(S)-2-[(2-Ammonio-phenyl)-sulfanyl-methyl]pyrrolidinium dibromide.

In the title compound, C(11)H(18)N(2)S(2+)·2Br(-), the pyrrolidine ring displays a half-chair conformation, with the flap C atom lying 0.522 (5) Å out of the plane of the other four atoms. The methyl-ene C atom, which connects the pyrrolidinium ring and the thio-ether group, is displaced from the plane of four pyrrolidinium atoms by 0.690 (6) Å in the same direction as the flap C atom. The plane of four pyrrolidinium atoms is almost perpendicular to the benzene ring [dihedral angle = 75.02 (4)°]. The crystal structure is stabilized by hydrogen bonds between the N and Br atoms.

Related literature

The synthesis of (S)-(+)-2-bromo­methyl­pyrrolidine hydro­bromide was described by Xu et al. (2006 ▶). The development of asymmetric organocatalysis was reviewed by Seayad & List (2005 ▶).

Experimental

Crystal data

C11H18N2S2+·2Br−

M = 370.15

Orthorhombic,

a = 7.9399 (9) Å

b = 10.8427 (13) Å

c = 17.658 (2) Å

V = 1520.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 5.45 mm−1

T = 293 (2) K

0.49 × 0.42 × 0.36 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.103, T max = 0.137

8969 measured reflections

3311 independent reflections

1808 reflections with I > 2σ(I)

R int = 0.136

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.134

S = 0.83

3311 reflections

158 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.67 e Å−3

Δρmin = −0.50 e Å−3

Absolute structure: Flack (1983 ▶), 1394 Friedel pairs

Flack parameter: 0.00 (2)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2000 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021089/pk2105sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021089/pk2105Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H18N2S2+·2Br–	F000 = 736
Mr = 370.15	Dx = 1.617 Mg m−3
Orthorhombic, P212121	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1525 reflections
a = 7.9399 (9) Å	θ = 4.4–38.3º
b = 10.8427 (13) Å	µ = 5.45 mm−1
c = 17.658 (2) Å	T = 293 (2) K
V = 1520.2 (3) Å3	Prismatic, colorless
Z = 4	0.49 × 0.42 × 0.37 mm

Bruker SMART CCD area-detector diffractometer	3311 independent reflections
Radiation source: fine-focus sealed tube	1808 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.136
T = 293(2) K	θmax = 27.0º
φ and ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.103, Tmax = 0.137	k = −13→12
8969 measured reflections	l = −22→18

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.058	w = 1/[σ2(Fo2) + (0.049P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.134	(Δ/σ)max < 0.001
S = 0.83	Δρmax = 0.67 e Å−3
3311 reflections	Δρmin = −0.50 e Å−3
158 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraints	Extinction coefficient: 0.0005 (1)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1394 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.00 (2)

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

	x	y	z	Uiso*/Ueq
Br1	0.30470 (12)	−0.24305 (9)	−0.08797 (5)	0.0559 (3)
Br2	−0.38177 (12)	0.34415 (8)	0.06967 (5)	0.0526 (3)
S1	−0.0443 (3)	0.1034 (2)	0.14946 (13)	0.0524 (6)
N1	0.0399 (9)	0.3571 (6)	0.0600 (4)	0.0502 (18)
H1A	0.0636	0.2939	0.0288	0.060*
H1B	−0.0728	0.3650	0.0630	0.060*
N2	0.1147 (12)	−0.0815 (8)	0.0452 (5)	0.0487 (18)
C1	0.1159 (18)	0.4726 (9)	0.0308 (7)	0.083 (3)
H1C	0.0296	0.5273	0.0111	0.100*
H1D	0.1959	0.4549	−0.0093	0.100*
C2	0.2025 (14)	0.5297 (9)	0.0973 (7)	0.072 (3)
H2A	0.3237	0.5225	0.0921	0.087*
H2B	0.1735	0.6164	0.1013	0.087*
C3	0.1443 (14)	0.4625 (9)	0.1640 (6)	0.068 (3)
H3A	0.0420	0.4990	0.1840	0.081*
H3B	0.2297	0.4627	0.2033	0.081*
C4	0.1120 (12)	0.3339 (8)	0.1362 (4)	0.049 (2)
H4	0.2194	0.2901	0.1309	0.059*
C5	−0.0079 (11)	0.2577 (8)	0.1852 (4)	0.052 (2)
H5A	−0.1150	0.3004	0.1885	0.062*
H5B	0.0381	0.2519	0.2359	0.062*
C6	0.1553 (11)	0.0316 (8)	0.1640 (5)	0.047 (2)
C7	0.2504 (11)	0.0537 (9)	0.2270 (5)	0.056 (3)
H7	0.2117	0.1092	0.2632	0.068*
C8	0.4032 (13)	−0.0049 (10)	0.2382 (6)	0.073 (3)
H8	0.4680	0.0138	0.2805	0.087*
C9	0.4579 (14)	−0.0887 (10)	0.1879 (6)	0.071 (3)
H9	0.5602	−0.1285	0.1956	0.085*
C10	0.3611 (11)	−0.1161 (8)	0.1239 (5)	0.053 (2)
H10	0.3980	−0.1750	0.0893	0.063*
C11	0.2112 (12)	−0.0555 (8)	0.1123 (5)	0.045 (2)
H2C	0.157 (10)	−0.127 (6)	0.012 (4)	0.06 (3)*
H2D	0.094 (12)	−0.032 (6)	0.010 (3)	0.06 (3)*
H2E	0.043 (10)	−0.135 (7)	0.054 (6)	0.09 (4)*

	U11	U22	U33	U12	U13	U23
Br1	0.0514 (6)	0.0627 (5)	0.0536 (6)	0.0081 (5)	−0.0055 (4)	−0.0024 (5)
Br2	0.0526 (6)	0.0614 (5)	0.0438 (5)	0.0072 (5)	−0.0041 (4)	−0.0022 (5)
S1	0.0412 (14)	0.0682 (15)	0.0479 (14)	0.0052 (12)	0.0015 (11)	0.0049 (12)
N1	0.045 (4)	0.060 (4)	0.046 (4)	0.007 (4)	0.004 (3)	−0.001 (4)
N2	0.054 (5)	0.048 (5)	0.044 (5)	−0.003 (5)	0.002 (5)	−0.002 (4)
C1	0.105 (10)	0.061 (7)	0.084 (8)	0.010 (7)	0.005 (8)	0.006 (6)
C2	0.055 (7)	0.055 (6)	0.107 (10)	0.005 (5)	0.010 (7)	−0.017 (6)
C3	0.062 (8)	0.074 (7)	0.067 (7)	−0.006 (6)	−0.007 (6)	−0.021 (6)
C4	0.038 (5)	0.066 (6)	0.044 (5)	0.015 (5)	0.000 (4)	0.003 (5)
C5	0.053 (6)	0.070 (6)	0.033 (4)	0.019 (6)	0.002 (4)	−0.009 (5)
C6	0.033 (6)	0.062 (6)	0.046 (5)	0.008 (4)	−0.006 (4)	0.010 (4)
C7	0.043 (6)	0.077 (7)	0.048 (6)	0.012 (5)	0.003 (5)	0.000 (5)
C8	0.062 (8)	0.102 (8)	0.055 (7)	0.010 (7)	−0.022 (6)	−0.008 (6)
C9	0.054 (7)	0.103 (8)	0.056 (7)	0.028 (7)	−0.005 (6)	−0.001 (6)
C10	0.046 (6)	0.061 (6)	0.051 (5)	0.022 (5)	0.011 (5)	0.010 (4)
C11	0.044 (6)	0.059 (6)	0.031 (5)	0.000 (5)	0.000 (4)	0.007 (4)

Br1—H2C	2.47 (7)	C3—C4	1.500 (12)
Br2—H1B	2.4665	C3—H3A	0.9700
S1—C6	1.784 (8)	C3—H3B	0.9700
S1—C5	1.811 (9)	C4—C5	1.529 (12)
N1—C1	1.483 (12)	C4—H4	0.9800
N1—C4	1.484 (10)	C5—H5A	0.9700
N1—H1A	0.9000	C5—H5B	0.9700
N1—H1B	0.9000	C6—C7	1.366 (11)
N2—C11	1.438 (11)	C6—C11	1.388 (11)
N2—H2C	0.84 (7)	C7—C8	1.383 (13)
N2—H2D	0.84 (6)	C7—H7	0.9300
N2—H2E	0.83 (8)	C8—C9	1.343 (13)
C1—C2	1.495 (14)	C8—H8	0.9300
C1—H1C	0.9700	C9—C10	1.399 (13)
C1—H1D	0.9700	C9—H9	0.9300
C2—C3	1.460 (13)	C10—C11	1.374 (12)
C2—H2A	0.9700	C10—H10	0.9300
C2—H2B	0.9700
C6—S1—C5	102.2 (4)	N1—C4—C3	101.8 (7)
C1—N1—C4	107.5 (8)	N1—C4—C5	111.3 (7)
C1—N1—H1A	110.2	C3—C4—C5	115.1 (8)
C4—N1—H1A	110.2	N1—C4—H4	109.4
C1—N1—H1B	110.2	C3—C4—H4	109.4
C4—N1—H1B	110.2	C5—C4—H4	109.4
H1A—N1—H1B	108.5	C4—C5—S1	113.7 (6)
C11—N2—H2C	118 (6)	C4—C5—H5A	108.8
C11—N2—H2D	126 (6)	S1—C5—H5A	108.8
H2C—N2—H2D	87 (7)	C4—C5—H5B	108.8
C11—N2—H2E	111 (7)	S1—C5—H5B	108.8
H2C—N2—H2E	90 (9)	H5A—C5—H5B	107.7
H2D—N2—H2E	117 (10)	C7—C6—C11	118.6 (8)
N1—C1—C2	105.3 (9)	C7—C6—S1	122.1 (7)
N1—C1—H1C	110.7	C11—C6—S1	119.1 (7)
C2—C1—H1C	110.7	C6—C7—C8	121.3 (9)
N1—C1—H1D	110.7	C6—C7—H7	119.3
C2—C1—H1D	110.7	C8—C7—H7	119.3
H1C—C1—H1D	108.8	C9—C8—C7	120.0 (10)
C3—C2—C1	106.3 (8)	C9—C8—H8	120.0
C3—C2—H2A	110.5	C7—C8—H8	120.0
C1—C2—H2A	110.5	C8—C9—C10	120.1 (9)
C3—C2—H2B	110.5	C8—C9—H9	120.0
C1—C2—H2B	110.5	C10—C9—H9	120.0
H2A—C2—H2B	108.7	C11—C10—C9	119.6 (9)
C2—C3—C4	104.7 (7)	C11—C10—H10	120.2
C2—C3—H3A	110.8	C9—C10—H10	120.2
C4—C3—H3A	110.8	C10—C11—C6	120.3 (8)
C2—C3—H3B	110.8	C10—C11—N2	119.4 (8)
C4—C3—H3B	110.8	C6—C11—N2	120.3 (8)
H3A—C3—H3B	108.9
C4—N1—C1—C2	−12.2 (11)	C11—C6—C7—C8	2.8 (14)
N1—C1—C2—C3	−12.1 (11)	S1—C6—C7—C8	178.6 (8)
C1—C2—C3—C4	31.4 (11)	C6—C7—C8—C9	−2.4 (15)
C1—N1—C4—C3	30.7 (10)	C7—C8—C9—C10	0.5 (16)
C1—N1—C4—C5	153.8 (8)	C8—C9—C10—C11	1.0 (15)
C2—C3—C4—N1	−38.0 (10)	C9—C10—C11—C6	−0.6 (13)
C2—C3—C4—C5	−158.6 (8)	C9—C10—C11—N2	178.2 (9)
N1—C4—C5—S1	64.5 (8)	C7—C6—C11—C10	−1.3 (12)
C3—C4—C5—S1	179.7 (7)	S1—C6—C11—C10	−177.2 (6)
C6—S1—C5—C4	69.0 (6)	C7—C6—C11—N2	180.0 (8)
C5—S1—C6—C7	38.7 (8)	S1—C6—C11—N2	4.1 (11)
C5—S1—C6—C11	−145.6 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2E···Br1i	0.83 (8)	2.39 (8)	3.201 (9)	169 (10)
N2—H2D···Br2ii	0.84 (6)	2.48 (4)	3.277 (9)	159 (8)
N2—H2C···Br1	0.84 (7)	2.47 (7)	3.298 (9)	173 (8)
N1—H1B···Br2	0.90	2.47	3.355 (7)	169
N1—H1A···Br2ii	0.90	2.33	3.224 (7)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2E⋯Br1i	0.83 (8)	2.39 (8)	3.201 (9)	169 (10)
N2—H2D⋯Br2ii	0.84 (6)	2.48 (4)	3.277 (9)	159 (8)
N2—H2C⋯Br1	0.84 (7)	2.47 (7)	3.298 (9)	173 (8)
N1—H1B⋯Br2	0.90	2.47	3.355 (7)	169
N1—H1A⋯Br2ii	0.90	2.33	3.224 (7)	170

Symmetry codes: (i) ; (ii) .