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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2652.
Published online 2010 September 30. doi:  10.1107/S1600536810037761
PMCID: PMC2983258

Ethyl 2-benzamido-4,5,6,7-tetra­hydro-1-benzothio­phene-3-carboxyl­ate

Abstract

The mol­ecule of the title compound, C18H19NO3S, adopts an approximately planar conformation: the thio­phene and phenyl rings form a dihedral angle of 8.13 (11)° while the ethyl ester group (r.m.s. deviation = 0.0217 Å) is inclined at 1.25 (14) and 8.61 (13)°, respectively, to the thio­phene and phenyl rings. An intra­molecular N—H(...)O hydrogen bond with an S(6) ring motif occurs as well as an intra­molecular S(...)O hypervalent inter­action [S(...)O = 2.7369 (18) Å]. The cyclo­hexene ring adopts a half-chair conformation and is disordered over two positions with site occupation factors of 0.641 (6) and 0.359 (6). In the crystal, inversion dimers linked by pairs of O—H(...)O hydrogen bonds generate R 2 2(10) loops.

Related literature

For background on thio­phene derivatives, see: Dupin et al. (2002 [triangle]); Khan & Rolim (1983 [triangle]); Sabnis et al. (1999 [triangle]). For related structures, see: Harrison et al. (2006 [triangle]); Yathirajan et al. (2007 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2652-scheme1.jpg

Experimental

Crystal data

  • C18H19NO3S
  • M r = 329.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2652-efi1.jpg
  • a = 8.1061 (2) Å
  • b = 10.6593 (3) Å
  • c = 19.0554 (5) Å
  • β = 92.500 (1)°
  • V = 1644.92 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 296 K
  • 0.25 × 0.20 × 0.20 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.953, T max = 0.958
  • 12204 measured reflections
  • 2964 independent reflections
  • 2052 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.117
  • S = 1.01
  • 2964 reflections
  • 210 parameters
  • 6 restraints
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks text, I. DOI: 10.1107/S1600536810037761/gk2302sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037761/gk2302Isup2.hkl

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

Comment

Thiophenes and their condensed derivatives have been described in the literature (Khan & Rolim, 1983). Tetrahydro-1-benzothiophenes are intermediates for many useful products such as dyes and pharmaceuticals (Sabnis et al., 1999) and compounds containing thrombolytic activity (Dupin et al., 2002). The title compound (Fig. 1) has been prepared for the derivatization of other compounds.

The crystal structures of ethyl 2-acetylamino-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylate (Harrison et al., 2006) and i.e. ethyl 2-(propionylamino)-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylate (Yathirajan et al., 2007) have been published which are related to the title compound.

In the title compound, the heterocyclic ring A (S1/C8/C9/C10/C15) and the phenyl ring B (C1—C6) are planar. The dihedral angle between A/B is 8.13 (11)°. The ethyl ester group C (O2/C16/O3/C17/C18) is planar with r. m. s. deviation of 0.0217 Å and is inclined at 1.25 (14) and 8.61 (13)° with the rings A and B, respectively. In the title compound an S(6) ring motif (Bernstein et al., 1995) is formed due to intramolecular H-bonding of N—H···O type (Table 1, Fig. 1). Two methylene groups of the cyclohexene ring in half-chair conformation are disordered over two positions with site occupation factors of 0.641 (6) and 0.359 (6).

Experimental

Ethyl 2-amino-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylate (0.3 g, 1.0 mmol) was dissolved in 10 ml of chloroform. To this solution 0.15 ml of benzoyl chloride was added and heated under reflux for 9 h. The solvent was removed and the residue was recrystallized from ethanol to affoard the colorless prism.

Refinement

In the cyclohexene ring two methylene groups are disordered over two positions with site occupation factors of 0.641 (6) and 0.359 (6). The disordered C atoms were refined anisotropically with equal displacement parameters (EADP instruction of SHELXL97).

The H atoms were positioned geometrically (N—H = 0.86, C–H = 0.93–0.97 Å) and refined as riding with Uiso(H) = xUeq(C, N), where x = 1.5 for methyl and x = 1.2 for other H atoms.

Figures

Fig. 1.
View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii. The dotted line shows intramolecular hydrogen bonding.

Crystal data

C18H19NO3SF(000) = 696
Mr = 329.40Dx = 1.330 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2052 reflections
a = 8.1061 (2) Åθ = 2.5–25.3°
b = 10.6593 (3) ŵ = 0.21 mm1
c = 19.0554 (5) ÅT = 296 K
β = 92.500 (1)°Prism, colorless
V = 1644.92 (8) Å30.25 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer2964 independent reflections
Radiation source: fine-focus sealed tube2052 reflections with I > 2σ(I)
graphiteRint = 0.037
Detector resolution: 8.10 pixels mm-1θmax = 25.3°, θmin = 2.5°
ω scansh = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −12→12
Tmin = 0.953, Tmax = 0.958l = −22→22
12204 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0503P)2 + 0.4332P] where P = (Fo2 + 2Fc2)/3
2964 reflections(Δ/σ)max < 0.001
210 parametersΔρmax = 0.16 e Å3
6 restraintsΔρmin = −0.19 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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)

xyzUiso*/UeqOcc. (<1)
S10.75739 (8)0.64947 (6)0.09851 (3)0.0685 (2)
O10.9000 (2)0.82309 (16)0.01442 (9)0.0875 (7)
O20.8026 (2)0.41537 (14)−0.09850 (7)0.0658 (6)
O30.6816 (2)0.26412 (14)−0.03830 (7)0.0666 (6)
N10.8625 (2)0.63457 (16)−0.03524 (8)0.0527 (6)
C10.9770 (3)0.8019 (2)−0.10411 (11)0.0545 (7)
C20.9702 (3)0.7346 (2)−0.16629 (12)0.0679 (9)
C31.0262 (3)0.7864 (3)−0.22706 (13)0.0781 (10)
C41.0909 (3)0.9047 (3)−0.22675 (14)0.0804 (11)
C51.1013 (3)0.9711 (3)−0.16569 (16)0.0830 (11)
C61.0438 (3)0.9216 (2)−0.10479 (13)0.0697 (9)
C70.9121 (3)0.7563 (2)−0.03689 (12)0.0582 (8)
C80.7865 (2)0.5770 (2)0.01970 (10)0.0484 (7)
C90.7256 (2)0.45660 (19)0.01795 (10)0.0464 (7)
C100.6520 (2)0.4227 (2)0.08292 (10)0.0505 (7)
C110.5695 (3)0.2999 (2)0.09967 (11)0.0615 (8)
C12A0.5302 (8)0.2864 (5)0.1768 (3)0.0771 (13)0.641 (6)
C13A0.4684 (7)0.4071 (4)0.2069 (3)0.0771 (13)0.641 (6)
C140.5952 (3)0.5146 (3)0.20270 (12)0.0820 (10)
C150.6620 (3)0.5167 (2)0.12986 (11)0.0601 (8)
C160.7408 (3)0.3798 (2)−0.04470 (11)0.0518 (7)
C170.6953 (4)0.1819 (2)−0.09806 (13)0.0804 (10)
C180.6130 (4)0.0615 (3)−0.08052 (16)0.1017 (13)
C12B0.4639 (11)0.3191 (11)0.1642 (4)0.0771 (13)0.359 (6)
C13B0.5564 (13)0.3883 (8)0.2231 (4)0.0771 (13)0.359 (6)
H10.880060.58943−0.071570.0632*
H41.127710.93963−0.267970.0964*
H20.927510.65362−0.167050.0815*
H31.019810.74051−0.268600.0936*
H11A0.641110.231420.086920.0738*
H11B0.467740.292690.071200.0738*
H12A0.447090.221780.181360.0926*0.641 (6)
H12B0.628870.260100.203380.0926*0.641 (6)
H13A0.443020.393690.255570.0926*0.641 (6)
H13B0.367030.431380.181470.0926*0.641 (6)
H14A0.542760.594090.212470.0985*
H14B0.684760.501680.237380.0985*
H17A0.810520.16736−0.107240.0962*
H17B0.641830.21915−0.139550.0962*
H18A0.665590.02642−0.038880.1525*
H18B0.621800.00366−0.118810.1525*
H18C0.498610.07682−0.072590.1525*
H51.147761.05084−0.165170.0996*
H61.049690.96880−0.063710.0837*
H12C0.365490.366160.150210.0926*0.359 (6)
H12D0.429290.237980.181300.0926*0.359 (6)
H13C0.489490.390360.264020.0926*0.359 (6)
H13D0.657700.343710.235640.0926*0.359 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0836 (4)0.0704 (4)0.0522 (3)−0.0085 (3)0.0127 (3)−0.0147 (3)
O10.1332 (16)0.0676 (12)0.0634 (10)−0.0298 (11)0.0243 (10)−0.0167 (9)
O20.0950 (11)0.0567 (10)0.0472 (9)−0.0046 (8)0.0196 (8)−0.0014 (7)
O30.0983 (12)0.0495 (9)0.0532 (9)−0.0073 (8)0.0168 (8)−0.0036 (7)
N10.0610 (11)0.0512 (11)0.0463 (10)−0.0008 (8)0.0086 (8)−0.0027 (8)
C10.0553 (12)0.0529 (13)0.0555 (13)−0.0032 (10)0.0045 (10)0.0017 (11)
C20.0746 (15)0.0689 (16)0.0609 (14)−0.0185 (12)0.0098 (12)−0.0028 (13)
C30.0868 (18)0.089 (2)0.0591 (15)−0.0080 (15)0.0115 (13)−0.0011 (14)
C40.0936 (19)0.0776 (19)0.0714 (17)0.0040 (15)0.0196 (14)0.0237 (16)
C50.101 (2)0.0565 (16)0.093 (2)−0.0055 (14)0.0221 (16)0.0151 (15)
C60.0878 (17)0.0550 (15)0.0670 (15)−0.0053 (12)0.0108 (13)0.0003 (12)
C70.0642 (14)0.0529 (14)0.0576 (13)−0.0069 (11)0.0053 (10)−0.0027 (12)
C80.0476 (11)0.0559 (13)0.0418 (11)0.0043 (10)0.0031 (9)−0.0007 (9)
C90.0489 (11)0.0482 (12)0.0420 (11)0.0049 (9)0.0025 (9)0.0029 (9)
C100.0485 (12)0.0593 (14)0.0439 (11)0.0080 (10)0.0039 (9)0.0047 (10)
C110.0621 (13)0.0656 (15)0.0576 (13)0.0034 (11)0.0117 (10)0.0105 (11)
C12A0.076 (3)0.098 (2)0.0587 (18)0.004 (2)0.0198 (18)0.0171 (15)
C13A0.076 (3)0.098 (2)0.0587 (18)0.004 (2)0.0198 (18)0.0171 (15)
C140.0943 (18)0.105 (2)0.0479 (13)0.0045 (16)0.0172 (12)−0.0045 (14)
C150.0626 (14)0.0730 (16)0.0452 (12)0.0009 (11)0.0096 (10)−0.0011 (11)
C160.0594 (13)0.0505 (13)0.0456 (12)0.0025 (10)0.0044 (10)0.0043 (10)
C170.127 (2)0.0565 (15)0.0587 (15)−0.0111 (15)0.0169 (14)−0.0116 (12)
C180.154 (3)0.0614 (18)0.090 (2)−0.0203 (18)0.0097 (19)−0.0084 (16)
C12B0.076 (3)0.098 (2)0.0587 (18)0.004 (2)0.0198 (18)0.0171 (15)
C13B0.076 (3)0.098 (2)0.0587 (18)0.004 (2)0.0198 (18)0.0171 (15)

Geometric parameters (Å, °)

S1—C81.714 (2)C13B—C141.440 (9)
S1—C151.732 (2)C14—C151.512 (3)
O1—C71.217 (3)C17—C181.491 (4)
O2—C161.221 (3)C2—H20.9300
O3—C161.331 (3)C3—H30.9300
O3—C171.445 (3)C4—H40.9300
N1—C71.359 (3)C5—H50.9300
N1—C81.381 (2)C6—H60.9300
N1—H10.8600C11—H11A0.9700
C1—C21.384 (3)C11—H11B0.9700
C1—C61.386 (3)C12A—H12A0.9700
C1—C71.488 (3)C12A—H12B0.9700
C2—C31.378 (3)C12B—H12D0.9700
C3—C41.366 (4)C12B—H12C0.9700
C4—C51.361 (4)C13A—H13B0.9700
C5—C61.375 (4)C13A—H13A0.9700
C8—C91.375 (3)C13B—H13C0.9700
C9—C101.444 (3)C13B—H13D0.9700
C9—C161.457 (3)C14—H14A0.9700
C10—C151.343 (3)C14—H14B0.9700
C10—C111.510 (3)C17—H17A0.9700
C11—C12A1.524 (6)C17—H17B0.9700
C11—C12B1.542 (8)C18—H18B0.9600
C12A—C13A1.503 (7)C18—H18C0.9600
C12B—C13B1.514 (12)C18—H18A0.9600
C13A—C141.544 (6)
C8—S1—C1590.83 (10)C1—C6—H6120.00
C16—O3—C17116.70 (17)C5—C6—H6120.00
C7—N1—C8125.72 (18)C10—C11—H11A109.00
C7—N1—H1117.00C10—C11—H11B109.00
C8—N1—H1117.00C12A—C11—H11A109.00
C2—C1—C6118.0 (2)C12A—C11—H11B109.00
C2—C1—C7124.4 (2)H11A—C11—H11B108.00
C6—C1—C7117.5 (2)C12B—C11—H11A131.00
C1—C2—C3120.6 (2)C12B—C11—H11B88.00
C2—C3—C4120.5 (2)C11—C12A—H12A109.00
C3—C4—C5119.6 (3)C11—C12A—H12B109.00
C4—C5—C6120.8 (3)C13A—C12A—H12A109.00
C1—C6—C5120.5 (2)C13A—C12A—H12B109.00
O1—C7—C1123.0 (2)H12A—C12A—H12B108.00
O1—C7—N1120.4 (2)C13B—C12B—H12C109.00
N1—C7—C1116.61 (19)C11—C12B—H12C109.00
S1—C8—C9112.26 (14)C11—C12B—H12D109.00
S1—C8—N1123.14 (16)C13B—C12B—H12D109.00
N1—C8—C9124.60 (18)H12C—C12B—H12D108.00
C8—C9—C16120.08 (17)C12A—C13A—H13A109.00
C10—C9—C16127.95 (18)C14—C13A—H13A109.00
C8—C9—C10111.98 (17)C14—C13A—H13B109.00
C11—C10—C15121.34 (18)C12A—C13A—H13B109.00
C9—C10—C11126.98 (18)H13A—C13A—H13B108.00
C9—C10—C15111.67 (19)C14—C13B—H13C109.00
C10—C11—C12B108.7 (5)C14—C13B—H13D109.00
C10—C11—C12A113.5 (3)C12B—C13B—H13C109.00
C11—C12A—C13A112.0 (4)C12B—C13B—H13D109.00
C11—C12B—C13B112.4 (7)H13C—C13B—H13D108.00
C12A—C13A—C14112.4 (4)C13A—C14—H14A110.00
C12B—C13B—C14111.2 (7)C13A—C14—H14B110.00
C13A—C14—C15108.9 (3)C15—C14—H14A110.00
C13B—C14—C15110.7 (4)C13B—C14—H14A131.00
S1—C15—C10113.26 (16)C13B—C14—H14B81.00
S1—C15—C14120.80 (18)C15—C14—H14B110.00
C10—C15—C14125.9 (2)H14A—C14—H14B108.00
O2—C16—C9124.47 (19)C18—C17—H17A110.00
O3—C16—C9113.69 (18)O3—C17—H17A110.00
O2—C16—O3121.84 (19)O3—C17—H17B110.00
O3—C17—C18107.2 (2)H17A—C17—H17B109.00
C1—C2—H2120.00C18—C17—H17B110.00
C3—C2—H2120.00C17—C18—H18C109.00
C2—C3—H3120.00C17—C18—H18B109.00
C4—C3—H3120.00H18B—C18—H18C109.00
C3—C4—H4120.00H18A—C18—H18B109.00
C5—C4—H4120.00H18A—C18—H18C109.00
C4—C5—H5120.00C17—C18—H18A109.00
C6—C5—H5120.00
C15—S1—C8—N1179.88 (17)S1—C8—C9—C100.33 (19)
C15—S1—C8—C9−0.02 (15)S1—C8—C9—C16−179.36 (15)
C8—S1—C15—C10−0.32 (18)N1—C8—C9—C10−179.57 (16)
C8—S1—C15—C14−178.7 (2)N1—C8—C9—C160.8 (3)
C17—O3—C16—O20.5 (3)C8—C9—C10—C11178.53 (18)
C17—O3—C16—C9−178.9 (2)C8—C9—C10—C15−0.6 (2)
C16—O3—C17—C18−176.8 (2)C16—C9—C10—C11−1.8 (3)
C8—N1—C7—O14.4 (3)C16—C9—C10—C15179.1 (2)
C8—N1—C7—C1−174.38 (19)C8—C9—C16—O2−1.6 (3)
C7—N1—C8—S1−5.3 (3)C8—C9—C16—O3177.88 (18)
C7—N1—C8—C9174.55 (19)C10—C9—C16—O2178.8 (2)
C6—C1—C2—C3−0.9 (4)C10—C9—C16—O3−1.8 (3)
C7—C1—C2—C3176.9 (2)C9—C10—C11—C12A170.4 (3)
C2—C1—C6—C50.0 (4)C15—C10—C11—C12A−10.6 (4)
C7—C1—C6—C5−178.0 (2)C9—C10—C15—S10.6 (2)
C2—C1—C7—O1−170.1 (2)C9—C10—C15—C14178.9 (2)
C2—C1—C7—N18.6 (3)C11—C10—C15—S1−178.60 (16)
C6—C1—C7—O17.7 (4)C11—C10—C15—C14−0.3 (3)
C6—C1—C7—N1−173.6 (2)C10—C11—C12A—C13A39.9 (5)
C1—C2—C3—C40.7 (4)C11—C12A—C13A—C14−59.8 (6)
C2—C3—C4—C50.6 (4)C12A—C13A—C14—C1546.7 (5)
C3—C4—C5—C6−1.6 (4)C13A—C14—C15—S1160.7 (3)
C4—C5—C6—C11.3 (4)C13A—C14—C15—C10−17.5 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O20.862.022.664 (2)131
C6—H6···O1i0.932.443.242 (3)145
C11—H11A···O30.972.452.845 (3)104

Symmetry codes: (i) −x+2, −y+2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2302).

References

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