(R)-(+)-Dimeth-yl[4-oxido-2-oxo-1-(1-phenyl-eth-yl)-1,2,5,6-tetra-hydro-pyridin-3-yl]sulfonium.

In the title zwitterionic compound, C(15)H(19)NO(2)S, the six-membered heterocycle adopts a sofa conformation. The negative charge is delocalized along the carbonyl and enolate system on the ring and the positive charge is localized on the S atom. Two inter-molecular C-H⋯O inter-actions help to establish the packing.

Related literature

For background to the synthesis of chiral non-racemic zwitterionic 4-alk­oxy-3-sulfonium ylide pyridine-2-ones, 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 ▶); Koruzňjak et al., 2003 ▶). For ring conformation analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H19NO2S

M = 277.37

Orthorhombic,

a = 5.9860 (17) Å

b = 7.4050 (14) Å

c = 31.589 (5) Å

V = 1400.2 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 293 K

0.5 × 0.4 × 0.2 mm

Data collection

Siemens P4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.728, T max = 0.846

3016 measured reflections

2683 independent reflections

1928 reflections with I > 2σ(I)

R int = 0.045

3 standard reflections every 97 reflections intensity decay: 3%

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.153

S = 1.03

2683 reflections

172 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.39 e Å−3

Absolute structure: Flack (1983 ▶), 532 Friedel pairs

Flack parameter: −0.01 (16)

Data collection: XSCANS (Siemens, 1994 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536810052955/bt5438sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052955/bt5438Isup2.hkl

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

C15H19NO2S	F(000) = 592
Mr = 277.37	Dx = 1.316 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 46 reflections
a = 5.9860 (17) Å	θ = 21.3–35.1°
b = 7.4050 (14) Å	µ = 0.23 mm−1
c = 31.589 (5) Å	T = 293 K
V = 1400.2 (5) Å3	Prism, colorless
Z = 4	0.5 × 0.4 × 0.2 mm

Siemens P4 diffractometer	Rint = 0.045
graphite	θmax = 29.0°, θmin = 2.6°
2θ/ω scans	h = −1→8
Absorption correction: ψ scan (North et al., 1968)	k = −1→10
Tmin = 0.728, Tmax = 0.846	l = −43→1
3016 measured reflections	3 standard reflections every 97 reflections
2683 independent reflections	intensity decay: 3%
1928 reflections with I > 2σ(I)

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)] = 0.061	H-atom parameters constrained
wR(F2) = 0.153	w = 1/[σ2(Fo2) + (0.0631P)2 + 1.1965P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2683 reflections	Δρmax = 0.63 e Å−3
172 parameters	Δρmin = −0.39 e Å−3
0 restraints	Absolute structure: Flack (1983), 532 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (16)

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	1.10027 (19)	0.87732 (14)	0.03372 (3)	0.0323 (2)
O1	0.8859 (6)	0.5383 (4)	0.05505 (8)	0.0393 (7)
N1	0.7630 (6)	0.6122 (4)	0.12114 (10)	0.0300 (7)
O2	1.0851 (7)	1.1013 (4)	0.11356 (10)	0.0511 (9)
C9	0.8558 (7)	0.3759 (6)	0.19114 (12)	0.0351 (9)
H9	0.9723	0.4434	0.1798	0.042*
C1	0.8724 (7)	0.6511 (5)	0.08437 (10)	0.0278 (8)
C6	0.6341 (8)	0.4423 (5)	0.12418 (12)	0.0345 (10)
H6	0.7011	0.3572	0.1041	0.041*
C4	0.8971 (9)	0.8843 (6)	0.15731 (11)	0.0373 (9)
H4A	1.0124	0.8199	0.1727	0.045*
H4B	0.8501	0.9863	0.1744	0.045*
C3	0.9911 (8)	0.9518 (6)	0.11576 (12)	0.0340 (9)
C8	0.6557 (7)	0.3579 (5)	0.16847 (12)	0.0305 (9)
C10	0.8816 (9)	0.2937 (6)	0.23044 (13)	0.0404 (10)
H10	1.0143	0.3077	0.2454	0.049*
C15	1.3821 (8)	0.9447 (7)	0.04512 (13)	0.0427 (11)
H15A	1.4586	0.9711	0.0191	0.064*
H15B	1.4578	0.8487	0.0596	0.064*
H15C	1.3805	1.0505	0.0627	0.064*
C2	0.9708 (7)	0.8304 (5)	0.08140 (11)	0.0285 (9)
C5	0.7006 (8)	0.7604 (6)	0.14990 (12)	0.0345 (10)
H5A	0.6507	0.7108	0.1767	0.041*
H5B	0.578	0.8286	0.1377	0.041*
C13	0.4867 (8)	0.2558 (6)	0.18589 (14)	0.0396 (10)
H13	0.3523	0.2426	0.1714	0.048*
C12	0.5156 (9)	0.1720 (6)	0.22507 (14)	0.0445 (11)
H12	0.401	0.1021	0.2363	0.053*
C11	0.7107 (9)	0.1916 (6)	0.24725 (14)	0.0443 (12)
H11	0.7278	0.1363	0.2735	0.053*
C14	0.9890 (9)	1.0887 (7)	0.01517 (15)	0.0544 (13)
H14A	1.0569	1.1193	−0.0114	0.082*
H14B	1.0205	1.1817	0.0355	0.082*
H14C	0.8304	1.078	0.0115	0.082*
C7	0.3927 (9)	0.4733 (7)	0.10987 (16)	0.0524 (13)
H7A	0.3922	0.5252	0.082	0.079*
H7B	0.3199	0.5539	0.1293	0.079*
H7C	0.3147	0.36	0.1094	0.079*

	U11	U22	U33	U12	U13	U23
S1	0.0354 (5)	0.0314 (4)	0.0300 (4)	−0.0059 (5)	0.0034 (5)	0.0035 (4)
O1	0.056 (2)	0.0317 (14)	0.0304 (13)	−0.0091 (19)	0.0042 (15)	−0.0028 (11)
N1	0.0319 (17)	0.0246 (15)	0.0334 (15)	−0.0086 (18)	0.0047 (14)	0.0014 (14)
O2	0.066 (2)	0.0325 (15)	0.0543 (17)	−0.023 (2)	0.0150 (19)	−0.0100 (13)
C9	0.034 (2)	0.0334 (19)	0.0379 (19)	−0.002 (2)	0.0054 (17)	0.0015 (18)
C1	0.030 (2)	0.0288 (18)	0.0245 (15)	−0.003 (2)	−0.0033 (16)	0.0029 (14)
C6	0.040 (3)	0.0282 (18)	0.0352 (19)	−0.010 (2)	0.0001 (19)	0.0041 (16)
C4	0.052 (2)	0.0315 (18)	0.0287 (17)	−0.007 (3)	0.009 (2)	−0.0067 (16)
C3	0.037 (2)	0.0305 (19)	0.0348 (19)	−0.003 (2)	0.0052 (19)	−0.0037 (17)
C8	0.036 (2)	0.0214 (17)	0.0341 (18)	0.0030 (19)	0.0052 (17)	−0.0042 (15)
C10	0.042 (2)	0.041 (2)	0.039 (2)	0.006 (3)	−0.001 (2)	−0.0008 (18)
C15	0.031 (2)	0.055 (3)	0.042 (2)	−0.006 (3)	0.008 (2)	0.001 (2)
C2	0.033 (2)	0.0234 (17)	0.0292 (17)	−0.0035 (18)	0.0036 (16)	0.0020 (14)
C5	0.042 (2)	0.030 (2)	0.0321 (19)	−0.002 (2)	0.0077 (19)	−0.0005 (16)
C13	0.034 (2)	0.037 (2)	0.048 (2)	−0.003 (2)	0.001 (2)	0.0091 (19)
C12	0.046 (3)	0.040 (2)	0.048 (3)	−0.006 (3)	0.012 (2)	0.013 (2)
C11	0.057 (3)	0.041 (2)	0.035 (2)	0.013 (3)	0.009 (2)	0.0050 (19)
C14	0.051 (3)	0.057 (3)	0.055 (3)	0.004 (3)	0.004 (2)	0.026 (2)
C7	0.042 (3)	0.057 (3)	0.058 (3)	−0.016 (3)	−0.015 (3)	0.019 (2)

S1—C2	1.729 (4)	C8—C13	1.378 (6)
S1—C15	1.796 (5)	C10—C11	1.379 (7)
S1—C14	1.799 (5)	C10—H10	0.93
O1—C1	1.250 (4)	C15—H15A	0.96
N1—C1	1.364 (5)	C15—H15B	0.96
N1—C5	1.473 (5)	C15—H15C	0.96
N1—C6	1.479 (5)	C5—H5A	0.97
O2—C3	1.244 (5)	C5—H5B	0.97
C9—C10	1.391 (6)	C13—C12	1.395 (6)
C9—C8	1.402 (6)	C13—H13	0.93
C9—H9	0.93	C12—C11	1.369 (7)
C1—C2	1.455 (5)	C12—H12	0.93
C6—C7	1.531 (7)	C11—H11	0.93
C6—C8	1.538 (5)	C14—H14A	0.96
C6—H6	0.98	C14—H14B	0.96
C4—C5	1.510 (6)	C14—H14C	0.96
C4—C3	1.513 (5)	C7—H7A	0.96
C4—H4A	0.97	C7—H7B	0.96
C4—H4B	0.97	C7—H7C	0.96
C3—C2	1.415 (5)
C2—S1—C15	107.6 (2)	H15A—C15—H15B	109.5
C2—S1—C14	107.0 (2)	S1—C15—H15C	109.5
C15—S1—C14	99.9 (2)	H15A—C15—H15C	109.5
C1—N1—C5	119.4 (3)	H15B—C15—H15C	109.5
C1—N1—C6	119.0 (3)	C3—C2—C1	124.4 (3)
C5—N1—C6	117.5 (3)	C3—C2—S1	120.1 (3)
C10—C9—C8	120.6 (4)	C1—C2—S1	114.9 (3)
C10—C9—H9	119.7	N1—C5—C4	110.5 (3)
C8—C9—H9	119.7	N1—C5—H5A	109.5
O1—C1—N1	121.4 (3)	C4—C5—H5A	109.5
O1—C1—C2	122.4 (3)	N1—C5—H5B	109.5
N1—C1—C2	116.2 (3)	C4—C5—H5B	109.5
N1—C6—C7	110.2 (4)	H5A—C5—H5B	108.1
N1—C6—C8	111.2 (3)	C8—C13—C12	120.5 (4)
C7—C6—C8	114.1 (4)	C8—C13—H13	119.8
N1—C6—H6	107	C12—C13—H13	119.8
C7—C6—H6	107	C11—C12—C13	120.9 (4)
C8—C6—H6	107	C11—C12—H12	119.6
C5—C4—C3	110.8 (3)	C13—C12—H12	119.6
C5—C4—H4A	109.5	C12—C11—C10	119.6 (4)
C3—C4—H4A	109.5	C12—C11—H11	120.2
C5—C4—H4B	109.5	C10—C11—H11	120.2
C3—C4—H4B	109.5	S1—C14—H14A	109.5
H4A—C4—H4B	108.1	S1—C14—H14B	109.5
O2—C3—C2	124.2 (4)	H14A—C14—H14B	109.5
O2—C3—C4	120.7 (4)	S1—C14—H14C	109.5
C2—C3—C4	115.1 (3)	H14A—C14—H14C	109.5
C13—C8—C9	118.4 (4)	H14B—C14—H14C	109.5
C13—C8—C6	121.6 (4)	C6—C7—H7A	109.5
C9—C8—C6	119.9 (4)	C6—C7—H7B	109.5
C11—C10—C9	120.1 (5)	H7A—C7—H7B	109.5
C11—C10—H10	120	C6—C7—H7C	109.5
C9—C10—H10	120	H7A—C7—H7C	109.5
S1—C15—H15A	109.5	H7B—C7—H7C	109.5
S1—C15—H15B	109.5
C5—N1—C1—O1	−164.3 (4)	O2—C3—C2—S1	5.4 (7)
C6—N1—C1—O1	−7.7 (6)	C4—C3—C2—S1	−172.1 (3)
C5—N1—C1—C2	15.5 (5)	O1—C1—C2—C3	−169.5 (4)
C6—N1—C1—C2	172.0 (3)	N1—C1—C2—C3	10.7 (6)
C1—N1—C6—C7	−90.2 (5)	O1—C1—C2—S1	1.8 (5)
C5—N1—C6—C7	66.8 (5)	N1—C1—C2—S1	−178.0 (3)
C1—N1—C6—C8	142.2 (4)	C15—S1—C2—C3	46.9 (4)
C5—N1—C6—C8	−60.8 (5)	C14—S1—C2—C3	−59.6 (4)
C5—C4—C3—O2	151.0 (4)	C15—S1—C2—C1	−124.8 (3)
C5—C4—C3—C2	−31.4 (6)	C14—S1—C2—C1	128.7 (3)
C10—C9—C8—C13	−0.6 (6)	C1—N1—C5—C4	−48.4 (5)
C10—C9—C8—C6	−177.2 (4)	C6—N1—C5—C4	154.7 (3)
N1—C6—C8—C13	149.8 (4)	C3—C4—C5—N1	54.5 (5)
C7—C6—C8—C13	24.4 (6)	C9—C8—C13—C12	−0.3 (6)
N1—C6—C8—C9	−33.6 (5)	C6—C8—C13—C12	176.3 (4)
C7—C6—C8—C9	−159.1 (4)	C8—C13—C12—C11	0.9 (7)
C8—C9—C10—C11	0.8 (6)	C13—C12—C11—C10	−0.7 (7)
O2—C3—C2—C1	176.3 (4)	C9—C10—C11—C12	−0.2 (7)
C4—C3—C2—C1	−1.2 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7C···O2i	0.96	2.36	3.315 (6)	172
C15—H15A···O1ii	0.96	2.38	3.167 (5)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7C⋯O2i	0.96	2.36	3.315 (6)	172
C15—H15A⋯O1ii	0.96	2.38	3.167 (5)	138

Symmetry codes: (i) ; (ii) .