(S)-2-[(S,E)-4-(4-Chloro-phen-yl)-1-nitro-but-3-en-2-yl]cyclo-hexa-none.

The title compound, C(16)H(18)ClNO(3), was obtained by the organocatalytic asymmetric Michael addition of cyclo-hexa-none to 1-chloro-4-[(1E,3E)-4-nitro-buta-1,3-dien-yl]benzene. The double bond has an E configuration. The cyclo-hexa-none ring adopts a chair conformation. The conformation of the mol-ecule is stabilized by a weak intra-molecular C-H⋯O hydrogen bond.

Related literature

For asymmetric Michael addition reactions employing chiral organo­catalysts, see: Belot et al. (2008 ▶); Dalko & Moisan (2004 ▶); Yu et al. (2009 ▶). For details of the synthesis, see: Xu et al. (2008 ▶); For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H18ClNO3

M = 307.78

Orthorhombic,

a = 5.5300 (3) Å

b = 8.5175 (6) Å

c = 34.0903 (18) Å

V = 1605.71 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 296 K

0.48 × 0.32 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.879, T max = 0.933

15644 measured reflections

2148 independent reflections

1391 reflections with F 2 > 2σ(F 2)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.124

S = 1.00

2148 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983 ▶), 1486 Friedel pairs

Flack parameter: 0.27 (18)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029213/bx2224sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029213/bx2224Isup2.hkl

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

C16H18ClNO3	F(000) = 648.00
Mr = 307.78	Dx = 1.273 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9533 reflections
a = 5.5300 (3) Å	θ = 3.0–27.4°
b = 8.5175 (6) Å	µ = 0.25 mm−1
c = 34.0903 (18) Å	T = 296 K
V = 1605.71 (17) Å3	Chunk, colourless
Z = 4	0.48 × 0.32 × 0.28 mm

Rigaku R-AXIS RAPID diffractometer	1391 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1	Rint = 0.034
ω scans	θmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→6
Tmin = 0.879, Tmax = 0.933	k = −11→11
15644 measured reflections	l = −43→44
2148 independent reflections

Refinement on F2	(Δ/σ)max = 0.001
R[F2 > 2σ(F2)] = 0.044	Δρmax = 0.22 e Å−3
wR(F2) = 0.124	Δρmin = −0.27 e Å−3
S = 1.00	Extinction correction: SHELXL97 (Sheldrick, 2008)
2148 reflections	Extinction coefficient: 0.027 (2)
192 parameters	Absolute structure: Flack (1983), 1486 Friedel pairs
H-atom parameters constrained	Flack parameter: 0.27 (18)
w = 1/[σ2(Fo2) + (0.032P)2 + 1.2P] where P = (Fo2 + 2Fc2)/3

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

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).

	x	y	z	Uiso*/Ueq
Cl1	0.6163 (3)	0.6280 (2)	1.07164 (3)	0.1211 (6)
O1	0.9458 (5)	0.1436 (3)	0.77121 (8)	0.0735 (8)
O2	1.2699 (5)	0.5169 (4)	0.83637 (10)	0.0841 (9)
O3	0.9882 (6)	0.6855 (3)	0.84395 (12)	0.1019 (12)
N1	1.0607 (6)	0.5581 (4)	0.83299 (10)	0.0633 (8)
C1	0.8554 (6)	0.3047 (4)	0.84336 (9)	0.0497 (8)
C2	0.6749 (6)	0.1873 (4)	0.82559 (9)	0.0486 (7)
C3	0.6291 (9)	0.0456 (4)	0.85244 (10)	0.0705 (12)
C4	0.4412 (9)	−0.0647 (5)	0.83580 (12)	0.0801 (13)
C5	0.5077 (9)	−0.1218 (5)	0.79532 (12)	0.0764 (12)
C6	0.5632 (7)	0.0143 (4)	0.76796 (10)	0.0643 (10)
C7	0.7474 (7)	0.1200 (4)	0.78612 (10)	0.0532 (8)
C8	0.8838 (7)	0.4463 (4)	0.81622 (10)	0.0562 (9)
C9	0.7707 (7)	0.3624 (4)	0.88279 (9)	0.0552 (8)
C10	0.8919 (7)	0.3590 (4)	0.91561 (10)	0.0601 (9)
C11	0.8194 (7)	0.4250 (4)	0.95375 (10)	0.0596 (9)
C12	0.6144 (9)	0.5173 (5)	0.95838 (12)	0.0754 (12)
C13	0.5508 (9)	0.5783 (5)	0.99460 (12)	0.0809 (13)
C14	0.6932 (9)	0.5491 (5)	1.02636 (12)	0.0754 (12)
C15	0.8973 (10)	0.4591 (6)	1.02286 (12)	0.0837 (14)
C16	0.9577 (8)	0.3972 (5)	0.98675 (11)	0.0726 (12)
H1	1.0127	0.2531	0.8464	0.060*
H2	0.5206	0.2421	0.8221	0.058*
H9	0.6159	0.4048	0.8839	0.066*
H10	1.0415	0.3092	0.9148	0.072*
H12	0.5177	0.5386	0.9367	0.090*
H13	0.4118	0.6389	0.9972	0.097*
H15	0.9943	0.4398	1.0446	0.100*
H16	1.0952	0.3350	0.9846	0.087*
H31	0.7795	−0.0114	0.8558	0.085*
H32	0.5737	0.0833	0.8777	0.085*
H41	0.4259	−0.1546	0.8531	0.096*
H42	0.2875	−0.0101	0.8344	0.096*
H51	0.3737	−0.1816	0.7847	0.092*
H52	0.6493	−0.1886	0.7972	0.092*
H61	0.6255	−0.0263	0.7434	0.077*
H62	0.4162	0.0732	0.7631	0.077*
H81	0.9403	0.4111	0.7908	0.067*
H82	0.7287	0.4981	0.8133	0.067*

	U11	U22	U33	U12	U13	U23
Cl1	0.1546 (14)	0.1453 (13)	0.0635 (6)	−0.0040 (13)	0.0179 (8)	−0.0299 (7)
O1	0.0658 (17)	0.0833 (19)	0.0716 (16)	−0.0074 (17)	0.0162 (14)	−0.0129 (15)
O2	0.0494 (16)	0.086 (2)	0.117 (2)	−0.0064 (16)	−0.0101 (17)	0.006 (2)
O3	0.087 (2)	0.0605 (17)	0.158 (3)	−0.005 (2)	−0.018 (2)	−0.023 (2)
N1	0.0585 (19)	0.0535 (18)	0.078 (2)	−0.0089 (18)	−0.0045 (18)	0.0029 (17)
C1	0.0521 (19)	0.0498 (18)	0.0472 (16)	−0.0037 (18)	−0.0020 (16)	−0.0009 (15)
C2	0.0516 (18)	0.0480 (18)	0.0462 (15)	−0.0035 (17)	0.0013 (15)	−0.0015 (14)
C3	0.101 (3)	0.061 (2)	0.0486 (18)	−0.032 (2)	0.001 (2)	0.0005 (17)
C4	0.109 (3)	0.067 (2)	0.064 (2)	−0.037 (2)	0.000 (2)	−0.003 (2)
C5	0.095 (3)	0.058 (2)	0.076 (2)	−0.010 (2)	−0.009 (2)	−0.009 (2)
C6	0.072 (2)	0.068 (2)	0.0534 (19)	−0.009 (2)	−0.0023 (19)	−0.0126 (18)
C7	0.057 (2)	0.053 (2)	0.0501 (17)	0.0003 (19)	−0.0022 (17)	−0.0014 (16)
C8	0.060 (2)	0.050 (2)	0.0583 (19)	−0.014 (2)	−0.0097 (18)	0.0038 (16)
C9	0.058 (2)	0.055 (2)	0.0526 (17)	−0.0046 (19)	−0.0029 (17)	−0.0023 (17)
C10	0.063 (2)	0.064 (2)	0.0537 (18)	0.005 (2)	−0.0053 (18)	−0.0025 (17)
C11	0.064 (2)	0.060 (2)	0.0547 (19)	−0.005 (2)	−0.0032 (18)	−0.0040 (17)
C12	0.079 (2)	0.089 (3)	0.058 (2)	0.010 (2)	−0.006 (2)	−0.006 (2)
C13	0.085 (3)	0.089 (3)	0.069 (2)	0.014 (3)	0.002 (2)	−0.012 (2)
C14	0.090 (3)	0.079 (2)	0.058 (2)	−0.012 (3)	0.006 (2)	−0.007 (2)
C15	0.097 (3)	0.101 (3)	0.053 (2)	−0.006 (3)	−0.011 (2)	−0.005 (2)
C16	0.075 (2)	0.085 (3)	0.059 (2)	0.004 (2)	−0.011 (2)	−0.003 (2)

Cl1—C14	1.736 (4)	C14—C15	1.370 (7)
O1—C7	1.226 (4)	C15—C16	1.380 (5)
O2—N1	1.214 (4)	C1—H1	0.980
O3—N1	1.216 (4)	C2—H2	0.980
N1—C8	1.480 (5)	C3—H31	0.970
C1—C2	1.537 (4)	C3—H32	0.970
C1—C8	1.528 (4)	C4—H41	0.970
C1—C9	1.506 (4)	C4—H42	0.970
C2—C3	1.536 (5)	C5—H51	0.970
C2—C7	1.516 (4)	C5—H52	0.970
C3—C4	1.512 (6)	C6—H61	0.970
C4—C5	1.509 (5)	C6—H62	0.970
C5—C6	1.519 (5)	C8—H81	0.970
C6—C7	1.494 (5)	C8—H82	0.970
C9—C10	1.305 (4)	C9—H9	0.930
C10—C11	1.472 (5)	C10—H10	0.930
C11—C12	1.389 (6)	C12—H12	0.930
C11—C16	1.381 (5)	C13—H13	0.930
C12—C13	1.385 (6)	C15—H15	0.930
C13—C14	1.362 (6)	C16—H16	0.930
O2—N1—O3	122.9 (3)	C2—C3—H32	108.8
O2—N1—C8	118.7 (3)	C4—C3—H31	108.8
O3—N1—C8	118.4 (3)	C4—C3—H32	108.8
C2—C1—C8	110.0 (2)	H31—C3—H32	109.5
C2—C1—C9	111.2 (2)	C3—C4—H41	108.8
C8—C1—C9	108.3 (2)	C3—C4—H42	108.8
C1—C2—C3	112.5 (2)	C5—C4—H41	108.8
C1—C2—C7	115.1 (2)	C5—C4—H42	108.8
C3—C2—C7	106.0 (2)	H41—C4—H42	109.5
C2—C3—C4	112.2 (3)	C4—C5—H51	109.0
C3—C4—C5	112.1 (3)	C4—C5—H52	109.0
C4—C5—C6	111.4 (3)	C6—C5—H51	109.0
C5—C6—C7	110.1 (3)	C6—C5—H52	109.0
O1—C7—C2	122.9 (3)	H51—C5—H52	109.5
O1—C7—C6	122.5 (3)	C5—C6—H61	109.3
C2—C7—C6	114.5 (3)	C5—C6—H62	109.3
N1—C8—C1	110.0 (2)	C7—C6—H61	109.3
C1—C9—C10	126.8 (3)	C7—C6—H62	109.3
C9—C10—C11	127.5 (3)	H61—C6—H62	109.5
C10—C11—C12	122.6 (3)	N1—C8—H81	109.3
C10—C11—C16	120.2 (3)	N1—C8—H82	109.3
C12—C11—C16	117.2 (3)	C1—C8—H81	109.3
C11—C12—C13	121.4 (4)	C1—C8—H82	109.3
C12—C13—C14	119.6 (4)	H81—C8—H82	109.5
Cl1—C14—C13	119.6 (3)	C1—C9—H9	116.6
Cl1—C14—C15	119.7 (3)	C10—C9—H9	116.6
C13—C14—C15	120.6 (4)	C9—C10—H10	116.2
C14—C15—C16	119.4 (4)	C11—C10—H10	116.2
C11—C16—C15	121.8 (4)	C11—C12—H12	119.3
C2—C1—H1	109.1	C13—C12—H12	119.3
C8—C1—H1	109.1	C12—C13—H13	120.2
C9—C1—H1	109.1	C14—C13—H13	120.2
C1—C2—H2	107.6	C14—C15—H15	120.3
C3—C2—H2	107.6	C16—C15—H15	120.3
C7—C2—H2	107.6	C11—C16—H16	119.1
C2—C3—H31	108.8	C15—C16—H16	119.1
O2—N1—C8—C1	64.7 (4)	C3—C4—C5—C6	−52.9 (5)
O3—N1—C8—C1	−112.9 (3)	C4—C5—C6—C7	52.5 (5)
C2—C1—C8—N1	−179.0 (2)	C5—C6—C7—O1	118.3 (4)
C8—C1—C2—C3	−177.3 (3)	C5—C6—C7—C2	−58.0 (4)
C8—C1—C2—C7	61.1 (3)	C1—C9—C10—C11	175.2 (3)
C2—C1—C9—C10	126.2 (4)	C9—C10—C11—C12	−7.3 (6)
C9—C1—C2—C3	−57.3 (4)	C9—C10—C11—C16	173.2 (4)
C9—C1—C2—C7	−178.8 (2)	C10—C11—C12—C13	−179.8 (4)
C8—C1—C9—C10	−112.8 (4)	C10—C11—C16—C15	179.0 (4)
C9—C1—C8—N1	59.2 (3)	C12—C11—C16—C15	−0.6 (6)
C1—C2—C3—C4	176.8 (3)	C16—C11—C12—C13	−0.2 (6)
C1—C2—C7—O1	7.5 (5)	C11—C12—C13—C14	0.8 (7)
C1—C2—C7—C6	−176.2 (3)	C12—C13—C14—Cl1	179.0 (3)
C3—C2—C7—O1	−117.6 (4)	C12—C13—C14—C15	−0.5 (7)
C3—C2—C7—C6	58.7 (4)	Cl1—C14—C15—C16	−179.8 (3)
C7—C2—C3—C4	−56.6 (4)	C13—C14—C15—C16	−0.3 (6)
C2—C3—C4—C5	56.4 (4)	C14—C15—C16—C11	0.8 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H81···O1	0.97	2.37	3.020 (4)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H81⋯O1	0.97	2.37	3.020 (4)	124