1-Methyl-4-[(1E)-2-nitro­prop-1-en-1-yl]benzene

Li, Z.-B.; Shen, L.-L.; Zheng, J.-A.

doi:10.1107/S1600536812025913

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2065

https://doi.org/10.1107/S1600536812025913

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1-Methyl-4-[(1E)-2-nitroprop-1-en-1-yl]benzene

Zhao-Bo Li,^a,^b ^* Li-Li Shen ^b and Jian-An Zheng ^c

^aHangzhou Minsheng Pharmaceutical Group Co. Ltd, Hangzhou 310000, People's Republic of China, ^bState Key Laboratory Breeding Base of Green Chemistry–Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and ^cJiaxing Zhonghua Chemical Industry Co. Ltd, Daqiao Town Nanhu District, Jiaxing 314006, People's Republic of China
^*Correspondence e-mail: boyzb@163.com

(Received 8 May 2012; accepted 7 June 2012; online 13 June 2012)

The title compound, C₁₀H₁₁NO₂, adopts an E conformation about the C=C bond. The C=C—C=C torsion angle is 32.5 (3)°. The crystal structure features weak intermolecular C—H⋯O interactions.

Related literature

For background to the chemistry of nitroalkenes, see: Ballini & Petrini (2004 ); Berner et al. (2002 ); Ono (2001 ). For a related structure, see: Yang et al. (2010 ).

Experimental

Crystal data

C₁₀H₁₁NO₂
M_r = 177.20
Orthorhombic, P b c a
a = 11.0610 (5) Å
b = 7.5840 (4) Å
c = 22.6420 (11) Å
V = 1899.36 (16) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.58 × 0.43 × 0.36 mm

Data collection

Rigaku R-AXIS-RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.941, T_max = 0.969
16972 measured reflections
2162 independent reflections
1325 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.134
S = 1.00
2162 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O1ⁱ	0.93	2.55	3.369 (2)	147
C2—H2⋯O2ⁱⁱ	0.93	2.66	3.551 (3)	162
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalClear (Rigaku, 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 ).

Supporting information

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025913/zq2167sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025913/zq2167Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025913/zq2167Isup3.cml

checkCIF report

Comment top

Nitroalkenes are important organic intermediates, since they can be converted to synthetically useful N- and O-containing organic molecules, such as amines, aldehydes, carboxylic acids, or denitrated compounds (Ono, 2001; Berner et al., 2002; Ballini & Petrini, 2004). As a contribution in this field, we have synthesized a series of nitroalkenes by employing benzaldehydes and nitroethane (Yang et al., 2010). We report here the crystal structure of the title compound (Fig. 1).

The molecule adopts an E configuration with respect to the C8=C9 double bond. The torsion angle C9—C8—C1—C6 is 32.5 (3)°. In the crystal structure, the molecules interact through weak intermolecular C8—H8···O1ⁱ and C2—H2···O2ⁱⁱ hydrogen bonds (symmetry codes: i = -x+1, -y, -z+1; ii = x+1/2, -y+1/2, -z+1; Fig. 2 and Table 1).

Related literature top

For background to the chemistry of nitroalkenes, see: Ballini & Petrini (2004); Berner et al. (2002); Ono (2001). For a related structure, see: Yang et al. (2010).

Experimental top

To a solution of p-tolualdehyde (50 mmol) in AcOH (25 mL), nitroethane (75 mmol) was added, followed by butylamine (100 mmol, 7.4 mL). The mixture was sonicated at 60 °C, until GC showed full conversion of the aldehyde. The mixture was poured into ice water, the precipitate was filtered off, washed with water and recrystallized from EtOH/EtOAc to give the final product. Single crystals were obtained by slow evaporation of a n-hexane/EtOAc (10:1, v/v) solution.

Structure description top

For background to the chemistry of nitroalkenes, see: Ballini & Petrini (2004); Berner et al. (2002); Ono (2001). For a related structure, see: Yang et al. (2010).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalClear (Rigaku, 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atomic labeling scheme; displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. View of the intermolecular interactions illustrated as dashed lines.

1-Methyl-4-[(1E)-2-nitroprop-1-en-1-yl]benzene top

Crystal data top

C₁₀H₁₁NO₂	F(000) = 752
M_r = 177.20	D_x = 1.239 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9467 reflections
a = 11.0610 (5) Å	θ = 3.2–27.4°
b = 7.5840 (4) Å	µ = 0.09 mm⁻¹
c = 22.6420 (11) Å	T = 296 K
V = 1899.36 (16) Å³	Chunk, yellow
Z = 8	0.58 × 0.43 × 0.36 mm

Data collection top

Rigaku R-AXIS-RAPID/ZJUG diffractometer	2162 independent reflections
Radiation source: rotating anode	1325 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.4°
ω scans	h = −14→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→9
T_min = 0.941, T_max = 0.969	l = −29→29
16972 measured reflections

Refinement top

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0552P)² + 0.4885P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2162 reflections	Δρ_max = 0.15 e Å⁻³
121 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (12)

Crystal data top

C₁₀H₁₁NO₂	V = 1899.36 (16) Å³
M_r = 177.20	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.0610 (5) Å	µ = 0.09 mm⁻¹
b = 7.5840 (4) Å	T = 296 K
c = 22.6420 (11) Å	0.58 × 0.43 × 0.36 mm

Data collection top

Rigaku R-AXIS-RAPID/ZJUG diffractometer	2162 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1325 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.969	R_int = 0.033
16972 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.00	Δρ_max = 0.15 e Å⁻³
2162 reflections	Δρ_min = −0.17 e Å⁻³
121 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.35993 (13)	0.1487 (2)	0.63005 (7)	0.0487 (4)
C2	0.46387 (14)	0.2326 (2)	0.65095 (8)	0.0577 (4)
H2	0.5248	0.2634	0.6246	0.069*
C3	0.47750 (16)	0.2703 (2)	0.71015 (8)	0.0643 (5)
H3	0.5464	0.3300	0.7227	0.077*
C4	0.39139 (17)	0.2218 (2)	0.75151 (8)	0.0614 (5)
C5	0.29031 (16)	0.1324 (2)	0.73072 (8)	0.0615 (5)
H5	0.2318	0.0957	0.7575	0.074*
C6	0.27416 (14)	0.0963 (2)	0.67157 (7)	0.0547 (4)
H6	0.2053	0.0363	0.6592	0.066*
C7	0.4073 (2)	0.2610 (3)	0.81617 (9)	0.0938 (7)
H7A	0.4047	0.1529	0.8382	0.141*
H7B	0.3435	0.3374	0.8292	0.141*
H7C	0.4839	0.3177	0.8223	0.141*
C8	0.34896 (14)	0.1144 (2)	0.56645 (7)	0.0531 (4)
H8	0.4211	0.0963	0.5462	0.064*
C9	0.24878 (15)	0.1058 (2)	0.53415 (7)	0.0524 (4)
C10	0.12094 (14)	0.1404 (3)	0.55103 (8)	0.0676 (5)
H10A	0.0791	0.0304	0.5557	0.101*
H10B	0.0824	0.2087	0.5207	0.101*
H10C	0.1189	0.2043	0.5876	0.101*
N1	0.26510 (15)	0.0587 (2)	0.47133 (7)	0.0689 (4)
O1	0.36592 (15)	0.0320 (3)	0.45180 (6)	0.1156 (7)
O2	0.17592 (15)	0.0466 (3)	0.44070 (7)	0.1107 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0436 (8)	0.0448 (8)	0.0577 (9)	0.0026 (6)	−0.0012 (7)	0.0014 (7)
C2	0.0443 (8)	0.0582 (10)	0.0705 (11)	−0.0013 (7)	−0.0040 (8)	0.0051 (8)
C3	0.0588 (10)	0.0554 (10)	0.0788 (12)	−0.0025 (8)	−0.0221 (9)	−0.0002 (8)
C4	0.0758 (11)	0.0482 (9)	0.0602 (10)	0.0081 (8)	−0.0150 (9)	−0.0001 (8)
C5	0.0675 (11)	0.0592 (10)	0.0576 (10)	−0.0005 (8)	0.0030 (8)	0.0056 (8)
C6	0.0527 (9)	0.0527 (9)	0.0587 (9)	−0.0081 (7)	−0.0020 (7)	0.0009 (7)
C7	0.134 (2)	0.0821 (14)	0.0653 (12)	0.0051 (14)	−0.0291 (13)	−0.0057 (10)
C8	0.0474 (8)	0.0563 (9)	0.0555 (9)	0.0029 (7)	0.0031 (7)	0.0019 (7)
C9	0.0535 (8)	0.0525 (9)	0.0512 (8)	0.0023 (7)	−0.0009 (7)	0.0009 (7)
C10	0.0500 (9)	0.0809 (12)	0.0718 (11)	0.0055 (9)	−0.0033 (8)	0.0057 (9)
N1	0.0687 (10)	0.0811 (11)	0.0570 (9)	0.0123 (8)	−0.0067 (8)	−0.0012 (8)
O1	0.0869 (11)	0.197 (2)	0.0625 (9)	0.0435 (12)	0.0054 (8)	−0.0159 (10)
O2	0.0889 (11)	0.1695 (18)	0.0737 (10)	0.0049 (11)	−0.0255 (8)	−0.0238 (10)

Geometric parameters (Å, º) top

C1—C2	1.396 (2)	C7—H7A	0.9600
C1—C6	1.394 (2)	C7—H7B	0.9600
C1—C8	1.468 (2)	C7—H7C	0.9600
C2—C3	1.379 (2)	C8—C9	1.329 (2)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.386 (3)	C9—N1	1.478 (2)
C3—H3	0.9300	C9—C10	1.488 (2)
C4—C5	1.390 (2)	C10—H10A	0.9600
C4—C7	1.504 (3)	C10—H10B	0.9600
C5—C6	1.378 (2)	C10—H10C	0.9600
C5—H5	0.9300	N1—O2	1.2094 (19)
C6—H6	0.9300	N1—O1	1.217 (2)

C2—C1—C6	117.50 (15)	H7A—C7—H7B	109.5
C2—C1—C8	118.77 (14)	C4—C7—H7C	109.5
C6—C1—C8	123.69 (14)	H7A—C7—H7C	109.5
C3—C2—C1	120.94 (16)	H7B—C7—H7C	109.5
C3—C2—H2	119.5	C9—C8—C1	128.09 (14)
C1—C2—H2	119.5	C9—C8—H8	116.0
C2—C3—C4	121.78 (16)	C1—C8—H8	116.0
C2—C3—H3	119.1	C8—C9—N1	116.07 (14)
C4—C3—H3	119.1	C8—C9—C10	129.97 (15)
C3—C4—C5	116.99 (16)	N1—C9—C10	113.95 (14)
C3—C4—C7	121.66 (18)	C9—C10—H10A	109.5
C5—C4—C7	121.35 (19)	C9—C10—H10B	109.5
C6—C5—C4	122.02 (16)	H10A—C10—H10B	109.5
C6—C5—H5	119.0	C9—C10—H10C	109.5
C4—C5—H5	119.0	H10A—C10—H10C	109.5
C5—C6—C1	120.70 (15)	H10B—C10—H10C	109.5
C5—C6—H6	119.7	O2—N1—O1	121.78 (17)
C1—C6—H6	119.7	O2—N1—C9	118.09 (16)
C4—C7—H7A	109.5	O1—N1—C9	120.13 (15)
C4—C7—H7B	109.5

C6—C1—C2—C3	−3.5 (2)	C8—C1—C6—C5	179.77 (15)
C8—C1—C2—C3	178.93 (15)	C2—C1—C8—C9	−150.12 (16)
C1—C2—C3—C4	2.3 (3)	C6—C1—C8—C9	32.5 (3)
C2—C3—C4—C5	0.2 (2)	C1—C8—C9—N1	−176.58 (15)
C2—C3—C4—C7	179.15 (17)	C1—C8—C9—C10	4.9 (3)
C3—C4—C5—C6	−1.4 (2)	C8—C9—N1—O2	178.77 (17)
C7—C4—C5—C6	179.65 (17)	C10—C9—N1—O2	−2.5 (2)
C4—C5—C6—C1	0.1 (3)	C8—C9—N1—O1	−0.8 (3)
C2—C1—C6—C5	2.3 (2)	C10—C9—N1—O1	177.99 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1	0.93	2.28	2.677 (2)	105
C8—H8···O1ⁱ	0.93	2.55	3.369 (2)	147
C2—H2···O2ⁱⁱ	0.93	2.66	3.551 (3)	162

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₂
M_r	177.20
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	11.0610 (5), 7.5840 (4), 22.6420 (11)
V (Å³)	1899.36 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.58 × 0.43 × 0.36

Data collection
Diffractometer	Rigaku R-AXIS-RAPID/ZJUG
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.941, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	16972, 2162, 1325
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.134, 1.00
No. of reflections	2162
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.17

Computer programs: PROCESS-AUTO (Rigaku, 2006), PROCESS-AUTO (Rigaku, 2006), CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1ⁱ	0.930	2.55	3.369 (2)	147
C2—H2···O2ⁱⁱ	0.930	2.66	3.551 (3)	162

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, −z+1.

Acknowledgements

The authors thank Mr Jianming Gu for the single-crystal X-ray analysis. They are also grateful for financial support from the State Key Laboratory Breeding Base of Green Chemistry–Synthesis Technology of Zhejiang University of Technology (GCTKF2012010).

References

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