4-Methyl-N-[(5-nitro­thio­phen-2-yl)methyl­idene]aniline

Cai, M.; Wang, X.; Sun, T.

doi:10.1107/S1600536811030297

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2218

doi:10.1107/S1600536811030297

Open

access

4-Methyl-N-[(5-nitrothiophen-2-yl)methylidene]aniline

Mingjian Cai,^a ^* Xiuge Wang ^a and Tao Sun ^a

^aDepartment of Chemistry, Tangshan Normal University, Tangshan 063000, People's Republic of China
^*Correspondence e-mail: cmj_1237@yahoo.com.cn

(Received 12 July 2011; accepted 27 July 2011; online 2 August 2011)

The title compound, C₁₂H₁₀N₂O₂S, is a Schiff base formed from p-toluidine and 5-nitrothiophene-2-carbaldehyde. The C=N bond adopts an E configuration. The benzene and thiophene rings form a dihedral angle of 9.2 (1)°.

Related literature

For the use of Schiff bases as polydentate ligands, see: Bourget-Merle et al.(2002 ); Halbach & Hamaker (2006 ); Meiswinkel & Werner (2004 ); Xiao et al. (2006 ); Lagadic (2006 ). For their biological activity, see: Siddiqui et al. (2006 ).

Experimental

Crystal data

C₁₂H₁₀N₂O₂S
M_r = 246.28
Monoclinic, P 2₁ /n
a = 4.7606 (4) Å
b = 22.415 (2) Å
c = 10.7008 (15) Å
β = 92.566 (13)°
V = 1140.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 ) T_min = 0.947, T_max = 0.968
14437 measured reflections
2699 independent reflections
2325 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.098
S = 1.09
2699 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2009 ); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811030297/ld2020sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030297/ld2020Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030297/ld2020Isup3.cml

checkCIF report

Comment top

In recent years, heterocycle-containing Schiff bases have gained much attention as versatile polydentate ligands suitable for various metal chelations resulting in a variety of interesting coordination modes (Xiao et al., 2006; Bourget-Merle et al., 2002; Meiswinkel & Werner, 2004; Halbach & Hamaker, 2006; Lagadic, 2006). They also represent an important class of biologically active compounds (Siddiqui et al., 2006). Herein, we report the synthesis and crystal structure of the title compound (I), a new heterocycle-containing Schiff base. The molecular structure of (I) is shown on Fig. 1. In the molecule of (I), the two aromatic benzene and thiophene rings form a dihedral angle of 9.2 (1)°. The deviation from planarity can be explained by steric repulsion between the phenyl ring and methylene group.

Related literature top

For the use of Schiff bases as polydentate ligands, see: Bourget-Merle et al.(2002); Halbach & Hamaker (2006); Meiswinkel & Werner (2004); Xiao et al. (2006); Lagadic (2006). For their biological activity, see: Siddiqui et al. (2006).

Experimental top

The solution of p-toluidine and 5-nitrothiophene-2-carbaldehyde in methanol was stirred for 10 h at ambient temperature. Then the crude product was isolated by filtration and recrystallized from methanol to yield yellowish title compound. Finally, the compound was dissolved in a small amount of acetone and the solution was kept for 3 days at ambient temperature to give rise to yellowish needle-like crystals by slowly evaporating the solvent.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2002); cell refinement: CrystalClear (Rigaku/MSC, 2002); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2009); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2006).

Figures top

Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

4-Methyl-N-[(5-nitrothiophen-2-yl)methylidene]aniline top

Crystal data top

C₁₂H₁₀N₂O₂S	F(000) = 512
M_r = 246.28	D_x = 1.434 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.7606 (4) Å	Cell parameters from 4173 reflections
b = 22.415 (2) Å	θ = 1.8–27.9°
c = 10.7008 (15) Å	µ = 0.27 mm⁻¹
β = 92.566 (13)°	T = 113 K
V = 1140.7 (2) Å³	Prism, colorless
Z = 4	0.20 × 0.18 × 0.12 mm

Data collection top

Rigaku Saturn724 CCD diffractometer	2699 independent reflections
Radiation source: rotating anode	2325 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.043
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 1.8°
ω and ϕ scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	k = −29→29
T_min = 0.947, T_max = 0.968	l = −13→14
14437 measured reflections

Refinement top

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) = 0.098	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0505P)² + 0.1298P] where P = (F_o² + 2F_c²)/3
2699 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₂H₁₀N₂O₂S	V = 1140.7 (2) Å³
M_r = 246.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.7606 (4) Å	µ = 0.27 mm⁻¹
b = 22.415 (2) Å	T = 113 K
c = 10.7008 (15) Å	0.20 × 0.18 × 0.12 mm
β = 92.566 (13)°

Data collection top

Rigaku Saturn724 CCD diffractometer	2699 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	2325 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.968	R_int = 0.043
14437 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.09	Δρ_max = 0.30 e Å⁻³
2699 reflections	Δρ_min = −0.27 e Å⁻³
155 parameters

Special details top

Experimental. Rigaku CrystalClear-SM Expert 2.0 r2

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	0.12948 (8)	0.223694 (17)	0.24141 (3)	0.01725 (12)
O1	−0.4301 (2)	0.10562 (5)	0.14443 (11)	0.0279 (3)
O2	−0.2638 (2)	0.13512 (5)	0.32720 (10)	0.0257 (3)
N1	0.5743 (3)	0.32247 (6)	0.21001 (11)	0.0170 (3)
N2	−0.2748 (3)	0.13695 (6)	0.21144 (12)	0.0200 (3)
C1	1.3858 (3)	0.51381 (7)	0.21589 (19)	0.0294 (4)
H1A	1.5510	0.5020	0.1704	0.044*
H1B	1.4432	0.5230	0.3028	0.044*
H1C	1.2998	0.5492	0.1763	0.044*
C2	1.1750 (3)	0.46324 (7)	0.21303 (16)	0.0220 (3)
C3	1.0879 (3)	0.43701 (7)	0.10002 (15)	0.0223 (3)
H3	1.1645	0.4507	0.0248	0.027*
C4	0.8909 (3)	0.39115 (7)	0.09487 (14)	0.0197 (3)
H4	0.8337	0.3742	0.0164	0.024*
C5	0.7759 (3)	0.36966 (7)	0.20461 (14)	0.0169 (3)
C6	0.8680 (3)	0.39494 (7)	0.31778 (14)	0.0199 (3)
H6	0.7965	0.3804	0.3935	0.024*
C7	1.0628 (3)	0.44113 (7)	0.32203 (16)	0.0233 (4)
H7	1.1207	0.4579	0.4005	0.028*
C8	0.4454 (3)	0.30556 (7)	0.10888 (14)	0.0189 (3)
H8	0.4859	0.3248	0.0327	0.023*
C9	0.2385 (3)	0.25772 (7)	0.10682 (14)	0.0173 (3)
C10	0.1041 (3)	0.23474 (7)	0.00118 (14)	0.0208 (3)
H10	0.1382	0.2483	−0.0809	0.025*
C11	−0.0895 (3)	0.18913 (7)	0.02644 (14)	0.0194 (3)
H11	−0.2003	0.1683	−0.0354	0.023*
C12	−0.0955 (3)	0.17906 (7)	0.15201 (14)	0.0166 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0186 (2)	0.0195 (2)	0.01358 (19)	0.00044 (15)	−0.00004 (15)	−0.00052 (14)
O1	0.0285 (6)	0.0275 (6)	0.0275 (6)	−0.0102 (5)	−0.0009 (5)	−0.0022 (5)
O2	0.0313 (7)	0.0288 (6)	0.0174 (6)	−0.0008 (5)	0.0046 (5)	0.0029 (5)
N1	0.0166 (6)	0.0168 (6)	0.0174 (6)	0.0015 (5)	0.0004 (5)	0.0009 (5)
N2	0.0205 (7)	0.0200 (7)	0.0195 (7)	0.0020 (5)	0.0019 (5)	0.0003 (5)
C1	0.0210 (8)	0.0204 (8)	0.0472 (11)	−0.0026 (7)	0.0047 (8)	0.0001 (8)
C2	0.0153 (7)	0.0165 (8)	0.0345 (9)	0.0031 (6)	0.0018 (7)	0.0011 (7)
C3	0.0198 (8)	0.0211 (8)	0.0264 (8)	0.0025 (6)	0.0061 (7)	0.0057 (7)
C4	0.0202 (8)	0.0203 (8)	0.0187 (8)	0.0022 (6)	0.0008 (6)	−0.0005 (6)
C5	0.0134 (7)	0.0162 (7)	0.0210 (8)	0.0022 (6)	0.0002 (6)	0.0009 (6)
C6	0.0191 (7)	0.0218 (8)	0.0187 (7)	−0.0004 (6)	−0.0004 (6)	0.0023 (6)
C7	0.0222 (8)	0.0230 (8)	0.0245 (8)	−0.0011 (7)	−0.0025 (7)	−0.0018 (7)
C8	0.0194 (7)	0.0206 (8)	0.0168 (7)	0.0007 (6)	0.0019 (6)	0.0025 (6)
C9	0.0172 (7)	0.0189 (7)	0.0158 (7)	0.0018 (6)	0.0013 (6)	0.0005 (6)
C10	0.0211 (8)	0.0272 (8)	0.0142 (7)	−0.0010 (7)	0.0004 (6)	0.0013 (6)
C11	0.0185 (7)	0.0224 (8)	0.0173 (7)	−0.0005 (6)	0.0007 (6)	−0.0032 (6)
C12	0.0157 (7)	0.0168 (7)	0.0173 (7)	0.0007 (6)	0.0013 (6)	−0.0016 (6)

Geometric parameters (Å, º) top

S1—C12	1.7237 (15)	C3—H3	0.9500
S1—C9	1.7298 (15)	C4—C5	1.403 (2)
O1—N2	1.2271 (16)	C4—H4	0.9500
O2—N2	1.2382 (16)	C5—C6	1.390 (2)
N1—C8	1.277 (2)	C6—C7	1.389 (2)
N1—C5	1.4312 (19)	C6—H6	0.9500
N2—C12	1.4398 (19)	C7—H7	0.9500
C1—C2	1.513 (2)	C8—C9	1.456 (2)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—C10	1.374 (2)
C1—H1C	0.9800	C10—C11	1.411 (2)
C2—C3	1.391 (2)	C10—H10	0.9500
C2—C7	1.395 (2)	C11—C12	1.364 (2)
C3—C4	1.391 (2)	C11—H11	0.9500

C12—S1—C9	89.77 (7)	C4—C5—N1	125.10 (13)
C8—N1—C5	118.86 (13)	C7—C6—C5	121.08 (15)
O1—N2—O2	124.27 (13)	C7—C6—H6	119.5
O1—N2—C12	118.08 (13)	C5—C6—H6	119.5
O2—N2—C12	117.65 (13)	C6—C7—C2	121.15 (15)
C2—C1—H1A	109.5	C6—C7—H7	119.4
C2—C1—H1B	109.5	C2—C7—H7	119.4
H1A—C1—H1B	109.5	N1—C8—C9	122.04 (14)
C2—C1—H1C	109.5	N1—C8—H8	119.0
H1A—C1—H1C	109.5	C9—C8—H8	119.0
H1B—C1—H1C	109.5	C10—C9—C8	125.35 (14)
C3—C2—C7	117.78 (14)	C10—C9—S1	111.94 (12)
C3—C2—C1	120.39 (15)	C8—C9—S1	122.70 (11)
C7—C2—C1	121.84 (15)	C9—C10—C11	113.47 (14)
C4—C3—C2	121.40 (15)	C9—C10—H10	123.3
C4—C3—H3	119.3	C11—C10—H10	123.3
C2—C3—H3	119.3	C12—C11—C10	110.57 (14)
C3—C4—C5	120.55 (14)	C12—C11—H11	124.7
C3—C4—H4	119.7	C10—C11—H11	124.7
C5—C4—H4	119.7	C11—C12—N2	125.62 (14)
C6—C5—C4	118.01 (14)	C11—C12—S1	114.25 (12)
C6—C5—N1	116.87 (13)	N2—C12—S1	120.10 (11)

C7—C2—C3—C4	1.4 (2)	N1—C8—C9—S1	5.1 (2)
C1—C2—C3—C4	−178.92 (14)	C12—S1—C9—C10	0.04 (12)
C2—C3—C4—C5	−0.6 (2)	C12—S1—C9—C8	179.15 (13)
C3—C4—C5—C6	−0.9 (2)	C8—C9—C10—C11	−179.16 (14)
C3—C4—C5—N1	−179.45 (13)	S1—C9—C10—C11	−0.08 (17)
C8—N1—C5—C6	167.13 (14)	C9—C10—C11—C12	0.09 (19)
C8—N1—C5—C4	−14.3 (2)	C10—C11—C12—N2	178.01 (13)
C4—C5—C6—C7	1.6 (2)	C10—C11—C12—S1	−0.06 (17)
N1—C5—C6—C7	−179.80 (14)	O1—N2—C12—C11	2.7 (2)
C5—C6—C7—C2	−0.7 (2)	O2—N2—C12—C11	−176.72 (14)
C3—C2—C7—C6	−0.8 (2)	O1—N2—C12—S1	−179.35 (11)
C1—C2—C7—C6	179.55 (14)	O2—N2—C12—S1	1.25 (18)
C5—N1—C8—C9	179.73 (13)	C9—S1—C12—C11	0.01 (12)
N1—C8—C9—C10	−175.90 (15)	C9—S1—C12—N2	−178.17 (12)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂O₂S
M_r	246.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	4.7606 (4), 22.415 (2), 10.7008 (15)
β (°)	92.566 (13)
V (Å³)	1140.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.20 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2002)
T_min, T_max	0.947, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	14437, 2699, 2325
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.098, 1.09
No. of reflections	2699
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.27

Computer programs: CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Crystal Impact, 2009), CrystalStructure (Rigaku/MSC, 2006).

References

Bourget-Merle, L., Lappert, M. F. & Severn, J. R. (2002). Chem. Rev. 102, 3031–3065. Web of Science CrossRef PubMed CAS Google Scholar
Crystal Impact (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Halbach, D. P. & Hamaker, C. G. (2006). J. Organomet. Chem. 691, 3349–3361. Web of Science CSD CrossRef CAS Google Scholar
Lagadic, I. L. (2006). Microporous Mesoporous Mater. 95, 226–233. Web of Science CrossRef CAS Google Scholar
Meiswinkel, A. & Werner, H. (2004). Inorg. Chim. Acta, 357, 2855–2862. Web of Science CrossRef CAS Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2006). CrystalStructure. Rigaku/MSC, 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
Siddiqui, H. L., Iqbal, A., Ahmad, S. & Weaver, G. W. (2006). Molecules, 11, 206–211. Web of Science CrossRef PubMed CAS Google Scholar
Xiao, F. R., Chen, L., Wang, J. D., Wu, R. L., Yue, F. & Li, J. (2006). Acta Chim. Sin. 64, 1517–1522. CAS Google Scholar