organic compounds
1-[(Methylsulfonyl)oxy]pyridin-1-ium methanesulfonate
aLeibniz-Institut für Katalyse e. V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany
*Correspondence e-mail: jola.pospech@catalysis.de
The title molecular salt, C6H8NO3S+·CH3O3S−, consists of a cationic sulfonated pyridine N-oxide moiety and a methanesulfonate anion. An N—O bond length of 1.4004 (15) Å is observed in the cation. In the crystal, weak C—H⋯O interactions link the components into a three-dimensional network.
Keywords: crystal structure; pyridinium cation; sulfonate anion.
CCDC reference: 2113673
Structure description
Zhen-Chu & Stang (1984) reported the synthesis of 1-{[(trifluoromethyl)sulfonyl]oxy}pyridin-1-ium trifluoromethanesulfonate from pyridine N-oxide and trifluoromethanesulfonic anhydride. The reactivity of O-sulfonyl pyridinium salts toward nucleophiles and their substitution of the 2-position as reaction products were described by Umemoto et al. (1996). Rössler et al. (2019) reported the photochemical application of 1-{[(trifluoromethyl)sulfonyl]oxy}pyridin-1-ium trifluoromethanesulfonate, which allows direct amination of and heteroarenes.
Here, we report the formation of 1-[(methylsulfonyl)oxy]pyridin-1-ium methanesulfonate, C6H8NO3S+·CH3O3S−, obtained from the reaction of pyridine-N-oxide and methanesulfonic anhydride. Its molecular structure (Fig. 1) consists of a cationic sulfonated pyridine N-oxide moiety and a methanesulfonate anion. The N—O bond length of 1.4004 (15) Å is similar to that observed in 1-{[(trifluoromethyl)sulfonyl]oxy}pyridin-1-ium trifluoromethanesulfonate [N—O = 1.4095 (11) Å; Rössler et al., 2019]. Furthermore, O1 is 0.19 Å out of the pyridinium plane in the title compound and the N1—O1—S1—C6 torsion angle is 66.72 (11)°.
In the crystal, the components are linked by C—H⋯O interactions into a three-dimensional network (Table 1); the C5—H5⋯O4 bond with H⋯O = 2.19 Å is notably short.
Synthesis and crystallization
Following a modified literature procedure of Rössler et al. (2019), a stirred solution of pyridine N-oxide (3.00 g, 31.6 mmol, 1.0 eq.) in DCM (100 ml) was treated dropwise with a solution of methanesulfonic anhydride (7.13 g, 37.9 mmol, 1.3 eq.) in DCM at −30°C. After complete addition, the reaction mixture was stirred for 2 h and allowed to warm to room temperature. The white precipitate was filtered and washed with fresh DCM (30 ml). Additional drying in vacuo yields the title compound (6.40 g, 23.8 mmol, 75%). Colourless needles suitable for X-ray analysis were obtained by cooling a warm saturated acetonitrile solution to −30°C (Caution: heating to > 50°C leads to decomposition of the title compound.). 1H NMR (400 MHz, acetonitrile-d3) δ 8.7 (s, 2H), 8.1 (s, 1H), 7.9 (s, 2H), 3.5 (s, 2H), 2.6 (s, 3H). 13C NMR (101 MHz, acetonitrile-d3) δ 140.62, 129.10, 41.78, 39.65. IR (ATR, neat, cm−1): 3108 (w), 3013 (w), 2986 (w), 2943 (w), 1606 (w), 1479 (w), 1428 (w), 1381 (m), 1330 (w), 1315 (w), 1289 (w), 1182 (s), 1163 (s), 1144 (m), 1040 (s), 1002 (m), 984 (s), 818 (m), 789 (s), 762 (s), 672 (m), 655 (s), 602 (w), 554 (s), 520 (s), 507 (s), 489 (m), 456 (m), 421 (m). Analysis (%) calculated for C7H11NO6S2: C, 31.22; H, 4.12; N, 5.20; S, 23.81. Found: C, 31.02; H, 4.61; N, 4.93; S, 23.62.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 2113673
https://doi.org/10.1107/S2414314621010269/hb4392sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621010269/hb4392Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314621010269/hb4392Isup3.cml
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).C6H8NO3S+·CH3O3S− | F(000) = 560 |
Mr = 269.29 | Dx = 1.628 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9335 (3) Å | Cell parameters from 8765 reflections |
b = 7.6255 (3) Å | θ = 2.2–30.6° |
c = 18.3875 (7) Å | µ = 0.50 mm−1 |
β = 99.0734 (14)° | T = 150 K |
V = 1098.47 (7) Å3 | Needle, colourless |
Z = 4 | 0.36 × 0.08 × 0.08 mm |
Bruker APEXII CCD diffractometer | 3400 independent reflections |
Radiation source: fine-focus sealed tube | 2732 reflections with I > 2σ(I) |
Detector resolution: 8.3333 pixels mm-1 | Rint = 0.033 |
φ and ω scans | θmax = 30.7°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −11→11 |
Tmin = 0.84, Tmax = 0.96 | k = −10→10 |
27689 measured reflections | l = −26→26 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0491P)2 + 0.5052P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3400 reflections | Δρmax = 0.48 e Å−3 |
147 parameters | Δρmin = −0.29 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7438 (2) | 0.3898 (2) | 0.41962 (9) | 0.0246 (3) | |
H1 | 0.710677 | 0.472427 | 0.381358 | 0.030* | |
C2 | 0.6250 (2) | 0.3078 (3) | 0.45464 (10) | 0.0314 (4) | |
H2 | 0.507103 | 0.332900 | 0.440638 | 0.038* | |
C3 | 0.6775 (2) | 0.1881 (2) | 0.51058 (10) | 0.0297 (4) | |
H3 | 0.595713 | 0.131149 | 0.534962 | 0.036* | |
C4 | 0.8495 (2) | 0.1523 (2) | 0.53060 (9) | 0.0248 (3) | |
H4 | 0.886377 | 0.070444 | 0.568762 | 0.030* | |
C5 | 0.96647 (19) | 0.2354 (2) | 0.49509 (8) | 0.0203 (3) | |
H5 | 1.085198 | 0.213089 | 0.508170 | 0.024* | |
C6 | 0.95043 (19) | 0.3470 (2) | 0.27306 (8) | 0.0215 (3) | |
H6A | 0.993775 | 0.324167 | 0.226919 | 0.032* | |
H6B | 0.886302 | 0.457327 | 0.268887 | 0.032* | |
H6C | 0.875225 | 0.250804 | 0.282868 | 0.032* | |
C7 | 0.5041 (2) | 0.4202 (3) | 0.19949 (11) | 0.0349 (4) | |
H7A | 0.549811 | 0.518471 | 0.174279 | 0.052* | |
H7B | 0.583596 | 0.321159 | 0.202500 | 0.052* | |
H7C | 0.489657 | 0.456406 | 0.249278 | 0.052* | |
N1 | 0.90840 (16) | 0.34870 (16) | 0.44154 (7) | 0.0182 (2) | |
O1 | 1.02878 (14) | 0.45125 (15) | 0.41284 (6) | 0.0228 (2) | |
O2 | 1.18327 (14) | 0.19494 (16) | 0.36976 (7) | 0.0269 (3) | |
O3 | 1.23496 (15) | 0.50071 (17) | 0.33542 (7) | 0.0295 (3) | |
O4 | 0.33727 (14) | 0.30518 (17) | 0.07686 (6) | 0.0259 (3) | |
O5 | 0.24872 (14) | 0.20919 (15) | 0.19056 (6) | 0.0252 (2) | |
O6 | 0.19265 (15) | 0.50693 (16) | 0.14815 (7) | 0.0285 (3) | |
S1 | 1.12073 (5) | 0.36235 (5) | 0.34493 (2) | 0.01954 (10) | |
S2 | 0.30549 (4) | 0.35686 (5) | 0.15000 (2) | 0.01779 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0256 (7) | 0.0232 (8) | 0.0244 (8) | 0.0051 (6) | 0.0019 (6) | −0.0025 (6) |
C2 | 0.0202 (7) | 0.0375 (10) | 0.0370 (9) | 0.0025 (7) | 0.0063 (7) | −0.0092 (8) |
C3 | 0.0301 (8) | 0.0286 (9) | 0.0345 (9) | −0.0074 (7) | 0.0174 (7) | −0.0081 (7) |
C4 | 0.0364 (9) | 0.0188 (7) | 0.0211 (7) | −0.0004 (6) | 0.0103 (6) | −0.0008 (6) |
C5 | 0.0234 (7) | 0.0191 (7) | 0.0185 (7) | 0.0017 (6) | 0.0037 (5) | −0.0021 (5) |
C6 | 0.0213 (7) | 0.0232 (8) | 0.0196 (7) | −0.0004 (6) | 0.0018 (5) | −0.0006 (6) |
C7 | 0.0247 (8) | 0.0409 (11) | 0.0374 (10) | −0.0099 (8) | −0.0006 (7) | −0.0060 (8) |
N1 | 0.0205 (6) | 0.0158 (6) | 0.0191 (6) | −0.0019 (5) | 0.0058 (5) | −0.0019 (5) |
O1 | 0.0279 (5) | 0.0188 (5) | 0.0228 (5) | −0.0065 (4) | 0.0080 (4) | −0.0023 (4) |
O2 | 0.0254 (6) | 0.0273 (6) | 0.0288 (6) | 0.0067 (5) | 0.0068 (5) | 0.0053 (5) |
O3 | 0.0290 (6) | 0.0309 (7) | 0.0301 (6) | −0.0125 (5) | 0.0092 (5) | 0.0003 (5) |
O4 | 0.0234 (5) | 0.0336 (7) | 0.0218 (5) | 0.0011 (5) | 0.0066 (4) | −0.0027 (5) |
O5 | 0.0286 (6) | 0.0198 (6) | 0.0284 (6) | −0.0039 (5) | 0.0082 (5) | 0.0022 (5) |
O6 | 0.0326 (6) | 0.0242 (6) | 0.0304 (6) | 0.0097 (5) | 0.0098 (5) | 0.0047 (5) |
S1 | 0.01875 (17) | 0.01993 (19) | 0.02037 (18) | −0.00212 (13) | 0.00443 (13) | 0.00094 (13) |
S2 | 0.01614 (16) | 0.01827 (18) | 0.01905 (18) | −0.00070 (12) | 0.00307 (12) | 0.00026 (13) |
C1—N1 | 1.3418 (19) | C6—H6B | 0.9800 |
C1—C2 | 1.373 (2) | C6—H6C | 0.9800 |
C1—H1 | 0.9500 | C7—S2 | 1.7586 (17) |
C2—C3 | 1.389 (3) | C7—H7A | 0.9800 |
C2—H2 | 0.9500 | C7—H7B | 0.9800 |
C3—C4 | 1.383 (3) | C7—H7C | 0.9800 |
C3—H3 | 0.9500 | N1—O1 | 1.4004 (15) |
C4—C5 | 1.371 (2) | O1—S1 | 1.6847 (11) |
C4—H4 | 0.9500 | O2—S1 | 1.4188 (12) |
C5—N1 | 1.336 (2) | O3—S1 | 1.4195 (12) |
C5—H5 | 0.9500 | O4—S2 | 1.4610 (12) |
C6—S1 | 1.7384 (15) | O5—S2 | 1.4605 (12) |
C6—H6A | 0.9800 | O6—S2 | 1.4500 (12) |
N1—C1—C2 | 117.39 (15) | S2—C7—H7B | 109.5 |
N1—C1—H1 | 121.3 | H7A—C7—H7B | 109.5 |
C2—C1—H1 | 121.3 | S2—C7—H7C | 109.5 |
C1—C2—C3 | 119.94 (15) | H7A—C7—H7C | 109.5 |
C1—C2—H2 | 120.0 | H7B—C7—H7C | 109.5 |
C3—C2—H2 | 120.0 | C5—N1—C1 | 125.35 (14) |
C4—C3—C2 | 119.65 (16) | C5—N1—O1 | 117.54 (12) |
C4—C3—H3 | 120.2 | C1—N1—O1 | 116.47 (13) |
C2—C3—H3 | 120.2 | N1—O1—S1 | 117.09 (9) |
C5—C4—C3 | 119.68 (16) | O2—S1—O3 | 120.71 (7) |
C5—C4—H4 | 120.2 | O2—S1—O1 | 107.09 (7) |
C3—C4—H4 | 120.2 | O3—S1—O1 | 98.72 (7) |
N1—C5—C4 | 117.98 (14) | O2—S1—C6 | 111.99 (8) |
N1—C5—H5 | 121.0 | O3—S1—C6 | 113.03 (8) |
C4—C5—H5 | 121.0 | O1—S1—C6 | 102.42 (7) |
S1—C6—H6A | 109.5 | O6—S2—O5 | 112.42 (7) |
S1—C6—H6B | 109.5 | O6—S2—O4 | 112.76 (7) |
H6A—C6—H6B | 109.5 | O5—S2—O4 | 111.97 (7) |
S1—C6—H6C | 109.5 | O6—S2—C7 | 107.14 (9) |
H6A—C6—H6C | 109.5 | O5—S2—C7 | 105.72 (9) |
H6B—C6—H6C | 109.5 | O4—S2—C7 | 106.25 (8) |
S2—C7—H7A | 109.5 | ||
O1—N1—C1—C2 | −171.14 (14) | C2—C1—N1—C5 | −0.5 (2) |
N1—C1—C2—C3 | 0.2 (3) | C2—C1—N1—O1 | −171.14 (14) |
C1—C2—C3—C4 | 0.0 (3) | C5—N1—O1—S1 | 85.36 (14) |
C2—C3—C4—C5 | 0.1 (3) | C1—N1—O1—S1 | −103.28 (13) |
C3—C4—C5—N1 | −0.3 (2) | N1—O1—S1—O2 | −51.23 (11) |
C4—C5—N1—C1 | 0.6 (2) | N1—O1—S1—O3 | −177.23 (10) |
C4—C5—N1—O1 | 171.09 (13) | N1—O1—S1—C6 | 66.72 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O5i | 0.95 | 2.29 | 3.1745 (19) | 154 |
C3—H3···O4ii | 0.95 | 2.35 | 3.132 (2) | 139 |
C4—H4···O2iii | 0.95 | 2.42 | 3.254 (2) | 146 |
C5—H5···O4iv | 0.95 | 2.19 | 3.1008 (19) | 159 |
C6—H6A···O5v | 0.98 | 2.39 | 3.1840 (19) | 137 |
C6—H6B···O5i | 0.98 | 2.38 | 3.3023 (19) | 157 |
C6—H6C···O6vi | 0.98 | 2.36 | 3.261 (2) | 152 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y, −z+1; (iv) x+1, −y+1/2, z+1/2; (v) x+1, y, z; (vi) −x+1, y−1/2, −z+1/2. |
Funding information
Financial support by the DFG is gratefully acknowledged (DFG, grant No. 401007518).
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