(S)-2-(Pyrrolidinium-2-ylmethyl­sulfan­yl)pyridinium dibromide

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

doi:10.1107/S1600536808008313

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1142

doi:10.1107/S1600536808008313

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(S)-2-(Pyrrolidinium-2-ylmethylsulfanyl)pyridinium dibromide

Shuai Zhang,^a Yifeng Wang,^a Aibao Xia ^a and Shuping Luo ^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: shuaizhang867@gmail.com

(Received 6 March 2008; accepted 27 March 2008; online 24 May 2008)

In the title compound, C₁₀H₁₆N₂S²⁺·2Br⁻, the pyrrolidine ring displays an envelope conformation, with the flap C atom lying 0.484 (5) Å out of the plane of the rest of the pyrrolidine ring. The thioether group connects the pyridine ring and the 2-methylpyrrolidine group. Both pyrrolidine NH bonds form hydrogen bonds to the bromide anions. These hydrogen bonds link the cations and anions in a helical chain along the c axis.

Related literature

For related literature, see: Ishii et al. (2004 ); Xu et al. (2007 ); Larson (1970 ).

Experimental

Crystal data

C₁₀H₁₆N₂S²⁺·2Br⁻
M_r = 356.12
Trigonal, P 3₂
a = 8.9892 (9) Å
c = 15.4567 (14) Å
V = 1081.66 (18) Å³
Z = 3
Mo Kα radiation
μ = 5.76 mm⁻¹
T = 296 (1) K
0.35 × 0.30 × 0.23 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi,1995 ) T_min = 0.162, T_max = 0.266
10585 measured reflections
3169 independent reflections
1902 reflections with F² > 2.0σ(F²)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.108
S = 1.01
3169 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.53 e Å⁻³
Absolute structure: Flack (1983 ), 1037 Friedel pairs
Flack parameter: 0.017 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2⋯Br1	0.86	2.45	3.278 (7)	163
N1—H3⋯Br1ⁱ	0.86	2.43	3.271 (5)	165
Symmetry code: (i) $[-x+y, -x+1, z+{\script{1\over 3}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808008313/pk2087sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008313/pk2087Isup2.hkl

checkCIF report

Comment top

In recent years, proline and its derivatives have been studied extensively because of their ability to catalyze a large number of reactions (Ishii et al., 2004). The title compound is a hydrobromide of an ionic compound that was synthesized from L-proline. It was prepared as a kind of ionic organocatalyst for use in the asymmetric Michael addition of carbonyl compounds to nitroalkenes (Xu et al., 2007). The compound consists of two ionic pairs, protonated ammoniums and Br^- anions. The chiral atom C1 has the expected S conformation, and the C1/C3/C4/N1 atoms of pyrrolidine are almost coplanar. The distance of atom C2 to the C1/C3/C4/N1 mean plane is 0.484 (5) Å, while the distance of atom C5 to the plane is 0.865 (9) Å. In addition, the dihedral angle of the C1/N1/C3/C4 mean plane and the pyridine ring is 67.82 (4) °. The thioether group connects the pyridine ring and the 2-methylpyrrolidine group, the torsion angle of C6—S1—C5—C1 is 97.13 (4) °.

Related literature top

For related literature, see: Ishii et al. (2004); Xu et al. (2007); Larson (1970).

Experimental top

The title compound was readily synthesized by treating 2-mercaptopyridine with (S)-(+)-2-bromomethylpyrrolidine hydrobromide in MeCN. The compound (S)-(+)-2-bromomethylpyrrolidine hydrobromide was obtained from commercially available L-proline by reduction with NaBH₄ and subsequent bromination with PBr₃. Suitable crystals were obtained by slow evaporation of methanol 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: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).

Figures top

	Fig. 1. The asymmetric unit of the title compound, with the atomic labeling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Hydrogen bonding in the title compound. Symmetry codes: (i) 1-y, 1+x-y, -1/3+z; (ii) 1-y, 1+x-y, 2/3+z; (iii) -x+y, 1-x, 1/3+z.

(S)-2-(Pyrrolidinium-2-ylmethylsulfanyl)pyridinium dibromide top

Crystal data top

C₁₀H₁₆N₂S²⁺·2Br⁻	D_x = 1.640 Mg m⁻³
M_r = 356.12	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₂	Cell parameters from 5169 reflections
Hall symbol: P 32	θ = 3.7–27.4°
a = 8.9892 (9) Å	µ = 5.76 mm⁻¹
c = 15.4567 (14) Å	T = 296 K
V = 1081.66 (18) Å³	Chunk, colorless
Z = 3	0.35 × 0.30 × 0.23 mm
F(000) = 528.00

Data collection top

Rigaku R-AXIS RAPID diffractometer	1902 reflections with F² > 2.0σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.061
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi,1995)	h = −11→11
T_min = 0.162, T_max = 0.266	k = −11→10
10585 measured reflections	l = −18→20
3169 independent reflections

Refinement top

Refinement on F²	w = 1/[0.7600σ(F_o²)]/(4F_o²)
R[F² > 2σ(F²)] = 0.036	(Δ/σ)_max = 0.013
wR(F²) = 0.108	Δρ_max = 0.67 e Å⁻³
S = 1.01	Δρ_min = −0.53 e Å⁻³
3169 reflections	Extinction correction: Larson (1970) Crystallographic Computing eq. 22
138 parameters	Extinction coefficient: 385 (18)
0 restraints	Absolute structure: Flack (1983), 1037 Friedel Pairs
H-atom parameters constrained	Absolute structure parameter: 0.017 (2)

Crystal data top

C₁₀H₁₆N₂S²⁺·2Br⁻	Z = 3
M_r = 356.12	Mo Kα radiation
Trigonal, P3₂	µ = 5.76 mm⁻¹
a = 8.9892 (9) Å	T = 296 K
c = 15.4567 (14) Å	0.35 × 0.30 × 0.23 mm
V = 1081.66 (18) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3169 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi,1995)	1902 reflections with F² > 2.0σ(F²)
T_min = 0.162, T_max = 0.266	R_int = 0.061
10585 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.108	Δρ_max = 0.67 e Å⁻³
S = 1.01	Δρ_min = −0.53 e Å⁻³
3169 reflections	Absolute structure: Flack (1983), 1037 Friedel Pairs
138 parameters	Absolute structure parameter: 0.017 (2)
0 restraints

Special details top

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Br1	0.51453 (17)	0.87503 (13)	0.16904 (9)	0.1032 (4)
Br2	0.10004 (11)	0.14553 (10)	0.04190 (9)	0.0605 (2)
S1	0.0678 (3)	0.4733 (3)	0.31433 (12)	0.0671 (7)
N1	0.4515 (9)	0.5570 (8)	0.2963 (3)	0.067 (2)
N2	0.0359 (7)	0.6865 (8)	0.2110 (3)	0.053 (2)
C1	0.3184 (9)	0.4069 (9)	0.2462 (4)	0.053 (2)
C2	0.3905 (11)	0.2858 (11)	0.2388 (5)	0.071 (3)
C3	0.5771 (13)	0.4004 (16)	0.2379 (8)	0.086 (5)
C4	0.6121 (14)	0.5513 (18)	0.2933 (7)	0.077 (5)
C5	0.1434 (10)	0.3261 (10)	0.2879 (4)	0.059 (2)
C6	0.0388 (9)	0.5412 (9)	0.2143 (4)	0.050 (2)
C7	0.0160 (10)	0.4576 (10)	0.1352 (4)	0.059 (2)
C8	−0.0040 (10)	0.5283 (11)	0.0612 (4)	0.066 (2)
C9	−0.0037 (10)	0.6817 (12)	0.0635 (4)	0.067 (2)
C10	0.0138 (10)	0.7576 (11)	0.1396 (4)	0.062 (2)
H1	0.3105	0.4460	0.1880	0.064*
H2	0.4673	0.6511	0.2735	0.080*
H3	0.4187	0.5509	0.3491	0.080*
H7	0.0144	0.3534	0.1330	0.071*
H8	−0.0180	0.4724	0.0087	0.079*
H9	−0.0154	0.7310	0.0130	0.080*
H10	0.0108	0.8593	0.1432	0.074*
H21	0.3560	0.2085	0.2879	0.085*
H22	0.3522	0.2195	0.1857	0.085*
H31	0.6169	0.4377	0.1793	0.103*
H32	0.6343	0.3421	0.2614	0.103*
H41	0.6450	0.5369	0.3511	0.092*
H42	0.7033	0.6564	0.2682	0.092*
H51	0.1477	0.2708	0.3409	0.071*
H52	0.0614	0.2403	0.2484	0.071*
H201	0.0494	0.7403	0.2590	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1369 (10)	0.0925 (8)	0.0513 (4)	0.0357 (7)	0.0061 (5)	0.0034 (4)
Br2	0.0670 (6)	0.0510 (5)	0.0630 (4)	0.0292 (4)	0.0073 (4)	0.0054 (3)
S1	0.0848 (16)	0.0802 (16)	0.0554 (11)	0.0555 (14)	0.0125 (10)	0.0098 (10)
N1	0.072 (4)	0.063 (4)	0.053 (3)	0.026 (4)	−0.001 (3)	−0.006 (3)
N2	0.055 (4)	0.055 (4)	0.053 (3)	0.029 (3)	0.011 (2)	0.003 (2)
C1	0.052 (4)	0.046 (4)	0.058 (4)	0.022 (4)	−0.001 (3)	−0.001 (3)
C2	0.055 (5)	0.082 (6)	0.084 (5)	0.040 (5)	0.000 (4)	−0.005 (4)
C3	0.070 (8)	0.088 (10)	0.090 (14)	0.032 (7)	0.004 (7)	−0.000 (10)
C4	0.061 (7)	0.083 (14)	0.093 (10)	0.041 (9)	−0.004 (6)	−0.003 (10)
C5	0.051 (5)	0.063 (5)	0.065 (5)	0.030 (4)	0.011 (3)	0.009 (3)
C6	0.056 (5)	0.041 (4)	0.060 (4)	0.030 (4)	0.008 (3)	−0.003 (3)
C7	0.075 (5)	0.056 (5)	0.055 (4)	0.040 (4)	0.002 (3)	0.002 (3)
C8	0.071 (6)	0.078 (6)	0.053 (4)	0.041 (5)	0.001 (3)	0.001 (4)
C9	0.077 (6)	0.082 (6)	0.053 (4)	0.049 (5)	−0.002 (3)	0.002 (4)
C10	0.088 (6)	0.061 (5)	0.050 (4)	0.048 (5)	0.002 (3)	0.009 (3)

Geometric parameters (Å, º) top

S1—C5	1.811 (11)	N1—H3	0.860
S1—C6	1.729 (7)	N2—H201	0.860
N1—C1	1.496 (8)	C1—H1	0.980
N1—C4	1.471 (18)	C2—H21	0.970
N2—C6	1.321 (12)	C2—H22	0.970
N2—C10	1.339 (10)	C3—H31	0.970
C1—C2	1.524 (16)	C3—H32	0.970
C1—C5	1.508 (10)	C4—H41	0.970
C2—C3	1.465 (12)	C4—H42	0.970
C3—C4	1.499 (9)	C5—H51	0.970
C6—C7	1.396 (9)	C5—H52	0.970
C7—C8	1.363 (12)	C7—H7	0.930
C8—C9	1.379 (16)	C8—H8	0.930
C9—C10	1.329 (10)	C9—H9	0.930
N1—H2	0.860	C10—H10	0.930

C5—S1—C6	103.5 (4)	C1—C2—H22	110.8
C1—N1—C4	108.0 (8)	C3—C2—H21	110.8
C6—N2—C10	125.8 (6)	C3—C2—H22	110.8
N1—C1—C2	104.4 (7)	H21—C2—H22	109.5
N1—C1—C5	112.6 (6)	C2—C3—H31	110.3
C2—C1—C5	113.7 (6)	C2—C3—H32	110.3
C1—C2—C3	104.2 (8)	C4—C3—H31	110.3
C2—C3—C4	106.2 (11)	C4—C3—H32	110.3
N1—C4—C3	106.5 (8)	H31—C3—H32	109.5
S1—C5—C1	115.3 (6)	N1—C4—H41	110.2
S1—C6—N2	117.7 (5)	N1—C4—H42	110.2
S1—C6—C7	126.9 (7)	C3—C4—H41	110.2
N2—C6—C7	115.4 (7)	C3—C4—H42	110.2
C6—C7—C8	120.2 (9)	H41—C4—H42	109.5
C7—C8—C9	120.7 (7)	S1—C5—H51	108.0
C8—C9—C10	118.4 (8)	S1—C5—H52	108.0
N2—C10—C9	119.5 (10)	C1—C5—H51	108.0
C1—N1—H2	109.8	C1—C5—H52	108.0
C1—N1—H3	109.8	H51—C5—H52	109.5
C4—N1—H2	109.8	C6—C7—H7	119.9
C4—N1—H3	109.8	C8—C7—H7	119.9
H2—N1—H3	109.5	C7—C8—H8	119.7
C6—N2—H201	117.1	C9—C8—H8	119.7
C10—N2—H201	117.1	C8—C9—H9	120.8
N1—C1—H1	108.7	C10—C9—H9	120.8
C2—C1—H1	108.7	N2—C10—H10	120.2
C5—C1—H1	108.7	C9—C10—H10	120.2
C1—C2—H21	110.8

C5—S1—C6—N2	−159.4 (5)	N1—C1—C5—S1	51.7 (8)
C5—S1—C6—C7	21.3 (8)	C2—C1—C5—S1	170.2 (5)
C6—S1—C5—C1	66.8 (5)	C5—C1—C2—C3	−153.7 (7)
C1—N1—C4—C3	2.2 (10)	C1—C2—C3—C4	32.4 (11)
C4—N1—C1—C2	17.3 (7)	C2—C3—C4—N1	−22.0 (12)
C4—N1—C1—C5	141.1 (8)	S1—C6—C7—C8	−179.4 (6)
C6—N2—C10—C9	−1.5 (12)	N2—C6—C7—C8	1.2 (11)
C10—N2—C6—S1	−179.6 (5)	C6—C7—C8—C9	−0.6 (10)
C10—N2—C6—C7	−0.1 (9)	C7—C8—C9—C10	−1.0 (12)
N1—C1—C2—C3	−30.6 (8)	C8—C9—C10—N2	2.1 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···Br1	0.86	2.45	3.278 (7)	163
N1—H3···Br1ⁱ	0.86	2.43	3.271 (5)	165

Symmetry code: (i) −x+y, −x+1, z+1/3.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₆N₂S²⁺·2Br⁻
M_r	356.12
Crystal system, space group	Trigonal, P3₂
Temperature (K)	296
a, c (Å)	8.9892 (9), 15.4567 (14)
V (Å³)	1081.66 (18)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	5.76
Crystal size (mm)	0.35 × 0.30 × 0.23

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi,1995)
T_min, T_max	0.162, 0.266
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	10585, 3169, 1902
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.108, 1.01
No. of reflections	3169
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.53
Absolute structure	Flack (1983), 1037 Friedel Pairs
Absolute structure parameter	0.017 (2)

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···Br1	0.860	2.447	3.278 (7)	163
N1—H3···Br1ⁱ	0.860	2.434	3.271 (5)	165

Symmetry code: (i) −x+y, −x+1, z+1/3.

Acknowledgements

We thank Professor Jian-Ming Gu of Zhejiang University for his help.

References

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