1-Allyl-2,3-cyclo­pentenopyridinium chloride

Partl, G.; Bentivoglio, G.; Laus, G.; Gelbrich, T.; Wurst, K.; Huppertz, H.; Schottenberger, H.

doi:10.1107/S2414314617006691

organic compounds

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ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170669

https://doi.org/10.1107/S2414314617006691

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1-Allyl-2,3-cyclopentenopyridinium chloride

Gabriel Partl,^a Gino Bentivoglio,^a Gerhard Laus,^a Thomas Gelbrich,^a Klaus Wurst,^a Hubert Huppertz ^a and Herwig Schottenberger ^a ^*

^aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80, 6020 Innsbruck, Austria
^*Correspondence e-mail: herwig.schottenberger@uibk.ac.at

Edited by J. Simpson, University of Otago, New Zealand (Received 27 April 2017; accepted 4 May 2017; online 9 May 2017)

The title compound, C₁₁H₁₄N⁺·Cl⁻, was obtained by reaction of 2,3-cyclopentenopyridine and allyl chloride. A network of weak C—H⋯Cl hydrogen bonds is observed in the crystal structure.

Keywords: crystal structure; allyl; chloride; hydrogen bond; pyridine.

CCDC reference: 1547806

Structure description

The title compound has been prepared in a continuation of our interest in chloride-based ionic liquids as solvents for cellulose (Bentivoglio et al., 2006 ; Wang et al., 2012 ; Liu et al., 2016 ). The reactions of cycloalkenopyridines have been reviewed by Beschke (1978 ). Related structures of 2,3-cyclopentenopyridinium salts are rare (Ammon & Jensen, 1966 ; Albov et al., 2004 ). A similar 1-allylpyridinium chloride has been reported recently (Bentivoglio et al., 2017 ).

In the title compound, the allyl group is twisted out of the plane of the heterocyclic ring by 84°.. The cyclopentene ring adopts a typical envelope conformation. The two possible conformations of the envelope are mirrored in the two components of positional disorder. The components C3 and C3A are located out of the C1/C2–C5 plane by 0.28 (1) and 0.25 (3) Å, respectively, a with a final occupancy ratio of 0.71 (2):0.29 (2).

In the crystal, weak C—H⋯Cl hydrogen bonds (Fig. 1, Table 1) create a network in which the chloride ions are fivefold coordinated by the pyridinium cations (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Cl1	0.98	2.80	3.748 (2)	164
C9—H9A⋯Cl1	0.98	2.64	3.584 (2)	163
C2—H2B⋯Cl1ⁱ	0.98	2.67	3.643 (2)	175
C7—H7⋯Cl1ⁱⁱ	0.94	2.75	3.545 (2)	143
C8—H8⋯Cl1ⁱⁱⁱ	0.94	2.59	3.510 (2)	166
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom labels and 50% probability displacement ellipsoids for non-H atoms. The minor-disorder component is represented by open bonds. C—H⋯Cl hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (iii) −x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

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

Synthesis and crystallization

A solution of freshly distilled 2,3-cyclopentenopyridine (5.0 g, 42.0 mmol) and allyl chloride (6.4 g, 83.6 mmol) in CH₃CN (5 ml) was refluxed for 48 h. The product was precipitated by the addition of Et₂O (100 ml), kept in the freezer overnight, then filtered off, washed with Et₂O, and dried in vacuo yielding 7.6 g (92%) of a deliquescent powder. A solution of the crude product in CH₂Cl₂ was treated with charcoal to give a grey solid, which was further purified by slow evaporation of a CH₂Cl₂/EtOAc (2:1) solution. After removal of an initial blackish precipitate, colourless crystals separated from the filtrate, m.p. 427 K.

¹H NMR (300 MHz, DMSO-d₆): δ 9.12 (dd, J = 6.2, 1.2 Hz, 1H), 8.48 (dd, J = 7.8, 1.2 Hz, 1H), 7.95 (dd, J = 7.8, 6.2 Hz, 1H), 6.11 (ddt, J = 16.4, 10.3, 5.9 Hz, 1H), 5.48–5.24 (m, 4H), 3.40 (t, J = 7.7 Hz, 2H), 3.12 (t, J = 7.6 Hz, 2H), 2.18 (quin, J = 7.8 Hz, 2H) p.p.m. ¹³C NMR (75 MHz, DMSO-d₆): δ 161.1, 144.8, 142.0, 140.9, 130.7, 125.6, 120.7, 59.5, 31.2, 30.5, 22.0 p.p.m. IR (neat): ν 3382, 2965, 2898, 2830, 1617, 1489, 1467, 1430, 1340, 1290, 1207, 1011, 958, 822, 739 cm⁻¹.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The disordered cyclopentene ring was refined using six geometrical restraints (SADI) for chemically equivalent, corresponding 1,2- and 1,3-distances in the two disorder components. The disordered C3 and C3A positions were both refined anisotropically, and their final relative occupancies were 0.71 (2) and 0.29 (2).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N⁺·Cl⁻
M_r	195.68
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	233
a, b, c (Å)	8.1093 (3), 9.1624 (5), 14.6575 (7)
β (°)	94.241 (3)
V (Å³)	1086.08 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.31
Crystal size (mm)	0.28 × 0.16 × 0.11

Data collection
Diffractometer	Nonius KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections	6048, 1905, 1617
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.092, 1.05
No. of reflections	1906
No. of parameters	140
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.15
Computer programs: COLLECT (Hooft, 1998 ), DENZO and SCALEPACK (Otwinowski & Minor, 1997 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1547806

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617006691/sj4107sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006691/sj4107Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617006691/sj4107Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314617006691/sj4107Isup4.cml

checkCIF report

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: COLLECT (Hooft, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008).

1-Allyl-2,3-cyclopentenopyridinium chloride top

Crystal data top

C₁₁H₁₄N⁺·Cl⁻	F(000) = 416
M_r = 195.68	D_x = 1.197 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.1093 (3) Å	Cell parameters from 8675 reflections
b = 9.1624 (5) Å	θ = 1.0–25.0°
c = 14.6575 (7) Å	µ = 0.31 mm⁻¹
β = 94.241 (3)°	T = 233 K
V = 1086.08 (9) Å³	Prism, colourless
Z = 4	0.28 × 0.16 × 0.11 mm

Data collection top

Nonius KappaCCD diffractometer	R_int = 0.028
Detector resolution: 9.6 pixels mm^-1	θ_max = 25.0°, θ_min = 2.6°
phi– and ω–scans	h = −9→9
6048 measured reflections	k = −10→10
1905 independent reflections	l = −17→15
1617 reflections with I > 2σ(I)

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0447P)² + 0.2786P] where P = (F_o² + 2F_c²)/3
1906 reflections	(Δ/σ)_max < 0.001
140 parameters	Δρ_max = 0.14 e Å⁻³
6 restraints	Δρ_min = −0.15 e Å⁻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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.03447 (5)	0.44823 (5)	0.28693 (3)	0.04502 (17)
N1	−0.10204 (15)	0.79887 (14)	0.10639 (9)	0.0386 (3)
C1	0.02285 (19)	0.74677 (18)	0.06053 (11)	0.0394 (4)
C2	0.1815 (2)	0.6849 (2)	0.10083 (13)	0.0488 (5)
H2A	0.1623	0.6094	0.1462	0.059*	0.71 (2)
H2B	0.2524	0.7611	0.1296	0.059*	0.71 (2)
H2C	0.153 (8)	0.584 (8)	0.129 (5)	0.059*	0.29 (2)
H2D	0.217 (9)	0.716 (9)	0.140 (5)	0.059*	0.29 (2)
C4	0.1684 (3)	0.6863 (3)	−0.06749 (15)	0.0723 (7)
H4A	0.2347	0.7640	−0.0926	0.087*	0.71 (2)
H4B	0.1445	0.6120	−0.1147	0.087*	0.71 (2)
H4C	0.196 (11)	0.700 (10)	−0.116 (6)	0.087*	0.29 (2)
H4D	0.140 (11)	0.567 (10)	−0.075 (6)	0.087*	0.29 (2)
C5	0.0123 (2)	0.7463 (2)	−0.03423 (12)	0.0517 (5)
C6	−0.1289 (3)	0.7974 (3)	−0.08175 (13)	0.0665 (6)
H6	−0.1391	0.7956	−0.1460	0.080*
C7	−0.2548 (3)	0.8511 (3)	−0.03341 (14)	0.0668 (6)
H7	−0.3515	0.8873	−0.0648	0.080*
C8	−0.2398 (2)	0.8519 (2)	0.05995 (13)	0.0534 (5)
H8	−0.3259	0.8898	0.0924	0.064*
C9	−0.0906 (2)	0.80459 (18)	0.20819 (10)	0.0407 (4)
H9A	−0.0333	0.7173	0.2327	0.049*
H9B	−0.2022	0.8049	0.2297	0.049*
C10	0.0005 (2)	0.93774 (19)	0.24313 (12)	0.0457 (4)
H10	0.1149	0.9443	0.2372	0.055*
C11	−0.0739 (2)	1.0444 (2)	0.28143 (14)	0.0563 (5)
H11A	−0.1883	1.0393	0.2879	0.068*
H11B	−0.0135	1.1267	0.3027	0.068*
C3	0.2577 (9)	0.6200 (9)	0.0171 (3)	0.0669 (18)	0.71 (2)
H3A	0.3759	0.6428	0.0191	0.080*	0.71 (2)
H3B	0.2446	0.5136	0.0164	0.080*	0.71 (2)
C3A	0.2852 (12)	0.672 (3)	0.0183 (4)	0.068 (5)	0.29 (2)
H3A1	0.3687	0.7497	0.0200	0.082*	0.29 (2)
H3A2	0.3419	0.5777	0.0190	0.082*	0.29 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0394 (3)	0.0451 (3)	0.0500 (3)	−0.00190 (17)	0.00033 (18)	0.00391 (18)
N1	0.0414 (7)	0.0383 (7)	0.0366 (7)	−0.0004 (6)	0.0058 (6)	0.0037 (6)
C1	0.0391 (8)	0.0408 (9)	0.0388 (9)	−0.0073 (7)	0.0058 (7)	−0.0021 (7)
C2	0.0409 (10)	0.0592 (13)	0.0463 (11)	0.0019 (8)	0.0032 (8)	−0.0069 (9)
C4	0.0610 (13)	0.108 (2)	0.0496 (12)	−0.0036 (13)	0.0160 (10)	−0.0213 (13)
C5	0.0518 (10)	0.0659 (12)	0.0379 (9)	−0.0095 (9)	0.0068 (8)	−0.0041 (8)
C6	0.0705 (13)	0.0918 (16)	0.0364 (10)	−0.0073 (12)	−0.0016 (9)	0.0086 (10)
C7	0.0595 (12)	0.0861 (16)	0.0536 (12)	0.0114 (11)	−0.0045 (10)	0.0169 (11)
C8	0.0473 (10)	0.0590 (12)	0.0540 (11)	0.0100 (9)	0.0049 (8)	0.0103 (9)
C9	0.0473 (9)	0.0402 (9)	0.0354 (9)	0.0019 (7)	0.0091 (7)	0.0028 (7)
C10	0.0371 (9)	0.0547 (11)	0.0456 (10)	−0.0013 (8)	0.0057 (7)	−0.0010 (8)
C11	0.0509 (10)	0.0498 (11)	0.0689 (13)	−0.0064 (9)	0.0092 (9)	−0.0076 (9)
C3	0.062 (3)	0.074 (4)	0.067 (3)	0.009 (2)	0.0206 (18)	−0.0084 (18)
C3A	0.050 (6)	0.092 (13)	0.064 (7)	0.011 (6)	0.017 (4)	−0.004 (5)

Geometric parameters (Å, º) top

N1—C1	1.344 (2)	C5—C6	1.377 (3)
N1—C8	1.355 (2)	C6—C7	1.376 (3)
N1—C9	1.489 (2)	C6—H6	0.9400
C1—C5	1.385 (2)	C7—C8	1.365 (3)
C1—C2	1.487 (2)	C7—H7	0.9400
C2—C3A	1.527 (7)	C8—H8	0.9400
C2—C3	1.534 (4)	C9—C10	1.497 (2)
C2—H2A	0.9800	C9—H9A	0.9800
C2—H2B	0.9800	C9—H9B	0.9800
C2—H2C	1.05 (8)	C10—C11	1.298 (3)
C2—H2D	0.69 (7)	C10—H10	0.9400
C4—C5	1.495 (3)	C11—H11A	0.9400
C4—C3	1.516 (5)	C11—H11B	0.9400
C4—C3A	1.523 (7)	C3—H3A	0.9800
C4—H4A	0.9800	C3—H3B	0.9800
C4—H4B	0.9800	C3A—H3A1	0.9800
C4—H4C	0.78 (9)	C3A—H3A2	0.9800
C4—H4D	1.12 (9)

C1—N1—C8	120.00 (15)	C7—C6—C5	118.78 (18)
C1—N1—C9	121.34 (13)	C7—C6—H6	120.6
C8—N1—C9	118.62 (14)	C5—C6—H6	120.6
N1—C1—C5	120.63 (15)	C8—C7—C6	120.28 (19)
N1—C1—C2	126.75 (15)	C8—C7—H7	119.9
C5—C1—C2	112.62 (15)	C6—C7—H7	119.9
C1—C2—C3A	103.0 (4)	N1—C8—C7	120.71 (17)
C1—C2—C3	102.6 (2)	N1—C8—H8	119.6
C1—C2—H2A	111.2	C7—C8—H8	119.6
C3—C2—H2A	111.2	N1—C9—C10	111.36 (13)
C1—C2—H2B	111.2	N1—C9—H9A	109.4
C3—C2—H2B	111.2	C10—C9—H9A	109.4
H2A—C2—H2B	109.2	N1—C9—H9B	109.4
C1—C2—H2C	106 (4)	C10—C9—H9B	109.4
C3A—C2—H2C	113 (4)	H9A—C9—H9B	108.0
C1—C2—H2D	118 (7)	C11—C10—C9	121.86 (16)
C3A—C2—H2D	118 (7)	C11—C10—H10	119.1
H2C—C2—H2D	97 (7)	C9—C10—H10	119.1
C5—C4—C3	104.2 (2)	C10—C11—H11A	120.0
C5—C4—C3A	104.6 (4)	C10—C11—H11B	120.0
C5—C4—H4A	110.9	H11A—C11—H11B	120.0
C3—C4—H4A	110.9	C4—C3—C2	107.6 (3)
C5—C4—H4B	110.9	C4—C3—H3A	110.2
C3—C4—H4B	110.9	C2—C3—H3A	110.2
H4A—C4—H4B	108.9	C4—C3—H3B	110.2
C5—C4—H4C	123 (7)	C2—C3—H3B	110.2
C3A—C4—H4C	125 (7)	H3A—C3—H3B	108.5
C5—C4—H4D	103 (4)	C4—C3A—C2	107.6 (6)
C3A—C4—H4D	96 (4)	C4—C3A—H3A1	110.2
H4C—C4—H4D	98 (8)	C2—C3A—H3A1	110.2
C6—C5—C1	119.57 (18)	C4—C3A—H3A2	110.2
C6—C5—C4	130.74 (18)	C2—C3A—H3A2	110.2
C1—C5—C4	109.68 (17)	H3A1—C3A—H3A2	108.5

C8—N1—C1—C5	−0.2 (2)	C3A—C4—C5—C1	−8.5 (11)
C9—N1—C1—C5	−178.01 (15)	C1—C5—C6—C7	1.6 (3)
C8—N1—C1—C2	−179.96 (18)	C4—C5—C6—C7	−178.2 (2)
C9—N1—C1—C2	2.2 (2)	C5—C6—C7—C8	−0.7 (3)
N1—C1—C2—C3A	−169.5 (11)	C1—N1—C8—C7	1.1 (3)
C5—C1—C2—C3A	10.7 (11)	C9—N1—C8—C7	179.00 (18)
N1—C1—C2—C3	170.1 (4)	C6—C7—C8—N1	−0.7 (3)
C5—C1—C2—C3	−9.7 (4)	C1—N1—C9—C10	82.79 (18)
N1—C1—C5—C6	−1.2 (3)	C8—N1—C9—C10	−95.10 (18)
C2—C1—C5—C6	178.66 (18)	N1—C9—C10—C11	110.0 (2)
N1—C1—C5—C4	178.66 (17)	C5—C4—C3—C2	−18.0 (7)
C2—C1—C5—C4	−1.5 (2)	C1—C2—C3—C4	16.9 (6)
C3—C4—C5—C6	−168.0 (4)	C5—C4—C3A—C2	14.9 (17)
C3A—C4—C5—C6	171.4 (11)	C1—C2—C3A—C4	−15.5 (17)
C3—C4—C5—C1	12.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl1	0.98	2.80	3.748 (2)	164
C9—H9A···Cl1	0.98	2.64	3.584 (2)	163
C2—H2B···Cl1ⁱ	0.98	2.67	3.643 (2)	175
C7—H7···Cl1ⁱⁱ	0.94	2.75	3.545 (2)	143
C8—H8···Cl1ⁱⁱⁱ	0.94	2.59	3.510 (2)	166

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x−1/2, y+1/2, −z+1/2.

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