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

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

doi:10.1107/S1600536811010622

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o983

doi:10.1107/S1600536811010622

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

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

^aHangzhou Minsheng Pharmaceutical Group Co. Ltd, Hangzhou 310000, People's Republic of China, ^bZhejiang University of Technology, Hangzhou 310000, People's Republic of China, and ^cHangzhou Radio & TV University, Hangzhou 310000, People's Republic of China
^*Correspondence e-mail: lzb@hz.cn

(Received 15 March 2011; accepted 22 March 2011; online 26 March 2011)

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.

Related literature

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

Experimental

Crystal data

C₇H₇NO₂S
M_r = 169.20
Monoclinic, P 2₁ /n
a = 6.7545 (6) Å
b = 16.6940 (13) Å
c = 7.4527 (4) Å
β = 110.640 (7)°
V = 786.42 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 296 K
0.31 × 0.18 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.879, T_max = 0.942
5936 measured reflections
1362 independent reflections
971 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.170
S = 1.00
1362 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.60	3.511 (5)	168
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811010622/jh2274sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010622/jh2274Isup2.hkl

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 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).

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

	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 interaction illustrated as dash lines.

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

Crystal data top

C₇H₇NO₂S	F(000) = 352
M_r = 169.20	D_x = 1.429 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3534 reflections
a = 6.7545 (6) Å	θ = 3.2–27.4°
b = 16.6940 (13) Å	µ = 0.36 mm⁻¹
c = 7.4527 (4) Å	T = 296 K
β = 110.640 (7)°	Prism, yellow
V = 786.42 (10) Å³	0.31 × 0.18 × 0.17 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1362 independent reflections
Radiation source: rolling anode	971 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
ω scans	h = −7→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −19→19
T_min = 0.879, T_max = 0.942	l = −8→8
5936 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)] = 0.049	H-atom parameters constrained
wR(F²) = 0.170	w = 1/[σ²(F_o²) + (0.0837P)² + 0.8184P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
1362 reflections	Δρ_max = 0.39 e Å⁻³
102 parameters	Δρ_min = −0.33 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: 0.0067 (6)

Crystal data top

C₇H₇NO₂S	V = 786.42 (10) Å³
M_r = 169.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7545 (6) Å	µ = 0.36 mm⁻¹
b = 16.6940 (13) Å	T = 296 K
c = 7.4527 (4) Å	0.31 × 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)
T_min = 0.879, T_max = 0.942	R_int = 0.035
5936 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.00	Δρ_max = 0.39 e Å⁻³
1362 reflections	Δρ_min = −0.33 e Å⁻³
102 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
S1	0.21787 (15)	0.56891 (6)	0.61453 (16)	0.0684 (5)
C4	0.4914 (5)	0.5654 (2)	0.7041 (5)	0.0496 (8)
C3	0.6192 (5)	0.4976 (2)	0.7933 (4)	0.0500 (8)
H3	0.7644	0.5067	0.8373	0.060*
N1	0.7349 (5)	0.36806 (18)	0.9203 (4)	0.0584 (8)
O2	0.9190 (4)	0.39008 (17)	0.9632 (5)	0.0775 (9)
C2	0.5624 (5)	0.4238 (2)	0.8227 (5)	0.0493 (8)
O1	0.6885 (5)	0.30107 (17)	0.9578 (5)	0.0832 (9)
C5	0.5793 (6)	0.64019 (19)	0.6781 (5)	0.0512 (8)
H5	0.7230	0.6515	0.7150	0.061*
C1	0.3450 (6)	0.3888 (2)	0.7708 (6)	0.0652 (10)
H1A	0.2975	0.3941	0.8775	0.098*
H1B	0.3487	0.3332	0.7398	0.098*
H1C	0.2496	0.4168	0.6621	0.098*
C7	0.2176 (6)	0.6653 (2)	0.5463 (6)	0.0698 (11)
H7	0.0948	0.6947	0.4869	0.084*
C6	0.4120 (6)	0.6951 (2)	0.5863 (6)	0.0675 (11)
H6	0.4365	0.7475	0.5568	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0499 (6)	0.0587 (7)	0.0895 (8)	−0.0017 (4)	0.0158 (5)	0.0006 (5)
C4	0.0447 (19)	0.051 (2)	0.0507 (19)	−0.0015 (14)	0.0131 (15)	−0.0040 (14)
C3	0.0419 (17)	0.052 (2)	0.052 (2)	−0.0039 (14)	0.0124 (15)	−0.0078 (15)
N1	0.0557 (19)	0.0507 (19)	0.0660 (19)	0.0060 (14)	0.0180 (15)	0.0000 (14)
O2	0.0474 (15)	0.0661 (18)	0.107 (2)	0.0055 (12)	0.0125 (15)	0.0016 (16)
C2	0.0468 (18)	0.0464 (19)	0.0532 (19)	0.0018 (14)	0.0157 (15)	−0.0040 (14)
O1	0.079 (2)	0.0533 (17)	0.118 (3)	0.0078 (14)	0.0349 (18)	0.0175 (16)
C5	0.056 (2)	0.0418 (18)	0.0499 (19)	0.0022 (14)	0.0116 (15)	0.0006 (14)
C1	0.054 (2)	0.056 (2)	0.082 (3)	−0.0085 (17)	0.0198 (19)	0.0007 (19)
C7	0.058 (2)	0.058 (2)	0.083 (3)	0.0100 (18)	0.012 (2)	0.002 (2)
C6	0.074 (3)	0.047 (2)	0.076 (3)	−0.0032 (18)	0.019 (2)	0.0038 (18)

Geometric parameters (Å, º) top

S1—C7	1.688 (4)	C2—C1	1.499 (5)
S1—C4	1.730 (3)	C5—C6	1.429 (5)
C4—C5	1.425 (5)	C5—H5	0.9300
C4—C3	1.436 (5)	C1—H1A	0.9600
C3—C2	1.331 (5)	C1—H1B	0.9600
C3—H3	0.9300	C1—H1C	0.9600
N1—O1	1.220 (4)	C7—C6	1.336 (5)
N1—O2	1.226 (4)	C7—H7	0.9300
N1—C2	1.469 (4)	C6—H6	0.9300

C7—S1—C4	92.09 (18)	C4—C5—H5	125.4
C5—C4—C3	122.8 (3)	C6—C5—H5	125.4
C5—C4—S1	110.9 (2)	C2—C1—H1A	109.5
C3—C4—S1	126.3 (3)	C2—C1—H1B	109.5
C2—C3—C4	130.0 (3)	H1A—C1—H1B	109.5
C2—C3—H3	115.0	C2—C1—H1C	109.5
C4—C3—H3	115.0	H1A—C1—H1C	109.5
O1—N1—O2	122.3 (3)	H1B—C1—H1C	109.5
O1—N1—C2	118.1 (3)	C6—C7—S1	113.0 (3)
O2—N1—C2	119.6 (3)	C6—C7—H7	123.5
C3—C2—N1	116.3 (3)	S1—C7—H7	123.5
C3—C2—C1	129.2 (3)	C7—C6—C5	114.7 (4)
N1—C2—C1	114.5 (3)	C7—C6—H6	122.7
C4—C5—C6	109.3 (3)	C5—C6—H6	122.7

C7—S1—C4—C5	−0.3 (3)	O1—N1—C2—C1	−3.2 (5)
C7—S1—C4—C3	179.8 (3)	O2—N1—C2—C1	177.6 (3)
C5—C4—C3—C2	−177.7 (3)	C3—C4—C5—C6	−179.8 (3)
S1—C4—C3—C2	2.1 (6)	S1—C4—C5—C6	0.3 (4)
C4—C3—C2—N1	−179.7 (3)	C4—S1—C7—C6	0.2 (4)
C4—C3—C2—C1	0.0 (6)	S1—C7—C6—C5	−0.1 (5)
O1—N1—C2—C3	176.6 (3)	C4—C5—C6—C7	−0.2 (5)
O2—N1—C2—C3	−2.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.60	3.511 (5)	168

Symmetry code: (i) −x+3/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₇H₇NO₂S
M_r	169.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.7545 (6), 16.6940 (13), 7.4527 (4)
β (°)	110.640 (7)
V (Å³)	786.42 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.31 × 0.18 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.879, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	5936, 1362, 971
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.170, 1.00
No. of reflections	1362
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.33

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku Americas and 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···O2ⁱ	0.930	2.597	3.511 (5)	168

Symmetry code: (i) −x+3/2, y+1/2, −z+3/2.

Acknowledgements

The authors are grateful to Mr Jianming Gu for the X-ray single crystal analysis.

References

Ballini, R. & Petrini, M. (2004). Tetrahedron, 60, 1017–1047. Web of Science CrossRef CAS Google Scholar
Berner, O. M., Tedeschi, L. & Enders, D. (2002). Eur. J. Org. Chem. 12, 1877–1894. CrossRef Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ono, N. (2001). The Nitro Group in Organic Synthesis. New York: Wiley-VCH. Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku Americas and Rigaku (2007). CrystalStructure. Rigaku Americas, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar