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

Abstract

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,

• a = 4.7606 (4) Å

• b = 22.415 (2) Å

• c = 10.7008 (15) Å

• β = 92.566 (13)°

• V = 1140.7 (2) ų

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811030297/ld2020Isup3.cml

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were positioned geometrically(C—H=0.93–0.98 Å),and refined as riding with U_iso(H)=1.2U_eq of the adjacent carbon atom (1.5U_eq for methyl hydrogens). The positions of methyl hydrogens were rotationally optimized (AFIX 137).

Figures

Fig. 1.

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

Crystal data

C12H10N2O2S	F(000) = 512
Mr = 246.28	Dx = 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

Rigaku Saturn724 CCD diffractometer	2699 independent reflections
Radiation source: rotating anode	2325 reflections with I > 2σ(I)
multilayer	Rint = 0.043
Detector resolution: 14.22 pixels mm-1	θmax = 27.9°, θmin = 1.8°
ω and φ scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	k = −29→29
Tmin = 0.947, Tmax = 0.968	l = −13→14
14437 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) = 0.098	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0505P)2 + 0.1298P] where P = (Fo2 + 2Fc2)/3
2699 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)