(E)-1-Bromo-4-(2-nitro­prop-1-en­yl)benzene

Li, B.

doi:10.1107/S1600536809048910

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3174

doi:10.1107/S1600536809048910

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(E)-1-Bromo-4-(2-nitroprop-1-enyl)benzene

Bailin Li ^a ^*

^aDepartment of Pharmaceutical and Chemical Engineering, Taizhou College, Linhai, Zhejiang 317000, People's Republic of China
^*Correspondence e-mail: bailinli1972@gmail.com

(Received 11 November 2009; accepted 17 November 2009; online 21 November 2009)

The title compound, C₉H₈BrNO₂, which was synthesized by the condensation of 4-bromobenzaldehyde with nitroethane, possesses a trans configuration. The dihedral angle between the benzene ring and the mean plane of the double bond is 7.31 (3)°. The crystal structure is stabilized by short intermolecular Br⋯O contacts [3.168 (4) Å].

Related literature

For general background to nitroalkenes as intermediates in the preparation of numerous products including insecticides and pharmacologically active substances, see: Boelle et al. (1998 ); Vallejos et al. (2005 ). For related structures, see: Boys et al. (1993 ); Mugnoli et al. (1991 ).

Experimental

Crystal data

C₉H₈BrNO₂
M_r = 242.07
Triclinic, $[P \overline 1]$
a = 6.9787 (5) Å
b = 7.4123 (5) Å
c = 9.7659 (6) Å
α = 105.435 (2)°
β = 95.087 (2)°
γ = 104.323 (2)°
V = 465.31 (5) Å³
Z = 2
Mo Kα radiation
μ = 4.38 mm⁻¹
T = 296 K
0.21 × 0.19 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.388, T_max = 0.703
4605 measured reflections
2112 independent reflections
1303 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.00
2112 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.71 e Å⁻³

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048910/zq2017sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048910/zq2017Isup2.hkl

checkCIF report

Comment top

Nitroalkenes are valuable intermediates for preparation of numerous products including insecticides and pharmacologically active substances (Boelle et al., 1998 and Vallejos et al., 2005) in which the nitro group can be easily transformed into a variety of groups with different functionalities, such as amine, carbonyl groups, etc.. In this article, the crystal structure of the title compound (E)-1-bromo-4-(2-nitroprop-1-enyl)benzene is presented (Fig. 1). The dihedral angle between the benzene ring and the mean plan of the double bond H7/C7/C8/C9 is 7.31 (3) °. The crystal structure is stabilized by short intermolecular Br—O contacts [3.168 (4) Å].

Related literature top

For general background to nitroalkenes as intermediates in the preparation of numerous products including insecticides and pharmacologically active substances, see: Boelle et al. (1998); Vallejos et al. (2005). For related structures, see: Boys et al. (1993); Mugnoli et al. (1991).

Experimental top

To a solution of 4-bromobenzaldehyde (50 mmol) in AcOH (25 ml), nitroethane (75 mmol) was added, followed by butylamine (100 mmol, 7.4 ml). The mixture was sonicated at 333 K, until TLC showed full conversion of aldehyde. The mixture was poured into ice water, the precipitate was filtered off, washed with water and recrystallized from EtOH to give (E)-1-bromo-4-(2-nitroprop-1-enyl)benzene. Suitable crystals of the title compound were obtained by slow evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2007); program(s) used to solve structure: SHELXL97 (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 (I) with the atomic labeling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Molecular packing of the title compound (I) viewed down the a axis.

(E)-1-Bromo-4-(2-nitroprop-1-enyl)benzene top

Crystal data top

C₉H₈BrNO₂	Z = 2
M_r = 242.07	F(000) = 240
Triclinic, P1	D_x = 1.728 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9787 (5) Å	Cell parameters from 3184 reflections
b = 7.4123 (5) Å	θ = 3.1–27.4°
c = 9.7659 (6) Å	µ = 4.38 mm⁻¹
α = 105.435 (2)°	T = 296 K
β = 95.087 (2)°	Platelet, yellow
γ = 104.323 (2)°	0.21 × 0.19 × 0.08 mm
V = 465.31 (5) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2112 independent reflections
Radiation source: rolling anode	1303 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→8
T_min = 0.388, T_max = 0.703	l = −12→12
4605 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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.012P)² + 0.950P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2112 reflections	Δρ_max = 0.46 e Å⁻³
120 parameters	Δρ_min = −0.71 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0149 (13)

Crystal data top

C₉H₈BrNO₂	γ = 104.323 (2)°
M_r = 242.07	V = 465.31 (5) Å³
Triclinic, P1	Z = 2
a = 6.9787 (5) Å	Mo Kα radiation
b = 7.4123 (5) Å	µ = 4.38 mm⁻¹
c = 9.7659 (6) Å	T = 296 K
α = 105.435 (2)°	0.21 × 0.19 × 0.08 mm
β = 95.087 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2112 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1303 reflections with I > 2σ(I)
T_min = 0.388, T_max = 0.703	R_int = 0.027
4605 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.00	Δρ_max = 0.46 e Å⁻³
2112 reflections	Δρ_min = −0.71 e Å⁻³
120 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
Br1	0.90197 (7)	0.24927 (9)	0.09032 (5)	0.0754 (2)
N1	0.2076 (6)	0.2311 (6)	0.7592 (4)	0.0660 (10)
O1	0.2341 (5)	0.2609 (6)	0.8891 (4)	0.0937 (12)
O2	0.0411 (5)	0.1719 (7)	0.6875 (4)	0.1038 (14)
C8	0.3870 (6)	0.2659 (6)	0.6875 (4)	0.0514 (9)
C1	0.7334 (6)	0.2408 (6)	0.2327 (4)	0.0567 (10)
C5	0.4097 (6)	0.1824 (7)	0.2989 (4)	0.0631 (12)
H5	0.2712	0.1456	0.2720	0.076*
C7	0.3513 (6)	0.2154 (7)	0.5461 (4)	0.0594 (11)
H7	0.2165	0.1633	0.5051	0.071*
C4	0.4907 (6)	0.2283 (6)	0.4430 (4)	0.0524 (10)
C3	0.6976 (6)	0.2770 (8)	0.4767 (5)	0.0776 (15)
H3	0.7569	0.3055	0.5720	0.093*
C9	0.5777 (7)	0.3501 (9)	0.7900 (5)	0.0825 (16)
H9A	0.6349	0.2476	0.7987	0.099*
H9B	0.5528	0.4165	0.8825	0.099*
H9C	0.6694	0.4409	0.7555	0.099*
C2	0.8179 (6)	0.2840 (8)	0.3723 (5)	0.0742 (14)
H2	0.9565	0.3183	0.3976	0.089*
C6	0.5299 (6)	0.1901 (7)	0.1943 (4)	0.0680 (13)
H6	0.4727	0.1609	0.0985	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0560 (3)	0.1058 (5)	0.0598 (3)	0.0136 (2)	0.0153 (2)	0.0237 (3)
N1	0.055 (2)	0.081 (3)	0.055 (2)	0.0147 (19)	0.0103 (18)	0.014 (2)
O1	0.076 (2)	0.142 (4)	0.056 (2)	0.019 (2)	0.0205 (17)	0.025 (2)
O2	0.0467 (19)	0.173 (4)	0.074 (2)	0.017 (2)	0.0114 (17)	0.020 (2)
C8	0.045 (2)	0.056 (3)	0.050 (2)	0.0112 (18)	0.0092 (17)	0.0142 (19)
C1	0.052 (2)	0.066 (3)	0.052 (2)	0.013 (2)	0.0100 (19)	0.019 (2)
C5	0.042 (2)	0.087 (3)	0.050 (2)	0.012 (2)	−0.0015 (18)	0.012 (2)
C7	0.043 (2)	0.077 (3)	0.051 (2)	0.015 (2)	0.0032 (17)	0.012 (2)
C4	0.042 (2)	0.064 (3)	0.048 (2)	0.0140 (19)	0.0039 (16)	0.013 (2)
C3	0.050 (2)	0.134 (5)	0.044 (2)	0.024 (3)	−0.0013 (19)	0.022 (3)
C9	0.052 (3)	0.122 (5)	0.055 (3)	0.008 (3)	0.003 (2)	0.015 (3)
C2	0.038 (2)	0.123 (4)	0.055 (3)	0.018 (2)	0.0015 (19)	0.022 (3)
C6	0.047 (2)	0.103 (4)	0.045 (2)	0.013 (2)	0.0013 (18)	0.017 (2)

Geometric parameters (Å, º) top

Br1—C1	1.902 (4)	C7—C4	1.466 (5)
N1—O2	1.214 (5)	C7—H7	0.9300
N1—O1	1.217 (4)	C4—C3	1.385 (6)
N1—C8	1.488 (5)	C3—C2	1.380 (6)
C8—C7	1.314 (5)	C3—H3	0.9300
C8—C9	1.478 (6)	C9—H9A	0.9600
C1—C2	1.357 (6)	C9—H9B	0.9600
C1—C6	1.366 (6)	C9—H9C	0.9600
C5—C6	1.381 (6)	C2—H2	0.9300
C5—C4	1.388 (5)	C6—H6	0.9300
C5—H5	0.9300

O2—N1—O1	122.1 (4)	C5—C4—C7	117.7 (4)
O2—N1—C8	119.7 (4)	C2—C3—C4	121.6 (4)
O1—N1—C8	118.2 (4)	C2—C3—H3	119.2
C7—C8—C9	130.9 (4)	C4—C3—H3	119.2
C7—C8—N1	115.8 (4)	C8—C9—H9A	109.5
C9—C8—N1	113.2 (3)	C8—C9—H9B	109.5
C2—C1—C6	120.5 (4)	H9A—C9—H9B	109.5
C2—C1—Br1	119.2 (3)	C8—C9—H9C	109.5
C6—C1—Br1	120.3 (3)	H9A—C9—H9C	109.5
C6—C5—C4	121.6 (4)	H9B—C9—H9C	109.5
C6—C5—H5	119.2	C1—C2—C3	119.9 (4)
C4—C5—H5	119.2	C1—C2—H2	120.0
C8—C7—C4	130.1 (4)	C3—C2—H2	120.0
C8—C7—H7	115.0	C1—C6—C5	119.5 (4)
C4—C7—H7	115.0	C1—C6—H6	120.2
C3—C4—C5	116.9 (4)	C5—C6—H6	120.2
C3—C4—C7	125.4 (4)

O2—N1—C8—C7	−4.8 (6)	C8—C7—C4—C5	−173.5 (5)
O1—N1—C8—C7	174.2 (5)	C5—C4—C3—C2	1.5 (8)
O2—N1—C8—C9	176.1 (5)	C7—C4—C3—C2	179.4 (5)
O1—N1—C8—C9	−4.9 (6)	C6—C1—C2—C3	−0.1 (8)
C9—C8—C7—C4	−0.7 (9)	Br1—C1—C2—C3	−179.5 (4)
N1—C8—C7—C4	−179.7 (4)	C4—C3—C2—C1	−0.6 (8)
C6—C5—C4—C3	−1.8 (7)	C2—C1—C6—C5	−0.2 (8)
C6—C5—C4—C7	−179.8 (4)	Br1—C1—C6—C5	179.2 (4)
C8—C7—C4—C3	8.7 (8)	C4—C5—C6—C1	1.1 (8)

Experimental details

Crystal data
Chemical formula	C₉H₈BrNO₂
M_r	242.07
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.9787 (5), 7.4123 (5), 9.7659 (6)
α, β, γ (°)	105.435 (2), 95.087 (2), 104.323 (2)
V (Å³)	465.31 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.38
Crystal size (mm)	0.21 × 0.19 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.388, 0.703
No. of measured, independent and observed [I > 2σ(I)] reflections	4605, 2112, 1303
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.00
No. of reflections	2112
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.71

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

References

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