Methyl 2-(thio­phene-2-carboxamido)­benzoate

Singh, D.P.; Pratap, S.; Butcher, R.J.; Gupta, S.K.

doi:10.1107/S160053681202082X

organic compounds

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Volume 68| Part 6| June 2012| Page o1765

doi:10.1107/S160053681202082X

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Methyl 2-(thiophene-2-carboxamido)benzoate

Durga Prasad Singh,^a Seema Pratap,^a ^* Ray J. Butcher ^b and Sushil K. Gupta ^c

^aDepartment of Chemistry, M.M.V., Banaras Hindu University, Varanasi 221 005, India, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^cSchool of Studies in Chemistry, Jiwaji University, Gwalior, India
^*Correspondence e-mail: drseemapratap@gmail.com

(Received 20 March 2012; accepted 8 May 2012; online 16 May 2012)

The title compound, C₁₃H₁₁NO₃S, was synthesized from methyl anthranilate, triethylamine and 2-thiophenoyl chloride in benzene. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. The dihedral angle between the rings is 2.74 (12)°. In the crystal, C—H⋯O interactions link neighbouring molecules into a three-dimensional network.

Related literature

For the synthesis, see: Sladowska et al. (1980 ).

Experimental

Crystal data

C₁₃H₁₁NO₃S
M_r = 261.29
Orthorhombic, P c a 2₁
a = 19.2845 (4) Å
b = 3.86753 (8) Å
c = 15.6430 (3) Å
V = 1166.71 (4) Å³
Z = 4
Cu Kα radiation
μ = 2.48 mm⁻¹
T = 123 K
0.45 × 0.18 × 0.04 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012 ) T_min = 0.573, T_max = 0.908
2379 measured reflections
1422 independent reflections
1381 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.090
S = 1.04
1422 reflections
168 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 206 Friedel pairs
Flack parameter: −0.02 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2	0.85 (2)	1.99 (3)	2.665 (3)	135 (4)
C9—H9A⋯O2ⁱ	0.95	2.43	3.380 (3)	174
C13—H13A⋯O1ⁱⁱ	0.98	2.52	3.433 (4)	154
Symmetry codes: (i) $[-x+1, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+2, z]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681202082X/bt5852sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202082X/bt5852Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681202082X/bt5852Isup3.cml

checkCIF report

Comment top

As part of our studies of substituent effects on the structures of amides, we report here the crystal structure of the amide, methyl 2-(thiophene-2-carboxamido)benzoate. The structure of the title compound is shown in Fig. 1. The conformation of the molecule with respect to the carbonyl and anthranilate part is nearly planar as reflected by torsion angles C4—C5—N1—C6, C6—N1—C5—O1 and C3—C4—C5—O1 of 179.6 (2), -0.8 (5) and 178.3 (3) Å respectively. The 2-thiophenoyl and anthranilate groups are trans to each other across the C5—N1 bond. Bonds C5—O1 and C12—O2 show typical double bond character with bond lengths of 1.226 (3) and 1.211 (4) respectively, while N1—C5, N1—C6 and C12—O3 show partial double bond character with bond lengths of 1.365 (4), 1.401 (4), and 1.329 (3) Å respectively. All bond length and bond angles confirm the sp² hybridization for all C and N atoms except C₁₃, indicating that the whole molecule is planar.

Related literature top

For the synthesis, see: Sladowska et al. (1980).

Experimental top

The title compound was synthesized using the literature procedure (Sladowska et al., 1980). To a solution of methyl anthranilate (10 mmol) and triethyl amine(10mmol) in benzene(30 ml) was added 2-thiophenoyl chloride (10 mmol) in benzene(10 ml) with stirring at room temperature. After stirring for three hour, the reaction mixture was washed successively with water, dilute HCl and aqueous Na₂CO₃ and the organic layer was dried over dry Na₂SO₄. After removal of the solvent, the residue was recrystallized from ethanol. Colorless, needles type crystal suitable for X-ray diffraction were obtained after few days. Yield 78%.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of compound(I) showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular hydrogen bond is shown as dashed lines.
	Fig. 2. Part of the crystal structure of (I) showing intramolecular and intermolecular interactions as dashed lines.

Methyl 2-(thiophene-2-carboxamido)benzoate top

Crystal data top

C₁₃H₁₁NO₃S	F(000) = 544
M_r = 261.29	D_x = 1.488 Mg m⁻³
Orthorhombic, Pca2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2c -2ac	Cell parameters from 1440 reflections
a = 19.2845 (4) Å	θ = 2.8–75.1°
b = 3.86753 (8) Å	µ = 2.48 mm⁻¹
c = 15.6430 (3) Å	T = 123 K
V = 1166.71 (4) Å³	Needle, colorless
Z = 4	0.45 × 0.18 × 0.04 mm

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	1422 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1381 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 10.5081 pixels mm^-1	θ_max = 75.2°, θ_min = 4.6°
ω scans	h = −15→23
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012)	k = −4→4
T_min = 0.573, T_max = 0.908	l = −6→19
2379 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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0597P)² + 0.0898P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1422 reflections	Δρ_max = 0.21 e Å⁻³
168 parameters	Δρ_min = −0.27 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 206 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

Crystal data top

C₁₃H₁₁NO₃S	V = 1166.71 (4) Å³
M_r = 261.29	Z = 4
Orthorhombic, Pca2₁	Cu Kα radiation
a = 19.2845 (4) Å	µ = 2.48 mm⁻¹
b = 3.86753 (8) Å	T = 123 K
c = 15.6430 (3) Å	0.45 × 0.18 × 0.04 mm

Data collection top

Agilent Xcalibur Ruby Gemini diffractometer	1422 independent reflections
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012)	1381 reflections with I > 2σ(I)
T_min = 0.573, T_max = 0.908	R_int = 0.033
2379 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	Δρ_max = 0.21 e Å⁻³
S = 1.04	Δρ_min = −0.27 e Å⁻³
1422 reflections	Absolute structure: Flack (1983), 206 Friedel pairs
168 parameters	Absolute structure parameter: −0.02 (2)
2 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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	0.25886 (3)	0.20133 (16)	0.72770 (5)	0.03006 (19)
O1	0.28253 (10)	0.3657 (6)	0.54680 (14)	0.0304 (4)
O2	0.51080 (11)	0.8922 (6)	0.60945 (13)	0.0339 (5)
O3	0.57519 (10)	1.1406 (5)	0.50816 (14)	0.0308 (4)
N1	0.38872 (12)	0.6290 (6)	0.56315 (15)	0.0252 (5)
H1B	0.4151 (18)	0.698 (9)	0.603 (2)	0.037 (10)*
C1	0.29286 (16)	0.2186 (7)	0.8287 (2)	0.0307 (6)
H1A	0.2694	0.1372	0.8781	0.037*
C2	0.35685 (16)	0.3611 (8)	0.8301 (2)	0.0304 (6)
H2A	0.3831	0.3919	0.8810	0.037*
C3	0.38110 (14)	0.4607 (7)	0.74725 (17)	0.0249 (5)
H3A	0.4251	0.5621	0.7364	0.030*
C4	0.33202 (13)	0.3900 (7)	0.68499 (18)	0.0251 (5)
C5	0.33132 (14)	0.4577 (7)	0.59160 (18)	0.0247 (6)
C6	0.40520 (13)	0.7321 (7)	0.4797 (2)	0.0231 (5)
C7	0.36094 (14)	0.6720 (7)	0.41074 (19)	0.0262 (6)
H7A	0.3173	0.5642	0.4201	0.031*
C8	0.38002 (15)	0.7678 (7)	0.3290 (2)	0.0279 (6)
H8A	0.3498	0.7185	0.2826	0.034*
C9	0.44255 (15)	0.9352 (7)	0.31331 (18)	0.0277 (6)
H9A	0.4550	1.0010	0.2569	0.033*
C10	0.48604 (14)	1.0039 (7)	0.38091 (19)	0.0261 (6)
H10A	0.5284	1.1221	0.3708	0.031*
C11	0.46910 (13)	0.9032 (7)	0.46454 (18)	0.0241 (6)
C12	0.51909 (14)	0.9743 (7)	0.53544 (18)	0.0253 (5)
C13	0.62744 (16)	1.2115 (9)	0.5729 (2)	0.0359 (7)
H13A	0.6645	1.3525	0.5479	0.054*
H13B	0.6469	0.9929	0.5937	0.054*
H13C	0.6062	1.3367	0.6206	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0264 (3)	0.0293 (3)	0.0345 (4)	−0.0023 (2)	0.0046 (3)	0.0010 (4)
O1	0.0248 (9)	0.0361 (10)	0.0303 (10)	−0.0051 (8)	−0.0037 (8)	−0.0012 (9)
O2	0.0329 (10)	0.0454 (11)	0.0235 (10)	−0.0104 (9)	−0.0042 (9)	0.0033 (10)
O3	0.0254 (9)	0.0401 (11)	0.0268 (9)	−0.0077 (9)	−0.0033 (9)	0.0017 (9)
N1	0.0234 (10)	0.0295 (11)	0.0227 (11)	−0.0024 (9)	−0.0005 (9)	−0.0013 (9)
C1	0.0342 (14)	0.0284 (14)	0.0294 (15)	0.0026 (11)	0.0072 (12)	0.0021 (12)
C2	0.0341 (14)	0.0299 (13)	0.0272 (14)	0.0021 (12)	0.0037 (12)	0.0013 (12)
C3	0.0281 (12)	0.0242 (11)	0.0224 (12)	−0.0015 (10)	0.0044 (11)	0.0004 (10)
C4	0.0230 (12)	0.0226 (12)	0.0298 (14)	0.0020 (10)	0.0037 (11)	0.0009 (10)
C5	0.0245 (12)	0.0208 (12)	0.0288 (14)	0.0035 (10)	0.0019 (11)	0.0001 (10)
C6	0.0239 (13)	0.0211 (11)	0.0243 (12)	0.0017 (9)	0.0006 (11)	−0.0002 (11)
C7	0.0232 (12)	0.0263 (13)	0.0290 (15)	−0.0009 (10)	−0.0042 (12)	−0.0018 (11)
C8	0.0301 (13)	0.0282 (12)	0.0255 (14)	0.0035 (11)	−0.0094 (12)	−0.0020 (11)
C9	0.0333 (13)	0.0287 (14)	0.0210 (12)	0.0050 (11)	0.0007 (11)	0.0033 (11)
C10	0.0256 (12)	0.0251 (13)	0.0277 (14)	0.0007 (11)	0.0018 (11)	0.0005 (10)
C11	0.0239 (12)	0.0218 (11)	0.0267 (14)	0.0028 (10)	−0.0032 (11)	−0.0021 (11)
C12	0.0240 (12)	0.0260 (12)	0.0258 (13)	0.0006 (10)	−0.0017 (10)	−0.0011 (10)
C13	0.0292 (14)	0.0416 (17)	0.0370 (16)	−0.0082 (12)	−0.0090 (14)	0.0002 (15)

Geometric parameters (Å, º) top

S1—C1	1.711 (3)	C4—C5	1.484 (4)
S1—C4	1.723 (3)	C6—C7	1.395 (4)
O1—C5	1.226 (3)	C6—C11	1.419 (3)
O2—C12	1.211 (4)	C7—C8	1.381 (4)
O3—C12	1.329 (3)	C7—H7A	0.9500
O3—C13	1.454 (4)	C8—C9	1.390 (4)
N1—C5	1.365 (4)	C8—H8A	0.9500
N1—C6	1.401 (4)	C9—C10	1.375 (4)
N1—H1B	0.852 (19)	C9—H9A	0.9500
C1—C2	1.352 (4)	C10—C11	1.404 (4)
C1—H1A	0.9500	C10—H10A	0.9500
C2—C3	1.431 (4)	C11—C12	1.495 (4)
C2—H2A	0.9500	C13—H13A	0.9800
C3—C4	1.385 (4)	C13—H13B	0.9800
C3—H3A	0.9500	C13—H13C	0.9800

C1—S1—C4	91.59 (15)	C8—C7—H7A	119.7
C12—O3—C13	115.6 (3)	C6—C7—H7A	119.7
C5—N1—C6	128.7 (2)	C7—C8—C9	121.3 (3)
C5—N1—H1B	113 (3)	C7—C8—H8A	119.4
C6—N1—H1B	117 (3)	C9—C8—H8A	119.4
C2—C1—S1	112.4 (2)	C10—C9—C8	118.9 (3)
C2—C1—H1A	123.8	C10—C9—H9A	120.6
S1—C1—H1A	123.8	C8—C9—H9A	120.6
C1—C2—C3	113.2 (3)	C9—C10—C11	121.4 (2)
C1—C2—H2A	123.4	C9—C10—H10A	119.3
C3—C2—H2A	123.4	C11—C10—H10A	119.3
C4—C3—C2	111.1 (2)	C10—C11—C6	119.2 (2)
C4—C3—H3A	124.4	C10—C11—C12	119.4 (2)
C2—C3—H3A	124.4	C6—C11—C12	121.4 (3)
C3—C4—C5	131.5 (2)	O2—C12—O3	122.8 (3)
C3—C4—S1	111.7 (2)	O2—C12—C11	125.2 (3)
C5—C4—S1	116.7 (2)	O3—C12—C11	112.1 (2)
O1—C5—N1	125.2 (3)	O3—C13—H13A	109.5
O1—C5—C4	121.2 (3)	O3—C13—H13B	109.5
N1—C5—C4	113.5 (2)	H13A—C13—H13B	109.5
C7—C6—N1	122.3 (2)	O3—C13—H13C	109.5
C7—C6—C11	118.6 (3)	H13A—C13—H13C	109.5
N1—C6—C11	119.1 (3)	H13B—C13—H13C	109.5
C8—C7—C6	120.6 (3)

C4—S1—C1—C2	0.0 (2)	C11—C6—C7—C8	2.0 (4)
S1—C1—C2—C3	−0.5 (3)	C6—C7—C8—C9	−1.9 (4)
C1—C2—C3—C4	0.8 (4)	C7—C8—C9—C10	0.3 (4)
C2—C3—C4—C5	177.1 (3)	C8—C9—C10—C11	1.2 (4)
C2—C3—C4—S1	−0.8 (3)	C9—C10—C11—C6	−1.1 (4)
C1—S1—C4—C3	0.4 (2)	C9—C10—C11—C12	178.1 (2)
C1—S1—C4—C5	−177.8 (2)	C7—C6—C11—C10	−0.5 (4)
C6—N1—C5—O1	−0.8 (5)	N1—C6—C11—C10	179.4 (3)
C6—N1—C5—C4	179.6 (2)	C7—C6—C11—C12	−179.7 (2)
C3—C4—C5—O1	178.3 (3)	N1—C6—C11—C12	0.2 (4)
S1—C4—C5—O1	−3.9 (4)	C13—O3—C12—O2	1.5 (4)
C3—C4—C5—N1	−2.1 (4)	C13—O3—C12—C11	−178.4 (2)
S1—C4—C5—N1	175.66 (19)	C10—C11—C12—O2	−178.1 (3)
C5—N1—C6—C7	1.1 (4)	C6—C11—C12—O2	1.0 (4)
C5—N1—C6—C11	−178.8 (3)	C10—C11—C12—O3	1.7 (4)
N1—C6—C7—C8	−177.9 (3)	C6—C11—C12—O3	−179.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2	0.85 (2)	1.99 (3)	2.665 (3)	135 (4)
C9—H9A···O2ⁱ	0.95	2.43	3.380 (3)	174
C13—H13A···O1ⁱⁱ	0.98	2.52	3.433 (4)	154

Symmetry codes: (i) −x+1, −y+2, z−1/2; (ii) x+1/2, −y+2, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁NO₃S
M_r	261.29
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	123
a, b, c (Å)	19.2845 (4), 3.86753 (8), 15.6430 (3)
V (Å³)	1166.71 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.48
Crystal size (mm)	0.45 × 0.18 × 0.04

Data collection
Diffractometer	Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction	Analytical (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.573, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	2379, 1422, 1381
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.04
No. of reflections	1422
No. of parameters	168
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27
Absolute structure	Flack (1983), 206 Friedel pairs
Absolute structure parameter	−0.02 (2)

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2	0.852 (19)	1.99 (3)	2.665 (3)	135 (4)
C9—H9A···O2ⁱ	0.95	2.43	3.380 (3)	174.2
C13—H13A···O1ⁱⁱ	0.98	2.52	3.433 (4)	154.3

Symmetry codes: (i) −x+1, −y+2, z−1/2; (ii) x+1/2, −y+2, z.

Acknowledgements

DPS and SP are grateful to Banaras Hindu University, Varanasi, for financial support. RJB acknowledges the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer. SKG wishes to acknowledge the USIEF for the award of a Fulbright–Nehru Senior Research Fellowship.

References

Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sladowska, H., Sieklucka-Dziuba, M., Rajtar, G., Sodowski, M., Kleinrok, Z., Kirino, O., Yamamoto, S. & Kato, T. (1980). Agric. Biol. Chem. 44, 2143–2147. Google Scholar