Trichlates, an Unattended Class of Compounds: Characterization of Cl3CSO2Cl, and (H5O2)[Cl3CSO3]

Mertens, Alisha; van Gerven, David; Kunert, Ilka; Wickleder, Mathias S.

doi:10.1002/chem.202302128

Cited by 4 publications

(1 citation statement)

References 34 publications

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“…[23] Furthermore, we crystallized the acid chloride of trichloromethanesulfonic acid, Cl 3 CSO 2 Cl, in this way. [24] Encouraged by these results, we now gained in the same way single crystals of CH 3 SO 3 H that allow for a reliable structure elucidation. Along with the solid-state structure of methanesulfonic acid, we also present the structure of the respective anhydride (CH 3 ) 2 S 2 O 5 .…”

Section: Introductionmentioning

confidence: 92%

In situ Crystallization of Methanesulfonic Acid, CH₃SO₃H, and Serendipitous Single Crystal Formation of its Anhydride, (CH₃)₂S₂O₅

van Gerven,

Mertens,

Eppers

et al. 2024

Zeitschrift anorg allge chemie

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Methanesulfonic acid, CH3SO3H, has been crystallized using an in situ technique on a single crystal diffractometer. The crystal structure is monoclinic (P21/c, Z = 4, a = 842.07(4) pm, b = 582.20(3) pm, c = 820.38(4) pm, β = 106.459(2)°) and stamped by the presence of strong hydrogen bonds. Single crystals of the anhydride of methanesulfonic acid, (CH3)2S2O5, formed as a side product in the reaction of bis‐trimethylsilyl‐sulfate, [(CH3)3SiO]2SO2 with SO3 in a sealed glass ampoule. The monoclinic crystal structure (P21/n, Z = 12, a = 1794.5(2) pm, b = 831.75(7) pm, 1383.4(1) pm, β = 110.630(4)°) shows three crystallographically different (CH3)2S2O5 molecules in the unit cell. According to the orientation of the CH3 groups with respect to each other the (CH3)2S2O5 molecule appears as the so‐called trans‐conformer. The structure of both molecules is corroborated by quantum mechanical DFT calculations.

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Section: Introductionmentioning

confidence: 92%

In situ Crystallization of Methanesulfonic Acid, CH₃SO₃H, and Serendipitous Single Crystal Formation of its Anhydride, (CH₃)₂S₂O₅

van Gerven,

Mertens,

Eppers

et al. 2024

Zeitschrift anorg allge chemie

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Triflate's bigger brother: The unprecedented tribrate anion, [Br₃CSO₃]⁻

Mertens,

Eppers,

van Gerven

et al. 2024

Chemistry A European J

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The synthesis of the unprecedented [Br3CSO3]− anion starts with the bromination of phenylmethanesulfonate, C6H5OSO2CH3, with KOBr leading to C6H5OSO2CBr3. The formation of the [CBr3] moiety has been proved, also by an X‐ray structure determination of the compound (triclinic, P‐1, a=685.9(2), b=698.1(2), c=1190.2(3) pm, α=93.99(1)°, β=97.42(1)°, γ=94.45(1)°). The ester C6H5OSO2CBr3 can be split under basic conditions. The resulting acid provides access to the yet unknown tribromomethanesulfates (“tribrates”). K[Br3CSO3] ⋅ H2O, the first tribrate known so far has been characterized comprehensively, including an X‐ray structure determination (monoclinic, C2/c, a=2267.1(2), b=1282.25(8), c=2618.2(2) pm, β=111.266(2)°), vibrational spectroscopy and theoretical calculations. Moreover, the thermal analysis shows that, after loss of the crystal water, the tribrate decomposes between 530 and 630 K.

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The Molecular Structures of Lithium Trichlate, Li[Cl₃CSO₃]⋅2H₂O, and Lithium Tribrate, Li[Br₃CSO₃]⋅2H₂O

Mertens,

Eppers,

van Gerven

et al. 2024

Eur J Inorg Chem

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Lithium trichlate, Li[Cl3CSO3]∙2H2O (triclinic, P1, Z = 2, a = 630.29(3) pm, b = 630.65(3) pm, c = 1246.10(6) pm, α = 100.657(2)°, β = 97.813(2)°, γ = 107.994(2)°) was obtained from the reaction of (H5O2)[Cl3CSO3] and LiOH in aqueous solution. Similarly, colourless single crystals of the tribrate Li[Br3CSO3]∙2H2O (triclinic, P1, Z = 4, a = 634.65(4) pm, b = 636.83(4) pm, c = 2496.8(2) pm, α = 83.518°, β = 86.081(5)°, γ = 72.061(5)°) form in the reaction of aqueous Br3CSO3H and LiOH. The acid (H2O2)[Cl3CSO3] was obtained from the chlorination of CS2, followed by oxidation of the intermediate Cl3CSCl with H2O2. The bromo derivative Br3CSO3H has been prepared by bromination of phenylsulfonate with KOBr and subsequent ion exchange of the obtained potassium salt. Both lithium compounds exhibit molecular dimers according to {Li2(X3CSO3)2/1(H2O)2/1(H2O)2/2} with the Li+ ions in tetrahedral coordination of oxygen atoms. The difference in the crystal structures result from the variation of the orientation of the dimers with respect to each other. The experimental findings for the dimers are in good agreement with DFT calculations.

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Trichlates, an Unattended Class of Compounds: Characterization of Cl₃CSO₂Cl, and (H₅O₂)[Cl₃CSO₃]

Cited by 4 publications

References 34 publications

In situ Crystallization of Methanesulfonic Acid, CH₃SO₃H, and Serendipitous Single Crystal Formation of its Anhydride, (CH₃)₂S₂O₅

In situ Crystallization of Methanesulfonic Acid, CH₃SO₃H, and Serendipitous Single Crystal Formation of its Anhydride, (CH₃)₂S₂O₅

Triflate's bigger brother: The unprecedented tribrate anion, [Br₃CSO₃]⁻

The Molecular Structures of Lithium Trichlate, Li[Cl₃CSO₃]⋅2H₂O, and Lithium Tribrate, Li[Br₃CSO₃]⋅2H₂O

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Trichlates, an Unattended Class of Compounds: Characterization of Cl3CSO2Cl, and (H5O2)[Cl3CSO3]

Cited by 4 publications

References 34 publications

In situ Crystallization of Methanesulfonic Acid, CH3SO3H, and Serendipitous Single Crystal Formation of its Anhydride, (CH3)2S2O5

In situ Crystallization of Methanesulfonic Acid, CH3SO3H, and Serendipitous Single Crystal Formation of its Anhydride, (CH3)2S2O5

Triflate's bigger brother: The unprecedented tribrate anion, [Br3CSO3]−

The Molecular Structures of Lithium Trichlate, Li[Cl3CSO3]⋅2H2O, and Lithium Tribrate, Li[Br3CSO3]⋅2H2O

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Trichlates, an Unattended Class of Compounds: Characterization of Cl₃CSO₂Cl, and (H₅O₂)[Cl₃CSO₃]

In situ Crystallization of Methanesulfonic Acid, CH₃SO₃H, and Serendipitous Single Crystal Formation of its Anhydride, (CH₃)₂S₂O₅

In situ Crystallization of Methanesulfonic Acid, CH₃SO₃H, and Serendipitous Single Crystal Formation of its Anhydride, (CH₃)₂S₂O₅

Triflate's bigger brother: The unprecedented tribrate anion, [Br₃CSO₃]⁻

The Molecular Structures of Lithium Trichlate, Li[Cl₃CSO₃]⋅2H₂O, and Lithium Tribrate, Li[Br₃CSO₃]⋅2H₂O