1-(3-Phenyl­prop-2-yn­yl)pyrrolidinium chloride

Pang, T.; Lu, H.; Pang, T.

doi:10.1107/S1600536809042329

organic compounds

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Volume 65| Part 11| November 2009| Page o2806

https://doi.org/10.1107/S1600536809042329

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1-(3-Phenylprop-2-ynyl)pyrrolidinium chloride

Tao Pang,^a ^* Hui Lu ^a and Tao Pang ^a

^aKey Laboratory of Pesticides and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: leileitaotao6666@163.com

(Received 9 September 2009; accepted 15 October 2009; online 23 October 2009)

The title compound C₁₃H₁₆N⁺·Cl⁻, an achiral salt, was synthesized by a three-component coupling reaction in the presence of copper(I) iodide. The configuration of five-membered ring is close to an envelope conformation. The crystal structure is stabilized by intermolecular C—H⋯Cl and N—H⋯Cl interactions.

Related literature

For the preparation of the title compound, see: Nilsson et al. (1992 ). For background to propargylamines, see: Dyker (1999 ); Hattori et al. (1993 ); Konishi et al. (1990 ).

Experimental

Crystal data

C₁₃H₁₆N⁺·Cl⁻
M_r = 221.72
Monoclinic, P 2₁ /c
a = 10.9504 (2) Å
b = 11.3553 (3) Å
c = 11.1951 (2) Å
β = 117.008 (1)°
V = 1240.24 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 298 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
10560 measured reflections
2432 independent reflections
2353 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.158
S = 1.27
2432 reflections
139 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Cl1ⁱ	0.93	2.81	3.726 (3)	170
C9—H9A⋯Cl1ⁱⁱ	0.97	2.61	3.547 (3)	164
N1—H1⋯Cl1ⁱⁱⁱ	0.868 (10)	2.161 (10)	3.028 (2)	178 (3)
Symmetry codes: (i) x+1, y, z+1; (ii) -x+1, -y+2, -z+1; (iii) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809042329/pb2009sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042329/pb2009Isup2.hkl

checkCIF report

Comment top

Propargylamines, which have interesting biological activities, are compounds of versatile and important synthetic intermediates. (Konishi et al., 1990; Hattori et al., 1993; Dyker et al.,1999). The reaction which a three component procedure between terminal alkynes, formaldehyde and secondary amines and give rise to the propargylamines with rapid reaction rates by the introduction of copper (I) catalysts.

Here we report the crystal structure of the title compound (Fig. 1). The length of the N1—C9 bond in this compound was found to be 1.479 Å, which is approximate with the length of ordinary N—C single bond (1.47 Å).The four carbon atoms of the five–member ring are not in the same plane, the torsion angle is 14.92 °. It was close to the envelope conformation.

X-ray analysis reveals that the crystal structure is stabilized by C—H···Cl interaction and N—H···Cl interaction.

Related literature top

For the preparation of the title compound, see: Nilsson et al. (1992). For background to propargylamines, see: Dyker (1999); Hattori et al. (1993); Konishi et al. (1990).

Experimental top

The title compound was synthesized according to the literature procedure of Nilsson et al. (1992).

Single crystals suitable for X–ray diffraction were prepared by slow evaporation of a solution of the title compound in chloroform : methanol (20 : 1) and adding 1d HCl at room temperature.

Structure description top

X-ray analysis reveals that the crystal structure is stabilized by C—H···Cl interaction and N—H···Cl interaction.

For the preparation of the title compound, see: Nilsson et al. (1992). For background to propargylamines, see: Dyker (1999); Hattori et al. (1993); Konishi et al. (1990).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by spheres of arbitrary radius.

1-(3-Phenylprop-2-ynyl)pyrrolidinium chloride top

Crystal data top

C₁₃H₁₆N⁺·Cl⁻	F(000) = 472
M_r = 221.72	D_x = 1.187 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5548 reflections
a = 10.9504 (2) Å	θ = 2.7–28.1°
b = 11.3553 (3) Å	µ = 0.28 mm⁻¹
c = 11.1951 (2) Å	T = 298 K
β = 117.008 (1)°	Block, colorless
V = 1240.24 (4) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2353 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 26.0°, θ_min = 2.1°
φ and ω scans	h = −13→13
10560 measured reflections	k = −14→14
2432 independent reflections	l = −13→13

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	w = 1/[σ²(F_o²) + (0.053P)² + 0.6238P] where P = (F_o² + 2F_c²)/3
2432 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.35 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₁₆N⁺·Cl⁻	V = 1240.24 (4) Å³
M_r = 221.72	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.9504 (2) Å	µ = 0.28 mm⁻¹
b = 11.3553 (3) Å	T = 298 K
c = 11.1951 (2) Å	0.20 × 0.10 × 0.10 mm
β = 117.008 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2353 reflections with I > 2σ(I)
10560 measured reflections	R_int = 0.054
2432 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	1 restraint
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	Δρ_max = 0.35 e Å⁻³
2432 reflections	Δρ_min = −0.21 e Å⁻³
139 parameters

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.

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 > 2sigma(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
C1	0.6296 (3)	0.8606 (2)	0.7343 (3)	0.0493 (6)
C2	0.4916 (3)	0.8723 (3)	0.6473 (3)	0.0620 (7)
H2	0.4636	0.9243	0.5755	0.074*
C3	0.3957 (3)	0.8078 (3)	0.6660 (4)	0.0735 (9)
H3	0.3032	0.8162	0.6069	0.088*
C4	0.4359 (4)	0.7315 (3)	0.7707 (4)	0.0774 (10)
H4	0.3708	0.6878	0.7831	0.093*
C5	0.5724 (4)	0.7188 (3)	0.8581 (4)	0.0734 (9)
H5	0.5991	0.6663	0.9294	0.088*
C6	0.6697 (3)	0.7830 (2)	0.8413 (3)	0.0590 (7)
H6	0.7620	0.7746	0.9013	0.071*
C7	0.7303 (3)	0.9288 (2)	0.7156 (3)	0.0551 (7)
C8	0.8158 (3)	0.9840 (2)	0.7040 (3)	0.0570 (7)
C9	0.9214 (3)	1.0575 (2)	0.6955 (3)	0.0581 (7)
H9A	0.9276	1.1316	0.7410	0.070*
H9B	0.8952	1.0748	0.6021	0.070*
C10	1.1669 (3)	1.0766 (3)	0.7524 (3)	0.0666 (8)
H10A	1.1679	1.0699	0.6665	0.080*
H10B	1.1513	1.1584	0.7666	0.080*
C11	1.2991 (3)	1.0342 (3)	0.8625 (3)	0.0759 (9)
H11A	1.3503	1.0994	0.9190	0.091*
H11B	1.3545	0.9971	0.8258	0.091*
C12	1.2620 (4)	0.9460 (3)	0.9424 (3)	0.0784 (9)
H12A	1.2790	0.8662	0.9227	0.094*
H12B	1.3153	0.9601	1.0378	0.094*
C13	1.1110 (3)	0.9647 (3)	0.8992 (3)	0.0640 (8)
H13A	1.0679	0.8928	0.9081	0.077*
H13B	1.0967	1.0265	0.9513	0.077*
Cl1	0.03151 (7)	0.70879 (6)	0.07738 (7)	0.0545 (2)
N1	1.0572 (2)	0.99964 (19)	0.7561 (2)	0.0491 (5)
H1	1.051 (3)	0.9386 (17)	0.707 (2)	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0479 (14)	0.0489 (14)	0.0587 (15)	−0.0012 (11)	0.0308 (12)	−0.0117 (12)
C2	0.0534 (16)	0.0660 (17)	0.0676 (18)	0.0029 (13)	0.0284 (14)	0.0021 (14)
C3	0.0471 (16)	0.082 (2)	0.090 (2)	−0.0070 (15)	0.0306 (16)	−0.0131 (18)
C4	0.079 (2)	0.075 (2)	0.103 (3)	−0.0238 (18)	0.063 (2)	−0.019 (2)
C5	0.095 (3)	0.0597 (18)	0.078 (2)	−0.0041 (16)	0.051 (2)	0.0032 (15)
C6	0.0556 (16)	0.0596 (17)	0.0616 (17)	0.0044 (13)	0.0265 (14)	−0.0063 (13)
C7	0.0528 (15)	0.0557 (15)	0.0642 (17)	−0.0009 (12)	0.0329 (14)	−0.0069 (12)
C8	0.0559 (16)	0.0579 (16)	0.0628 (17)	−0.0023 (13)	0.0317 (14)	−0.0067 (13)
C9	0.0617 (17)	0.0524 (15)	0.0664 (18)	−0.0038 (13)	0.0345 (15)	−0.0002 (13)
C10	0.0595 (17)	0.0709 (19)	0.0699 (19)	−0.0164 (14)	0.0297 (15)	0.0096 (15)
C11	0.0622 (19)	0.095 (2)	0.070 (2)	−0.0112 (17)	0.0293 (17)	−0.0061 (18)
C12	0.080 (2)	0.085 (2)	0.0586 (18)	0.0083 (18)	0.0219 (17)	0.0059 (16)
C13	0.081 (2)	0.0623 (17)	0.0562 (17)	−0.0052 (15)	0.0383 (16)	0.0044 (13)
Cl1	0.0537 (4)	0.0555 (4)	0.0528 (4)	0.0018 (3)	0.0228 (3)	0.0045 (3)
N1	0.0566 (13)	0.0470 (12)	0.0498 (12)	−0.0099 (10)	0.0296 (11)	−0.0019 (9)

Geometric parameters (Å, º) top

C1—C2	1.383 (4)	C9—H9B	0.9700
C1—C6	1.388 (4)	C10—C11	1.492 (5)
C1—C7	1.439 (4)	C10—N1	1.501 (3)
C2—C3	1.372 (4)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C3—C4	1.360 (5)	C11—C12	1.516 (5)
C3—H3	0.9300	C11—H11A	0.9700
C4—C5	1.372 (5)	C11—H11B	0.9700
C4—H4	0.9300	C12—C13	1.512 (5)
C5—C6	1.373 (4)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—H6	0.9300	C13—N1	1.488 (3)
C7—C8	1.182 (4)	C13—H13A	0.9700
C8—C9	1.465 (4)	C13—H13B	0.9700
C9—N1	1.479 (4)	N1—H1	0.868 (10)
C9—H9A	0.9700

C2—C1—C6	119.1 (3)	N1—C10—H10A	110.5
C2—C1—C7	120.7 (3)	C11—C10—H10B	110.5
C6—C1—C7	120.3 (3)	N1—C10—H10B	110.5
C3—C2—C1	120.6 (3)	H10A—C10—H10B	108.7
C3—C2—H2	119.7	C10—C11—C12	106.3 (3)
C1—C2—H2	119.7	C10—C11—H11A	110.5
C4—C3—C2	120.1 (3)	C12—C11—H11A	110.5
C4—C3—H3	120.0	C10—C11—H11B	110.5
C2—C3—H3	120.0	C12—C11—H11B	110.5
C3—C4—C5	120.2 (3)	H11A—C11—H11B	108.7
C3—C4—H4	119.9	C13—C12—C11	105.4 (3)
C5—C4—H4	119.9	C13—C12—H12A	110.7
C4—C5—C6	120.6 (3)	C11—C12—H12A	110.7
C4—C5—H5	119.7	C13—C12—H12B	110.7
C6—C5—H5	119.7	C11—C12—H12B	110.7
C5—C6—C1	119.6 (3)	H12A—C12—H12B	108.8
C5—C6—H6	120.2	N1—C13—C12	102.8 (2)
C1—C6—H6	120.2	N1—C13—H13A	111.2
C8—C7—C1	178.0 (3)	C12—C13—H13A	111.2
C7—C8—C9	176.5 (3)	N1—C13—H13B	111.2
C8—C9—N1	112.1 (2)	C12—C13—H13B	111.2
C8—C9—H9A	109.2	H13A—C13—H13B	109.1
N1—C9—H9A	109.2	C9—N1—C13	115.9 (2)
C8—C9—H9B	109.2	C9—N1—C10	112.3 (2)
N1—C9—H9B	109.2	C13—N1—C10	104.7 (2)
H9A—C9—H9B	107.9	C9—N1—H1	107 (2)
C11—C10—N1	106.1 (2)	C13—N1—H1	110 (2)
C11—C10—H10A	110.5	C10—N1—H1	106.3 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cl1ⁱ	0.93	2.81	3.726 (3)	170
C9—H9A···Cl1ⁱⁱ	0.97	2.61	3.547 (3)	164
N1—H1···Cl1ⁱⁱⁱ	0.87 (1)	2.16 (1)	3.028 (2)	178 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆N⁺·Cl⁻
M_r	221.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.9504 (2), 11.3553 (3), 11.1951 (2)
β (°)	117.008 (1)
V (Å³)	1240.24 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10560, 2432, 2353
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.158, 1.27
No. of reflections	2432
No. of parameters	139
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.21

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cl1ⁱ	0.93	2.81	3.726 (3)	170.4
C9—H9A···Cl1ⁱⁱ	0.97	2.61	3.547 (3)	163.6
N1—H1···Cl1ⁱⁱⁱ	0.868 (10)	2.161 (10)	3.028 (2)	178 (3)

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

Acknowledgements

The author is grateful to Central China Normal University for support.

References

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