(7aS)-(-)-Dimeth-yl(1-oxido-3-oxo-5,6,7,7a-tetra-hydro-3H-pyrrolizin-2-yl)sulfonium.

In the zwitterionic title compound, C(9)H(13)NO(2)S, the pyrrolidine heterocycle adopts an envelope conformation (with the C atom in the 7-position as the flap). The negative charge is delocalized over the two carbonyl groups and the C atom connecting them. The positive charge is located on the S atom. Two inter-molecular C-H⋯O inter-actions are observed. The molecular geometry at the S atom is trigonal pyramidal.

Related literature

For background to the synthesis of chiral non-racemic zwitterionic compounds, see: Zang et al. (2008 ▶); Kappe et al. (1983 ▶); Palillero et al. (2009 ▶). For the biological activity of related structures, see: Basco et al. (1994 ▶); Koruznjak et al. (2003 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C9H13NO2S

M = 199.26

Orthorhombic,

a = 5.8761 (3) Å

b = 9.0858 (5) Å

c = 17.7107 (9) Å

V = 945.56 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 130 K

0.46 × 0.33 × 0.07 mm

Data collection

Oxford Xcalibur Atlas Gemini diffractometer

Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.895, T max = 0.976

6356 measured reflections

1873 independent reflections

1736 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.065

S = 1.04

1873 reflections

120 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.26 e Å−3

Absolute structure: Flack (1983 ▶), with 758 Friedel pairs

Flack parameter: −0.07 (7)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812003601/bt5793sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003601/bt5793Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812003601/bt5793Isup3.cml

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

C9H13NO2S	Dx = 1.406 Mg m−3
Mr = 199.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4129 reflections
a = 5.8761 (3) Å	θ = 3.5–26.0°
b = 9.0858 (5) Å	µ = 0.31 mm−1
c = 17.7107 (9) Å	T = 130 K
V = 945.56 (9) Å3	Plate, colourless
Z = 4	0.46 × 0.33 × 0.07 mm
F(000) = 424

Oxford Xcalibur Atlas Gemini diffractometer	1873 independent reflections
Graphite monochromator	1736 reflections with I > 2σ(I)
Detector resolution: 10.4685 pixels mm-1	Rint = 0.037
ω scans	θmax = 26.1°, θmin = 3.7°
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2002)	h = −7→7
Tmin = 0.895, Tmax = 0.976	k = −10→11
6356 measured reflections	l = −18→21

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H-atom parameters constrained
wR(F2) = 0.065	w = 1/[σ2(Fo2) + (0.0385P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1873 reflections	Δρmax = 0.20 e Å−3
120 parameters	Δρmin = −0.26 e Å−3
0 restraints	Absolute structure: Flack (1983), with 758 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.07 (7)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
S1	0.72287 (7)	0.59085 (4)	0.01093 (2)	0.01852 (12)
O1	0.6977 (3)	0.26576 (13)	0.09183 (7)	0.0293 (3)
O2	0.4048 (2)	0.74463 (12)	0.13031 (6)	0.0229 (3)
N1	0.4198 (2)	0.53624 (15)	0.20467 (8)	0.0172 (3)
C1	0.4721 (3)	0.61719 (18)	0.14100 (9)	0.0172 (4)
C2	0.6056 (3)	0.52340 (19)	0.09255 (9)	0.0188 (4)
C3	0.6092 (3)	0.37738 (18)	0.11921 (10)	0.0193 (4)
C4	0.4806 (3)	0.38002 (17)	0.19391 (9)	0.0173 (4)
H4	0.5823	0.3464	0.2358	0.021*
C5	0.2519 (3)	0.30179 (17)	0.19885 (10)	0.0216 (4)
H5A	0.2702	0.1975	0.2138	0.026*
H5B	0.1682	0.3069	0.1504	0.026*
C6	0.1329 (3)	0.3908 (2)	0.26032 (10)	0.0228 (4)
H6A	0.1871	0.3614	0.3111	0.027*
H6B	−0.0341	0.3772	0.2579	0.027*
C7	0.1984 (3)	0.55113 (19)	0.24287 (10)	0.0222 (4)
H7A	0.0847	0.5982	0.2094	0.027*
H7B	0.2125	0.6096	0.2898	0.027*
C8	1.0123 (3)	0.5311 (2)	0.01195 (12)	0.0296 (4)
H8A	1.0832	0.5535	−0.0368	0.044*
H8B	1.0179	0.4248	0.0209	0.044*
H8C	1.0946	0.5823	0.0523	0.044*
C9	0.6187 (4)	0.4744 (3)	−0.06291 (11)	0.0370 (5)
H9A	0.6929	0.5007	−0.1106	0.056*
H9B	0.4538	0.4873	−0.0679	0.056*
H9C	0.6523	0.3715	−0.0507	0.056*

	U11	U22	U33	U12	U13	U23
S1	0.0209 (2)	0.0186 (2)	0.0160 (2)	0.00209 (17)	0.00126 (16)	0.00138 (16)
O1	0.0388 (8)	0.0202 (6)	0.0290 (7)	0.0101 (6)	0.0091 (6)	0.0018 (5)
O2	0.0311 (7)	0.0156 (6)	0.0220 (6)	0.0036 (5)	0.0008 (6)	−0.0003 (5)
N1	0.0200 (8)	0.0147 (7)	0.0170 (7)	−0.0002 (6)	0.0002 (6)	−0.0023 (6)
C1	0.0173 (9)	0.0194 (9)	0.0150 (8)	−0.0035 (7)	−0.0038 (7)	−0.0014 (7)
C2	0.0205 (9)	0.0190 (8)	0.0169 (9)	0.0022 (8)	0.0023 (8)	0.0016 (7)
C3	0.0178 (9)	0.0193 (9)	0.0209 (9)	−0.0004 (7)	−0.0012 (7)	0.0003 (7)
C4	0.0176 (8)	0.0165 (8)	0.0179 (9)	0.0031 (7)	−0.0021 (7)	0.0013 (7)
C5	0.0213 (10)	0.0186 (8)	0.0250 (9)	−0.0018 (8)	−0.0005 (8)	−0.0005 (7)
C6	0.0166 (9)	0.0247 (10)	0.0272 (9)	−0.0060 (8)	0.0030 (7)	−0.0001 (8)
C7	0.0236 (10)	0.0210 (8)	0.0221 (9)	−0.0006 (8)	0.0067 (8)	−0.0029 (7)
C8	0.0191 (9)	0.0384 (10)	0.0314 (10)	0.0013 (8)	0.0018 (8)	0.0086 (9)
C9	0.0366 (13)	0.0563 (13)	0.0181 (10)	−0.0149 (11)	−0.0006 (9)	−0.0074 (10)

S1—C2	1.7146 (17)	C5—H5A	0.99
S1—C8	1.7851 (18)	C5—H5B	0.99
S1—C9	1.7900 (19)	C6—C7	1.538 (3)
O1—C3	1.238 (2)	C6—H6A	0.99
O2—C1	1.238 (2)	C6—H6B	0.99
N1—C1	1.381 (2)	C7—H7A	0.99
N1—C7	1.473 (2)	C7—H7B	0.99
N1—C4	1.476 (2)	C8—H8A	0.98
C1—C2	1.442 (2)	C8—H8B	0.98
C2—C3	1.408 (2)	C8—H8C	0.98
C3—C4	1.524 (2)	C9—H9A	0.98
C4—C5	1.523 (2)	C9—H9B	0.98
C4—H4	1	C9—H9C	0.98
C5—C6	1.526 (2)
C2—S1—C8	105.40 (9)	H5A—C5—H5B	109.3
C2—S1—C9	105.50 (9)	C5—C6—C7	104.11 (14)
C8—S1—C9	98.84 (11)	C5—C6—H6A	110.9
C1—N1—C7	121.50 (14)	C7—C6—H6A	110.9
C1—N1—C4	110.68 (13)	C5—C6—H6B	110.9
C7—N1—C4	111.17 (13)	C7—C6—H6B	110.9
O2—C1—N1	123.51 (15)	H6A—C6—H6B	109
O2—C1—C2	129.47 (15)	N1—C7—C6	103.08 (13)
N1—C1—C2	106.99 (14)	N1—C7—H7A	111.1
C3—C2—C1	111.43 (15)	C6—C7—H7A	111.1
C3—C2—S1	127.84 (13)	N1—C7—H7B	111.1
C1—C2—S1	120.61 (13)	C6—C7—H7B	111.1
O1—C3—C2	130.27 (16)	H7A—C7—H7B	109.1
O1—C3—C4	124.12 (15)	S1—C8—H8A	109.5
C2—C3—C4	105.60 (14)	S1—C8—H8B	109.5
N1—C4—C5	103.19 (13)	H8A—C8—H8B	109.5
N1—C4—C3	104.31 (13)	S1—C8—H8C	109.5
C5—C4—C3	118.71 (14)	H8A—C8—H8C	109.5
N1—C4—H4	110	H8B—C8—H8C	109.5
C5—C4—H4	110	S1—C9—H9A	109.5
C3—C4—H4	110	S1—C9—H9B	109.5
C4—C5—C6	101.43 (13)	H9A—C9—H9B	109.5
C4—C5—H5A	111.5	S1—C9—H9C	109.5
C6—C5—H5A	111.5	H9A—C9—H9C	109.5
C4—C5—H5B	111.5	H9B—C9—H9C	109.5
C6—C5—H5B	111.5
C7—N1—C1—O2	34.5 (2)	S1—C2—C3—C4	179.92 (13)
C4—N1—C1—O2	167.62 (15)	C1—N1—C4—C5	−116.83 (15)
C7—N1—C1—C2	−143.55 (15)	C7—N1—C4—C5	21.34 (17)
C4—N1—C1—C2	−10.39 (18)	C1—N1—C4—C3	7.84 (18)
O2—C1—C2—C3	−168.74 (17)	C7—N1—C4—C3	146.01 (13)
N1—C1—C2—C3	9.1 (2)	O1—C3—C4—N1	176.79 (16)
O2—C1—C2—S1	7.6 (3)	C2—C3—C4—N1	−2.07 (18)
N1—C1—C2—S1	−174.58 (12)	O1—C3—C4—C5	−69.1 (2)
C8—S1—C2—C3	−52.18 (19)	C2—C3—C4—C5	112.01 (16)
C9—S1—C2—C3	51.81 (19)	N1—C4—C5—C6	−37.44 (16)
C8—S1—C2—C1	132.16 (15)	C3—C4—C5—C6	−152.13 (15)
C9—S1—C2—C1	−123.85 (16)	C4—C5—C6—C7	40.51 (17)
C1—C2—C3—O1	177.13 (18)	C1—N1—C7—C6	136.85 (15)
S1—C2—C3—O1	1.1 (3)	C4—N1—C7—C6	3.89 (18)
C1—C2—C3—C4	−4.1 (2)	C5—C6—C7—N1	−27.69 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2i	1.00	2.55	3.4145 (19)	145
C7—H7B···O1ii	0.99	2.59	3.570 (2)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2i	1.00	2.55	3.4145 (19)	145
C7—H7B⋯O1ii	0.99	2.59	3.570 (2)	173

Symmetry codes: (i) ; (ii) .