1-Allyl-2-methyl­pyridinium chloride

Bentivoglio, G.; Laus, G.; Kahlenberg, V.; Röder, T.; Schottenberger, H.

doi:10.1107/S2414314617005983

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170598

https://doi.org/10.1107/S2414314617005983

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1-Allyl-2-methylpyridinium chloride

Gino Bentivoglio,^a Gerhard Laus,^a Volker Kahlenberg,^b Thomas Röder ^c and Herwig Schottenberger ^a ^*

^aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80, 6020 Innsbruck, Austria, ^bUniversity of Innsbruck, Institute of Mineralogy and Petrography, Innrain 52, 6020 Innsbruck, Austria, and ^cLenzing AG, Global R&D, Werkstrasse 2, 4860 Lenzing, Austria
^*Correspondence e-mail: herwig.schottenberger@uibk.ac.at

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 April 2017; accepted 20 April 2017; online 28 April 2017)

The title molecular salt, C₉H₁₂N⁺·Cl⁻, was obtained by reaction of 2-methylpyridine and allyl chloride. A network of C—H⋯Cl hydrogen bonds is observed in the crystal structure.

Keywords: allyl; chloride; crystal structure; pyridine.

CCDC reference: 1545055

Structure description

Chloride-based ionic liquids (salts melting below 373 K) are suitable solvents for cellulose dissolution (Wang et al., 2012 ; Liu et al., 2016 ) and for fibre spinning. The numerous advantages of ionic liquids, such as non-volatility, thermal stability, chemical modifiability, and low melting points are countervailed by their disadvantages, such as aquatic toxicity, corrosivity, and a high energy input required for pulp preparation and removal of water (Bentivoglio et al., 2006 ). In particular, it has been found that some ionic liquids promote degradation of cellulose. The molecular mass distribution of the reconstituted cellulose samples was determined by gel permeation chromatography (Schelosky et al., 1999 ). Degradation was exceptionally strong (from 200 kDa down to 24 kDa) in the present ionic liquid. The solubility of cellulose in a series of pyridinium chlorides was studied by quantum-chemical calculations (Sashina et al., 2012 ).

The title compound has been described as a `sirupy liquid' (Ramsay, 1876 ). It has now been crystallized but still qualifies as an ionic liquid (melting at 367 K). In the crystal structure, the allyl group is twisted out of the plane of the heterocyclic ring. Weak C—H⋯Cl hydrogen bonds (Fig. 1, Table 1) create a three-dimensional network in which the chloride ions are sixfold coordinated toward the pyridinium cations (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1	0.95	2.82	3.701 (2)	155
C7—H7A⋯Cl1ⁱ	0.98	2.78	3.695 (2)	157
C4—H4A⋯Cl1ⁱⁱ	0.99	2.76	3.698 (2)	159
C4—H4B⋯Cl1ⁱ	0.99	2.72	3.609 (2)	149
C6—H6⋯Cl1ⁱⁱⁱ	0.95	2.64	3.545 (2)	161
C3—H3⋯Cl1ⁱⁱ	0.95	2.57	3.454 (2)	155
Symmetry codes: (i) x, y+1, z; (ii) -x+2, -y, -z+1; (iii) -x+2, -y, -z+2.

Figure 1
The molecular structure of the title compound, showing the atom labels and 50% probability displacement ellipsoids for non-H atoms. The C—H⋯Cl hydrogen bonds are shown as dashed lines. Symmetry codes: (i) x, y + 1, z; (ii) −x + 2, −y, −z + 1; (iii) −x + 2, −y, −z + 2.

Figure 2
Sixfold-coordinated chloride ions in the unit cell of the title compound. Only hydrogen atoms involved in contacts are shown.

Related structures with similar hydrogen bond networks include N-allylpyrrolidinium chloride (Laus et al., 2008 ), N-allylpyridinium bromide (Seethalakshmi et al., 2013 ) and N-allylimidazolium iodides (Fei et al., 2006 ).

Synthesis and crystallization

To 2-methylpyridine (18.9 g, 0.20 mol) was added an excess of allyl chloride (18.6 g, 0.24 mol). The reaction mixture was refluxed for 72 h. Excess allyl chloride was removed under reduced pressure. The crude product was washed with Et₂O (50 ml) and dried on a high vacuum line giving 1-allyl-2-methylpyridinium chloride as a brown powder (17.4 g, 51%), m.p. 364–367 K. Colourless plates were recrystallized from a solvent mixture of acetone/CH₂Cl₂. ¹H NMR (300 MHz, DMSO-d₆): δ 2.93 (3H, s), 5.10 (1H, d, J = 17.2 Hz), 5.35 (1H, d, J = 10.6 Hz), 5.66 (2H, d, J = 5.6 Hz), 6.00 (1H, m), 7.92 (1H, t, J = 6.8 Hz), 8.00 (1H, d, J = 7.9 Hz), 8.41 (1H, t, J = 7.6 Hz), 9.70 (1H, d, J = 5.9) p.p.m. ¹³C NMR (75 MHz, DMSO-d₆): δ 20.5, 60.0, 120.9, 126.2, 130.0, 130.1, 145.5, 146.9, 155.0 p.p.m. IR (neat): ν 3009, 2921, 2438, 1622, 1573, 1503, 1478, 1455, 1421, 1296, 1158, 1141, 1053, 1004, 930, 829, 794, 770, 710, 663 cm⁻¹.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₂N⁺·Cl⁻
M_r	169.65
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	6.9617 (17), 7.5941 (19), 9.464 (2)
α, β, γ (°)	86.06 (2), 82.118 (19), 67.102 (18)
V (Å³)	456.48 (19)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.35
Crystal size (mm)	0.4 × 0.38 × 0.1

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )
T_min, T_max	0.904, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	3066, 1616, 1465
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.05
No. of reflections	1616
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17
Computer programs: X-AREA and X-RED (Stoe & Cie, 1997 ), SIR2002 (Burla et al., 2003 ), SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1545055

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617005983/hb4138sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005983/hb4138Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005983/hb4138Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005983/hb4138Isup4.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 1997); cell refinement: X-AREA (Stoe & Cie, 1997); data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008).

1-Allyl-2-methylpyridinium chloride top

Crystal data top

C₉H₁₂N⁺·Cl⁻	Z = 2
M_r = 169.65	F(000) = 180
Triclinic, P1	D_x = 1.234 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9617 (17) Å	Cell parameters from 3556 reflections
b = 7.5941 (19) Å	θ = 2.2–27.2°
c = 9.464 (2) Å	µ = 0.35 mm⁻¹
α = 86.06 (2)°	T = 173 K
β = 82.118 (19)°	Fragment of a plate, colorless
γ = 67.102 (18)°	0.4 × 0.38 × 0.1 mm
V = 456.48 (19) Å³

Data collection top

Stoe IPDS 2 diffractometer	1616 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1465 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 6.67 pixels mm^-1	θ_max = 25.4°, θ_min = 2.2°
rotation method scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −8→9
T_min = 0.904, T_max = 0.985	l = −11→11
3066 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0261P)² + 0.1555P] where P = (F_o² + 2F_c²)/3
1616 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 > 2σ(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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.89617 (6)	−0.22917 (5)	0.72298 (4)	0.02896 (12)
N1	1.00030 (18)	0.21870 (17)	0.71106 (12)	0.0243 (3)
C1	0.6310 (2)	0.2941 (2)	0.67241 (16)	0.0294 (3)
H1	0.6544	0.1621	0.6801	0.035*
C2	1.3379 (2)	−0.0309 (2)	0.68650 (17)	0.0314 (3)
H2	1.4525	−0.1182	0.6277	0.038*
C3	1.1628 (2)	0.0914 (2)	0.62917 (16)	0.0281 (3)
H3	1.1553	0.0868	0.5301	0.034*
C4	0.8179 (2)	0.3488 (2)	0.63906 (15)	0.0272 (3)
H4A	0.8591	0.3451	0.5346	0.033*
H4B	0.7789	0.4814	0.67	0.033*
C5	1.0027 (2)	0.2277 (2)	0.85415 (15)	0.0268 (3)
C6	1.1772 (2)	0.1022 (2)	0.91430 (16)	0.0322 (3)
H6	1.1808	0.1042	1.0141	0.039*
C7	0.8237 (3)	0.3733 (2)	0.94055 (16)	0.0350 (4)
H7A	0.8066	0.5014	0.9031	0.052*
H7B	0.8518	0.3622	1.0401	0.052*
H7C	0.6948	0.352	0.9352	0.052*
C8	1.3453 (2)	−0.0254 (2)	0.83142 (17)	0.0331 (3)
H8	1.4654	−0.1089	0.8734	0.04*
C9	0.4376 (2)	0.4194 (2)	0.69139 (19)	0.0394 (4)
H9A	0.4102	0.5522	0.6842	0.047*
H9B	0.3246	0.3776	0.7123	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02934 (19)	0.02856 (19)	0.02593 (19)	−0.00806 (14)	−0.00311 (14)	0.00060 (13)
N1	0.0225 (6)	0.0264 (6)	0.0247 (6)	−0.0108 (5)	−0.0011 (5)	0.0002 (5)
C1	0.0283 (7)	0.0250 (7)	0.0353 (8)	−0.0100 (6)	−0.0063 (6)	0.0000 (6)
C2	0.0242 (7)	0.0315 (8)	0.0357 (8)	−0.0093 (6)	0.0026 (6)	−0.0024 (6)
C3	0.0279 (7)	0.0321 (8)	0.0254 (7)	−0.0137 (6)	0.0012 (6)	−0.0032 (6)
C4	0.0262 (7)	0.0275 (7)	0.0258 (7)	−0.0083 (6)	−0.0038 (6)	0.0022 (6)
C5	0.0283 (7)	0.0299 (7)	0.0245 (7)	−0.0149 (6)	−0.0001 (6)	0.0003 (6)
C6	0.0328 (8)	0.0390 (8)	0.0269 (8)	−0.0162 (7)	−0.0059 (6)	0.0040 (6)
C7	0.0368 (8)	0.0370 (9)	0.0269 (8)	−0.0108 (7)	0.0006 (7)	−0.0024 (6)
C8	0.0256 (7)	0.0358 (8)	0.0378 (9)	−0.0117 (6)	−0.0071 (7)	0.0055 (7)
C9	0.0288 (8)	0.0333 (8)	0.0542 (11)	−0.0108 (7)	−0.0037 (7)	0.0015 (7)

Geometric parameters (Å, º) top

N1—C3	1.351 (2)	C4—H4B	0.9900
N1—C5	1.364 (2)	C5—C6	1.385 (2)
N1—C4	1.4882 (19)	C5—C7	1.489 (2)
C1—C9	1.307 (2)	C6—C8	1.376 (2)
C1—C4	1.502 (2)	C6—H6	0.9500
C1—H1	0.9500	C7—H7A	0.9800
C2—C3	1.368 (2)	C7—H7B	0.9800
C2—C8	1.383 (2)	C7—H7C	0.9800
C2—H2	0.9500	C8—H8	0.9500
C3—H3	0.9500	C9—H9A	0.9500
C4—H4A	0.9900	C9—H9B	0.9500

C3—N1—C5	121.20 (13)	N1—C5—C6	118.28 (14)
C3—N1—C4	117.55 (13)	N1—C5—C7	119.86 (14)
C5—N1—C4	121.25 (13)	C6—C5—C7	121.84 (14)
C9—C1—C4	123.20 (15)	C8—C6—C5	120.98 (15)
C9—C1—H1	118.4	C8—C6—H6	119.5
C4—C1—H1	118.4	C5—C6—H6	119.5
C3—C2—C8	118.97 (15)	C5—C7—H7A	109.5
C3—C2—H2	120.5	C5—C7—H7B	109.5
C8—C2—H2	120.5	H7A—C7—H7B	109.5
N1—C3—C2	121.21 (15)	C5—C7—H7C	109.5
N1—C3—H3	119.4	H7A—C7—H7C	109.5
C2—C3—H3	119.4	H7B—C7—H7C	109.5
N1—C4—C1	112.07 (12)	C6—C8—C2	119.33 (15)
N1—C4—H4A	109.2	C6—C8—H8	120.3
C1—C4—H4A	109.2	C2—C8—H8	120.3
N1—C4—H4B	109.2	C1—C9—H9A	120.0
C1—C4—H4B	109.2	C1—C9—H9B	120.0
H4A—C4—H4B	107.9	H9A—C9—H9B	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl1	0.95	2.82	3.701 (2)	155
C7—H7A···Cl1ⁱ	0.98	2.78	3.695 (2)	157
C4—H4A···Cl1ⁱⁱ	0.99	2.76	3.698 (2)	159
C4—H4B···Cl1ⁱ	0.99	2.72	3.609 (2)	149
C6—H6···Cl1ⁱⁱⁱ	0.95	2.64	3.545 (2)	161
C3—H3···Cl1ⁱⁱ	0.95	2.57	3.454 (2)	155

Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y, −z+1; (iii) −x+2, −y, −z+2.

References

Bentivoglio, G., Röder, T., Fasching, M., Buchberger, M., Schottenberger, H. & Sixta, H. (2006). Lenz. Ber. 86, 154–161. CAS Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fei, Z., Kuang, D., Zhao, D., Klein, C., Ang, W. H., Zakeeruddin, S. M., Grätzel, M. & Dyson, P. J. (2006). Inorg. Chem. 45, 10407–10409. Web of Science CSD CrossRef PubMed CAS Google Scholar
Laus, G., Bentivoglio, G., Kahlenberg, V., Griesser, U. J., Schottenberger, H. & Nauer, G. (2008). CrystEngComm, 10, 748–752. CrossRef CAS Google Scholar
Liu, Y.-R., Thomsen, K., Nie, Y., Zhang, S.-J. & Meyer, A. S. (2016). Green Chem. 18, 6246–6254. CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ramsay, W. (1876). Philos. Mag. Ser. 5, 2, 269–281. Google Scholar
Sashina, E. S., Kashirskii, D. A. & Martynova, E. V. (2012). Russ. J. Gen. Chem. 82, 729–735. CrossRef CAS Google Scholar
Schelosky, N., Röder, T. & Baldinger, T. (1999). Papier 53, 728–738. CAS Google Scholar
Seethalakshmi, T., Venkatesan, P., Nallu, M., Lynch, D. E. & Thamotharan, S. (2013). Acta Cryst. E69, o884. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1997). X-AREA and X-RED. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Wang, H., Gurau, G. & Rogers, R. D. (2012). Chem. Soc. Rev. 41, 1519–1537. CrossRef CAS PubMed Google Scholar

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