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

Mukhtar, A.; Tahir, M.N.; Khan, M.A.; Ather, A.Q.; Khan, M.N.

doi:10.1107/S160053681202524X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2042

https://doi.org/10.1107/S160053681202524X

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

Asma Mukhtar,^a M. Nawaz Tahir,^b ^* Misbahul Ain Khan,^a Abdul Qayyum Ather ^c and Muhammad Naeem Khan ^c

^aInstitute of Chemistry, University of the Punjab, Lahore, Pakistan, ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, and ^cApplied Chemistry Research Center, PCSIR Laboratories Complex, Lahore 54600, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 3 June 2012; accepted 3 June 2012; online 13 June 2012)

In the title compound, C₁₃H₁₇NO₃S, the dihedral angles between the thiophene ring and the ethyl ester and acetamide groups are 5.21 (13) and 10.06 (16)°, respectively. The cyclohezene ring adopts a half-chair conformation. An S(6) ring is formed due to an intramolecular N—H⋯O hydrogen bond. In the crystal, molecules are linked by C—H⋯O interactions between the tetrahydro-1-benzothiophene unit and the ethyl ester group, forming C(7) chains propagating along the b-axis direction.

Related literature

For related structures, see: Mukhtar et al. (2010a ,b ).

Experimental

Crystal data

C₁₃H₁₇NO₃S
M_r = 267.34
Monoclinic, P 2₁ /c
a = 10.4267 (4) Å
b = 16.6554 (7) Å
c = 8.0961 (3) Å
β = 109.610 (1)°
V = 1324.43 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.28 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.953, T_max = 0.958
9994 measured reflections
2389 independent reflections
1831 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.105
S = 1.05
2389 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.86	2.03	2.674 (2)	131
C7—H7B⋯O3ⁱ	0.97	2.50	3.392 (3)	153
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681202524X/hb6836sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202524X/hb6836Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681202524X/hb6836Isup3.cml

checkCIF report

Comment top

We reported the crystal structures of ethyl 2-benzamido-4,5,6,7-tetrahydro-1- benzothiophene-3-carboxylate (Mukhtar et al., 2010a) and diethyl 5-acetamido-3-methylthiophene-2,4-dicarboxylate (Mukhtar et al., 2010b) which are related to the tile compound (I), (Fig. 1).

In (I), the thiophene ring A (S1/C8/C3/C2/C9), ethyl ester group B (O1/C1/O3/C10/C11) and acetamide moiety C (N1/C12/O2/C13) are planar with r. m. s. deviation of 0.0034, 0.0560 and 0.0029 Å, respectively. The dihedral angle between A/B, A/C and B/C is 5.21 (13), 5.17 (14) and 10.06 (16)°, respectively. In the title compound an S(6) ring motif is formed due to intramolecular H-bonding of N—H···O type (Table 1, Fig. 1). The molecules are linked in the form of C(7) chains extending along the [010] direction due to C—H···O type of H-bonding.

Related literature top

For related structures, see: Mukhtar et al. (2010a,b).

Experimental top

Ethyl 2-amino-4,5,6,7-tetrahydrobenzothiophene-3-carboxylate (0.3 g, 1 mmol) was dissolved in chloroform and in this solution 1 ml of acetyl chloride was added. The reaction mixture was refluxed for 8 h. The solvent was removed and the residue was recrystallized by ethanol to get colorless prisms of (I). m.p. 383 K, yield: 0.24 g, 85%.

Structure description top

For related structures, see: Mukhtar et al. (2010a,b).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line show intramolecular H-bonding.
	Fig. 2. The partial packing, which shows that molecules form C(7) chains extending along the b axis.

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

Crystal data top

C₁₃H₁₇NO₃S	F(000) = 568
M_r = 267.34	D_x = 1.341 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1831 reflections
a = 10.4267 (4) Å	θ = 2.4–25.3°
b = 16.6554 (7) Å	µ = 0.24 mm⁻¹
c = 8.0961 (3) Å	T = 296 K
β = 109.610 (1)°	Prism, colorless
V = 1324.43 (9) Å³	0.28 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2389 independent reflections
Radiation source: fine-focus sealed tube	1831 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.3°, θ_min = 2.4°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −19→19
T_min = 0.953, T_max = 0.958	l = −9→9
9994 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0403P)² + 0.4757P] where P = (F_o² + 2F_c²)/3
2389 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₃H₁₇NO₃S	V = 1324.43 (9) Å³
M_r = 267.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4267 (4) Å	µ = 0.24 mm⁻¹
b = 16.6554 (7) Å	T = 296 K
c = 8.0961 (3) Å	0.28 × 0.20 × 0.18 mm
β = 109.610 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2389 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1831 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.958	R_int = 0.032
9994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	Δρ_max = 0.27 e Å⁻³
2389 reflections	Δρ_min = −0.16 e Å⁻³
165 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
S1	−0.07735 (6)	0.14705 (4)	0.26031 (7)	0.0539 (2)
O1	0.22774 (14)	−0.08502 (9)	0.4124 (2)	0.0570 (5)
O2	−0.31724 (17)	0.09817 (13)	0.0095 (2)	0.0848 (8)
O3	0.03140 (16)	−0.11247 (10)	0.2017 (2)	0.0646 (6)
N1	−0.15117 (16)	0.00537 (11)	0.0871 (2)	0.0514 (6)
C1	0.1049 (2)	−0.06486 (13)	0.3047 (3)	0.0471 (7)
C2	0.06878 (18)	0.01882 (12)	0.3219 (2)	0.0408 (6)
C3	0.14704 (19)	0.07906 (12)	0.4432 (2)	0.0414 (6)
C4	0.2851 (2)	0.06876 (13)	0.5811 (3)	0.0488 (7)
C5	0.3212 (3)	0.13991 (14)	0.7081 (3)	0.0653 (8)
C6	0.2832 (3)	0.21870 (14)	0.6192 (3)	0.0690 (9)
C7	0.1317 (2)	0.22493 (13)	0.5254 (3)	0.0591 (8)
C8	0.0810 (2)	0.14974 (12)	0.4223 (3)	0.0459 (7)
C9	−0.05484 (19)	0.04848 (13)	0.2159 (3)	0.0444 (7)
C10	0.2653 (3)	−0.16924 (14)	0.4095 (4)	0.0742 (10)
C11	0.3917 (3)	−0.18249 (18)	0.5583 (4)	0.0926 (13)
C12	−0.2783 (2)	0.03142 (17)	−0.0096 (3)	0.0592 (9)
C13	−0.3644 (2)	−0.02882 (17)	−0.1363 (3)	0.0729 (9)
H1	−0.12894	−0.04227	0.06581	0.0616*
H4A	0.35340	0.06365	0.52467	0.0585*
H4B	0.28594	0.01977	0.64624	0.0585*
H5A	0.27501	0.13359	0.79324	0.0783*
H5B	0.41841	0.13940	0.77120	0.0783*
H6A	0.33036	0.22575	0.53537	0.0828*
H6B	0.31193	0.26133	0.70545	0.0828*
H7A	0.08553	0.23261	0.61017	0.0709*
H7B	0.11222	0.27086	0.44724	0.0709*
H10A	0.27966	−0.18170	0.29995	0.0889*
H10B	0.19331	−0.20356	0.42015	0.0889*
H11A	0.37805	−0.16655	0.66514	0.1389*
H11B	0.46381	−0.15119	0.54198	0.1389*
H11C	0.41548	−0.23836	0.56466	0.1389*
H13A	−0.41082	−0.00295	−0.24610	0.1095*
H13B	−0.43007	−0.05116	−0.08977	0.1095*
H13C	−0.30755	−0.07092	−0.15408	0.1095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0487 (3)	0.0506 (4)	0.0574 (4)	0.0098 (3)	0.0112 (3)	0.0046 (3)
O1	0.0475 (8)	0.0389 (9)	0.0741 (10)	0.0041 (7)	0.0066 (7)	−0.0051 (7)
O2	0.0593 (11)	0.0900 (15)	0.0849 (13)	0.0170 (10)	−0.0024 (9)	−0.0038 (11)
O3	0.0608 (10)	0.0489 (10)	0.0724 (10)	−0.0073 (8)	0.0068 (8)	−0.0142 (8)
N1	0.0423 (10)	0.0563 (12)	0.0496 (10)	−0.0041 (8)	0.0077 (8)	−0.0017 (9)
C1	0.0448 (12)	0.0451 (13)	0.0505 (12)	−0.0040 (10)	0.0148 (10)	−0.0003 (10)
C2	0.0381 (10)	0.0407 (12)	0.0439 (11)	−0.0022 (9)	0.0142 (8)	0.0012 (9)
C3	0.0441 (11)	0.0401 (12)	0.0407 (10)	−0.0008 (9)	0.0152 (9)	0.0028 (9)
C4	0.0471 (12)	0.0443 (12)	0.0481 (12)	−0.0007 (9)	0.0069 (9)	0.0002 (10)
C5	0.0655 (15)	0.0544 (15)	0.0590 (14)	−0.0056 (12)	−0.0015 (12)	−0.0052 (12)
C6	0.0776 (17)	0.0502 (15)	0.0660 (15)	−0.0082 (12)	0.0067 (13)	−0.0079 (12)
C7	0.0723 (16)	0.0418 (14)	0.0577 (13)	0.0061 (11)	0.0147 (12)	−0.0016 (10)
C8	0.0488 (12)	0.0424 (12)	0.0461 (11)	0.0033 (9)	0.0154 (9)	0.0028 (10)
C9	0.0428 (11)	0.0465 (12)	0.0448 (11)	−0.0016 (9)	0.0159 (9)	0.0035 (9)
C10	0.0717 (17)	0.0403 (14)	0.103 (2)	0.0095 (12)	0.0192 (15)	−0.0085 (13)
C11	0.0626 (17)	0.0620 (18)	0.139 (3)	0.0162 (14)	0.0149 (18)	0.0113 (18)
C12	0.0469 (13)	0.0751 (18)	0.0500 (13)	−0.0002 (12)	0.0087 (10)	0.0071 (12)
C13	0.0527 (14)	0.096 (2)	0.0562 (14)	−0.0106 (14)	0.0001 (11)	0.0007 (14)

Geometric parameters (Å, º) top

S1—C8	1.731 (2)	C10—C11	1.474 (4)
S1—C9	1.714 (2)	C12—C13	1.499 (4)
O1—C1	1.328 (3)	C4—H4A	0.9700
O1—C10	1.459 (3)	C4—H4B	0.9700
O2—C12	1.211 (3)	C5—H5A	0.9700
O3—C1	1.218 (3)	C5—H5B	0.9700
N1—C9	1.382 (3)	C6—H6A	0.9700
N1—C12	1.364 (3)	C6—H6B	0.9700
N1—H1	0.8600	C7—H7A	0.9700
C1—C2	1.463 (3)	C7—H7B	0.9700
C2—C9	1.378 (3)	C10—H10A	0.9700
C2—C3	1.449 (3)	C10—H10B	0.9700
C3—C4	1.506 (3)	C11—H11A	0.9600
C3—C8	1.346 (3)	C11—H11B	0.9600
C4—C5	1.531 (3)	C11—H11C	0.9600
C5—C6	1.485 (3)	C13—H13A	0.9600
C6—C7	1.509 (4)	C13—H13B	0.9600
C7—C8	1.499 (3)	C13—H13C	0.9600

C8—S1—C9	91.19 (10)	C4—C5—H5A	109.00
C1—O1—C10	115.95 (19)	C4—C5—H5B	109.00
C9—N1—C12	126.0 (2)	C6—C5—H5A	109.00
C9—N1—H1	117.00	C6—C5—H5B	109.00
C12—N1—H1	117.00	H5A—C5—H5B	108.00
O1—C1—O3	122.1 (2)	C5—C6—H6A	109.00
O3—C1—C2	124.3 (2)	C5—C6—H6B	109.00
O1—C1—C2	113.63 (18)	C7—C6—H6A	109.00
C1—C2—C9	119.95 (18)	C7—C6—H6B	109.00
C1—C2—C3	128.32 (17)	H6A—C6—H6B	108.00
C3—C2—C9	111.72 (18)	C6—C7—H7A	110.00
C2—C3—C8	111.88 (17)	C6—C7—H7B	110.00
C2—C3—C4	127.17 (18)	C8—C7—H7A	110.00
C4—C3—C8	120.95 (18)	C8—C7—H7B	110.00
C3—C4—C5	111.59 (19)	H7A—C7—H7B	108.00
C4—C5—C6	113.14 (19)	O1—C10—H10A	110.00
C5—C6—C7	111.6 (2)	O1—C10—H10B	110.00
C6—C7—C8	109.67 (18)	C11—C10—H10A	110.00
C3—C8—C7	126.2 (2)	C11—C10—H10B	110.00
S1—C8—C3	112.99 (16)	H10A—C10—H10B	108.00
S1—C8—C7	120.80 (16)	C10—C11—H11A	109.00
N1—C9—C2	125.09 (19)	C10—C11—H11B	109.00
S1—C9—N1	122.70 (16)	C10—C11—H11C	109.00
S1—C9—C2	112.22 (16)	H11A—C11—H11B	109.00
O1—C10—C11	107.6 (2)	H11A—C11—H11C	109.00
N1—C12—C13	115.0 (2)	H11B—C11—H11C	109.00
O2—C12—N1	121.4 (2)	C12—C13—H13A	109.00
O2—C12—C13	123.5 (2)	C12—C13—H13B	109.00
C3—C4—H4A	109.00	C12—C13—H13C	109.00
C3—C4—H4B	109.00	H13A—C13—H13B	109.00
C5—C4—H4A	109.00	H13A—C13—H13C	110.00
C5—C4—H4B	109.00	H13B—C13—H13C	109.00
H4A—C4—H4B	108.00

C9—S1—C8—C3	−0.74 (18)	C9—C2—C3—C4	178.71 (19)
C9—S1—C8—C7	−179.82 (19)	C9—C2—C3—C8	−0.6 (2)
C8—S1—C9—N1	−179.31 (19)	C1—C2—C9—S1	179.01 (15)
C8—S1—C9—C2	0.37 (17)	C1—C2—C9—N1	−1.3 (3)
C10—O1—C1—O3	−4.5 (3)	C3—C2—C9—S1	0.0 (2)
C10—O1—C1—C2	175.9 (2)	C3—C2—C9—N1	179.72 (19)
C1—O1—C10—C11	−169.7 (2)	C2—C3—C4—C5	−167.96 (19)
C12—N1—C9—S1	−5.9 (3)	C8—C3—C4—C5	11.3 (3)
C12—N1—C9—C2	174.4 (2)	C2—C3—C8—S1	0.9 (2)
C9—N1—C12—O2	1.2 (4)	C2—C3—C8—C7	179.9 (2)
C9—N1—C12—C13	−177.8 (2)	C4—C3—C8—S1	−178.48 (15)
O1—C1—C2—C3	−2.4 (3)	C4—C3—C8—C7	0.6 (3)
O1—C1—C2—C9	178.80 (19)	C3—C4—C5—C6	−41.8 (3)
O3—C1—C2—C3	178.0 (2)	C4—C5—C6—C7	61.4 (3)
O3—C1—C2—C9	−0.8 (3)	C5—C6—C7—C8	−46.2 (3)
C1—C2—C3—C4	−0.2 (3)	C6—C7—C8—S1	−164.26 (17)
C1—C2—C3—C8	−179.5 (2)	C6—C7—C8—C3	16.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	2.03	2.674 (2)	131
C7—H7B···O3ⁱ	0.97	2.50	3.392 (3)	153

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₇NO₃S
M_r	267.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.4267 (4), 16.6554 (7), 8.0961 (3)
β (°)	109.610 (1)
V (Å³)	1324.43 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.28 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.953, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	9994, 2389, 1831
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.105, 1.05
No. of reflections	2389
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.16

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	2.03	2.674 (2)	131
C7—H7B···O3ⁱ	0.97	2.50	3.392 (3)	153

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

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

References

Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Mukhtar, A., Tahir, M. N., Khan, M. A. & Khan, M. N. (2010a). Acta Cryst. E66, o2652. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mukhtar, A., Tahir, M. N., Khan, M. A. & Khan, M. N. (2010b). Acta Cryst. E66, o3171. 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar