Diethyl 5-acetamido-3-methyl­thio­phene-2,4-dicarboxyl­ate

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

doi:10.1107/S1600536810045629

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3171

https://doi.org/10.1107/S1600536810045629

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Diethyl 5-acetamido-3-methylthiophene-2,4-dicarboxylate

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

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

(Received 6 November 2010; accepted 7 November 2010; online 13 November 2010)

The title compound, C₁₃H₁₇NO₅S, is approximately planar (r.m.s. deviation for the non-H atoms = 0.055 Å). Its conformation is stabilized by N—H⋯O and C—H⋯O hydrogen bonds, which both generate S(6) rings. The crystal packing only features van der Waals contacts.

Related literature

For a related crystal structure and background, see: Mukhtar et al. (2010 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₇NO₅S
M_r = 299.34
Monoclinic, P 2₁ /n
a = 15.933 (3) Å
b = 4.6028 (6) Å
c = 20.152 (3) Å
β = 106.005 (7)°
V = 1420.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.25 × 0.10 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.972, T_max = 0.983
10222 measured reflections
2518 independent reflections
1311 reflections with I > 2σ(I)
R_int = 0.094

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.172
S = 1.02
2518 reflections
186 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.99	2.652 (5)	133
C10—H10B⋯O4	0.96	2.24	2.995 (6)	135

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/S1600536810045629/hb5730sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045629/hb5730Isup2.hkl

checkCIF report

Comment top

We have reported the synthesis and crystal structure of (II) i.e., Ethyl 2-benzamido-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylate (Mukhtar et al., 2010). The title compound (I, Fig. 1) is being reported here in continuation to synthesize various thiophene derivatives.

The title compound essentially consists of monomers. In (I), the methylthiophene group A (C1—C4/S1/C10), acetamide group B (N1/C5/C6/O1), ethylester groups C (O2/C7/O3/C8/C9) and D (O4/C11/O5/C12/C13) are planar with r. m. s. deviation of 0.0049, 0.0033, 0.0224 and 0.0082 Å, respectively. The dihedral angle between A/B, A/C, A/D, B/C, B/D and C/D is 5.55 (29), 7.30 (32), 6.24 (25), 10.40 (36), 10.51 (29) and 12.08 (32)°, respectively. In the title compound two S(6) ring motifs (Bernstein et al., 1995) are formed due to intramolecular H-bondings of C—H···O and N—H···O types (Table 1, Fig. 1). There does not exist any appreciable π interaction.

Related literature top

For a related crystal structure and background, see: Mukhtar et al. (2010). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A mixture of (0.3 g, 1 mmol) diethyl 2-amino-4-methylthiophene- 3,5-dicarboxylate, dissolved in chloroform and 0.1 ml of acetyl chloride was heated at 330 K for 10 h. The solvent of resultant product was removed and the residue was recrystallized from ethanol to give orange needles of the title compound. m.p. 394 K; yield: 0.25 g; 85%.

Structure description top

For a related crystal structure and background, see: Mukhtar et al. (2010). For graph-set notation, see: Bernstein et al. (1995).

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. H-atoms are shown as small spheres of arbitrary radii. The dotted lines represents the intramolecular H-bondings.

Diethyl 5-acetamido-3-methylthiophene-2,4-dicarboxylate top

Crystal data top

C₁₃H₁₇NO₅S	F(000) = 632
M_r = 299.34	D_x = 1.400 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1311 reflections
a = 15.933 (3) Å	θ = 2.1–25.1°
b = 4.6028 (6) Å	µ = 0.25 mm⁻¹
c = 20.152 (3) Å	T = 296 K
β = 106.005 (7)°	Needle, orange
V = 1420.6 (4) Å³	0.25 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2518 independent reflections
Radiation source: fine-focus sealed tube	1311 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.094
Detector resolution: 8.20 pixels mm^-1	θ_max = 25.1°, θ_min = 2.1°
ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −5→5
T_min = 0.972, T_max = 0.983	l = −20→24
10222 measured reflections

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)] = 0.065	H-atom parameters constrained
wR(F²) = 0.172	w = 1/[σ²(F_o²) + (0.0583P)² + 0.3244P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2518 reflections	Δρ_max = 0.25 e Å⁻³
186 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Crystal data top

C₁₃H₁₇NO₅S	V = 1420.6 (4) Å³
M_r = 299.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.933 (3) Å	µ = 0.25 mm⁻¹
b = 4.6028 (6) Å	T = 296 K
c = 20.152 (3) Å	0.25 × 0.10 × 0.08 mm
β = 106.005 (7)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2518 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1311 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.983	R_int = 0.094
10222 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.02	Δρ_max = 0.25 e Å⁻³
2518 reflections	Δρ_min = −0.23 e Å⁻³
186 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	0.31949 (8)	0.0384 (2)	0.49921 (6)	0.0506 (5)
O1	0.2674 (2)	0.0997 (7)	0.35864 (17)	0.0745 (17)
O2	0.1065 (2)	0.7124 (7)	0.48056 (18)	0.0619 (12)
O3	0.1245 (2)	0.6438 (6)	0.59347 (17)	0.0568 (12)
O4	0.4142 (3)	−0.1121 (7)	0.6963 (2)	0.0805 (17)
O5	0.4407 (2)	−0.2748 (6)	0.59982 (16)	0.0583 (11)
N1	0.1981 (2)	0.3879 (7)	0.4170 (2)	0.0505 (16)
C1	0.2371 (3)	0.2886 (8)	0.4826 (3)	0.0431 (16)
C2	0.2152 (3)	0.3811 (9)	0.5411 (2)	0.0441 (17)
C3	0.2680 (3)	0.2433 (9)	0.6015 (2)	0.0448 (16)
C4	0.3277 (3)	0.0560 (9)	0.5869 (2)	0.0470 (17)
C5	0.2156 (3)	0.2958 (10)	0.3575 (3)	0.058 (2)
C6	0.1661 (3)	0.4472 (11)	0.2930 (3)	0.072 (2)
C7	0.1450 (3)	0.5918 (9)	0.5342 (3)	0.0504 (19)
C8	0.0519 (3)	0.8434 (10)	0.5883 (3)	0.0568 (19)
C9	0.0353 (4)	0.8550 (11)	0.6579 (3)	0.081 (2)
C10	0.2625 (3)	0.2958 (10)	0.6742 (2)	0.0622 (19)
C11	0.3963 (3)	−0.1159 (10)	0.6338 (3)	0.0559 (19)
C12	0.5140 (3)	−0.4391 (10)	0.6418 (3)	0.067 (2)
C13	0.5539 (3)	−0.6035 (10)	0.5932 (3)	0.0692 (19)
H1	0.15902	0.52060	0.41285	0.0604*
H6A	0.18642	0.38122	0.25496	0.1074*
H6B	0.17496	0.65304	0.29852	0.1074*
H6C	0.10496	0.40458	0.28401	0.1074*
H8A	0.00031	0.77509	0.55396	0.0687*
H8B	0.06655	1.03516	0.57495	0.0687*
H9A	0.08548	0.93427	0.69089	0.1219*
H9B	0.02430	0.66237	0.67177	0.1219*
H9C	−0.01457	0.97565	0.65561	0.1219*
H10A	0.27447	0.49656	0.68603	0.0934*
H10B	0.30462	0.17622	0.70576	0.0934*
H10C	0.20497	0.24802	0.67713	0.0934*
H12A	0.49428	−0.57346	0.67146	0.0802*
H12B	0.55670	−0.30905	0.67064	0.0802*
H13A	0.57324	−0.46835	0.56419	0.1038*
H13B	0.51108	−0.73156	0.56500	0.1038*
H13C	0.60277	−0.71498	0.61936	0.1038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0497 (8)	0.0563 (7)	0.0508 (9)	0.0004 (6)	0.0222 (6)	−0.0001 (6)
O1	0.081 (3)	0.088 (3)	0.057 (3)	0.026 (2)	0.023 (2)	−0.0013 (19)
O2	0.063 (2)	0.076 (2)	0.052 (2)	0.0152 (18)	0.025 (2)	0.0064 (18)
O3	0.056 (2)	0.068 (2)	0.054 (2)	0.0086 (16)	0.0279 (18)	0.0036 (16)
O4	0.095 (3)	0.094 (3)	0.050 (3)	0.029 (2)	0.016 (2)	0.005 (2)
O5	0.055 (2)	0.0638 (19)	0.057 (2)	0.0108 (16)	0.0172 (18)	0.0064 (16)
N1	0.054 (3)	0.059 (2)	0.044 (3)	0.0083 (18)	0.023 (2)	0.003 (2)
C1	0.041 (3)	0.047 (2)	0.046 (3)	−0.005 (2)	0.020 (2)	0.002 (2)
C2	0.042 (3)	0.049 (3)	0.045 (3)	−0.004 (2)	0.018 (2)	−0.005 (2)
C3	0.041 (3)	0.050 (2)	0.047 (3)	−0.009 (2)	0.018 (3)	0.000 (2)
C4	0.046 (3)	0.054 (3)	0.046 (3)	−0.006 (2)	0.021 (2)	0.002 (2)
C5	0.061 (4)	0.067 (3)	0.052 (4)	−0.007 (3)	0.025 (3)	−0.001 (3)
C6	0.078 (4)	0.094 (4)	0.050 (4)	0.005 (3)	0.029 (3)	0.005 (3)
C7	0.051 (3)	0.051 (3)	0.056 (4)	−0.012 (2)	0.026 (3)	−0.004 (3)
C8	0.046 (3)	0.065 (3)	0.063 (4)	0.009 (2)	0.021 (3)	−0.002 (3)
C9	0.075 (4)	0.114 (4)	0.070 (4)	0.016 (3)	0.046 (3)	0.001 (3)
C10	0.065 (4)	0.078 (3)	0.047 (3)	0.005 (3)	0.021 (3)	0.000 (3)
C11	0.053 (3)	0.057 (3)	0.058 (4)	−0.002 (2)	0.016 (3)	0.000 (3)
C12	0.058 (4)	0.070 (3)	0.068 (4)	0.010 (3)	0.010 (3)	0.010 (3)
C13	0.054 (3)	0.076 (3)	0.083 (4)	0.016 (3)	0.028 (3)	0.008 (3)

Geometric parameters (Å, º) top

S1—C1	1.709 (5)	C8—C9	1.498 (8)
S1—C4	1.738 (4)	C12—C13	1.510 (7)
O1—C5	1.219 (6)	C6—H6A	0.9600
O2—C7	1.220 (6)	C6—H6B	0.9600
O3—C7	1.344 (6)	C6—H6C	0.9600
O3—C8	1.458 (6)	C8—H8A	0.9700
O4—C11	1.212 (7)	C8—H8B	0.9700
O5—C11	1.331 (6)	C9—H9A	0.9600
O5—C12	1.452 (6)	C9—H9B	0.9600
N1—C1	1.375 (7)	C9—H9C	0.9600
N1—C5	1.371 (7)	C10—H10A	0.9600
N1—H1	0.8600	C10—H10B	0.9600
C1—C2	1.386 (7)	C10—H10C	0.9600
C2—C3	1.424 (6)	C12—H12A	0.9700
C2—C7	1.458 (7)	C12—H12B	0.9700
C3—C10	1.511 (6)	C13—H13A	0.9600
C3—C4	1.374 (6)	C13—H13B	0.9600
C4—C11	1.464 (7)	C13—H13C	0.9600
C5—C6	1.494 (8)

C1—S1—C4	90.4 (3)	H6A—C6—H6B	109.00
C7—O3—C8	115.5 (4)	H6A—C6—H6C	109.00
C11—O5—C12	116.3 (4)	H6B—C6—H6C	109.00
C1—N1—C5	126.3 (4)	O3—C8—H8A	110.00
C1—N1—H1	117.00	O3—C8—H8B	110.00
C5—N1—H1	117.00	C9—C8—H8A	110.00
S1—C1—N1	122.1 (4)	C9—C8—H8B	110.00
N1—C1—C2	124.3 (4)	H8A—C8—H8B	109.00
S1—C1—C2	113.6 (4)	C8—C9—H9A	109.00
C1—C2—C7	119.3 (4)	C8—C9—H9B	109.00
C1—C2—C3	111.3 (4)	C8—C9—H9C	109.00
C3—C2—C7	129.4 (4)	H9A—C9—H9B	109.00
C2—C3—C10	125.4 (4)	H9A—C9—H9C	109.00
C2—C3—C4	112.2 (4)	H9B—C9—H9C	109.00
C4—C3—C10	122.4 (4)	C3—C10—H10A	110.00
C3—C4—C11	129.7 (4)	C3—C10—H10B	109.00
S1—C4—C11	117.7 (4)	C3—C10—H10C	110.00
S1—C4—C3	112.6 (3)	H10A—C10—H10B	109.00
O1—C5—N1	120.8 (5)	H10A—C10—H10C	109.00
O1—C5—C6	123.7 (5)	H10B—C10—H10C	109.00
N1—C5—C6	115.5 (4)	O5—C12—H12A	110.00
O2—C7—O3	121.4 (4)	O5—C12—H12B	110.00
O3—C7—C2	113.7 (4)	C13—C12—H12A	110.00
O2—C7—C2	124.9 (5)	C13—C12—H12B	110.00
O3—C8—C9	107.3 (4)	H12A—C12—H12B	108.00
O4—C11—O5	122.4 (5)	C12—C13—H13A	109.00
O4—C11—C4	125.6 (5)	C12—C13—H13B	110.00
O5—C11—C4	111.9 (4)	C12—C13—H13C	110.00
O5—C12—C13	107.3 (4)	H13A—C13—H13B	109.00
C5—C6—H6A	110.00	H13A—C13—H13C	109.00
C5—C6—H6B	110.00	H13B—C13—H13C	109.00
C5—C6—H6C	109.00

C4—S1—C1—N1	178.4 (4)	N1—C1—C2—C7	1.7 (7)
C4—S1—C1—C2	−0.8 (4)	C1—C2—C3—C4	0.6 (6)
C1—S1—C4—C3	1.1 (4)	C1—C2—C3—C10	179.3 (4)
C1—S1—C4—C11	−177.0 (4)	C7—C2—C3—C4	179.9 (5)
C8—O3—C7—O2	2.2 (6)	C7—C2—C3—C10	−1.4 (8)
C8—O3—C7—C2	−177.3 (4)	C1—C2—C7—O2	−5.3 (7)
C7—O3—C8—C9	175.9 (4)	C1—C2—C7—O3	174.1 (4)
C12—O5—C11—O4	−1.7 (7)	C3—C2—C7—O2	175.3 (5)
C12—O5—C11—C4	176.1 (4)	C3—C2—C7—O3	−5.2 (7)
C11—O5—C12—C13	179.5 (4)	C2—C3—C4—S1	−1.1 (5)
C5—N1—C1—S1	3.2 (6)	C2—C3—C4—C11	176.7 (5)
C5—N1—C1—C2	−177.7 (4)	C10—C3—C4—S1	−179.9 (3)
C1—N1—C5—O1	3.2 (7)	C10—C3—C4—C11	−2.1 (8)
C1—N1—C5—C6	−177.9 (4)	S1—C4—C11—O4	174.8 (4)
S1—C1—C2—C3	0.3 (5)	S1—C4—C11—O5	−2.9 (5)
S1—C1—C2—C7	−179.2 (3)	C3—C4—C11—O4	−2.9 (8)
N1—C1—C2—C3	−178.9 (4)	C3—C4—C11—O5	179.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.99	2.652 (5)	133
C10—H10B···O4	0.96	2.24	2.995 (6)	135

Experimental details

Crystal data
Chemical formula	C₁₃H₁₇NO₅S
M_r	299.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	15.933 (3), 4.6028 (6), 20.152 (3)
β (°)	106.005 (7)
V (Å³)	1420.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.25 × 0.10 × 0.08

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.972, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	10222, 2518, 1311
R_int	0.094
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.172, 1.02
No. of reflections	2518
No. of parameters	186
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23

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···O2	0.86	1.99	2.652 (5)	133
C10—H10B···O4	0.96	2.24	2.995 (6)	135

Acknowledgements

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.

References

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