Protonated oxalyl chloride and the ClCO+ cation

Steiner, S.; Djordjevic, K.; Bockmair, V.; Hollenwäger, D.; Kornath, A.J.

doi:10.1107/S2053229624010714

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STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 80| Part 12| December 2024|

https://doi.org/10.1107/S2053229624010714

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Protonated oxalyl chloride and the ClCO⁺ cation

Sebastian Steiner,^a ^* Kristina Djordjevic,^a Valentin Bockmair,^a Dirk Hollenwäger ^a and Andreas J. Kornath ^a ‡

^aDepartment Chemie, Ludwig-Maximilians Universität, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany
^*Correspondence e-mail: sebastian.steiner@cup.uni-muenchen.de

Edited by M. Yousufuddin, University of North Texas at Dallas, USA (Received 23 September 2024; accepted 5 November 2024; online 20 November 2024)

The reactions of oxalyl chloride were investigated in the binary superacidic systems HF/SbF₅ and DF/SbF₅. O-Monoprotonated oxalyl chloride was isolated and represents the first example of a protonated acyl chloride. Diprotonated oxalyl chloride is only stable in solution. Salts of the ClCO⁺ cation were synthesized from the reactions of oxalyl chloride or COClF with SbF₅ in 1,1,1,2-tetrafluoroethane (R-134a, CF₃CFH₂). The colourless salts were characterized by low-temperature vibrational spectroscopy, NMR spectroscopy and single-crystal X-ray diffraction. (1,2-Dichloro-2-oxoethylidene)oxidanium hexafluoridoantimonate(V), [C₂O(OH)Cl₂][SbF₆], crystallizes in the monoclinic space group P2₁ and carbonyl chloride hexadecafluoridotriarsenate(V) [ClCO][Sb₃F₁₆], in the trigonal space group P3₁, with two and three formula units per unit cell, respectively. Monoprotonated oxalyl chloride and the ClCO⁺ cation both display very short C—Cl bonds with a strong double-bond character.

Keywords: oxalyl chloride; chlorocarbonyl cation; superacid; protonation; structure elucidation; crystal structure.

CCDC references: 2304793; 2304777

1. Introduction

Oxalyl chloride was first prepared by Fauconnier in 1892 by the reaction of diethyl oxalate and phosphorus pentachloride (Fauconnier, 1892 ). Nowadays, it is commercially produced by the photochlorination of ethylene carbonate (Pfoertner & Oppenländer, 2012 ). Due to its high reactivity, oxalyl chloride is one of the most versatile organic reagents in chemical syntheses. Among others, it is used in chlorinations, oxidations, reductions, dehydrations, decarboxylations or formylation reactions (Masaki & Fukui, 1977 ; Omura & Swern, 1978 ; Shiri & Kazemi, 2017 ; Denton et al., 2012 ; Wasserman & Tremper, 1977 ; Mendelson & Hayden, 1996 ). The best-known applications are its use in Friedel–Crafts reactions (Alexandrou, 1969 ; Ketcha & Gribble, 1985 ) or the Swern oxidation, i.e. the oxidation of primary and secondary alcohols to aldehydes and ketones (Omura & Swern, 1978).

The reactivity of oxalyl chloride towards strong Lewis acids has been thoroughly investigated. Thus, the chlorocarbonyl cation (ClCO⁺) is observed in the reaction of oxalyl chloride with SbF₅ (Prakash et al., 1991 ). The ClCO⁺ cation is a representative of the compound class of linear triatomic molecules, such as OCS, ONP or ONS⁺, for which numerous theoretical calculations have been performed (Peterson et al., 1991 ; Pak & Woods, 1997 ). It can be synthesized by reacting SbF₅ with either oxalyl chloride, phosgene or carbonyl chloride fluoride. Furthermore, the reaction of carbon monoxide with chlorine in SO₂ClF/SbF₅ leads to the formation of the ClCO⁺ cation (Prakash et al., 1991; Bernhardt et al., 1999 ; Christe et al., 1999 ). The latter was investigated by Olah in 1991 using NMR spectroscopy (Prakash et al., 1991), while Aubke characterized the species by Raman and IR spectroscopy for the first time in 1999 (Bernhardt et al., 1999). However, it has not yet been possible to elucidate the crystal structure of the cation due to its high reactivity. This prompted us to isolate the ClCO⁺ cation and to perform single-crystal X-ray diffraction analysis to structurally characterize the cation and to compare its bond lengths with isoelectronic molecules such as OCS, which shows a short C—S bond with a strong C=S double-bond character (Pak & Woods, 1997).

Furthermore, in previous studies by our group, mono- and diprotonated species of oxalic acid, pyruvic acid and parabanic acid were isolated and characterized, whereas the dications constitute vicinal superelectrophiles (Schickinger et al., 2018 ; Virmani et al., 2022 ; Beck et al., 2020 ). In addition, we recently investigated the reactivity of haloacetyl fluorides in superacidic media and observed the protonation of the carbonyl bond, as well as HF addition to the latter, as in the case of dichloroacetyl fluoride (Steiner et al., 2022 , 2024 ). This prompted us to perform investigations on the reactivity of oxalyl chloride in the superacidic system HF/SbF₅.

2. Results and discussion

2.1. Syntheses and properties of [C₂O(OX)Cl₂][SbF₆] (X = H or D), [C₂(OH)₂Cl₂][Sb_nF_5n+1]₂, [ClCO][Sb₃F₁₅Cl] and [ClCO][Sb₃F₁₆]

Oxalyl chloride was reacted in the binary superacidic systems HF/SbF₅ and DF/SbF₅. According to reaction (1) in Scheme 1, [C₂O(OH)Cl₂][SbF₆] (1) and [C₂O(OD)Cl₂][SbF₆] (2) were obtained as O-monoprotonated species of oxalyl chloride in quantitative yields as colourless solids.

To obtain the diprotonated species, oxalyl chloride was reacted in the binary superacidic system HF/SbF₅ with an excess of the strong Lewis acid SbF₅. However, even with a tenfold excess of SbF₅, the isolation of diprotonated oxalyl chloride (3) as a solid was not possible. Instead of the desired species, monoprotonated oxalyl chloride (1) was obtained. To investigate the reaction of oxalyl chloride in anhydrous hydrogen fluoride (aHF) at −60 °C with an excess of SbF₅, NMR spectroscopy was performed employing eight equivalents of SbF₅. Accordingly, the measured ¹H, ¹⁹F and ¹³C NMR spectra indicate the presence of 3 in the solution, as presented in reaction (2) in Scheme 2. Salts 1 and 2 show thermal decomposition at −45 °C.

[ClCO][Sb₃F₁₅Cl] (4) was synthesized by reacting oxalyl chloride with three equivalents of SbF₅ in 1,1,1,2-tetrafluoroethane (R-134a, CF₃CFH₂) at −78 °C. 4 was obtained as a colourless solid according to reaction (3) in Scheme 3. To avoid mixed occupancies of the fluorine positions of the anion with chlorine, carbonyl chloride fluoride was reacted under the same conditions to form [ClCO][Sb₃F₁₆] (5), as presented in reaction (4) in Scheme 3 (Prakash et al., 1991; Bernhardt et al., 1999; Christe et al., 1999).

2.2. Vibrational spectroscopy

The low-temperature Raman (Ra) and infrared (IR) spectra of [C₂O(OH)Cl₂][SbF₆] (1), [C₂O(OD)Cl₂][SbF₆] (2) and C₂O₂Cl₂ are illustrated in Fig. 1. The complete vibrational frequencies of 1, 2, 4 and 5, as well as of oxalyl chloride and carbonyl chloride fluoride, are provided in the supporting information (see Figs. S1–S3 and Tables S1–S5) (Bernhardt et al., 1999; Davis et al., 1993 ; Nielsen et al., 1952 ).

Figure 1
Low-temperature Raman (bottom) and IR spectra (top) of [C₂O(OX)Cl₂][SbF₆] (1 and 2) (X = H or D) and C₂O₂Cl₂.

For the [C₂O(OH)Cl₂]⁺ cation with C_s symmetry, 15 fundamental vibrational modes are expected, all of which are Raman and IR active. ν_s(O—H) is superposed by condensed water in the IR spectra due to the measuring method. Furthermore, the O—H stretching vibration shows low intensity in the Raman spectra due to the poor polarizability of the O—H group, which does not apply to the O—D group. The O—D stretching vibration of the D-isotopomeric species 2 is observed at 2157 cm⁻¹ in the Raman spectrum and at 2388 cm⁻¹ in the IR spectrum. The C=O stretching vibration of the protonated COCl moiety is detected at 1607 cm⁻¹ (Ra) (1 and 2), as well as at 1605 (1) and 1593 cm⁻¹ (2) (IR), and is significantly red-shifted (by approximately 165 cm⁻¹) compared to the starting material. The vibrations are red-shifted by around 100–150 cm⁻¹ in comparison to the corresponding vibrations of protonated acyl fluorides (Steiner et al., 2022, 2024; Bayer et al., 2022 ). The ν_s(C=O) of the adjacent unprotonated carbonyl group is not affected by the protonation. The C—Cl stretching vibration of the protonated COCl moiety appears at 817 cm⁻¹ (2) in the Raman spectrum and at 833 cm⁻¹ (1), as well as at 818 cm⁻¹ (2), in the IR spectrum, i.e. blue-shifted by approximately 70 cm⁻¹. The ν_s(C—Cl) of the neighboring COCl moiety is not affected by protonation and occurs at 623 cm⁻¹ (2) in the Raman spectrum. Additionally, the C—C stretching vibration is detected at 1118 (Ra) (1) and 1117 cm⁻¹ (1 and 2) (IR), and is thus blue-shifted by approximately 20 cm⁻¹ in comparison to oxalyl chloride.

More vibrations are observed for the [SbF₆]⁻ anion than expected for ideal octahedral symmetry due to interionic interactions in the solid leading to a symmetry distortion (Weidlein et al., 1988 ).

2.3. Crystal structure of [C₂O(OH)Cl₂][SbF₆] (1)

The hexafluoridoantimonate of monoprotonated oxalyl chloride (1) crystallizes in the monoclinic space group P2₁ with two formula units per unit cell. The asymmetric unit is illustrated in Fig. 2. Crystal data and structure refinement details are provided in Table 1 and in the supporting information (Tables S6 and S7).

Table 1
Experimental details

Experiments were carried out with Mo Kα radiation using a Rigaku Xcalibur Sapphire3 diffractometer. Absorption was corrected for by multi-scan methods (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ).

	1	5
Crystal data
Chemical formula	(C₂HCl₂O₂)[SbF₆]	(CClO)[Sb₃F₁₆]
M_r	363.68	732.71
Crystal system, space group	Monoclinic, P2₁	Trigonal, P3₁
Temperature (K)	106	102
a, b, c (Å)	6.1616 (8), 10.8379 (10), 6.8805 (8)	8.0824 (3), 8.0824 (3), 18.3341 (8)
α, β, γ (°)	90, 106.472 (13), 90	90, 90, 120
V (Å³)	440.61 (9)	1037.22 (9)
Z	2	3
μ (mm⁻¹)	3.80	6.19
Crystal size (mm)	0.31 × 0.17 × 0.12	0.19 × 0.14 × 0.11

Data collection
T_min, T_max	0.737, 1.000	0.882, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8919, 2930, 2692	6310, 3334, 3029
R_int	0.042	0.044
(sin θ/λ)_max (Å⁻¹)	0.755	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.057, 1.04	0.038, 0.077, 1.03
No. of reflections	2930	3334
No. of parameters	122	199
No. of restraints	2	0
H-atom treatment	Only H-atom coordinates refined	–
Δρ_max, Δρ_min (e Å⁻³)	1.18, −0.66	1.36, −1.09
Absolute structure	Refined as an inversion twin	Twinning involves inversion, so Flack parameter cannot be determined
Absolute structure parameter	0.52 (3)	–
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2019 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Figure 2
The asymmetric unit of 1, with displacement ellipsoids drawn at the 50% probability level.

Due to the protonation, the C1—O1 bond length [1.225 (8) Å] is significantly elongated compared to the starting material [1.180 (2) Å; Danielson et al., 1995 ] and is longer than a formal C=O bond (1.18 Å; Allen et al., 1987 ). The C2—O2 bond length [1.184 (8) Å] of the adjacent unprotonated C=O bond is not affected by the protonation [1.180 (2) Å; Danielson et al., 1995]. Furthermore, the C1—Cl1 bond length [1.647 (7) Å] is significantly shortened compared to the neutral compound [1.747 (3) Å; Danielson et al., 1995] and is in the range between a formal C—Cl single bond (1.76 Å; Allen et al., 1987) and a C=Cl double bond (1.56 Å; Holleman et al., 1987 ). The same applies for the C2—Cl2 bond length [1.693 (7) Å] [cf. 1.747 (3) Å for oxalyl chloride; Danielson et al., 1995]. The elongation of the C=O bond and the shortening of the C—Cl bonds are consistent with the observed shifts of the ν_s(C=O) and ν_s(C—Cl) in the vibrational spectra. The C1—C2 bond length [1.550 (8) Å] is not affected by protonation [cf. 1.545 (8) Å for oxalyl chloride; Danielson et al., 1995]. This is consistent with the results observed for the mono- and diprotonated species of oxalic acid. In both cases, the protonation at the carbonyl groups does not affect the bond lengths of the C—C backbone (Schickinger et al., 2018).

The Sb—F bond lengths are in the range between 1.846 (4) and 1.941 (3) Å, and correspond with values reported in the literature (Minkwitz et al., 1999a ,b ; Minkwitz & Schneider, 1999 ). Due to interionic interactions, the anion displays distorted octahedral symmetry. The Sb1—F6 bond [1.941 (3) Å] is significantly longer than the other Sb—F bonds with it being involved in hydrogen bonding.

In the crystal structure of 1, the ions are arranged into chains along the a and b axes by the strong O1(—H1)⋯F6 hydrogen bond [2.421 (7) Å] and the C⋯F interactions C1⋯F2ⁱ [2.617 (7) Å; see Fig. 4 for symmetry codes] and C1⋯F4ⁱⁱ [2.565 (7) Å] (see Figs. S4–S5) (Jeffrey, 1997 ; Bondi, 1964 ). The chains are linked to each other by the Cl⋯F interaction Cl1⋯F3ⁱⁱⁱ [2.883 (5) Å] to form layers. All interatomic C⋯F and Cl⋯F contacts are below the sum of the van der Waals radii (3.17 and 3.22 Å; Bondi, 1964). Interatomic distances are listed in Table S7.

2.4. Crystal structure of [ClCO][Sb₃F₁₆] (5)

The crystal structures of 4 and 5 were both obtained by recrystallizing the salts from R-134a (CF₃CFH₂) at −40 °C. As 4 crystallizes as an inversion twin and shows mixed occupancies of all 16 crystallographic fluorine positions with chlorine, the structural parameters show high standard deviations. Therefore, the crystal structure of 5 is used for the discussion of all experimental parameters.

[ClCO][Sb₃F₁₆] (5) crystallizes in the trigonal space group P3₁ with three formula units per unit cell. The asymmetric unit is depicted in Fig. 3. Crystal data and structure refinement details are provided in Table 1 and in the supporting information (Tables S6 and S8).

Figure 3
The asymmetric unit of 5, with displacement ellipsoids drawn at the 50% probability level.

The C1—O1 bond length [1.105 (10) Å] is significantly shortened compared to ClFCO [1.173 (2) Å; Oberhammer, 1980 ]. It is in the range between a formal C=O double bond (1.19 Å) and a C≡O triple bond (1.07 Å) (Allen et al., 1987). It corresponds with the C=O bond length (1.1562 Å) of the isoelectronic molecule OCS (Pak & Woods, 1997). Furthermore, the C1—Cl1 bond length [1.571 (3) Å] is significantly shortened compared to ClFCO [1.725 (2) Å; Oberhammer, 1980]. It is in the range of a formal C=Cl double-bond length (1.56 Å) and thus displays a significant double-bond character (Allen et al., 1987). It corresponds with the C—Cl bond length [1.67 (2) Å] of ClCN (Beach & Turkevich, 1939 ). The Cl1—C1—O1 angle [176.1 (8)°] indicates the essentially linear structure of the cation.

The Sb—F bond lengths of the terminal F atoms are in the range between 1.831 (8) and 1.857 (7) Å. The bridging Sb—F bonds are longer than the terminal ones, with bond lengths up to 2.088 (8) Å. The bond angles Sb1—F6—Sb2 [146.0 (4)°] and Sb2—F11—Sb3 [156.6 (4)°] are also in good agreement with the literature (Faggiani et al., 1986 ; Gerken et al., 2002 ).

In the crystal structure of 5, the ions form a helical structure along the c axis via the C⋯F interaction C1⋯F5ⁱⁱ (2.75 Å) and the Cl⋯F interaction Cl1⋯F1 [2.56 (1) Å] (see Fig. 4, and Figs. S6–S7 in the supporting information). The cation displays a tetracoordinated C1 atom and further forms the interionic contacts C1⋯F4ⁱ (2.968 Å), C1⋯F14ⁱⁱⁱ (3.062 Å), C1⋯F15^iv (2.92 Å) and O1⋯F16^v [2.79 (2) Å] (see Fig. 4). All interatomic C⋯F, Cl⋯F and O⋯F contacts are below the sum of the van der Waals radii (3.17, 3.22 and 2.99 Å; Bondi, 1964). Selected interatomic distances are listed in Table S8.

Figure 4
Interatomic contacts of 5, with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) x − 1, y, z; (ii) −x + y, −x + 1, z − $[{1\over 3}]$ ; (iii) x, y + 1, z; (iv) −y, x − y, z + $[{1\over 3}]$ ; (v) x − 1, y + 1, z.

2.5. NMR spectroscopy

To trace the reactivity of oxalyl chloride in aHF and the binary superacidic system HF/SbF₅, the ¹H, ¹⁹F and ¹³C NMR spectra were measured at −60 °C with acetone-d₆ as the external standard. The measured NMR spectra and the complete NMR data of oxalyl chloride, 1 and 3 are listed in the supporting information (Figs. S8–S18).

The ¹³C NMR spectrum of oxalyl chloride dissolved in aHF at −60 °C shows a singlet at 161.1 ppm for both COCl moieties. Furthermore, no chlorine–fluorine exchange or HF addition to the carbonyl bond is observed under these conditions.

By first dissolving equimolar amounts of SbF₅ compared to oxalyl chloride in HF and then adding the acyl chloride, monoprotonated oxalyl chloride (1) is formed. The ¹H NMR spectrum shows a singlet at 10.03 ppm for the protonated carbonyl group. The ¹³C NMR spectrum displays two singlets located at 161.7 and 183.4 ppm. These are assigned to the carbonyl groups, whereas the NMR resonance of the protonated COCl moiety is significantly shifted downfield. The ¹⁹F NMR spectrum indicates chlorine–fluorine exchange initiated by the protonation of oxalyl chloride. Thus, the NMR resonance at 17.74 ppm indicates the formation of oxalyl fluoride. The ¹H, ¹⁹F and ¹³C NMR spectra of (COF)₂ at −60 °C in aHF are illustrated in Figs. S10–S11 (see supporting information). Furthermore, in the ¹⁹F NMR spectrum, the resonance at −124.78 ppm is assigned to the [SbF₆]⁻ anion (Dean & Gillespie, 1969 ).

Since the diprotonated oxalyl chloride (3) could not be isolated as a solid, the reaction of oxalyl chloride in HF/SbF₅ at −60 °C was investigated using NMR spectroscopy, whereas an eightfold amount of SbF₅ was applied. Accordingly, the NMR spectra indicate the presence of 3 in the solution. The ¹H NMR spectrum shows a singlet at 9.61 ppm for the protonated COCl⁺ moieties, whereas the ¹³C NMR spectrum displays a singlet at 183.1 ppm. Compared to the neutral compound, the ¹³C NMR resonance is significantly shifted downfield. Furthermore, in the ¹⁹F NMR spectrum, multiple resonances located in the range between −117.46 and −143.05 ppm are assigned to the [Sb_nF_5n+1]⁻ polyanions (Dean & Gillespie, 1969). Thus, diprotonated oxalyl chloride is stable in solution at −60 °C. However, after removal of the excess HF at −78 °C, it decomposes with the formation of 1. Furthermore, as in the NMR spectra of 1, a chlorine–fluorine exchange is observed, as the signal at 17.46 ppm indicates the formation of oxalyl fluoride. Additional signals in the ¹⁹F NMR spectra of 3 at −21.78 and −59.90 ppm are assigned to COF₂ and CF₃OH (Christe et al., 2007 ). The ¹H, ¹⁹F and ¹³C NMR spectra of COF₂ in aHF at −60 °C are depicted in the supporting information (Fig. S12). COF₂ is likely formed due to the decomposition of oxalyl fluoride under superacidic conditions.

3. Conclusions

Oxalyl chloride was reacted in the binary superacidic systems HF/SbF₅ and DF/SbF₅ to form the O-monoprotonated and its D-isotopomeric species as hexafluoridoantimonates. Both represent the first examples of protonated acyl chlorides. When the Lewis acid SbF₅ is applied in eightfold excess, diprotonated oxalyl chloride is formed, which is only stable in solution. By the reaction of oxalyl chloride or carbonyl chloride fluoride in the aprotic solvent 1,1,1,2-tetrafluoroethane (R-134a, CF₃CFH₂) with a threefold excess of SbF₅, salts of the chlorocarbonyl cation were isolated. The colourless salts were characterized by low-temperature vibrational spectroscopy and low-temperature NMR spectroscopy. The crystal structures of [C₂O(OH)Cl₂][SbF₆] and [ClCO][Sb₃F₁₆] were determined by single-crystal X-ray diffraction analysis. Monoprotonated oxalyl chloride and the chlorocarbonyl cation both display very short C—Cl bonds with strong double-bond character.

Supporting information

CCDC references: 2304793; 2304777

Crystal structure: contains datablocks I, 5, global. DOI: https://doi.org/10.1107/S2053229624010714/yd3050sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2053229624010714/yd30501sup2.hkl

Structure factors: contains datablock 5. DOI: https://doi.org/10.1107/S2053229624010714/yd30505sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229624010714/yd3050sup4.pdf

Computing details top

(1,2-Dichloro-2-oxoethylidene)oxidanium hexafluoridoantimonate(V) (I) top

Crystal data top

(C₂HCl₂O₂)[SbF₆]	F(000) = 336
M_r = 363.68	D_x = 2.741 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.1616 (8) Å	Cell parameters from 3114 reflections
b = 10.8379 (10) Å	θ = 3.1–29.8°
c = 6.8805 (8) Å	µ = 3.80 mm⁻¹
β = 106.472 (13)°	T = 106 K
V = 440.61 (9) Å³	Plate, colourless
Z = 2	0.31 × 0.17 × 0.12 mm

Data collection top

Rigaku Xcalibur Sapphire3 diffractometer	2930 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2692 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 15.9809 pixels mm^-1	θ_max = 32.5°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2020)	k = −15→15
T_min = 0.737, T_max = 1.000	l = −10→10
8919 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Only H-atom coordinates refined
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0195P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2930 reflections	Δρ_max = 1.18 e Å⁻³
122 parameters	Δρ_min = −0.65 e Å⁻³
2 restraints	Absolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.52 (3)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
Sb1	0.53137 (5)	0.40457 (3)	0.12537 (5)	0.01795 (9)
Cl1	0.1619 (3)	0.69867 (15)	0.2994 (3)	0.0292 (4)
Cl2	−0.1153 (3)	0.56726 (18)	0.7590 (3)	0.0328 (4)
F6	0.4922 (6)	0.4491 (3)	0.3867 (5)	0.0286 (8)
F4	0.6527 (7)	0.2572 (3)	0.2457 (6)	0.0384 (10)
O1	0.2117 (8)	0.5185 (4)	0.5476 (7)	0.0213 (9)
F3	0.5832 (7)	0.3631 (3)	−0.1181 (6)	0.0334 (9)
F5	0.2429 (7)	0.3389 (4)	0.0574 (6)	0.0446 (11)
F1	0.4165 (8)	0.5572 (4)	0.0299 (6)	0.0433 (11)
F2	0.8179 (7)	0.4748 (4)	0.2204 (6)	0.0431 (11)
C1	0.1102 (12)	0.6133 (6)	0.4793 (9)	0.0198 (13)
O2	−0.1927 (10)	0.7435 (5)	0.4961 (9)	0.0382 (14)
C2	−0.0817 (11)	0.6568 (6)	0.5680 (10)	0.0237 (14)
H1	0.313 (9)	0.504 (7)	0.490 (10)	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.01936 (15)	0.01674 (14)	0.01797 (15)	0.0007 (2)	0.00563 (11)	−0.0003 (2)
Cl1	0.0418 (10)	0.0241 (8)	0.0255 (8)	−0.0010 (7)	0.0155 (7)	0.0036 (6)
Cl2	0.0355 (10)	0.0360 (10)	0.0331 (10)	−0.0003 (7)	0.0200 (8)	0.0037 (7)
F6	0.032 (2)	0.035 (2)	0.0212 (18)	0.0070 (15)	0.0107 (15)	−0.0026 (14)
F4	0.060 (3)	0.024 (2)	0.027 (2)	0.0170 (19)	0.0054 (19)	0.0026 (15)
O1	0.024 (2)	0.018 (2)	0.024 (2)	0.0005 (17)	0.0105 (18)	−0.0030 (17)
F3	0.044 (2)	0.036 (2)	0.0244 (19)	0.0045 (16)	0.0163 (17)	−0.0041 (14)
F5	0.028 (2)	0.066 (3)	0.036 (2)	−0.0170 (19)	0.0026 (18)	0.006 (2)
F1	0.069 (3)	0.027 (2)	0.035 (2)	0.018 (2)	0.017 (2)	0.0101 (17)
F2	0.033 (2)	0.058 (3)	0.042 (2)	−0.020 (2)	0.0147 (19)	−0.013 (2)
C1	0.023 (3)	0.022 (3)	0.013 (3)	−0.003 (3)	0.002 (2)	−0.002 (2)
O2	0.039 (3)	0.038 (3)	0.040 (3)	0.017 (3)	0.015 (2)	0.011 (3)
C2	0.018 (3)	0.025 (3)	0.027 (3)	0.002 (2)	0.004 (3)	−0.003 (3)

Geometric parameters (Å, º) top

Sb1—F1	1.846 (4)	Cl1—C1	1.647 (7)
Sb1—F5	1.848 (4)	Cl2—C2	1.693 (7)
Sb1—F3	1.848 (4)	O1—C1	1.225 (8)
Sb1—F4	1.856 (3)	C1—C2	1.550 (8)
Sb1—F2	1.863 (4)	O2—C2	1.184 (8)
Sb1—F6	1.941 (3)

F1—Sb1—F5	90.6 (2)	F5—Sb1—F6	88.10 (17)
F1—Sb1—F3	92.44 (17)	F3—Sb1—F6	177.29 (18)
F5—Sb1—F3	94.5 (2)	F4—Sb1—F6	86.60 (16)
F1—Sb1—F4	174.63 (18)	F2—Sb1—F6	85.84 (17)
F5—Sb1—F4	91.05 (19)	O1—C1—C2	117.9 (6)
F3—Sb1—F4	92.51 (17)	O1—C1—Cl1	125.0 (6)
F1—Sb1—F2	89.3 (2)	C2—C1—Cl1	117.2 (6)
F5—Sb1—F2	173.9 (2)	O2—C2—C1	119.5 (7)
F3—Sb1—F2	91.58 (18)	O2—C2—Cl2	126.5 (6)
F4—Sb1—F2	88.5 (2)	C1—C2—Cl2	114.0 (5)
F1—Sb1—F6	88.36 (16)

O1—C1—C2—O2	−175.1 (7)	O1—C1—C2—Cl2	2.6 (7)
Cl1—C1—C2—O2	4.9 (8)	Cl1—C1—C2—Cl2	−177.4 (4)

Carbonyl chloride hexadecafluoridotriarsenate(V) (5) top

Crystal data top

(CClO)[Sb₃F₁₆]	D_x = 3.519 Mg m⁻³
M_r = 732.71	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁	Cell parameters from 2010 reflections
a = 8.0824 (3) Å	θ = 2.9–31.5°
c = 18.3341 (8) Å	µ = 6.19 mm⁻¹
V = 1037.22 (9) Å³	T = 102 K
Z = 3	Plate, colourless
F(000) = 984	0.19 × 0.14 × 0.11 mm

Data collection top

Rigaku Xcalibur Sapphire3 diffractometer	3334 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3029 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 15.9809 pixels mm^-1	θ_max = 32.0°, θ_min = 2.2°
ω scans	h = −9→12
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2020)	k = −12→9
T_min = 0.882, T_max = 1.000	l = −23→27
6310 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0262P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 1.36 e Å⁻³
3334 reflections	Δρ_min = −1.09 e Å⁻³
199 parameters	Absolute structure: Twinning involves inversion, so Flack parameter cannot be determined
0 restraints

Special details top

Refinement. Refined as a 4-component inversion twin

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

	x	y	z	U_iso*/U_eq
Sb2	0.63376 (11)	−0.03511 (10)	0.6093 (6)	0.01747 (16)
Sb3	0.61862 (11)	−0.00397 (11)	0.3929 (6)	0.01723 (15)
Sb1	0.36234 (12)	0.24398 (12)	0.5809 (6)	0.01933 (17)
Cl1	0.0670 (5)	0.5221 (5)	0.4818 (6)	0.0259 (6)
F6	0.4921 (10)	0.1038 (10)	0.6276 (7)	0.0217 (15)
F11	0.5841 (11)	−0.0061 (11)	0.5059 (7)	0.0259 (16)
F14	0.3543 (10)	−0.1218 (11)	0.3896 (7)	0.0253 (16)
F12	0.8757 (10)	0.1112 (12)	0.4172 (7)	0.0307 (18)
F3	0.1582 (11)	0.0903 (10)	0.6393 (7)	0.0289 (17)
F7	0.8440 (10)	0.2034 (10)	0.5984 (8)	0.0304 (18)
F1	0.2479 (12)	0.3677 (12)	0.5370 (7)	0.035 (2)
F15	0.6529 (11)	0.0015 (11)	0.2933 (8)	0.0297 (19)
F13	0.6347 (12)	0.2325 (11)	0.3976 (7)	0.0287 (18)
F2	0.2737 (11)	0.0514 (11)	0.5132 (7)	0.0297 (17)
F9	0.6597 (12)	−0.0508 (12)	0.7083 (8)	0.034 (2)
F16	0.5937 (11)	−0.2420 (10)	0.4091 (7)	0.0288 (17)
F4	0.5920 (11)	0.3809 (11)	0.5326 (7)	0.0313 (18)
F8	0.3967 (11)	−0.2487 (11)	0.6050 (7)	0.0314 (18)
F5	0.4618 (10)	0.4138 (11)	0.6581 (7)	0.0267 (16)
F10	0.7572 (12)	−0.1617 (12)	0.5794 (7)	0.0349 (19)
O1	−0.0886 (17)	0.7424 (16)	0.4599 (8)	0.043 (3)
C1	−0.029417	0.646600	0.467900	0.031 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb2	0.0197 (4)	0.0198 (4)	0.0159 (4)	0.0121 (3)	−0.0007 (3)	0.0003 (3)
Sb3	0.0173 (4)	0.0188 (4)	0.0146 (4)	0.0083 (3)	0.0003 (3)	−0.0002 (3)
Sb1	0.0240 (4)	0.0221 (4)	0.0182 (4)	0.0162 (4)	−0.0027 (3)	−0.0026 (3)
Cl1	0.0318 (17)	0.0268 (16)	0.0233 (15)	0.0177 (14)	−0.0020 (13)	0.0022 (13)
F6	0.026 (4)	0.033 (4)	0.015 (3)	0.022 (3)	0.000 (3)	0.000 (3)
F11	0.040 (4)	0.033 (4)	0.015 (3)	0.026 (4)	0.001 (3)	0.000 (3)
F14	0.021 (4)	0.033 (4)	0.019 (4)	0.011 (3)	−0.004 (3)	−0.005 (3)
F12	0.026 (4)	0.038 (5)	0.028 (4)	0.015 (4)	−0.005 (3)	−0.008 (3)
F3	0.026 (4)	0.033 (4)	0.030 (4)	0.017 (4)	−0.002 (3)	0.002 (3)
F7	0.019 (4)	0.019 (4)	0.046 (5)	0.004 (3)	0.002 (3)	−0.001 (3)
F1	0.049 (5)	0.043 (5)	0.028 (4)	0.034 (5)	−0.011 (4)	−0.002 (4)
F15	0.032 (4)	0.042 (5)	0.016 (4)	0.019 (4)	0.002 (3)	−0.003 (3)
F13	0.044 (5)	0.023 (4)	0.023 (4)	0.019 (4)	0.004 (3)	0.002 (3)
F2	0.036 (4)	0.032 (4)	0.027 (4)	0.021 (4)	−0.012 (3)	−0.009 (3)
F9	0.047 (5)	0.045 (5)	0.021 (5)	0.031 (4)	−0.006 (4)	0.001 (4)
F16	0.035 (4)	0.023 (4)	0.032 (4)	0.017 (3)	−0.007 (4)	−0.004 (3)
F4	0.036 (4)	0.029 (4)	0.031 (4)	0.019 (4)	0.007 (4)	0.003 (4)
F8	0.032 (4)	0.020 (4)	0.037 (5)	0.009 (3)	0.008 (4)	0.003 (3)
F5	0.034 (4)	0.028 (4)	0.023 (4)	0.019 (4)	−0.005 (3)	−0.007 (3)
F10	0.042 (5)	0.043 (5)	0.034 (5)	0.032 (4)	−0.005 (4)	−0.002 (4)
O1	0.058 (7)	0.056 (7)	0.043 (7)	0.049 (6)	0.003 (6)	0.000 (6)
C1	0.041 (8)	0.037 (8)	0.014 (6)	0.019 (7)	0.000 (5)	−0.005 (6)

Geometric parameters (Å, º) top

Sb2—F8	1.831 (8)	Sb3—F12	1.857 (7)
Sb2—F10	1.834 (7)	Sb3—F11	2.088 (8)
Sb2—F7	1.835 (7)	Sb1—F3	1.833 (8)
Sb2—F9	1.838 (8)	Sb1—F2	1.834 (7)
Sb2—F11	1.978 (8)	Sb1—F4	1.844 (8)
Sb2—F6	1.992 (6)	Sb1—F1	1.852 (7)
Sb3—F15	1.845 (8)	Sb1—F5	1.852 (7)
Sb3—F13	1.852 (7)	Sb1—F6	2.075 (7)
Sb3—F14	1.855 (7)	Cl1—C1	1.571 (3)
Sb3—F16	1.855 (7)	O1—C1	1.105 (10)

F8—Sb2—F10	93.8 (4)	F16—Sb3—F12	89.7 (4)
F8—Sb2—F7	165.6 (3)	F15—Sb3—F11	179.1 (4)
F10—Sb2—F7	94.4 (4)	F13—Sb3—F11	84.4 (3)
F8—Sb2—F9	94.6 (4)	F14—Sb3—F11	85.0 (3)
F10—Sb2—F9	98.3 (3)	F16—Sb3—F11	83.6 (3)
F7—Sb2—F9	95.9 (4)	F12—Sb3—F11	83.0 (3)
F8—Sb2—F11	83.8 (4)	F3—Sb1—F2	89.0 (3)
F10—Sb2—F11	88.8 (3)	F3—Sb1—F4	169.1 (3)
F7—Sb2—F11	84.6 (4)	F2—Sb1—F4	91.9 (4)
F9—Sb2—F11	172.9 (3)	F3—Sb1—F1	95.5 (4)
F8—Sb2—F6	85.0 (3)	F2—Sb1—F1	94.3 (4)
F10—Sb2—F6	172.2 (3)	F4—Sb1—F1	95.3 (4)
F7—Sb2—F6	85.3 (3)	F3—Sb1—F5	88.1 (3)
F9—Sb2—F6	89.5 (3)	F2—Sb1—F5	170.8 (3)
F11—Sb2—F6	83.5 (3)	F4—Sb1—F5	89.3 (4)
F15—Sb3—F13	95.1 (3)	F1—Sb1—F5	94.6 (4)
F15—Sb3—F14	95.8 (3)	F3—Sb1—F6	85.3 (3)
F13—Sb3—F14	90.0 (3)	F2—Sb1—F6	84.6 (3)
F15—Sb3—F16	96.9 (4)	F4—Sb1—F6	83.9 (3)
F13—Sb3—F16	168.0 (4)	F1—Sb1—F6	178.6 (3)
F14—Sb3—F16	88.5 (3)	F5—Sb1—F6	86.5 (3)
F15—Sb3—F12	96.2 (3)	Sb2—F6—Sb1	146.0 (4)
F13—Sb3—F12	89.3 (4)	Sb2—F11—Sb3	156.6 (4)
F14—Sb3—F12	168.0 (3)	O1—C1—Cl1	176.1 (8)

Footnotes

‡Deceased

Acknowledgements

We are grateful to the Department of Chemistry of the Ludwig Maximilian University, the Deutsche Forschungsgemeinschaft (DFG) and F-Select GmbH for the financial support of this work. Special thanks go to Professor Dr Konstantin Karaghiosoff for help with this work after Professor Dr Andreas J. Kornath passed away. Open access funding enabled and organized by Projekt DEAL.

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

Protonated oxalyl chloride and the ClCO+ cation

1. Introduction

2. Results and discussion

2.1. Syntheses and properties of [C2O(OX)Cl2][SbF6] (X = H or D), [C2(OH)2Cl2][SbnF5n+1]2, [ClCO][Sb3F15Cl] and [ClCO][Sb3F16]

2.2. Vibrational spectroscopy

2.3. Crystal structure of [C2O(OH)Cl2][SbF6] (1)

2.4. Crystal structure of [ClCO][Sb3F16] (5)

2.5. NMR spectroscopy

3. Conclusions

Supporting information

Footnotes

Acknowledgements

References

research papers

Protonated oxalyl chloride and the ClCO⁺ cation

2.1. Syntheses and properties of [C₂O(OX)Cl₂][SbF₆] (X = H or D), [C₂(OH)₂Cl₂][Sb_nF_5n+1]₂, [ClCO][Sb₃F₁₅Cl] and [ClCO][Sb₃F₁₆]

2.3. Crystal structure of [C₂O(OH)Cl₂][SbF₆] (1)

2.4. Crystal structure of [ClCO][Sb₃F₁₆] (5)