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Acta Cryst. (2011). E67, o983    [ doi:10.1107/S1600536811010622 ]

(E)-2-(2-Nitroprop-1-enyl)thiophene

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

Abstract top

The title compound, C7H7NO2S, adopts an E conformation about the C=C bond. The torsion angle C=C-C-C is -177.7 (3)°. The crystal structure features weak intermolecular by C-H...O interactions.

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 crystal structure of the title compound. The C2═C3 bond involves the E configuration with the C2—C3—C4—C5 torsion angle of 177.71 (3)° (Fig. 1). The atoms of the thiophene ring are coplanar. The conformation of (I) is stabilized by weak intermolecular by C6—H6···O2' interaction (Fig. 2 and Table 1).

Related literature top

For the use of nitroalkenes as organic intermediates, see: Ballini & Petrini (2004); Berner et al. (2002); Ono (2001).

Experimental top

To a solution of thiophene-2-carbaldehyde (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 an cyclohexane-EtOAc solution (10:1, v/v).

Refinement top

All H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93–0.96 Å, and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku Americas and 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
[Figure 1] Fig. 1. The asymmetric unit of the title compound with the atomic labeling scheme; displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The view of intermolecular interaction illustrated as dash lines.
(E)-2-(2-Nitroprop-1-enyl)thiophene top
Crystal data top
C7H7NO2SF(000) = 352
Mr = 169.20Dx = 1.429 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3534 reflections
a = 6.7545 (6) Åθ = 3.2–27.4°
b = 16.6940 (13) ŵ = 0.36 mm−1
c = 7.4527 (4) ÅT = 296 K
β = 110.640 (7)°Prism, yellow
V = 786.42 (10) Å30.31 × 0.18 × 0.17 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1362 independent reflections
Radiation source: rolling anode971 reflections with I > 2σ(I)
graphiteRint = 0.035
Detector resolution: 10.00 pixels mm-1θmax = 25.0°, θmin = 3.2°
ω scansh = −7→8
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −19→19
Tmin = 0.879, Tmax = 0.942l = −8→8
5936 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.170 w = 1/[σ2(Fo2) + (0.0837P)2 + 0.8184P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
1362 reflectionsΔρmax = 0.39 e Å−3
102 parametersΔρmin = −0.33 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0067 (6)
Crystal data top
C7H7NO2SV = 786.42 (10) Å3
Mr = 169.20Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.7545 (6) ŵ = 0.36 mm−1
b = 16.6940 (13) ÅT = 296 K
c = 7.4527 (4) Å0.31 × 0.18 × 0.17 mm
β = 110.640 (7)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1362 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		971 reflections with I > 2σ(I)
Tmin = 0.879, Tmax = 0.942Rint = 0.035
5936 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.170Δρmax = 0.39 e Å−3
S = 1.00Δρmin = −0.33 e Å−3
1362 reflectionsAbsolute structure: ?
102 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
S10.21787 (15)0.56891 (6)0.61453 (16)0.0684 (5)
C40.4914 (5)0.5654 (2)0.7041 (5)0.0496 (8)
C30.6192 (5)0.4976 (2)0.7933 (4)0.0500 (8)
H30.76440.50670.83730.060*
N10.7349 (5)0.36806 (18)0.9203 (4)0.0584 (8)
O20.9190 (4)0.39008 (17)0.9632 (5)0.0775 (9)
C20.5624 (5)0.4238 (2)0.8227 (5)0.0493 (8)
O10.6885 (5)0.30107 (17)0.9578 (5)0.0832 (9)
C50.5793 (6)0.64019 (19)0.6781 (5)0.0512 (8)
H50.72300.65150.71500.061*
C10.3450 (6)0.3888 (2)0.7708 (6)0.0652 (10)
H1A0.29750.39410.87750.098*
H1B0.34870.33320.73980.098*
H1C0.24960.41680.66210.098*
C70.2176 (6)0.6653 (2)0.5463 (6)0.0698 (11)
H70.09480.69470.48690.084*
C60.4120 (6)0.6951 (2)0.5863 (6)0.0675 (11)
H60.43650.74750.55680.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0499 (6)0.0587 (7)0.0895 (8)−0.0017 (4)0.0158 (5)0.0006 (5)
C40.0447 (19)0.051 (2)0.0507 (19)−0.0015 (14)0.0131 (15)−0.0040 (14)
C30.0419 (17)0.052 (2)0.052 (2)−0.0039 (14)0.0124 (15)−0.0078 (15)
N10.0557 (19)0.0507 (19)0.0660 (19)0.0060 (14)0.0180 (15)0.0000 (14)
O20.0474 (15)0.0661 (18)0.107 (2)0.0055 (12)0.0125 (15)0.0016 (16)
C20.0468 (18)0.0464 (19)0.0532 (19)0.0018 (14)0.0157 (15)−0.0040 (14)
O10.079 (2)0.0533 (17)0.118 (3)0.0078 (14)0.0349 (18)0.0175 (16)
C50.056 (2)0.0418 (18)0.0499 (19)0.0022 (14)0.0116 (15)0.0006 (14)
C10.054 (2)0.056 (2)0.082 (3)−0.0085 (17)0.0198 (19)0.0007 (19)
C70.058 (2)0.058 (2)0.083 (3)0.0100 (18)0.012 (2)0.002 (2)
C60.074 (3)0.047 (2)0.076 (3)−0.0032 (18)0.019 (2)0.0038 (18)
Geometric parameters (Å, °) top
S1—C71.688 (4)C2—C11.499 (5)
S1—C41.730 (3)C5—C61.429 (5)
C4—C51.425 (5)C5—H50.9300
C4—C31.436 (5)C1—H1A0.9600
C3—C21.331 (5)C1—H1B0.9600
C3—H30.9300C1—H1C0.9600
N1—O11.220 (4)C7—C61.336 (5)
N1—O21.226 (4)C7—H70.9300
N1—C21.469 (4)C6—H60.9300
C7—S1—C492.09 (18)C4—C5—H5125.4
C5—C4—C3122.8 (3)C6—C5—H5125.4
C5—C4—S1110.9 (2)C2—C1—H1A109.5
C3—C4—S1126.3 (3)C2—C1—H1B109.5
C2—C3—C4130.0 (3)H1A—C1—H1B109.5
C2—C3—H3115.0C2—C1—H1C109.5
C4—C3—H3115.0H1A—C1—H1C109.5
O1—N1—O2122.3 (3)H1B—C1—H1C109.5
O1—N1—C2118.1 (3)C6—C7—S1113.0 (3)
O2—N1—C2119.6 (3)C6—C7—H7123.5
C3—C2—N1116.3 (3)S1—C7—H7123.5
C3—C2—C1129.2 (3)C7—C6—C5114.7 (4)
N1—C2—C1114.5 (3)C7—C6—H6122.7
C4—C5—C6109.3 (3)C5—C6—H6122.7
C7—S1—C4—C5−0.3 (3)O1—N1—C2—C1−3.2 (5)
C7—S1—C4—C3179.8 (3)O2—N1—C2—C1177.6 (3)
C5—C4—C3—C2−177.7 (3)C3—C4—C5—C6−179.8 (3)
S1—C4—C3—C22.1 (6)S1—C4—C5—C60.3 (4)
C4—C3—C2—N1−179.7 (3)C4—S1—C7—C60.2 (4)
C4—C3—C2—C10.0 (6)S1—C7—C6—C5−0.1 (5)
O1—N1—C2—C3176.6 (3)C4—C5—C6—C7−0.2 (5)
O2—N1—C2—C3−2.6 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.603.511 (5)168
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.603.511 (5)168
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2.
Acknowledgements top

The authors are grateful to Mr Jianming Gu for the crystal analysis. what analysis exactly?

references
References top

Ballini, R. & Petrini, M. (2004). Tetrahedron, 60, 1017–1047.

Berner, O. M., Tedeschi, L. & Enders, D. (2002). Eur. J. Org. Chem. 12, 1877–1894.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Ono, N. (2001). The Nitro Group in Organic Synthesis. New York: Wiley-VCH.

Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku Americas and Rigaku (2007). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.