Methyl 2-(2-hydroxy­benzyl­ideneamino)-4,5,6,7-tetra­hydro-1-benzothio­phene-3-carboxyl­ate

Mehmet Akkurt; Selvi Karaca; Abdullah Mohamed Asiri; Orhan Büyükgüngör

doi:10.1107/S1600536808010489

. 2008 Apr 18;64(Pt 5):o869. doi: 10.1107/S1600536808010489

Methyl 2-(2-hydroxybenzylideneamino)-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylate

Mehmet Akkurt ^a,^*, Selvi Karaca ^a, Abdullah Mohamed Asiri ^b, Orhan Büyükgüngör ^c

PMCID: PMC2961328 PMID: 21202355

Abstract

In the title compound, C₁₇H₁₇NO₃S, the cyclohexene ring is essentially planar, with a maximum deviation of 0.006 (1) Å. The cyclohexene ring adopts a half-chair conformation. The dihedral angle between the thiophene and benzene rings is 29.7 (1)°. The molecular structure exhibits intramolecular O—H⋯O, O—H⋯N and C—H⋯S hydrogen bonds, which generate one S(5) and two S(6) motifs. There is also a C—H⋯π interaction between the cyclohexene ring system and the π-system of the benzene ring.

Related literature

For related literature, see: Akkurt et al. (2008 ▶); Allen et al. (1987 ▶); Asiri & Badahdah (2007 ▶); Bernstein et al. (1995 ▶); Cremer & Pople (1975 ▶); Etter (1990 ▶).

Experimental

Crystal data

C₁₇H₁₇NO₃S
M _r = 315.39
Monoclinic,
a = 7.6107 (4) Å
b = 21.2154 (9) Å
c = 11.1827 (7) Å
β = 123.342 (4)°
V = 1508.41 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 (2) K
0.60 × 0.47 × 0.23 mm

Data collection

Stoe IPDS2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.876, T _max = 0.950
8036 measured reflections
3086 independent reflections
2361 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.121
S = 0.99
3086 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808010489/is2289sup1.cif

e-64-0o869-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010489/is2289Isup2.hkl

e-64-0o869-Isup2.hkl^{(148.3KB, hkl)}

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
O1—H1⋯O2	0.82	2.50	3.102 (2)	132
O1—H1⋯N1	0.82	1.88	2.607 (2)	146
C7—H7⋯S1	0.93	2.69	3.0725 (19)	105
C15—H15A⋯Cgⁱ	0.97	2.92	3.782 (3)	150

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Symmetry code: (i) Inline graphic . Cg is the centroid of the benzene ring.

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS2 diffractometer (purchased under grant F.279 of the University Research Fund).

supplementary crystallographic information

Comment

In a previous paper, we reported the structure of 4-[(2-hydroxy-1-naphthyl)methylideneamino]benzoic acid (Akkurt et al., 2008). The present work is part of an ongoing investigation in the development of anil derivatives. Here, we report the structure of the title compound 2-[(2-hydroxybenzylidene)amino]-3-methoxycarbonyl-3,4,5,6- tetrahydrobenzo[d]thiophene, (I).

In the title compound (I) (Fig. 1), all bond lengths and angles are in normal range (Allen et al., 1987). The thiophene ring is essentially planar, with maximum deviations of 0.006 (1) Å for S1 and 0.006 (3) Å for C17. The cyclohexene ring adopts a half-chair conformation, with the puckering parameters Q_T = 0.502 (2) Å, θ = 52.1 (2)° and φ = 151.4 (3)° (Cremer & Pople, 1975). The dihedral angle between the thiophene ring and the benzene ring is 29.7 (1)°.

In the molecular structure, the intramolecular O1—H1···O2, and O1—H1···N1 hydrogen bonds form two pseudo-six membered rings [S(6) motifs (Bernstein et al., 1995; Etter, 1990)] and C7—H7···S1 forms a pseudo five membered ring [S(5) motif], thus locking the molecular conformation and eliminating flexibility (Fig. 1 and Table 1). There are also interactions of the C—H···π type [C15—H15A···π (-1 + x, 1/2 - y, -1/2 + z), H15···π = 2.91 Å, C15···π = 3.782 (3) Å] observed between the cyclohexene ring system and the π system of the benzene ring. A view of the packing of the title compound in the unit cell is shown in Fig. 2.

Experimental

A solution of 2-amino-3-methoxycarbonyl-3,4,5,6-tetrahydrobenzo[d]thieophene (2.0 g, 6.35 mmol) in pure ethanol was heated to its boiling temperature, and then 2-hydroxynaphthaldehyde (0.77 g, 6.35 mmol) dissolved in hot ethanol was added to the amine solution and the resulting mixture was then refluxed for 5 h. Cooling the mixture, filtering the precipitates and recrystalization from ethanol gave the pure product (Asiri & Badahdah, 2007). IR (KBr) ν (cm^-1); 1697 (C═O), 1604 (C═N), 1443 (C═C), 1323 (C—O) and 1136 (C—N) [yield 98%, m.p. 417 K].