5-(2-Cyano­benz­yl)-4,5,6,7-tetra­hydro­thieno[3,2-c]pyridin-2-yl acetate

Xiao-Shuai Xie; Shuai Mu; Ying Liu; Deng-Ke Liu

doi:10.1107/S1600536813009513

. 2013 Apr 13;69(Pt 5):o713. doi: 10.1107/S1600536813009513

5-(2-Cyanobenzyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridin-2-yl acetate

Xiao-Shuai Xie ^a,^b, Shuai Mu ^c, Ying Liu ^d,^*, Deng-Ke Liu ^d

PMCID: PMC3648246 PMID: 23723866

Abstract

In the title molecule, C₁₇H₁₆N₂O₂S, the tetrahydropyridine ring exhibits a half-chair conformation. The mean planes of the ester chain and benzene ring are twisted by 5.5 (1) and 81.32 (5)°, respectively, from the plane of thiophene ring. In the crystal, weak C—H⋯O interactions link molecules related by translation along [100] into chains.

Related literature

For the crystal structures of related compounds, see: Wang et al. (2010 ▶); Yang et al. (2012 ▶). For details of the synthesis, see: Zhou et al. (2011 ▶). graphic file with name e-69-0o713-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₆N₂O₂S
M _r = 312.38
Monoclinic,
a = 14.174 (3) Å
b = 5.9321 (12) Å
c = 18.796 (4) Å
β = 99.06 (3)°
V = 1560.7 (5) Å³
Z = 4
Cu Kα radiation
μ = 1.91 mm⁻¹
T = 113 K
0.26 × 0.24 × 0.22 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.636, T _max = 0.678
16000 measured reflections
3034 independent reflections
2819 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.098
S = 1.08
3034 reflections
201 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005 ▶).

Supplementary Material

Click here for additional data file.^{(18.9KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009513/cv5399sup1.cif

e-69-0o713-sup1.cif^{(18.9KB, cif)}

Click here for additional data file.^{(148.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009513/cv5399Isup2.hkl

e-69-0o713-Isup2.hkl^{(148.9KB, hkl)}

Click here for additional data file.^{(3KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536813009513/cv5399Isup3.cdx

Click here for additional data file.^{(5.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813009513/cv5399Isup4.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O2ⁱ	0.95	2.53	3.3346 (19)	143

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Symmetry code: (i) Inline graphic .

Acknowledgments

This project was supported by the National Major Scientific and Technological Special Project for "Significant New Drugs Development" (No. 2013ZX09102014). The authors also thank Mr Hai-Bin Song of Nankai University for the X-ray crystallographic determination and helpful suggestions.

supplementary crystallographic information

Comment

As a continuation of our structural study of tetrahydrothienopyridine derivatives (Yang et al., 2012), herein we present the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related compounds 5-[(2-cyclopropylcarbonyl)(2- fluorophenyl)methyl]-4,5,6,7-tetrahydrothieno[3,2-c]pyridin- 2-yl acetate (Prasugrel) (Wang et al., 2010) and 5-(2-chlorobenzyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridin-2-yl acetate (Yang et al., 2012). The ester chain in (I) is almost planar with a mean deviation of 0.0021 Å. The tetrahydropyridine ring exhibits a half-chair conformation. The mean planes of the ester chain and benzene ring are twisted at 5.5 (1) and 81.32 (5)°, respectively, from the plane of thiophene ring. In the crystal, weak C—H···O interactions (Table 1) link the molecules related by translation in [100] into chains.

Experimental

The title compound was prepared according to the method of Zhou et al. (2011). 19.2 g of 5,6,7,7a-tetrahydrothieno[3,2-c]pyridin-2(4H)-one hydrochloride and 29 g of N-methyl morpholine were dissolved in 100 ml of CHCl₃. 42.6 g of 2-(bromomethyl)benzonitrile was dropwised into the mixture and then refluxed for 4 h. After filtration, the resulting filtrate was evaporated under reduced pressure. The residue was dissolved in diethyl ether, adjust the pH=5 to get 2-{(2-oxo-7,7a-dihydrothieno [3,2-c]pyridin-5(2H,4H,6H)-yl)methyl} benzonitrile as an intermediate. The intermediate, together with 14.5 g of N-methyl morpholine and 10 g of acetic anhydride was dissolved in 150 ml of acetonitrile and stirred under 30°C for 2 h. The mixture was evaporated under reduced pressure and yellow oil was obtained. The oil was dissolved in CHCl₃, washed with saturated brines for 3 times. The crude product was purified by silica gel chromatography to give white powder. Colorless single crystals were grown from a methanol solution.