(S)-2-Amino-1-(pyrrolidinium-2-ylmeth­yl)pyridinium dibromide

Wang, Y.; Zhang, S.; Xia, A.; Luo, S.; Xu, D.

doi:10.1107/S1600536808001128

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o473

doi:10.1107/S1600536808001128

Open

access

(S)-2-Amino-1-(pyrrolidinium-2-ylmethyl)pyridinium dibromide

Yifeng Wang,^a Shuai Zhang,^a Aibao Xia,^a Shuping Luo ^a and Danqian Xu ^a ^*

^aState Key Laboratory Breeding Base of Green Chemistry – Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: yifengwang108@gmail.com

(Received 1 December 2007; accepted 11 January 2008; online 18 January 2008)

In the title compound, C₁₀H₁₇N₃²⁺·2Br⁻, the pyrrolidinium ring displays an envelope conformation, with the flap N atom lying 0.564 (6) Å from the mean plane of the remaining four C atoms. The attached methylene C atom, which connects the pyrrolidinium ring and the 2-aminopyridine group, is displaced from the plane of the four pyrrolidinium C atoms by 0.811 (8) Å in the same direction as the pyrrolidinium N atom. The amine N lies on the opposite side of this plane.

Related literature

The synthesis of (S)-(+)-2-bromomethylpyrrolidine hydrobromide is described by Xu et al. (2006 ). For related literature, see: Ishii et al. (2004 ); Larson (1970 ).

Experimental

Crystal data

C₁₀H₁₇N₃²⁺·2Br⁻
M_r = 339.07
Monoclinic, P 2₁
a = 10.5509 (5) Å
b = 6.1755 (3) Å
c = 10.8474 (6) Å
β = 107.4830 (14)°
V = 674.14 (6) Å³
Z = 2
Mo Kα radiation
μ = 6.01 mm⁻¹
T = 296 (1) K
0.37 × 0.32 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.110, T_max = 0.458
6601 measured reflections
2681 independent reflections
1943 reflections with F² > 2σ(F²)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.094
S = 1.01
2681 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.61 e Å⁻³
Absolute structure: Flack (1983 ), with 1013 Friedel pairs
Flack parameter: 0.002 (5)

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CrystalStructure; software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001128/cs2067sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001128/cs2067Isup2.hkl

checkCIF report

Comment top

Proline and its derivatives have been extensively studied due to their abilities to catalyze a wide range of reactions as organocatalysts in recent years (Ishii et al., 2004; Xu et al., 2006). The title compound, which could be readily synthesized from commercially available L-proline and 2-aminopyridine, can act as organocatalyst in the Michael addition of ketones to nitrostyrenes. These reactions afford the desired Michael adducts in good yields and moderate enantioselectivities. The title salt (S)-2-amino-1-(pyrrolidinium-2-ylmethyl)-pyridinium dibromide crystal structure (Fig. 1) is built of pyrrolidinium cations and bromide anions. The pyrrolidinium ring displays a fair half-chair conformation, with the flap atom N1 lying 0.564 (6) Å from the mean plane of C1/C2/C3/C4. The methylene C5 atom, which connects the pyrrolidinium ring and the 2-aminopyridine group, is displaced from the plane of four pyrrolidinium carbons by 0.811 (8) Å in the same direction as the N1 atom. The atom N3 of the amino group of pyrrolidinium and the atom N1 are on the opposite sides of the mean plane of C1/C2/C3/C4.

Related literature top

The synthesis of (S)-(+)-2-bromomethylpyrrolidine hydrobromide is described by Xu et al. (2006). For related literature, see: Ishii et al. (2004); Larson (1970).

Experimental top

The title compound was synthesized by treating 2-aminopyridine (0.94 g,10 mmol) with (S)-(+)-2-bromomethylpyrrolidine hydrobromide (2.50 g,10 mmol) in MeCN (30 ml) under stirring at 353 K for 24 h (yield 92%). The compound (S)-(+)-2-bromomethylpyrrolidine hydrobromide was obtained from commercially available L-proline by reduction with NaBH₄ and subsequent bromination with PBr₃ (Xu et al., 2006). Suitable crystals of the title compound were obtained by slow evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: CrystalStructure (Rigaku/MSC, 2004); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top

Fig. 1. The asymmetric unit of the crystal structure of the title compound with the atomic labeling scheme. Displacement ellipsoids are drawn at the 40% probability level.

(S)-2-Amino-1-(pyrrolidinium-2-ylmethyl)pyridinium dibromide top

Crystal data top

C₁₀H₁₇N₃²⁺·2Br⁻	F(000) = 336.00
M_r = 339.07	D_x = 1.670 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2yb	Cell parameters from 5483 reflections
a = 10.5509 (5) Å	θ = 3.2–27.5°
b = 6.1755 (3) Å	µ = 6.01 mm⁻¹
c = 10.8474 (6) Å	T = 296 K
β = 107.4830 (14)°	Platelet, colorless
V = 674.14 (6) Å³	0.37 × 0.32 × 0.13 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1943 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.052
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
T_min = 0.110, T_max = 0.458	k = −7→8
6601 measured reflections	l = −14→14
2681 independent reflections

Refinement top

Refinement on F²	(Δ/σ)_max < 0.001
R[F² > 2σ(F²)] = 0.034	Δρ_max = 0.41 e Å⁻³
wR(F²) = 0.094	Δρ_min = −0.61 e Å⁻³
S = 1.01	Extinction correction: Larson (1970), equation 22
2681 reflections	Extinction coefficient: 48 (6)
138 parameters	Absolute structure: Flack (1983), 1013 Friedel pairs
H-atom parameters constrained	Absolute structure parameter: 0.002 (5)
w = 1/[0.9800σ(F_o²)]/(4F_o²)

Crystal data top

C₁₀H₁₇N₃²⁺·2Br⁻	V = 674.14 (6) Å³
M_r = 339.07	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 10.5509 (5) Å	µ = 6.01 mm⁻¹
b = 6.1755 (3) Å	T = 296 K
c = 10.8474 (6) Å	0.37 × 0.32 × 0.13 mm
β = 107.4830 (14)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2681 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1943 reflections with F² > 2σ(F²)
T_min = 0.110, T_max = 0.458	R_int = 0.052
6601 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.094	Δρ_max = 0.41 e Å⁻³
S = 1.01	Δρ_min = −0.61 e Å⁻³
2681 reflections	Absolute structure: Flack (1983), 1013 Friedel pairs
138 parameters	Absolute structure parameter: 0.002 (5)

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

	x	y	z	U_iso*/U_eq
Br1	0.12426 (6)	0.7373 (2)	0.07481 (6)	0.0544 (2)
Br2	0.36075 (6)	0.4571 (2)	0.62553 (6)	0.0481 (2)
N1	0.2124 (4)	0.2325 (8)	0.0528 (4)	0.0394 (13)
N2	0.2014 (4)	0.1711 (7)	0.3238 (4)	0.0383 (14)
N3	0.3461 (4)	−0.1049 (8)	0.4252 (5)	0.0504 (17)
C1	0.3320 (5)	0.2156 (10)	0.1669 (5)	0.0373 (16)
C2	0.4356 (6)	0.3574 (10)	0.1293 (7)	0.050 (2)
C3	0.3902 (8)	0.3654 (13)	−0.0157 (8)	0.072 (3)
C4	0.2652 (7)	0.2334 (12)	−0.0600 (6)	0.058 (2)
C5	0.3056 (6)	0.2905 (8)	0.2915 (6)	0.0396 (19)
C6	0.0744 (6)	0.2588 (11)	0.2846 (6)	0.0473 (19)
C7	−0.0286 (6)	0.1613 (11)	0.3117 (7)	0.058 (2)
C8	−0.0044 (5)	−0.0355 (14)	0.3828 (6)	0.054 (2)
C9	0.1193 (6)	−0.1204 (10)	0.4205 (6)	0.048 (2)
C10	0.2260 (5)	−0.0171 (10)	0.3902 (5)	0.0399 (16)
H5	0.3628	0.0650	0.1770	0.045*
H6	0.0599	0.3881	0.2384	0.057*
H7	−0.1133	0.2214	0.2845	0.070*
H8	−0.0734	−0.1056	0.4033	0.065*
H9	0.1347	−0.2491	0.4671	0.057*
H21	0.4378	0.5019	0.1650	0.060*
H22	0.5232	0.2927	0.1605	0.060*
H31	0.3725	0.5138	−0.0450	0.087*
H32	0.4578	0.3046	−0.0494	0.087*
H41	0.2847	0.0872	−0.0817	0.070*
H42	0.2022	0.2998	−0.1346	0.070*
H51	0.3871	0.2743	0.3622	0.048*
H52	0.2804	0.4420	0.2820	0.048*
H111	0.1698	0.3502	0.0555	0.047*
H112	0.1607	0.1234	0.0491	0.047*
H301	0.4104	−0.0412	0.4065	0.061*
H302	0.3597	−0.2257	0.4666	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0568 (4)	0.0313 (3)	0.0617 (4)	0.0003 (3)	−0.0024 (3)	0.0000 (3)
Br2	0.0345 (3)	0.0652 (4)	0.0452 (4)	−0.0024 (3)	0.0130 (2)	0.0014 (3)
N1	0.035 (2)	0.038 (2)	0.044 (3)	0.003 (2)	0.011 (2)	−0.000 (2)
N2	0.035 (2)	0.047 (3)	0.036 (3)	0.005 (2)	0.014 (2)	−0.000 (2)
N3	0.031 (2)	0.060 (3)	0.063 (4)	0.008 (2)	0.017 (2)	0.015 (2)
C1	0.030 (2)	0.042 (3)	0.043 (3)	0.001 (2)	0.015 (2)	0.008 (2)
C2	0.047 (4)	0.057 (4)	0.048 (4)	−0.004 (3)	0.017 (3)	0.007 (3)
C3	0.070 (5)	0.088 (6)	0.065 (6)	0.003 (4)	0.030 (4)	0.016 (4)
C4	0.075 (4)	0.071 (4)	0.032 (3)	0.012 (5)	0.022 (3)	−0.003 (3)
C5	0.044 (3)	0.040 (4)	0.035 (3)	−0.002 (2)	0.013 (3)	0.002 (2)
C6	0.050 (3)	0.053 (3)	0.039 (3)	0.009 (3)	0.013 (3)	0.006 (3)
C7	0.034 (3)	0.084 (5)	0.057 (4)	0.004 (3)	0.015 (3)	−0.004 (3)
C8	0.029 (2)	0.088 (5)	0.052 (4)	0.006 (4)	0.023 (2)	−0.001 (4)
C9	0.041 (3)	0.064 (5)	0.042 (4)	−0.004 (3)	0.018 (3)	0.004 (2)
C10	0.031 (2)	0.047 (3)	0.039 (3)	0.003 (3)	0.008 (2)	−0.003 (3)

Geometric parameters (Å, º) top

N1—C1	1.483 (6)	N3—H301	0.860
N1—C4	1.490 (9)	N3—H302	0.860
N2—C5	1.451 (8)	C1—H5	0.980
N2—C6	1.388 (8)	C2—H21	0.970
N2—C10	1.351 (7)	C2—H22	0.970
N3—C10	1.325 (7)	C3—H31	0.970
C1—C2	1.547 (9)	C3—H32	0.970
C1—C5	1.532 (9)	C4—H41	0.970
C2—C3	1.501 (9)	C4—H42	0.970
C3—C4	1.501 (9)	C5—H51	0.970
C6—C7	1.350 (9)	C5—H52	0.970
C7—C8	1.421 (9)	C6—H6	0.930
C8—C9	1.351 (9)	C7—H7	0.930
C9—C10	1.415 (9)	C8—H8	0.930
N1—H111	0.860	C9—H9	0.930
N1—H112	0.860

C1—N1—C4	104.6 (4)	C1—C2—H21	110.5
C5—N2—C6	117.3 (4)	C1—C2—H22	110.5
C5—N2—C10	121.8 (4)	C3—C2—H21	110.5
C6—N2—C10	120.8 (5)	C3—C2—H22	110.5
N1—C1—C2	103.4 (4)	H21—C2—H22	109.5
N1—C1—C5	112.4 (4)	C2—C3—H31	110.1
C2—C1—C5	113.1 (4)	C2—C3—H32	110.1
C1—C2—C3	105.5 (5)	C4—C3—H31	110.1
C2—C3—C4	106.9 (7)	C4—C3—H32	110.1
N1—C4—C3	104.4 (5)	H31—C3—H32	109.5
N2—C5—C1	114.3 (4)	N1—C4—H41	110.7
N2—C6—C7	121.7 (6)	N1—C4—H42	110.7
C6—C7—C8	118.3 (6)	C3—C4—H41	110.7
C7—C8—C9	119.7 (6)	C3—C4—H42	110.7
C8—C9—C10	121.2 (6)	H41—C4—H42	109.5
N2—C10—N3	121.3 (5)	N2—C5—H51	108.3
N2—C10—C9	118.2 (5)	N2—C5—H52	108.3
N3—C10—C9	120.5 (5)	C1—C5—H51	108.3
C1—N1—H111	110.7	C1—C5—H52	108.3
C1—N1—H112	110.7	H51—C5—H52	109.5
C4—N1—H111	110.7	N2—C6—H6	119.2
C4—N1—H112	110.7	C7—C6—H6	119.2
H111—N1—H112	109.5	C6—C7—H7	120.8
C10—N3—H301	120.0	C8—C7—H7	120.8
C10—N3—H302	120.0	C7—C8—H8	120.1
H301—N3—H302	120.0	C9—C8—H8	120.1
N1—C1—H5	109.3	C8—C9—H9	119.4
C2—C1—H5	109.3	C10—C9—H9	119.4
C5—C1—H5	109.3

C1—N1—C4—C3	−38.1 (6)	N1—C1—C2—C3	−23.1 (6)
C4—N1—C1—C2	37.7 (6)	N1—C1—C5—N2	58.8 (6)
C4—N1—C1—C5	159.9 (5)	C2—C1—C5—N2	175.4 (4)
C5—N2—C6—C7	−179.0 (6)	C5—C1—C2—C3	−144.9 (5)
C6—N2—C5—C1	−95.2 (6)	C1—C2—C3—C4	0.0 (6)
C5—N2—C10—N3	−2.4 (8)	C2—C3—C4—N1	23.0 (7)
C5—N2—C10—C9	178.4 (5)	N2—C6—C7—C8	0.3 (8)
C10—N2—C5—C1	85.4 (6)	C6—C7—C8—C9	−0.4 (9)
C6—N2—C10—N3	178.2 (5)	C7—C8—C9—C10	−0.1 (8)
C6—N2—C10—C9	−0.9 (8)	C8—C9—C10—N2	0.8 (9)
C10—N2—C6—C7	0.4 (8)	C8—C9—C10—N3	−178.4 (6)

Experimental details

Crystal data
Chemical formula	C₁₀H₁₇N₃²⁺·2Br⁻
M_r	339.07
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	10.5509 (5), 6.1755 (3), 10.8474 (6)
β (°)	107.4830 (14)
V (Å³)	674.14 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.01
Crystal size (mm)	0.37 × 0.32 × 0.13

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.110, 0.458
No. of measured, independent and observed [F² > 2σ(F²)] reflections	6601, 2681, 1943
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.01
No. of reflections	2681
No. of parameters	138
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.61
Absolute structure	Flack (1983), 1013 Friedel pairs
Absolute structure parameter	0.002 (5)

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), CRYSTALS (Watkin et al., 1996).

Acknowledgements

The authors are grateful for the help of Professor Jian-Ming Gu of Zhejiang University.

References

Betteridge, P. W., Carruthers, J. R., Cooper, R. L., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ishii, T., Fujioka, S., Sekiguchi, Y. & Kotsuki, H. (2004). J. Am. Chem. Soc. 126, 9558–9559. Web of Science CrossRef PubMed CAS Google Scholar
Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291–294. Copenhagen: Munksgaard. Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Version 3.7. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, D. Q., Luo, S. P., Yue, H. D., Wang, L. P., Liu, Y. K. & Xu, Z. Y. (2006). Synlett, 16, 2569–2572. Web of Science CrossRef Google Scholar