Scholar
Olah, G. A., Calin, M. & O'Brien, D. H. (1967a). J. Am. Chem. Soc. 89, 3586–3590. CrossRef Google Scholar
Olah, G. A. & Mo, Y. K. (1973). J. Org. Chem. 38, 2682–2685. CrossRef Google Scholar
Olah, G. A., O'Brien, D. H. & Calin, M. (1967b). J. Am. Chem. Soc. 89, 3582–3586. CrossRef Google Scholar
Olah, G. A., Prakash, G. K. S., Molnár, A. & Sommer, J. (2009). Superacid Chemistry, 2nd ed. Chichester: John Wiley & Sons. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku OD (2025). CrysAlis PRO. Rigaku Corporation, Wrocław, Poland. Google Scholar
Saal, T., Blastik, Z. E., Haiges, R., Nirmalchandar, A., Baxter, A. F., Christe, K. O., Vasiliu, M., Dixon, D. A., Beier, P. & Prakash, G. K. S. (2020). Angew. Chem. Int. Ed. 59, 12520–12526. CSD CrossRef Google Scholar
Saal, T., Haiges, R. & Christe, K. O. (2023). Dalton Trans. 52, 18143–18147. CSD CrossRef PubMed Google Scholar
Schickinger, M., Siegert, M., Morgenstern, Y., Zischka, F., Stierstorfer, K. & Kornath, A. (2018). Z. Anorg. Allg. Chem. 644, 1564–1569. CSD CrossRef Google Scholar
Schwarzer, A., Seichter, W., Weber, E., Stoeckli-Evans, H., Losada, M. & Hulliger, J. (2004). CrystEngComm 6, 567–572. CSD CrossRef Google Scholar
Sekuur, Th. J. & Kranenburg, P. (1966). Tetrahedron Lett. 7, 4793–4795. CrossRef Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & McKinnon, J. J. (2002). CrystEngComm 4, 378–392. Web of Science CrossRef CAS Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stasko, D., Hoffmann, S. P., Kim, K.-C., Fackler, N. L. P., Larsen, A. S., Drovetskaya, T., Tham, F. S., Reed, C. A., Rickard, C. E. F., Boyd, P. D. W. & Stoyanov, E. S. (2002). J. Am. Chem. Soc. 124, 13869–13876. CSD CrossRef PubMed Google Scholar
Steiner, S., Djordjevic, K., Bockmair, V., Hollenwäger, D. & Kornath, A. J. (2024a). Acta Cryst. C80, 792–797. CSD CrossRef IUCr Journals Google Scholar
Steiner, S., Jessen, C., Nitzer, A., Bockmair, V. & Kornath, A. J. (2024b). J. Org. Chem. 89, 14399–14407. CSD CrossRef PubMed Google Scholar
Stuart, D., Wetmore, S. D. & Gerken, M. (2017). Angew. Chem. Int. Ed. 56, 16380–16384. CSD CrossRef Google Scholar
Stuart, D., Wetmore, S. D. & Gerken, M. (2019). J. Fluorine Chem. 221, 9–16. CrossRef Google Scholar
van der Linde, R., Dornseiffen, J. W., Veenland, J. U. & de Boer, Th. J. (1968). Spectrochim. Acta A 24, 2115–2119. CrossRef Google Scholar

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ISSN: 2053-2296

Volume 81| Part 10| October 2025| Pages 577-583

https://doi.org/10.1107/S2053229625007697

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research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Protonated deca­fluoro­benzo­phenone and the deca­fluoro­benzo­phenone–arsenic penta­fluoride adduct

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

2.2. Refinement

2.3. Raman spectroscopy

3. Results and discussion

4. Conclusion

Supporting information

Funding information

References

research papers

Protonated decafluorobenzophenone and the decafluorobenzophenone–arsenic pentafluoride adduct