Crystal structure of 5-[bis­(4-eth­oxy­phenyl)amino]­thio­phene-2-carbaldehyde

Jing-Yun Tan; Ming Kong; Jie-Ying Wu

doi:10.1107/S1600536814018984

. 2014 Aug 30;70(Pt 9):o1075–o1076. doi: 10.1107/S1600536814018984

Crystal structure of 5-[bis(4-ethoxyphenyl)amino]thiophene-2-carbaldehyde

Jing-Yun Tan ^a,^b, Ming Kong ^a,^b, Jie-Ying Wu ^a,^b,^*

PMCID: PMC4186151 PMID: 25309233

Abstract

In the title compound, C₂₁H₂₁NO₃S, the planes of the two benzene rings are nearly perpendicular to one another [dihedral angle = 84.50 (10)°] and they are oriented with respect to the plane of the thiophene ring at dihedral angles of 59.15 (9) and 66.61 (9)°. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming supramolecular chains propagating along the b-axis direction.

Keywords: crystal structure, thiophene-2-carbaldehyde, hydrogen bonding, supramolecular chains

Related literature

For applications of thiophene derivatives, see: Justin Thomas et al. (2008 ▶); Hansel et al. (2003 ▶); Mazzeo et al. (2003 ▶); Zhan et al. (2007 ▶); Bedworth et al. (1996 ▶); Raposo et al. (2011 ▶); Takekuma et al. (2005 ▶); Wurthner et al. (2002 ▶). For a related structure, see: Li et al. (2013 ▶).

Experimental

Crystal data

C₂₁H₂₁NO₃S
M _r = 367.45
Monoclinic,
a = 11.101 (3) Å
b = 10.457 (3) Å
c = 17.326 (5) Å
β = 104.473 (4)°
V = 1947.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: ψ scan (SADABS; Bruker, 2002 ▶) T _min = 0.946, T _max = 0.964
13574 measured reflections
3430 independent reflections
2596 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.134
S = 0.93
3430 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814018984/xu5814sup1.cif

e-70-o1075-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018984/xu5814Isup2.hkl

e-70-o1075-Isup2.hkl^{(168.2KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814018984/xu5814Isup3.cml

Click here for additional data file.^{(671.4KB, tif)}

. DOI: 10.1107/S1600536814018984/xu5814fig1.tif

The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms

Click here for additional data file.^{(315.6KB, tif)}

. DOI: 10.1107/S1600536814018984/xu5814fig2.tif

The infinite one-dimensional linear chain structure.

CCDC reference: 1016303

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O3ⁱ	0.97	2.55	3.470 (3)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

The work was supported by the National Natural Science Foundation of China (grant Nos. 21271004 and 51372003) and the Natural Science Foundation of Anhui Province (grant No. 1208085MB22).

supplementary crystallographic information

S1. Comment

Due to the outstanding electronic tenability and considerable chemical and environmental stability, thiophene derivatives have been widely used in solar cells (Justin Thomas et al., 2008; Hansel et al., 2003), organic light-emitting diodes (OLEDs) (Mazzeo et al., 2003), organic field-effect transistors (OFETs) (Zhan et al., 2007) and NLO devices (Bedworth et al., 1996; Raposo et al., 2011). Among them, the research of thiophene carboxaldehyde, which is an extremely important intermediate, is abundant (Takekuma et al., 2005; Wurthner et al., 2002). In this paper, a novel thiophene carboxaldehyde derivative, 5-(bis(4-ethoxyphenyl)amino)thiophene-2-carbaldehyde (Fig.1), was synthesized.

It possesses typical propeller structure, just the same with other triarylamine. The carbonyl group is coplanar with the thiophene ring, which indicates well conjugation. As shown in Fig.2, for the existence of intermolecular C2—H2A···O3 hydrogen bond, the one-dimensional linear chain structure was formed along b axis.

S2. Experimental

The intermediate bis(4-ethoxyphenyl)amine was synthesized according to following procedure. Cuprous iodide (0.95 g, 5 mmol), L-Proline (1.15 g, 10 mmol) and anhydrous potassium carbonate (13.8 g, 100 mmol) were placed in an oven-dried 250 ml Schlenk flask. The reaction vessel was evacuated and filled with prepurified argon, a process which was repeated three times. Then refined dimethylsulfoxide (100 ml) was added with a syringe under a counterflow of argon. After that, 4-Iodophenetole (12.5 g, 50 mmol), Phenetidine (8.23 g, 60 mmol) and a particle of 18-Crown-6 (0.1981 g, 0.75 mmol) were added. The reaction was stirred at 90 degrees celsius for 24 h. Upon completion of the reaction, the mixture was cooled to room temperature. The mixture was filtered through a Buchner funnel to remove the deposition. Then diluted with water (500 ml) and stirred for one day. A kind of grey educt were obtained after separate the water by a Buchner funnel again. Purification of the residue by column chromatography on silica gel (petroleum ether/ethyl acetate = 40:1) gave bis(4-ethoxyphenyl)amine as white powder, with yield of 41.3%. M.p.= 89 degrees celsius. ¹H NMR: (400 MHz, DMSO-d₆), d(p.p.m.): 1.33 (t, 6H), 3.93 (q,4H), 5.61 (s, 1H), 6.80 (d, 4H), 6.96 (d, 4H).

The synthesis of the title compound. Phenanthroline (0.45 g, 2.3 mmol), cuprous iodide (0.46 g, 2.4 mmol), anhydrous potassium carbonate (5.00 g, 36 mmol) and bis(4-ethoxyphenyl)amine (3.09 g, 12 mmol) were placed in an oven-dried 250 ml Schlenk flask. The reaction vessel was evacuated and filled with prepurified argon, a process which was repeated three times. Then refined dimethylsulfoxide (120 ml) and 1.90 g 5-Bromo-2-thiophenecarbalde-hyde (10 mmol) were added with a syringe under a counterflow of argon. At last, a particle of 18-Crown-6 (0.0396 g, 0.15 mmol) and two drops of Aliquat336 (0.0200 g, 0.05 mmol) were added. The reaction was stirred at 90 degrees celsius for 48 h. Upon completion of the reaction, the mixture was cooled to room temperature. The mixture was filtered through a Buchner funnel to remove the deposition. Then diluted with water (500 ml) and stirred for one day. A kind of yellowish-brown educt were obtained after separate the water by a Buchner funnel again. Purification of the residue by column chromatography on silica gel (Petroleum/Ethyl Acetate = 20:1) gave title compound as yellowish-brown particle, with yield of 45%. m.p.= 101 degrees celsius. ¹H NMR: (400 MHz, d-chloroform), d(p.p.m.): 1.42 (t, 6H), 4.04 (q, 4H), 6.17 (d,1H), 6.88 (d, 4H), 7.22 (d, 4H), 7.41 (d, 1H), 9.53 (s, 1H). ¹³C NMR(150 MHz, d₆-acetone): d(p.p.m.): 14.81, 63.77, 109.09, 115.54, 127.17, 127.99, 128.55, 138.71, 157.39, 166.42, 180.95. IR (KBr, cm^-1): 3058 (w), 2976 (m), 2931 (w), 2895 (w), 2790 (w), 1627 (s), 1508 (s), 1443 (vs), 1420 (m), 1392 (m), 1353 (m), 1244 (s), 1175 (m), 1054 (m), 824 (m).