(E)-1-Nitro-2-(2-nitro­prop-1-en­yl)benzene

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

doi:10.1107/S1600536812029947

organic compounds

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Volume 68| Part 8| August 2012| Page o2359

https://doi.org/10.1107/S1600536812029947

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(E)-1-Nitro-2-(2-nitroprop-1-enyl)benzene

Li-Li Shen,^a Zhao-Bo Li ^b,^c ^* and Jia-Jia Li ^d

^aZhejiang University of Technology, Hangzhou 310014, 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, ^cHangzhou Minsheng Pharmaceutical Group Co. Ltd, Hangzhou 310000, People's Republic of China, and ^dHangzhou Radio and Television University, Hangzhou 310000, People's Republic of China
^*Correspondence e-mail: boyzb@163.com

(Received 30 June 2012; accepted 1 July 2012; online 7 July 2012)

The title compound, C₉H₈N₂O₄, adopts an E conformation about the C=C bond. The CH_phenyl—C_phenyl—CH—C(—NO₂) torsion angle is −57.7 (3)°. The crystal structure features weak intermolecular C—H⋯O interactions.

Related literature

For background to nitroalkenes, see: Ballini & Petrini (2004 ); Berner et al. (2002 ); Ono (2001 ).

Experimental

Crystal data

C₉H₈N₂O₄
M_r = 208.17
Monoclinic, P 2₁ /n
a = 6.8274 (9) Å
b = 15.5666 (12) Å
c = 9.9045 (10) Å
β = 113.202 (3)°
V = 967.51 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.58 × 0.46 × 0.32 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.932, T_max = 0.964
7450 measured reflections
1736 independent reflections
1193 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.135
S = 1.00
1736 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O3ⁱ	0.93	2.60	3.163 (5)	119
C9—H9A⋯O2ⁱⁱ	0.96	2.70	3.403 (4)	131
Symmetry codes: (i) x-1, y, z-1; (ii) x+1, y, z.

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (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 datablocks I, global. DOI: https://doi.org/10.1107/S1600536812029947/ng5280sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029947/ng5280Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812029947/ng5280Isup3.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. We report here one of this nitroalkenes, i.e. the title compound. The C7═C8 bond involves the E configuration with the C3—C2—C7—C8 torsion angle of -57.7 (3)° (Fig. 1). The conformation of (I) is stabilized by weak intermolecular C6—H6···O3'and C9—H9A···O2' interactions (Fig. 2 and Table 1).

Related literature top

For background to nitroalkenes, see: Ballini & Petrini (2004); Berner et al. (2002); Ono (2001).

Experimental top

To a solution of 2-nitrobenzaldehyde (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 product. Single crystals were obtained by slow evaporation of a EtOH solution of the compound.

Structure description top

For background to nitroalkenes, see: Ballini & Petrini (2004); Berner et al. (2002); Ono (2001).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (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. The view of intermolecular interactions illustrated as dash lines.

(E)-1-Nitro-2-(2-nitroprop-1-enyl)benzene top

Crystal data top

C₉H₈N₂O₄	F(000) = 432
M_r = 208.17	D_x = 1.429 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5183 reflections
a = 6.8274 (9) Å	θ = 3.2–27.5°
b = 15.5666 (12) Å	µ = 0.12 mm⁻¹
c = 9.9045 (10) Å	T = 296 K
β = 113.202 (3)°	Chunk, yellow
V = 967.51 (18) Å³	0.58 × 0.46 × 0.32 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	1736 independent reflections
Radiation source: rotating anode	1193 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.2°, θ_min = 3.4°
ω scans	h = −7→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −18→18
T_min = 0.932, T_max = 0.964	l = −11→11
7450 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)] = 0.059	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.019P)² + 0.5218P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1736 reflections	Δρ_max = 0.26 e Å⁻³
138 parameters	Δρ_min = −0.21 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: 0.170 (12)

Crystal data top

C₉H₈N₂O₄	V = 967.51 (18) Å³
M_r = 208.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8274 (9) Å	µ = 0.12 mm⁻¹
b = 15.5666 (12) Å	T = 296 K
c = 9.9045 (10) Å	0.58 × 0.46 × 0.32 mm
β = 113.202 (3)°

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	1736 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1193 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.964	R_int = 0.072
7450 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
1736 reflections	Δρ_min = −0.21 e Å⁻³
138 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	0.5466 (4)	0.10207 (16)	0.2728 (3)	0.0619 (6)
C2	0.7192 (4)	0.14601 (15)	0.3747 (3)	0.0601 (6)
C3	0.8689 (4)	0.17747 (17)	0.3231 (3)	0.0709 (7)
H3	0.9876	0.2069	0.3873	0.085*
C4	0.8450 (5)	0.16585 (18)	0.1791 (3)	0.0774 (8)
H4	0.9474	0.1873	0.1480	0.093*
C5	0.6713 (5)	0.12290 (18)	0.0817 (3)	0.0782 (8)
H5	0.6548	0.1159	−0.0154	0.094*
C6	0.5215 (4)	0.09026 (17)	0.1286 (3)	0.0713 (7)
H6	0.4042	0.0604	0.0637	0.086*
C7	0.7489 (4)	0.16389 (15)	0.5287 (3)	0.0633 (7)
H7	0.6399	0.1925	0.5440	0.076*
C8	0.9185 (4)	0.14215 (15)	0.6453 (3)	0.0597 (6)
C9	1.1075 (4)	0.09071 (19)	0.6571 (3)	0.0789 (8)
H9A	1.0943	0.0736	0.5608	0.118*
H9B	1.1164	0.0405	0.7156	0.118*
H9C	1.2339	0.1247	0.7026	0.118*
N1	0.3819 (4)	0.06343 (17)	0.3147 (3)	0.0799 (7)
N2	0.9179 (4)	0.16809 (14)	0.7890 (2)	0.0702 (6)
O1	0.2593 (4)	0.01245 (18)	0.2313 (3)	0.1285 (10)
O2	0.3754 (4)	0.08268 (17)	0.4315 (3)	0.1097 (8)
O3	1.0659 (3)	0.14555 (14)	0.8995 (2)	0.0925 (7)
O4	0.7722 (4)	0.21184 (15)	0.7936 (2)	0.1023 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0613 (14)	0.0631 (15)	0.0609 (15)	0.0036 (12)	0.0238 (12)	0.0103 (11)
C2	0.0654 (14)	0.0611 (14)	0.0548 (13)	0.0078 (12)	0.0248 (12)	0.0053 (11)
C3	0.0736 (16)	0.0778 (17)	0.0626 (16)	−0.0069 (14)	0.0282 (13)	−0.0023 (13)
C4	0.0854 (18)	0.089 (2)	0.0661 (16)	−0.0078 (15)	0.0387 (15)	0.0021 (14)
C5	0.093 (2)	0.0868 (19)	0.0555 (15)	0.0000 (16)	0.0296 (15)	0.0035 (13)
C6	0.0718 (16)	0.0734 (17)	0.0591 (16)	0.0003 (13)	0.0155 (13)	0.0031 (13)
C7	0.0715 (15)	0.0649 (15)	0.0604 (15)	0.0069 (12)	0.0335 (13)	0.0019 (12)
C8	0.0699 (15)	0.0588 (14)	0.0530 (14)	−0.0005 (12)	0.0271 (12)	−0.0022 (11)
C9	0.0728 (17)	0.089 (2)	0.0725 (17)	0.0113 (14)	0.0258 (14)	−0.0033 (14)
N1	0.0720 (15)	0.0871 (17)	0.0793 (17)	−0.0004 (13)	0.0284 (13)	0.0154 (13)
N2	0.0839 (15)	0.0681 (14)	0.0606 (13)	0.0013 (12)	0.0305 (12)	−0.0016 (10)
O1	0.1249 (18)	0.146 (2)	0.1092 (19)	−0.0697 (18)	0.0400 (15)	−0.0081 (16)
O2	0.1001 (16)	0.144 (2)	0.1069 (18)	−0.0120 (14)	0.0642 (14)	−0.0012 (15)
O3	0.0962 (14)	0.1094 (16)	0.0554 (11)	0.0055 (12)	0.0120 (10)	−0.0029 (10)
O4	0.1208 (17)	0.1218 (18)	0.0747 (13)	0.0400 (15)	0.0497 (13)	0.0037 (12)

Geometric parameters (Å, º) top

C1—C6	1.382 (3)	C7—C8	1.318 (3)
C1—C2	1.392 (3)	C7—H7	0.9300
C1—N1	1.472 (3)	C8—C9	1.483 (3)
C2—C3	1.400 (3)	C8—N2	1.481 (3)
C2—C7	1.483 (3)	C9—H9A	0.9600
C3—C4	1.381 (3)	C9—H9B	0.9600
C3—H3	0.9300	C9—H9C	0.9600
C4—C5	1.372 (4)	N1—O1	1.212 (3)
C4—H4	0.9300	N1—O2	1.212 (3)
C5—C6	1.376 (4)	N2—O3	1.212 (3)
C5—H5	0.9300	N2—O4	1.221 (3)
C6—H6	0.9300

C6—C1—C2	122.6 (2)	C8—C7—C2	124.8 (2)
C6—C1—N1	116.1 (2)	C8—C7—H7	117.6
C2—C1—N1	121.3 (2)	C2—C7—H7	117.6
C3—C2—C1	116.0 (2)	C7—C8—C9	130.1 (2)
C3—C2—C7	119.1 (2)	C7—C8—N2	116.0 (2)
C1—C2—C7	124.8 (2)	C9—C8—N2	113.8 (2)
C4—C3—C2	121.7 (2)	C8—C9—H9A	109.5
C4—C3—H3	119.2	C8—C9—H9B	109.5
C2—C3—H3	119.2	H9A—C9—H9B	109.5
C5—C4—C3	120.5 (3)	C8—C9—H9C	109.5
C5—C4—H4	119.8	H9A—C9—H9C	109.5
C3—C4—H4	119.8	H9B—C9—H9C	109.5
C6—C5—C4	119.6 (2)	O1—N1—O2	122.5 (3)
C6—C5—H5	120.2	O1—N1—C1	118.3 (3)
C4—C5—H5	120.2	O2—N1—C1	119.1 (3)
C5—C6—C1	119.6 (2)	O3—N2—O4	122.0 (2)
C5—C6—H6	120.2	O3—N2—C8	118.1 (2)
C1—C6—H6	120.2	O4—N2—C8	119.9 (2)

C6—C1—C2—C3	−0.5 (4)	C1—C2—C7—C8	124.7 (3)
N1—C1—C2—C3	178.0 (2)	C2—C7—C8—C9	−5.5 (4)
C6—C1—C2—C7	177.1 (2)	C2—C7—C8—N2	178.6 (2)
N1—C1—C2—C7	−4.4 (4)	C6—C1—N1—O1	12.6 (4)
C1—C2—C3—C4	0.4 (4)	C2—C1—N1—O1	−166.0 (3)
C7—C2—C3—C4	−177.3 (2)	C6—C1—N1—O2	−168.4 (2)
C2—C3—C4—C5	0.2 (4)	C2—C1—N1—O2	13.1 (4)
C3—C4—C5—C6	−0.9 (4)	C7—C8—N2—O3	176.3 (2)
C4—C5—C6—C1	0.8 (4)	C9—C8—N2—O3	−0.3 (3)
C2—C1—C6—C5	−0.1 (4)	C7—C8—N2—O4	−4.6 (3)
N1—C1—C6—C5	−178.6 (2)	C9—C8—N2—O4	178.8 (2)
C3—C2—C7—C8	−57.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3ⁱ	0.93	2.60	3.163 (5)	119
C9—H9A···O2ⁱⁱ	0.96	2.70	3.403 (4)	131

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

Experimental details

Crystal data
Chemical formula	C₉H₈N₂O₄
M_r	208.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.8274 (9), 15.5666 (12), 9.9045 (10)
β (°)	113.202 (3)
V (Å³)	967.51 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.58 × 0.46 × 0.32

Data collection
Diffractometer	Rigaku R-AXIS RAPID/ZJUG
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.932, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	7450, 1736, 1193
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.135, 1.00
No. of reflections	1736
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (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
C6—H6···O3ⁱ	0.93	2.603	3.163 (5)	119
C9—H9A···O2ⁱⁱ	0.96	2.698	3.403 (4)	131

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

Acknowledgements

The authors are grateful to Mr Jianming Gu for the crystal 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 (grant No. GCTKF2012010).

References

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