(S)-3-[(S,E)-4-(4-Chloro-phen-yl)-1-nitro-but-3-en-2-yl]thian-4-one.

The title compound, C(15)H(16)ClNO(3)S, was obtained by the organocatalytic asymmetric Michael addition of thian-4-one to 1-chloro-4-[(1E,3E)-4-nitro-buta-1,3-dien-yl]benzene. The double bond has an E configuration and the thian-4-one six-membered ring adopts a chair conformation. The crystal structure is stabilized by weak inter-molecular C-H⋯O hydrogen bonds.

Related literature

For asymmetric Michael addition employing chiral organo­catalysts, see: Belot et al. (2008 ▶); Dalko & Moisan (2004 ▶); Xu et al. (2008 ▶); Yu et al. (2009 ▶).

Experimental

Crystal data

C15H16ClNO3S

M = 325.80

Orthorhombic,

a = 5.5220 (2) Å

b = 8.3833 (3) Å

c = 34.7414 (12) Å

V = 1608.27 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.38 mm−1

T = 296 K

0.34 × 0.28 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.865, T max = 0.932

15960 measured reflections

3666 independent reflections

2918 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.090

S = 1.00

3666 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 1501 Friedel pairs

Flack parameter: 0.03 (7)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2007 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536809043608/fk2005sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043608/fk2005Isup2.hkl

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

C15H16ClNO3S	F(000) = 680
Mr = 325.80	Dx = 1.346 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 12670 reflections
a = 5.5220 (2) Å	θ = 3.0–27.5°
b = 8.3833 (3) Å	µ = 0.38 mm−1
c = 34.7414 (12) Å	T = 296 K
V = 1608.27 (10) Å3	Block, colorless
Z = 4	0.34 × 0.28 × 0.19 mm

Rigaku R-AXIS RAPID diffractometer	3666 independent reflections
Radiation source: rotating anode	2918 reflections with I > 2σ(I)
graphite	Rint = 0.024
Detector resolution: 10.00 pixels mm-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −7→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
Tmin = 0.865, Tmax = 0.932	l = −45→45
15960 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032	w = 1/[σ2(Fo2) + (0.047P)2 + 0.182P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.090	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.16 e Å−3
3666 reflections	Δρmin = −0.20 e Å−3
191 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0061 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1501 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.03 (7)

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 > σ(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
C13	−0.1203 (6)	0.9836 (3)	0.01706 (6)	0.0747 (7)
S1	0.55221 (10)	0.17716 (7)	0.117335 (15)	0.06690 (17)
Cl1	−0.1215 (2)	1.11399 (9)	−0.022097 (18)	0.1245 (4)
C6	0.0659 (3)	0.5010 (2)	0.16547 (4)	0.0447 (4)
H6	−0.0877	0.4429	0.1634	0.054*
O1	0.0671 (3)	0.22754 (16)	0.21132 (4)	0.0613 (3)
C4	0.2745 (3)	0.3803 (2)	0.16338 (4)	0.0444 (4)
H4	0.4264	0.4371	0.1684	0.053*
N1	−0.1196 (3)	0.7113 (2)	0.20576 (4)	0.0555 (4)
C5	0.2912 (4)	0.3026 (2)	0.12328 (5)	0.0555 (4)
H5A	0.2954	0.3859	0.1039	0.067*
H5B	0.1466	0.2394	0.1189	0.067*
C8	0.0775 (3)	0.6222 (2)	0.13348 (5)	0.0476 (4)
H8	0.2189	0.6816	0.1310	0.057*
C7	0.0736 (3)	0.5865 (2)	0.20462 (5)	0.0496 (4)
H7A	0.0481	0.5101	0.2252	0.059*
H7B	0.2309	0.6356	0.2083	0.059*
C3	0.2507 (3)	0.2460 (2)	0.19269 (5)	0.0492 (4)
C9	−0.0980 (3)	0.6500 (2)	0.10879 (5)	0.0522 (4)
H9	−0.2357	0.5869	0.1113	0.063*
O3	−0.0587 (3)	0.84976 (18)	0.20651 (5)	0.0819 (5)
C2	0.4615 (4)	0.1319 (3)	0.19524 (6)	0.0669 (5)
H2A	0.4315	0.0550	0.2155	0.080*
H2B	0.6073	0.1906	0.2017	0.080*
C15	0.0781 (4)	0.8818 (2)	0.07241 (5)	0.0631 (5)
H15	0.2076	0.8847	0.0895	0.076*
O2	−0.3289 (3)	0.6674 (2)	0.20483 (5)	0.0838 (5)
C10	−0.1020 (3)	0.7694 (2)	0.07758 (5)	0.0519 (4)
C1	0.4989 (5)	0.0446 (3)	0.15734 (6)	0.0757 (6)
H1A	0.3568	−0.0196	0.1519	0.091*
H1B	0.6359	−0.0270	0.1599	0.091*
C11	−0.2923 (4)	0.7687 (3)	0.05161 (6)	0.0691 (6)
H11	−0.4169	0.6951	0.0547	0.083*
C12	−0.3010 (5)	0.8756 (3)	0.02114 (6)	0.0819 (7)
H12	−0.4291	0.8732	0.0038	0.098*
C14	0.0704 (5)	0.9901 (3)	0.04238 (6)	0.0745 (6)
H14	0.1920	1.0658	0.0394	0.089*

	U11	U22	U33	U12	U13	U23
C13	0.122 (2)	0.0560 (12)	0.0463 (9)	0.0278 (14)	−0.0102 (12)	0.0075 (8)
S1	0.0674 (3)	0.0707 (3)	0.0626 (3)	0.0147 (3)	0.0095 (2)	−0.0069 (2)
Cl1	0.2253 (11)	0.0834 (4)	0.0646 (3)	0.0384 (6)	−0.0194 (5)	0.0284 (3)
C6	0.0489 (8)	0.0463 (8)	0.0387 (7)	−0.0005 (8)	0.0019 (8)	0.0031 (6)
O1	0.0645 (8)	0.0616 (8)	0.0578 (7)	−0.0018 (7)	0.0091 (7)	0.0157 (6)
C4	0.0466 (8)	0.0457 (9)	0.0410 (8)	−0.0008 (7)	0.0026 (7)	0.0035 (7)
N1	0.0581 (9)	0.0606 (10)	0.0478 (8)	0.0061 (8)	−0.0027 (7)	−0.0059 (7)
C5	0.0667 (10)	0.0568 (11)	0.0428 (8)	0.0090 (9)	0.0022 (8)	0.0012 (8)
C8	0.0539 (10)	0.0429 (8)	0.0460 (8)	0.0007 (8)	0.0025 (8)	0.0031 (7)
C7	0.0516 (9)	0.0514 (10)	0.0457 (8)	0.0085 (8)	−0.0046 (8)	−0.0011 (7)
C3	0.0569 (10)	0.0486 (10)	0.0420 (8)	0.0003 (8)	−0.0041 (8)	0.0029 (7)
C9	0.0555 (10)	0.0536 (10)	0.0475 (9)	−0.0008 (9)	0.0003 (8)	0.0036 (7)
O3	0.1031 (12)	0.0509 (9)	0.0918 (11)	0.0066 (9)	−0.0103 (10)	−0.0046 (8)
C2	0.0719 (12)	0.0675 (13)	0.0615 (11)	0.0137 (11)	−0.0082 (10)	0.0124 (9)
C15	0.0780 (13)	0.0597 (11)	0.0516 (10)	−0.0048 (11)	−0.0136 (10)	0.0107 (8)
O2	0.0491 (8)	0.1071 (13)	0.0954 (11)	0.0053 (9)	0.0029 (7)	−0.0237 (11)
C10	0.0614 (10)	0.0519 (10)	0.0423 (8)	0.0094 (9)	−0.0049 (8)	0.0009 (7)
C1	0.0906 (16)	0.0619 (13)	0.0746 (13)	0.0252 (12)	−0.0040 (12)	0.0032 (10)
C11	0.0678 (12)	0.0778 (15)	0.0618 (11)	0.0038 (11)	−0.0150 (10)	0.0045 (10)
C12	0.0969 (18)	0.0897 (18)	0.0590 (11)	0.0216 (16)	−0.0267 (12)	0.0023 (12)
C14	0.1063 (17)	0.0566 (11)	0.0606 (11)	−0.0037 (14)	−0.0062 (13)	0.0150 (9)

C13—C12	1.355 (4)	C8—H8	0.9300
C13—C14	1.373 (4)	C7—H7A	0.9700
C13—Cl1	1.745 (2)	C7—H7B	0.9700
S1—C5	1.7959 (19)	C3—C2	1.509 (3)
S1—C1	1.804 (2)	C9—C10	1.476 (2)
C6—C8	1.507 (2)	C9—H9	0.9300
C6—C4	1.534 (2)	C2—C1	1.520 (3)
C6—C7	1.539 (2)	C2—H2A	0.9700
C6—H6	0.9800	C2—H2B	0.9700
O1—C3	1.213 (2)	C15—C10	1.382 (3)
C4—C3	1.524 (2)	C15—C14	1.383 (3)
C4—C5	1.541 (2)	C15—H15	0.9300
C4—H4	0.9800	C10—C11	1.385 (3)
N1—O3	1.209 (2)	C1—H1A	0.9700
N1—O2	1.213 (2)	C1—H1B	0.9700
N1—C7	1.494 (2)	C11—C12	1.388 (3)
C5—H5A	0.9700	C11—H11	0.9300
C5—H5B	0.9700	C12—H12	0.9300
C8—C9	1.315 (3)	C14—H14	0.9300
C12—C13—C14	121.62 (19)	O1—C3—C2	122.19 (16)
C12—C13—Cl1	119.81 (19)	O1—C3—C4	121.53 (16)
C14—C13—Cl1	118.5 (2)	C2—C3—C4	116.17 (15)
C5—S1—C1	98.11 (10)	C8—C9—C10	127.61 (17)
C8—C6—C4	112.19 (13)	C8—C9—H9	116.2
C8—C6—C7	109.65 (14)	C10—C9—H9	116.2
C4—C6—C7	109.17 (13)	C3—C2—C1	111.04 (16)
C8—C6—H6	108.6	C3—C2—H2A	109.4
C4—C6—H6	108.6	C1—C2—H2A	109.4
C7—C6—H6	108.6	C3—C2—H2B	109.4
C3—C4—C6	113.01 (13)	C1—C2—H2B	109.4
C3—C4—C5	107.25 (14)	H2A—C2—H2B	108.0
C6—C4—C5	111.50 (13)	C10—C15—C14	121.53 (19)
C3—C4—H4	108.3	C10—C15—H15	119.2
C6—C4—H4	108.3	C14—C15—H15	119.2
C5—C4—H4	108.3	C11—C10—C15	117.69 (18)
O3—N1—O2	123.82 (19)	C11—C10—C9	119.13 (18)
O3—N1—C7	118.28 (17)	C15—C10—C9	123.17 (16)
O2—N1—C7	117.86 (18)	C2—C1—S1	113.15 (17)
C4—C5—S1	113.56 (12)	C2—C1—H1A	108.9
C4—C5—H5A	108.9	S1—C1—H1A	108.9
S1—C5—H5A	108.9	C2—C1—H1B	108.9
C4—C5—H5B	108.9	S1—C1—H1B	108.9
S1—C5—H5B	108.9	H1A—C1—H1B	107.8
H5A—C5—H5B	107.7	C10—C11—C12	121.3 (2)
C9—C8—C6	124.67 (17)	C10—C11—H11	119.3
C9—C8—H8	117.7	C12—C11—H11	119.3
C6—C8—H8	117.7	C13—C12—C11	119.1 (2)
N1—C7—C6	109.27 (13)	C13—C12—H12	120.5
N1—C7—H7A	109.8	C11—C12—H12	120.5
C6—C7—H7A	109.8	C13—C14—C15	118.7 (2)
N1—C7—H7B	109.8	C13—C14—H14	120.6
C6—C7—H7B	109.8	C15—C14—H14	120.6
H7A—C7—H7B	108.3
C8—C6—C4—C3	−173.58 (14)	C6—C8—C9—C10	178.10 (17)
C7—C6—C4—C3	64.67 (18)	O1—C3—C2—C1	114.2 (2)
C8—C6—C4—C5	−52.68 (19)	C4—C3—C2—C1	−62.0 (2)
C7—C6—C4—C5	−174.43 (14)	C14—C15—C10—C11	−0.1 (3)
C3—C4—C5—S1	−62.42 (17)	C14—C15—C10—C9	178.8 (2)
C6—C4—C5—S1	173.37 (12)	C8—C9—C10—C11	172.61 (19)
C1—S1—C5—C4	56.38 (16)	C8—C9—C10—C15	−6.3 (3)
C4—C6—C8—C9	123.85 (19)	C3—C2—C1—S1	58.3 (2)
C7—C6—C8—C9	−114.67 (19)	C5—S1—C1—C2	−53.16 (18)
O3—N1—C7—C6	−112.49 (18)	C15—C10—C11—C12	0.8 (3)
O2—N1—C7—C6	65.5 (2)	C9—C10—C11—C12	−178.2 (2)
C8—C6—C7—N1	53.18 (19)	C14—C13—C12—C11	−0.2 (4)
C4—C6—C7—N1	176.45 (14)	Cl1—C13—C12—C11	177.53 (19)
C6—C4—C3—O1	9.8 (2)	C10—C11—C12—C13	−0.6 (4)
C5—C4—C3—O1	−113.44 (18)	C12—C13—C14—C15	0.9 (4)
C6—C4—C3—C2	−173.94 (15)	Cl1—C13—C14—C15	−176.91 (18)
C5—C4—C3—C2	62.78 (19)	C10—C15—C14—C13	−0.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O2i	0.97	2.45	3.368 (4)	158
C2—H2B···O1i	0.97	2.58	3.484 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O2i	0.97	2.45	3.368 (4)	158
C2—H2B⋯O1i	0.97	2.58	3.484 (3)	156

Symmetry code: (i) .