1-[(Methyl­sulfon­yl)­oxy]pyridin-1-ium methane­sulfonate

Taeufer, T.; Spannenberg, A.; Pospech, J.

doi:10.1107/S2414314621010269

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 10| October 2021| x211026

https://doi.org/10.1107/S2414314621010269

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1-[(Methylsulfonyl)oxy]pyridin-1-ium methanesulfonate

Tobias Taeufer,^a Anke Spannenberg ^a and Jola Pospech ^a ^*

^aLeibniz-Institut für Katalyse e. V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany
^*Correspondence e-mail: jola.pospech@catalysis.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 13 September 2021; accepted 4 October 2021; online 19 October 2021)

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 arenes 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)°.

Figure 1
Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

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.

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O4^iv	0.95	2.19	3.1008 (19)	159
C6—H6A⋯O5^v	0.98	2.39	3.1840 (19)	137
C6—H6B⋯O5ⁱ	0.98	2.38	3.3023 (19)	157
C6—H6C⋯O6^vi	0.98	2.36	3.261 (2)	152
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) ; (iv) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) x+1, y, z; (vi) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 crystal structure 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₈NO₃S⁺·CH₃O₃S⁻
M_r	269.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	7.9335 (3), 7.6255 (3), 18.3875 (7)
β (°)	99.0734 (14)
V (Å³)	1098.47 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.50
Crystal size (mm)	0.36 × 0.08 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.84, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	27689, 3400, 2732
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.718

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.05
No. of reflections	3400
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.29
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2113673

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621010269/hb4392sup1.cif

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

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: 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).

1-[(Methylsulfonyl)oxy]pyridin-1-ium methanesulfonate top

Crystal data top

C₆H₈NO₃S⁺·CH₃O₃S⁻	F(000) = 560
M_r = 269.29	D_x = 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

Data collection top

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	R_int = 0.033
φ and ω scans	θ_max = 30.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −11→11
T_min = 0.84, T_max = 0.96	k = −10→10
27689 measured reflections	l = −26→26

Refinement top

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(F_o²) + (0.0491P)² + 0.5052P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3400 reflections	Δρ_max = 0.48 e Å⁻³
147 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints

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	0.7438 (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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O4^iv	0.95	2.19	3.1008 (19)	159
C6—H6A···O5^v	0.98	2.39	3.1840 (19)	137
C6—H6B···O5ⁱ	0.98	2.38	3.3023 (19)	157
C6—H6C···O6^vi	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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