(E)-1-(5-Methyl­thio­phen-2-yl)-N-(4-nitro­phen­yl)methanimine

Alicea-Velázquez, N.L.; Crundwell, G.

doi:10.1107/S2414314619016018

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 12| December 2019| x191601

https://doi.org/10.1107/S2414314619016018

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(E)-1-(5-Methylthiophen-2-yl)-N-(4-nitrophenyl)methanimine

Nilda L. Alicea-Velázquez ^a and Guy Crundwell ^a ^*

^aDepartment of Chemistry & Biochemistry, Central Connecticut State University, 1619 Stanley Street, New Britain, CT 06053, USA
^*Correspondence e-mail: crundwellg@ccsu.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 November 2019; accepted 27 November 2019; online 3 December 2019)

The title compound, C₁₂H₁₀N₂O₂S, was synthesized via the acid-catalyzed condensation of 4-nitroaniline and 5-methyl-2-thiophenecarboxaldehyde in a methanol–water solution. The dihedral angle between the benzene and thiophene rings is 54.62 (3)°. No directional interactions could be identified in the extended structure.

Keywords: crystal structure; imine; thiophene.

CCDC reference: 1968444

Structure description

The molecular structure of the title compound is shown in Fig. 1. The methylthiophene group makes a dihedral angle of 54.62 (3)° with respect to the plane defined by the nitroaniline ring. Within the aniline ring, the nitro group is nearly coplanar with the phenyl ring [C9—C10—N2—O2 = 3.47 (4)°]. This slight twist of the nitro group is not as large as the 9.0 (3)° angle in (E)-N-(4-nitrophenyl)-1-(thiophen-2-yl)methanimine (Asiri et al., 2012 ). In the extended structure, no significant intermolecular interactions occur. A view of the unit cell along [010] is shown in Fig. 2.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Figure 2
A view of the unit-cell packing along [010].

Synthesis and crystallization

In a 50-ml Erlenmeyer flask, 1.26 g of 5-methyl-2-thiophene carboxaldehyde (10.0 mmol) were added to a solution of 10 ml of H₂O and 20 ml of a 2.5 mmol l⁻¹ solution of NH₄HF₂ in methanol (Lassagne et al., 2015 ). After swirling the solution to mix the liquids, 1.38 g (10.0 mmol) of 4-nitroaniline were added. The solution was stirred for 24 h even though a yellow precipitate had formed after 4 h. The resulting solid was filtered and washed with cold water then dried (2.03 g; 82%). Crystals were grown from CH₂Cl₂ solutions. Data: m.p. 429 K; ¹H NMR (CDCl₃, 300 MHz): δ = 2.59 (s, 3H), 6.86 (dd, 1H), 7.26 (m, 2H), 7.39 (d, 1H), 8.26 (m, 2H), 8.46 (s, 1H); ¹³C NMR (CDCl₃, 300 MHz): δ = 16.1, 121.5, 125.0, 126.7, 134.6, 139.8, 145.4, 148.1, 155.1, 157.4; ATR FTIR (cm⁻¹): 3398 (w), 2438 (s), 1610 (s), 1598 (s), 1503 (s), 1406 (s), 1198 (s), 1163 (s), 1106 (s), 1054 (s), 967 (s), 870 (s), 856 (s).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂O₂S
M_r	246.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.5979 (7), 7.3148 (3), 12.5931 (6)
β (°)	112.763 (5)
V (Å³)	1155.04 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.34 × 0.32 × 0.19

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO.]$ )
T_min, T_max	0.796, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	28914, 4318, 3467
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.781

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.07
No. of reflections	4318
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.33
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO.]$ ), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ) and OLEX2 (Bourhis et al., 2015 ).

Structural data

CCDC reference: 1968444

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016018/hb4328sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016018/hb4328Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619016018/hb4328Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: OLEX2 (Bourhis et al., 2015).

(E)-1-(5-Methylthiophen-2-yl)-N-(4-nitrophenyl)methanimine top

Crystal data top

C₁₂H₁₀N₂O₂S	D_x = 1.416 Mg m⁻³
M_r = 246.28	Melting point: 429 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.5979 (7) Å	Cell parameters from 8567 reflections
b = 7.3148 (3) Å	θ = 4.5–32.7°
c = 12.5931 (6) Å	µ = 0.27 mm⁻¹
β = 112.763 (5)°	T = 293 K
V = 1155.04 (9) Å³	Plate, yellow
Z = 4	0.34 × 0.32 × 0.19 mm
F(000) = 512

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	4318 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3467 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 16.1790 pixels mm^-1	θ_max = 33.7°, θ_min = 4.3°
ω scans	h = −20→21
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −11→11
T_min = 0.796, T_max = 1.000	l = −19→19
28914 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.056P)² + 0.2252P] where P = (F_o² + 2F_c²)/3
4318 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

H atoms were included in calculated positions with C—H distances of 0.93 Å and 0.96 Å based upon type of carbon atom and were included in the refinement in riding motion approximation with U_iso = 1.2U_eq(carrier) or 1.5U_eq(methyl carrier).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.86901 (12)	0.5813 (3)	0.40834 (15)	0.0629 (4)
H1A	0.9087	0.6247	0.4850	0.094*
H1B	0.9003	0.6280	0.3574	0.094*
H1C	0.8706	0.4501	0.4077	0.094*
C2	0.75619 (10)	0.64523 (16)	0.36931 (11)	0.0420 (2)
C3	0.70532 (11)	0.71403 (19)	0.43482 (11)	0.0472 (3)
H3	0.7381	0.7283	0.5142	0.057*
C4	0.59850 (11)	0.76142 (18)	0.37063 (11)	0.0454 (3)
H4	0.5532	0.8095	0.4031	0.054*
C5	0.56820 (9)	0.72928 (16)	0.25515 (10)	0.0383 (2)
C6	0.46547 (10)	0.76359 (16)	0.16459 (11)	0.0399 (2)
H6	0.4091	0.8003	0.1840	0.048*
C7	0.34681 (10)	0.76957 (16)	−0.02564 (10)	0.0387 (2)
C8	0.25773 (11)	0.68505 (19)	−0.01918 (11)	0.0450 (3)
H8	0.2649	0.6153	0.0452	0.054*
C9	0.15877 (11)	0.7036 (2)	−0.10729 (12)	0.0485 (3)
H9	0.0991	0.6471	−0.1031	0.058*
C10	0.15028 (11)	0.80772 (18)	−0.20170 (11)	0.0449 (3)
C11	0.23669 (12)	0.89611 (19)	−0.20981 (11)	0.0485 (3)
H11	0.2285	0.9684	−0.2734	0.058*
C12	0.33524 (11)	0.87551 (18)	−0.12212 (12)	0.0465 (3)
H12	0.3945	0.9324	−0.1271	0.056*
N1	0.44994 (9)	0.74494 (15)	0.05856 (9)	0.0433 (2)
N2	0.04664 (11)	0.8230 (2)	−0.29732 (11)	0.0588 (3)
O1	0.04178 (11)	0.9053 (2)	−0.38389 (10)	0.0808 (4)
O2	−0.03044 (10)	0.7504 (3)	−0.28855 (12)	0.0869 (4)
S1	0.67202 (2)	0.63767 (4)	0.22616 (3)	0.04172 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0446 (7)	0.0756 (10)	0.0608 (9)	0.0099 (7)	0.0119 (6)	0.0015 (8)
C2	0.0425 (6)	0.0397 (6)	0.0415 (6)	−0.0008 (4)	0.0138 (5)	0.0025 (4)
C3	0.0525 (7)	0.0503 (7)	0.0366 (6)	−0.0037 (5)	0.0149 (5)	−0.0031 (5)
C4	0.0483 (6)	0.0487 (6)	0.0429 (6)	−0.0010 (5)	0.0217 (5)	−0.0063 (5)
C5	0.0395 (5)	0.0359 (5)	0.0411 (5)	−0.0014 (4)	0.0173 (4)	−0.0012 (4)
C6	0.0392 (5)	0.0362 (5)	0.0448 (6)	−0.0008 (4)	0.0167 (5)	−0.0014 (4)
C7	0.0429 (6)	0.0353 (5)	0.0384 (5)	0.0025 (4)	0.0163 (4)	0.0003 (4)
C8	0.0466 (6)	0.0471 (6)	0.0396 (6)	−0.0020 (5)	0.0150 (5)	0.0058 (5)
C9	0.0444 (6)	0.0545 (7)	0.0451 (6)	−0.0036 (5)	0.0154 (5)	0.0009 (6)
C10	0.0472 (6)	0.0467 (6)	0.0360 (5)	0.0078 (5)	0.0108 (5)	−0.0034 (5)
C11	0.0618 (8)	0.0446 (6)	0.0391 (6)	0.0066 (6)	0.0196 (6)	0.0059 (5)
C12	0.0517 (7)	0.0456 (6)	0.0450 (6)	−0.0013 (5)	0.0218 (5)	0.0047 (5)
N1	0.0415 (5)	0.0451 (5)	0.0427 (5)	0.0026 (4)	0.0157 (4)	0.0029 (4)
N2	0.0564 (7)	0.0685 (8)	0.0422 (6)	0.0143 (6)	0.0088 (5)	−0.0060 (6)
O1	0.0834 (9)	0.0975 (10)	0.0456 (6)	0.0223 (7)	0.0075 (6)	0.0146 (6)
O2	0.0499 (7)	0.1314 (13)	0.0642 (8)	0.0002 (8)	0.0054 (6)	0.0030 (8)
S1	0.04364 (17)	0.04606 (17)	0.03761 (15)	0.00209 (12)	0.01807 (12)	−0.00092 (11)

Geometric parameters (Å, º) top

C1—H1A	0.9600	C7—C8	1.3901 (18)
C1—H1B	0.9600	C7—C12	1.3977 (17)
C1—H1C	0.9600	C7—N1	1.4045 (16)
C1—C2	1.4935 (19)	C8—H8	0.9300
C2—C3	1.3616 (19)	C8—C9	1.3801 (18)
C2—S1	1.7222 (13)	C9—H9	0.9300
C3—H3	0.9300	C9—C10	1.3788 (19)
C3—C4	1.405 (2)	C10—C11	1.379 (2)
C4—H4	0.9300	C10—N2	1.4612 (18)
C4—C5	1.3698 (17)	C11—H11	0.9300
C5—C6	1.4429 (17)	C11—C12	1.376 (2)
C5—S1	1.7246 (12)	C12—H12	0.9300
C6—H6	0.9300	N2—O1	1.2247 (19)
C6—N1	1.2760 (17)	N2—O2	1.218 (2)

H1A—C1—H1B	109.5	C8—C7—N1	122.47 (11)
H1A—C1—H1C	109.5	C12—C7—N1	118.10 (11)
H1B—C1—H1C	109.5	C7—C8—H8	119.7
C2—C1—H1A	109.5	C9—C8—C7	120.66 (12)
C2—C1—H1B	109.5	C9—C8—H8	119.7
C2—C1—H1C	109.5	C8—C9—H9	120.7
C1—C2—S1	121.10 (11)	C10—C9—C8	118.54 (12)
C3—C2—C1	127.90 (13)	C10—C9—H9	120.7
C3—C2—S1	111.01 (10)	C9—C10—C11	122.24 (12)
C2—C3—H3	123.3	C9—C10—N2	119.02 (13)
C2—C3—C4	113.39 (12)	C11—C10—N2	118.73 (13)
C4—C3—H3	123.3	C10—C11—H11	120.6
C3—C4—H4	123.6	C12—C11—C10	118.84 (12)
C5—C4—C3	112.81 (12)	C12—C11—H11	120.6
C5—C4—H4	123.6	C7—C12—H12	119.8
C4—C5—C6	127.64 (12)	C11—C12—C7	120.37 (13)
C4—C5—S1	110.91 (10)	C11—C12—H12	119.8
C6—C5—S1	121.45 (9)	C6—N1—C7	119.28 (11)
C5—C6—H6	119.1	O1—N2—C10	118.28 (15)
N1—C6—C5	121.75 (11)	O2—N2—C10	118.78 (14)
N1—C6—H6	119.1	O2—N2—O1	122.91 (14)
C8—C7—C12	119.33 (11)	C2—S1—C5	91.88 (6)

Acknowledgements

This research was funded by a CCSU-AAUP research grant.

References

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