5-[(2-Hy­droxy­eth­yl)(meth­yl)amino]­thio­phene-2-carbaldehyde

Sun, X.-S.; Shao, N.-Q.; Li, D.-D.

doi:10.1107/S1600536814012021

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o724

doi:10.1107/S1600536814012021

Open

access

5-[(2-Hydroxyethyl)(methyl)amino]thiophene-2-carbaldehyde

Xian-Shun Sun,^a,^b Nan-Qi Shao ^a,^b and Dan-Dan Li ^a,^b ^*

^aDepartment of Chemistry, Anhui University, Hefei 230039, People's Republic of China, and ^bKey Laboratory of Functional Inorganic Materials Chemistry, Hefei 230039, People's Republic of China
^*Correspondence e-mail: ahuddl09@126.com

(Received 12 April 2014; accepted 23 May 2014; online 31 May 2014)

In the title compound, C₈H₁₁NO₂S, the aldehyde group is approximately coplanar with the thiophene ring [maximum deviation = 0.023 (2) Å]. In the crystal, molecules are linked by O—H⋯O hydrogen bonds into supramolecular chains propagating along the a-axis direction.

CCDC reference: 996513

Related literature

For potential applications of thiophene derivatives, see: Encinas (2002 ). For a related thiophene derivative, see: Perašínová et al. (2006 ).

Experimental

Crystal data

C₈H₁₁NO₂S
M_r = 185.24
Orthorhombic, P c a 2₁
a = 15.764 (5) Å
b = 5.136 (5) Å
c = 11.028 (5) Å
V = 892.9 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
5828 measured reflections
1564 independent reflections
1514 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.067
S = 1.08
1564 reflections
111 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³
Absolute structure: Flack (1983 ), 756 Friedel pairs
Absolute structure parameter: −0.03 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.93	2.751 (2)	174
Symmetry code: (i) $[x-{\script{1\over 2}}, -y, z]$ .

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.

Supporting information

CCDC reference: 996513

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S1600536814012021/xu5786sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814012021/xu5786Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814012021/xu5786Isup3.cml

checkCIF report

Comment top

The introduction about the highpolarizability of sulfur atoms in thiophene rings leads to a stabilization of the conjugated chain and to excellent charge transport properties. Functional thiophene derivatives have attracted comprehensive interest among researchers all over the world and have actually been advanced to be among the most frequently used π-conjugated materials, in particular as active components in organic electronic devices and molecular electronics (Encinas et al., 2002). In the title compound (I) (Fig. 1), the S1—C4 bond length of 1.7398 (18) Å is longer than the corresponding S1—C15 bond length of 1.708 (2) Å in related thiophene derivative (Perašínová et al. 2006), which is due to the fact that there is a higher π-electron delocalized system in the molecule 5-(fluoren-9-ylidenemethyl)thiophene-2-carbaldehyde. In the crystal structure of (I), the molecules are interconnected, via hydrogen bonds (Table 1) [O1—H1···O2ⁱ; symmetry codes: (i) x - 1/2, -y, z], forming a one-dimensional structure (Fig. 2).

Related literature top

For potential applications of thiophene derivatives, see: Encinas (2002). For a related thiophene derivative, see: Perašínová et al. (2006).

Experimental top

A 0.86 g (4.5 mmol) amount of 5-bromothiophene-2-carbaldehyde, 1.13 g (15 mmol) of 2-(methylamino)ethanol, and 0.1 g of toluene-4-sulfonic acid were mixed and stirred at a bath temperature of 373 K for 20 h. The mixture was cooled, 25 mL of water was added. The organic layer and dichloromethane extracts were combined, washed with water, and dried over MgSO₄. Evaporation of the solvent, purification by column chromatography. ¹H NMR: (400 Hz, DMSO-d₆), d(p.p.m.):9.40 (s, 1H), 7.65 (d, 1H), 6.12 (d, 1H), 4.87 (t, 1H), 3.62 (q, 2H), 3.47 (t, 2H), 3.09 (s, 3H).

Computing details top

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

Figures top

	Fig. 1. : The molecular structure of the title compound (I) showing 30% probability displacement ellipsoids.
	Fig. 2. : The crystal packing of (I), showing O—H···O hydrogen-bonding interactions as dashed lines.

5-[(2-Hydroxyethyl)(methyl)amino]thiophene-2-carbaldehyde top

Crystal data top

C₈H₁₁NO₂S	F(000) = 392
M_r = 185.24	D_x = 1.378 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2c -2ac	Cell parameters from 3223 reflections
a = 15.764 (5) Å	θ = 2.6–26.8°
b = 5.136 (5) Å	µ = 0.32 mm⁻¹
c = 11.028 (5) Å	T = 293 K
V = 892.9 (10) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1514 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.0°, θ_min = 2.6°
phi and ω scans	h = −17→18
5828 measured reflections	k = −5→6
1564 independent reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0417P)² + 0.0567P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1564 reflections	Δρ_max = 0.14 e Å⁻³
111 parameters	Δρ_min = −0.13 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 756 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (7)

Crystal data top

C₈H₁₁NO₂S	V = 892.9 (10) Å³
M_r = 185.24	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 15.764 (5) Å	µ = 0.32 mm⁻¹
b = 5.136 (5) Å	T = 293 K
c = 11.028 (5) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1514 reflections with I > 2σ(I)
5828 measured reflections	R_int = 0.020
1564 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.067	Δρ_max = 0.14 e Å⁻³
S = 1.08	Δρ_min = −0.13 e Å⁻³
1564 reflections	Absolute structure: Flack (1983), 756 Friedel pairs
111 parameters	Absolute structure parameter: −0.03 (7)
1 restraint

Special details top

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	0.53676 (3)	0.28672 (8)	0.22080 (5)	0.04276 (14)
O1	0.32880 (9)	0.3310 (3)	0.35492 (15)	0.0575 (4)
H1	0.2888	0.2479	0.3274	0.086*
N1	0.40014 (10)	0.5376 (3)	0.13076 (14)	0.0446 (4)
C4	0.45817 (10)	0.3498 (4)	0.11400 (16)	0.0385 (4)
C5	0.46620 (12)	0.1849 (4)	0.01313 (18)	0.0459 (5)
H5	0.4301	0.1889	−0.0535	0.055*
C6	0.53411 (13)	0.0157 (4)	0.02439 (17)	0.0501 (5)
H6	0.5479	−0.1056	−0.0351	0.060*
C7	0.57958 (11)	0.0402 (4)	0.12977 (19)	0.0457 (4)
O2	0.68678 (9)	−0.0828 (4)	0.26743 (18)	0.0723 (5)
C2	0.39359 (13)	0.6822 (3)	0.24362 (18)	0.0460 (5)
H2A	0.3870	0.8658	0.2251	0.055*
H2B	0.4459	0.6617	0.2888	0.055*
C1	0.33673 (14)	0.5845 (5)	0.0376 (2)	0.0583 (6)
H1A	0.3644	0.6127	−0.0389	0.087*
H1B	0.3040	0.7356	0.0585	0.087*
H1C	0.2999	0.4362	0.0315	0.087*
C8	0.64980 (13)	−0.1077 (4)	0.1692 (2)	0.0553 (5)
H8	0.6700	−0.2351	0.1167	0.066*
C3	0.32038 (12)	0.5959 (4)	0.32204 (19)	0.0490 (5)
H3A	0.3184	0.7022	0.3947	0.059*
H3B	0.2676	0.6204	0.2783	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0454 (2)	0.0426 (2)	0.0403 (2)	0.00002 (17)	−0.0065 (2)	−0.0035 (3)
O1	0.0509 (8)	0.0526 (8)	0.0689 (10)	−0.0042 (7)	−0.0065 (8)	0.0180 (7)
N1	0.0451 (8)	0.0484 (9)	0.0403 (7)	0.0028 (7)	−0.0043 (7)	0.0008 (7)
C4	0.0413 (10)	0.0403 (9)	0.0338 (9)	−0.0082 (7)	0.0010 (7)	0.0035 (8)
C5	0.0524 (12)	0.0537 (12)	0.0317 (9)	−0.0072 (9)	0.0002 (8)	−0.0023 (8)
C6	0.0592 (13)	0.0510 (12)	0.0400 (10)	−0.0036 (9)	0.0120 (9)	−0.0060 (9)
C7	0.0433 (10)	0.0437 (10)	0.0500 (9)	−0.0024 (8)	0.0106 (8)	0.0003 (8)
O2	0.0587 (9)	0.0613 (10)	0.0969 (13)	0.0069 (8)	−0.0212 (9)	0.0000 (9)
C2	0.0446 (9)	0.0380 (9)	0.0555 (14)	−0.0031 (7)	0.0037 (8)	−0.0050 (8)
C1	0.0518 (12)	0.0673 (15)	0.0558 (12)	0.0036 (11)	−0.0106 (9)	0.0090 (10)
C8	0.0484 (11)	0.0469 (12)	0.0705 (13)	0.0010 (10)	0.0064 (12)	0.0012 (10)
C3	0.0494 (11)	0.0427 (10)	0.0550 (12)	0.0026 (9)	0.0057 (9)	−0.0005 (9)

Geometric parameters (Å, º) top

S1—C4	1.7398 (18)	C7—C8	1.411 (3)
S1—C7	1.751 (2)	O2—C8	1.237 (3)
O1—C3	1.414 (3)	C2—C3	1.509 (3)
O1—H1	0.8200	C2—H2A	0.9700
N1—C4	1.342 (3)	C2—H2B	0.9700
N1—C2	1.453 (2)	C1—H1A	0.9600
N1—C1	1.454 (3)	C1—H1B	0.9600
C4—C5	1.404 (3)	C1—H1C	0.9600
C5—C6	1.384 (3)	C8—H8	0.9300
C5—H5	0.9300	C3—H3A	0.9700
C6—C7	1.371 (3)	C3—H3B	0.9700
C6—H6	0.9300

C4—S1—C7	91.21 (10)	C3—C2—H2A	108.9
C3—O1—H1	109.5	N1—C2—H2B	108.9
C4—N1—C2	122.26 (16)	C3—C2—H2B	108.9
C4—N1—C1	119.38 (17)	H2A—C2—H2B	107.7
C2—N1—C1	118.15 (17)	N1—C1—H1A	109.5
N1—C4—C5	127.17 (17)	N1—C1—H1B	109.5
N1—C4—S1	121.74 (14)	H1A—C1—H1B	109.5
C5—C4—S1	111.08 (15)	N1—C1—H1C	109.5
C6—C5—C4	112.17 (18)	H1A—C1—H1C	109.5
C6—C5—H5	123.9	H1B—C1—H1C	109.5
C4—C5—H5	123.9	O2—C8—C7	125.7 (2)
C7—C6—C5	114.99 (18)	O2—C8—H8	117.1
C7—C6—H6	122.5	C7—C8—H8	117.1
C5—C6—H6	122.5	O1—C3—C2	110.98 (15)
C6—C7—C8	128.45 (19)	O1—C3—H3A	109.4
C6—C7—S1	110.53 (15)	C2—C3—H3A	109.4
C8—C7—S1	120.99 (17)	O1—C3—H3B	109.4
N1—C2—C3	113.27 (16)	C2—C3—H3B	109.4
N1—C2—H2A	108.9	H3A—C3—H3B	108.0

C2—N1—C4—C5	174.75 (18)	C5—C6—C7—C8	177.8 (2)
C1—N1—C4—C5	0.2 (3)	C5—C6—C7—S1	−0.2 (2)
C2—N1—C4—S1	−6.4 (2)	C4—S1—C7—C6	0.14 (15)
C1—N1—C4—S1	179.03 (15)	C4—S1—C7—C8	−178.05 (16)
C7—S1—C4—N1	−179.10 (15)	C4—N1—C2—C3	−103.3 (2)
C7—S1—C4—C5	−0.06 (15)	C1—N1—C2—C3	71.4 (2)
N1—C4—C5—C6	178.94 (18)	C6—C7—C8—O2	−177.4 (2)
S1—C4—C5—C6	0.0 (2)	S1—C7—C8—O2	0.5 (3)
C4—C5—C6—C7	0.1 (2)	N1—C2—C3—O1	60.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.93	2.751 (2)	174

Symmetry code: (i) x−1/2, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.93	2.751 (2)	173.9

Symmetry code: (i) x−1/2, −y, z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21271004), the Education Committee of Anhui Province (grant No. KJ2010A030) and the Undergraduate Innovative Test Program in Anhui University.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Encinas, S. (2002). Chem. Eur. J. 8, 137–150. Web of Science CSD CrossRef PubMed CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Perašínová, L., Štefko, M., Végh, D. & Kožíšek, J. (2006). Acta Cryst. E62, o3972–o3973. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar