4-Nitro-N-[(E)-thio­phen-2-yl­methyl­idene]aniline

Abstract

In the title compound, C₁₁H₈N₂O₂S, there is a twist in the mol­ecule, with the dihedral angle between the five- and six-membered rings being 31.77 (9)°. The nitro group is slightly twisted out of the plane of the benzene ring to which it is attached [O—N—C—C torsion angle = 9.0 (3)°]. The S and N atoms are syn. In the crystal, supra­molecular layers parallel to (-204) are formed by C—H⋯O and C—H⋯N inter­actions. These layers are connected into a three-dimensional architecture by π–π inter­actions occurring between centrosymmetrically related benzene rings [centroid–centroid distance = 3.6020 (11) Å].

Related literature  

For background to 2-substituted thio­phenes, see: Kleemann et al. (2006 ▶). For a related structure, see: Asiri et al. (2012 ▶).

Experimental  

Crystal data  

• C₁₁H₈N₂O₂S

• M _r = 232.25

• Monoclinic,

• a = 9.2754 (5) Å

• b = 11.9983 (9) Å

• c = 18.4996 (13) Å

• β = 92.772 (6)°

• V = 2056.4 (2) ų

• Z = 8

• Mo Kα radiation

• μ = 0.30 mm⁻¹

• T = 100 K

• 0.25 × 0.15 × 0.05 mm

Data collection  

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.692, T _max = 1.000

• 8697 measured reflections

• 2377 independent reflections

• 1869 reflections with I > 2σ(I)

• R _int = 0.050

Refinement  

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.111

• S = 1.04

• 2377 reflections

• 145 parameters

• H-atom parameters constrained

• Δρ_max = 0.29 e Å⁻³

• Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812028346/bt5953Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2i	0.95	2.50	3.412 (2)	160
C2—H2⋯N1ii	0.95	2.62	3.556 (2)	169

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Among the various useful properties exhibited by thiophenes are their biological activities (Kleemann et al., 2006). In continuation of structural studies of thienyl derivatives (Asiri et al., 2012), herein the crystal structure determination of the title compound, (4-nitrophenyl)thiophene-2-ylmethylene-amine (I), is described.

In (I), Fig. 1, the conformation about the N1═C5 bond [1.283 (2) Å] is E. A twist in the molecule is evident as seen in the value of the dihedral angle of 31.77 (9)° between the five- and six-membered rings. The major deviation from a planar torsion angle is -37.0 (3)° for C5—N1—C6—C11 indicating that the most significant twist occurs around the N1—C6 bond. The nitro group is slightly inclined with respect to the plane of the benzene ring to which it is attached as seen in the O2—N2—C9—C8 torsion angle of 9.0 (3)°. The S and N atoms are syn.

In the crystal packing, supramolecular layers parallel to (-2 0 4) are formed by C—H···O and C—H···N interactions, Table 1, which lead to 22-membered {···HC₂H···ONC₄N}₂ synthons (Fig 2). Layers aggregate to form a three-dimensional architecture by π—π interactions occurring between centrosymmetrically related benzene rings [inter-centroid distance = 3.6020 (11) Å for symmetry operation 1 - x, 1 - y, 1 - z], Fig. 3.

Experimental

A mixture of thiophen-2-carboxaldehyde (1.1 g, 0.01 M) and p-nitroaniline (1.4 g, 0.0 1M) in ethanol (10 ml) was heated on a water bath for 30 min, the solid which separated out was filtered, dried and recrystallized from ethanol as yellow prisms; M. pt: 375–376 K. Yield: 96%.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C—H = 0.95 Å, U_iso(H) = 1.2U_eq(C)] and were included in the refinement in the riding model approximation.

Figures

Fig. 1.

The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

Fig. 2.

A view of the supramolecular layer in the (-2 0 4) plane in (I) mediated by C—H···O and C—H···N interactions shown as orange and blue dashed lines, respectively.

Fig. 3.

A view in projection down the b axis of the unit-cell contents of (I), showing the stacking of supramolecular layers. The C—H···O, C—H···N and C—H—π interactions are shown as orange, blue and purple dashed lines, respectively.

Crystal data

C11H8N2O2S	F(000) = 960
Mr = 232.25	Dx = 1.500 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2057 reflections
a = 9.2754 (5) Å	θ = 2.8–27.5°
b = 11.9983 (9) Å	µ = 0.30 mm−1
c = 18.4996 (13) Å	T = 100 K
β = 92.772 (6)°	Prism, yellow
V = 2056.4 (2) Å3	0.25 × 0.15 × 0.05 mm
Z = 8

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	2377 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1869 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.050
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.8°
ω scan	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −13→15
Tmin = 0.692, Tmax = 1.000	l = −22→24
8697 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.049P)2 + 1.4742P] where P = (Fo2 + 2Fc2)/3
2377 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.22121 (5)	0.35279 (4)	0.24739 (3)	0.01985 (16)
O1	0.94206 (15)	0.49221 (12)	0.60866 (8)	0.0287 (4)
O2	0.92261 (17)	0.65565 (13)	0.55892 (8)	0.0330 (4)
N1	0.45609 (16)	0.40163 (13)	0.36388 (8)	0.0172 (3)
N2	0.88841 (17)	0.55649 (14)	0.56311 (9)	0.0213 (4)
C1	0.1448 (2)	0.24635 (16)	0.19692 (10)	0.0216 (4)
H1	0.0693	0.2567	0.1610	0.026*
C2	0.2041 (2)	0.14558 (16)	0.21402 (10)	0.0191 (4)
H2	0.1742	0.0776	0.1916	0.023*
C3	0.3151 (2)	0.15307 (15)	0.26874 (10)	0.0178 (4)
H3	0.3687	0.0909	0.2871	0.021*
C4	0.33686 (19)	0.26104 (15)	0.29257 (10)	0.0165 (4)
C5	0.44640 (19)	0.29889 (16)	0.34505 (10)	0.0168 (4)
H5	0.5128	0.2465	0.3661	0.020*
C6	0.56731 (19)	0.43424 (15)	0.41452 (10)	0.0156 (4)
C7	0.6258 (2)	0.54040 (16)	0.40547 (10)	0.0186 (4)
H7	0.5925	0.5852	0.3658	0.022*
C8	0.7316 (2)	0.58087 (16)	0.45373 (10)	0.0195 (4)
H8	0.7716	0.6530	0.4477	0.023*
C9	0.77767 (19)	0.51350 (16)	0.51104 (9)	0.0172 (4)
C10	0.7220 (2)	0.40827 (16)	0.52155 (10)	0.0186 (4)
H10	0.7565	0.3637	0.5612	0.022*
C11	0.6151 (2)	0.36890 (16)	0.47345 (10)	0.0190 (4)
H11	0.5742	0.2974	0.4805	0.023*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0209 (3)	0.0158 (3)	0.0223 (3)	0.00164 (19)	−0.00515 (19)	−0.00144 (18)
O1	0.0258 (8)	0.0328 (9)	0.0264 (8)	0.0027 (7)	−0.0107 (6)	0.0029 (6)
O2	0.0361 (9)	0.0281 (9)	0.0334 (9)	−0.0135 (7)	−0.0118 (7)	0.0019 (7)
N1	0.0164 (8)	0.0180 (8)	0.0169 (8)	−0.0001 (6)	−0.0022 (6)	−0.0005 (6)
N2	0.0182 (8)	0.0258 (10)	0.0196 (9)	−0.0014 (7)	−0.0017 (7)	−0.0019 (7)
C1	0.0191 (10)	0.0246 (11)	0.0203 (10)	−0.0014 (8)	−0.0060 (8)	−0.0028 (8)
C2	0.0213 (10)	0.0182 (10)	0.0175 (10)	−0.0024 (8)	−0.0015 (8)	−0.0021 (7)
C3	0.0190 (9)	0.0158 (10)	0.0183 (9)	0.0004 (7)	−0.0019 (7)	0.0011 (7)
C4	0.0160 (9)	0.0173 (9)	0.0160 (9)	0.0010 (7)	−0.0002 (7)	0.0003 (7)
C5	0.0161 (9)	0.0183 (10)	0.0161 (9)	0.0014 (8)	−0.0002 (7)	0.0023 (7)
C6	0.0133 (8)	0.0174 (9)	0.0160 (9)	0.0012 (7)	−0.0003 (7)	−0.0033 (7)
C7	0.0176 (9)	0.0203 (10)	0.0176 (9)	0.0011 (8)	−0.0008 (7)	0.0040 (7)
C8	0.0189 (9)	0.0181 (10)	0.0214 (10)	−0.0040 (8)	−0.0003 (8)	0.0006 (7)
C9	0.0124 (9)	0.0243 (10)	0.0148 (9)	−0.0006 (7)	−0.0009 (7)	−0.0035 (7)
C10	0.0202 (9)	0.0190 (10)	0.0165 (9)	0.0016 (8)	−0.0014 (7)	0.0008 (7)
C11	0.0220 (10)	0.0165 (9)	0.0184 (10)	−0.0003 (8)	−0.0001 (8)	−0.0005 (7)

Geometric parameters (Å, º)

S1—C1	1.7150 (19)	C4—C5	1.444 (2)
S1—C4	1.7246 (18)	C5—H5	0.9500
O1—N2	1.230 (2)	C6—C11	1.398 (3)
O2—N2	1.235 (2)	C6—C7	1.397 (3)
N1—C5	1.283 (2)	C7—C8	1.382 (3)
N1—C6	1.415 (2)	C7—H7	0.9500
N2—C9	1.467 (2)	C8—C9	1.384 (3)
C1—C2	1.359 (3)	C8—H8	0.9500
C1—H1	0.9500	C9—C10	1.382 (3)
C2—C3	1.411 (3)	C10—C11	1.383 (3)
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.380 (3)	C11—H11	0.9500
C3—H3	0.9500
C1—S1—C4	91.13 (9)	C4—C5—H5	119.3
C5—N1—C6	119.00 (16)	C11—C6—C7	119.63 (17)
O1—N2—O2	123.41 (16)	C11—C6—N1	123.71 (17)
O1—N2—C9	118.47 (16)	C7—C6—N1	116.58 (16)
O2—N2—C9	118.12 (16)	C8—C7—C6	120.68 (17)
C2—C1—S1	112.55 (15)	C8—C7—H7	119.7
C2—C1—H1	123.7	C6—C7—H7	119.7
S1—C1—H1	123.7	C7—C8—C9	118.21 (17)
C1—C2—C3	112.54 (17)	C7—C8—H8	120.9
C1—C2—H2	123.7	C9—C8—H8	120.9
C3—C2—H2	123.7	C10—C9—C8	122.53 (17)
C4—C3—C2	112.28 (17)	C10—C9—N2	118.91 (16)
C4—C3—H3	123.9	C8—C9—N2	118.56 (17)
C2—C3—H3	123.9	C9—C10—C11	118.88 (18)
C3—C4—C5	126.67 (18)	C9—C10—H10	120.6
C3—C4—S1	111.50 (14)	C11—C10—H10	120.6
C5—C4—S1	121.73 (14)	C10—C11—C6	120.05 (18)
N1—C5—C4	121.49 (17)	C10—C11—H11	120.0
N1—C5—H5	119.3	C6—C11—H11	120.0
C4—S1—C1—C2	0.33 (16)	N1—C6—C7—C8	177.85 (16)
S1—C1—C2—C3	−0.5 (2)	C6—C7—C8—C9	0.0 (3)
C1—C2—C3—C4	0.5 (2)	C7—C8—C9—C10	−0.1 (3)
C2—C3—C4—C5	−176.49 (17)	C7—C8—C9—N2	−179.10 (16)
C2—C3—C4—S1	−0.2 (2)	O1—N2—C9—C10	9.7 (3)
C1—S1—C4—C3	−0.06 (15)	O2—N2—C9—C10	−170.11 (18)
C1—S1—C4—C5	176.43 (16)	O1—N2—C9—C8	−171.17 (17)
C6—N1—C5—C4	−178.81 (16)	O2—N2—C9—C8	9.0 (3)
C3—C4—C5—N1	−179.32 (19)	C8—C9—C10—C11	−0.6 (3)
S1—C4—C5—N1	4.7 (3)	N2—C9—C10—C11	178.44 (16)
C5—N1—C6—C11	−37.0 (3)	C9—C10—C11—C6	1.3 (3)
C5—N1—C6—C7	146.04 (18)	C7—C6—C11—C10	−1.4 (3)
C11—C6—C7—C8	0.8 (3)	N1—C6—C11—C10	−178.30 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2i	0.95	2.50	3.412 (2)	160
C2—H2···N1ii	0.95	2.62	3.556 (2)	169

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