2-Acetyl­phenyl 5-methyl­thio­phene-2-carboxyl­ate

The non-H atoms of the mol­ecule of the title compound, C₁₄H₁₂O₃S, form three essentially planar fragments, viz. the thio­phene ring with the methyl C atom and carboxyl­ate group (maximum deviation 0.041 Å; fragment A), the oxy­phenyl ring with the central acetyl C atom (0.029 Å; B), and the acetyl group together with the phenyl C atom bonded to it (<0.001 Å; C). These planes form dihedral angles of 88.33 (7)° for A/B and 71.9 (2)° for B/C. The crystal structure is stabilized by intermolecular interactions of the C—H...O type [C...O = 3.492 (5) Å].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.112
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

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PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.89 Ratio

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S1. Comment

The title compound, (I), is a precursor used for the synthesis of 5-(4H-4-oxo-1-benzopyran-2-yl)-2-thiophenecarboxaldehyde (Göker et al., 2000). The synthesis of (I) was performed by the esterification of 2'-hydroxyacetophenone with 5-methyl-2-thiophenecarboxylic acid chloride in pyridine, as is shown in the Scheme. The structure of (I) was assigned based on the NMR, mass spectroscopy and elemental analysis. Here we report the results of its X-ray diffraction study.

An ORTEPIII (Burnett & Johnson, 1996) plot of (I) is shown in Fig. 1. The molecule of (I) is composed of three essentially planar fragments: the thiophene ring with the adjacent methyl and caroboxylate groups is planar within 0.041 Å,the oxyphenyl group with the central acetyl atom shows a maximum deviation of 0.029 Å, and the acetyl group with the phenyl C atom, bonded to it, is planar within the accuracy of the experiment (maximum deviation less than 0.001 Å). The planes of the first two fragments are orthogonal to each other [dihedral angle is equal to 88.33 (7)°]; the ortho-acetyl group plane is also almost normal to the phenyl ring [dihedral angle 71.9 (2)°].

The crystal structure is stabilized by intermolecular interaction of the C—H···O type [C14···O2ⁱ 3.492 (5) Å, C14—H143 0.97 (4) Å and C14—H143···O2ⁱ 154 (3)°; symmetry code: (i) x − 1, y, z].

S2. Experimental

5-Methyl-2-thiophenecarboxylic acid (8 g, 56.3 mmol) in 50 ml of SOCl₂ was refluxed for 2 h; the excess of the reagent was then evaporated under reduced pressure. o-Hydroxyacetophenone (7.65 g, 56.3 mmol) and 20 ml of pyridine were added to the residue and the mixture was heated for 0.5 h at 353 K. The mixture was then cooled and poured into ice water, acidified with HCl, and the resulting precipitate was filtered and washed with water. Crystallization from EtOH gave (I) (12.7 g, 86.8%) as colourless crystals, m.p. 383–385 K. Analysis calculated for C₁₄H₁₂O₃S: C 64.60, H 4.65, S 12.32%; found: C 64.55, H 4.64, S 12.16%.

S3. Refinement

The H atoms were located in the difference maps and refined isotropically. The C—H bond distances range from 0.89 to 0.99 Å, while U_iso values for H atoms are in the range 0.036–0.109 Ų.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. An ORTEPIII drawing of the title compound with atomic numbering scheme. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level; H atoms are shown as small spheres of arbitrary size.

(I)

Crystal data

C14H12O3S	Dx = 1.364 Mg m^−3
Mr = 260.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 25 reflections
a = 8.0088 (11) Å	θ = 2.6–26.3°
b = 14.3163 (16) Å	µ = 0.25 mm^−1
c = 22.103 (3) Å	T = 293 K
V = 2534.2 (5) Å^3	Prism, colourless
Z = 8	0.30 × 0.25 × 0.20 mm
F(000) = 1088

Data collection

Enraf-Nonius CAD-4 diffractometer	1275 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 26.3°, θmin = 2.8°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→17
Tmin = 0.928, Tmax = 0.951	l = 0→27
2551 measured reflections	3 standard reflections every 120 min
2551 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: difference Fourier map
wR(F^2) = 0.112	All H-atom parameters refined
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0431P)^2] where P = (Fo^2 + 2Fc^2)/3
2551 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.22905 (9)	0.07839 (6)	0.48719 (4)	0.0469 (3)
O1	0.1729 (2)	−0.05224 (13)	0.58824 (8)	0.0394 (5)
O2	0.3969 (3)	−0.01173 (16)	0.64400 (10)	0.0517 (6)
O3	0.0460 (3)	0.08943 (15)	0.65878 (11)	0.0629 (7)
C1	0.0088 (3)	−0.07142 (19)	0.67960 (12)	0.0330 (7)
C2	0.1177 (3)	−0.1083 (2)	0.63655 (12)	0.0347 (7)
C3	0.1635 (4)	−0.2004 (2)	0.63705 (15)	0.0418 (8)
H3	0.238 (4)	−0.2205 (19)	0.6084 (13)	0.043 (9)*
C4	0.1073 (4)	−0.2582 (2)	0.68263 (15)	0.0445 (8)
H4	0.142 (4)	−0.322 (2)	0.6810 (14)	0.069 (10)*
C5	0.0039 (4)	−0.2236 (2)	0.72668 (15)	0.0423 (8)
H5	−0.032 (3)	−0.2599 (18)	0.7575 (12)	0.040 (9)*
C6	−0.0469 (4)	−0.1309 (2)	0.72471 (15)	0.0412 (8)
H6	−0.116 (4)	−0.112 (2)	0.7547 (14)	0.053 (10)*
C7	0.4968 (5)	0.1722 (2)	0.49499 (15)	0.0473 (8)
H7	0.583 (3)	0.215 (2)	0.4851 (12)	0.046 (9)*
C8	0.3644 (4)	0.1597 (2)	0.45790 (13)	0.0405 (8)
C9	0.4907 (4)	0.1162 (2)	0.54708 (14)	0.0438 (8)
H9	0.568 (3)	0.1158 (19)	0.5762 (12)	0.036 (8)*
C10	0.3533 (4)	0.06153 (19)	0.54954 (12)	0.0364 (7)
C11	0.3144 (4)	−0.0026 (2)	0.59889 (14)	0.0371 (7)
C12	0.3333 (7)	0.2045 (3)	0.3980 (2)	0.0631 (11)
H121	0.220 (5)	0.216 (3)	0.3910 (17)	0.082 (14)*
H122	0.375 (6)	0.166 (3)	0.364 (2)	0.14 (2)*
H123	0.391 (5)	0.261 (3)	0.3968 (16)	0.089 (14)*
C13	−0.0448 (4)	0.0286 (2)	0.67836 (13)	0.0403 (8)
C14	−0.2141 (5)	0.0517 (3)	0.7023 (2)	0.0543 (10)
H141	−0.241 (4)	0.119 (3)	0.6966 (14)	0.074 (11)*
H142	−0.218 (5)	0.036 (3)	0.744 (2)	0.109 (16)*
H143	−0.300 (4)	0.017 (3)	0.6807 (16)	0.080 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0434 (5)	0.0465 (5)	0.0507 (5)	−0.0047 (4)	−0.0027 (4)	0.0119 (4)
O1	0.0416 (12)	0.0417 (12)	0.0348 (11)	−0.0098 (10)	0.0005 (9)	0.0069 (9)
O2	0.0497 (14)	0.0601 (15)	0.0454 (13)	−0.0128 (12)	−0.0055 (12)	0.0089 (12)
O3	0.0579 (15)	0.0349 (13)	0.0959 (19)	−0.0020 (13)	0.0151 (14)	0.0076 (13)
C1	0.0350 (15)	0.0299 (15)	0.0340 (16)	−0.0026 (14)	−0.0015 (14)	0.0004 (14)
C2	0.0372 (17)	0.0345 (17)	0.0324 (16)	−0.0047 (14)	−0.0016 (14)	0.0035 (13)
C3	0.0431 (18)	0.042 (2)	0.040 (2)	0.0006 (17)	0.0098 (17)	−0.0049 (16)
C4	0.054 (2)	0.0310 (18)	0.048 (2)	0.0008 (17)	−0.0022 (19)	−0.0023 (16)
C5	0.051 (2)	0.0353 (19)	0.0400 (19)	−0.0078 (16)	0.0010 (18)	0.0089 (16)
C6	0.0401 (19)	0.046 (2)	0.0381 (18)	−0.0056 (16)	0.0034 (16)	−0.0031 (17)
C7	0.054 (2)	0.0395 (18)	0.048 (2)	−0.0144 (18)	0.0120 (18)	−0.0021 (17)
C8	0.0461 (19)	0.0352 (17)	0.0403 (18)	0.0017 (15)	0.0104 (16)	0.0076 (15)
C9	0.046 (2)	0.052 (2)	0.0344 (18)	−0.0082 (18)	−0.0017 (17)	−0.0027 (16)
C10	0.0396 (17)	0.0343 (17)	0.0353 (17)	−0.0017 (14)	0.0047 (14)	−0.0003 (14)
C11	0.0367 (17)	0.0339 (16)	0.0408 (18)	0.0025 (14)	0.0050 (15)	−0.0029 (16)
C12	0.067 (3)	0.059 (3)	0.064 (3)	−0.002 (2)	0.000 (2)	0.026 (2)
C13	0.0434 (19)	0.0396 (18)	0.0379 (18)	−0.0026 (16)	−0.0038 (16)	−0.0029 (15)
C14	0.051 (2)	0.046 (2)	0.067 (3)	0.0090 (19)	0.006 (2)	−0.003 (2)

Geometric parameters (Å, º)

S1—C8	1.718 (3)	C6—H6	0.90 (3)
S1—C10	1.717 (3)	C7—C8	1.352 (4)
O1—C2	1.407 (3)	C7—C9	1.404 (4)
O1—C11	1.359 (3)	C7—H7	0.94 (3)
O2—C11	1.203 (3)	C8—C12	1.492 (5)
O3—C13	1.214 (3)	C9—C10	1.351 (4)
C1—C6	1.385 (4)	C9—H9	0.89 (3)
C1—C2	1.395 (4)	C10—C11	1.459 (4)
C1—C13	1.496 (4)	C12—H121	0.93 (4)
C2—C3	1.368 (4)	C12—H122	0.99 (5)
C3—C4	1.380 (4)	C12—H123	0.94 (4)
C3—H3	0.92 (3)	C13—C14	1.492 (5)
C4—C5	1.371 (4)	C14—H141	0.99 (4)
C4—H4	0.95 (3)	C14—H142	0.95 (5)
C5—C6	1.389 (4)	C14—H143	0.97 (4)
C5—H5	0.91 (3)
C10—S1—C8	91.83 (14)	C12—C8—S1	121.3 (3)
C11—O1—C2	115.4 (2)	C10—C9—C7	113.1 (3)
C6—C1—C2	117.4 (3)	C10—C9—H9	122.0 (18)
C6—C1—C13	120.6 (3)	C7—C9—H9	124.9 (18)
C2—C1—C13	122.0 (3)	C9—C10—C11	124.6 (3)
C3—C2—C1	121.8 (3)	C9—C10—S1	111.0 (2)
C3—C2—O1	118.1 (3)	C11—C10—S1	124.4 (2)
C1—C2—O1	119.8 (2)	O2—C11—O1	123.0 (3)
C2—C3—C4	119.8 (3)	O2—C11—C10	124.8 (3)
C2—C3—H3	118.2 (18)	O1—C11—C10	112.2 (3)
C4—C3—H3	121.8 (18)	C8—C12—H121	113 (2)
C5—C4—C3	119.9 (3)	C8—C12—H122	111 (3)
C5—C4—H4	123.4 (19)	H121—C12—H122	108 (4)
C3—C4—H4	116.7 (19)	C8—C12—H123	108 (2)
C4—C5—C6	120.0 (3)	H121—C12—H123	109 (3)
C4—C5—H5	121.4 (16)	H122—C12—H123	107 (4)
C6—C5—H5	118.6 (17)	O3—C13—C14	120.8 (3)
C1—C6—C5	121.0 (3)	O3—C13—C1	121.4 (3)
C1—C6—H6	123 (2)	C14—C13—C1	117.8 (3)
C5—C6—H6	116 (2)	C13—C14—H141	112 (2)
C8—C7—C9	113.2 (3)	C13—C14—H142	108 (3)
C8—C7—H7	121.3 (17)	H141—C14—H142	110 (3)
C9—C7—H7	125.5 (18)	C13—C14—H143	111 (2)
C7—C8—C12	127.8 (3)	H141—C14—H143	106 (3)
C7—C8—S1	110.9 (2)	H142—C14—H143	109 (3)
C6—C1—C2—C3	2.5 (4)	C10—S1—C8—C12	177.8 (3)
C13—C1—C2—C3	−178.5 (3)	C8—C7—C9—C10	−0.3 (4)
C6—C1—C2—O1	177.4 (2)	C7—C9—C10—C11	−179.2 (3)
C13—C1—C2—O1	−3.6 (4)	C7—C9—C10—S1	0.1 (4)
C11—O1—C2—C3	−95.5 (3)	C8—S1—C10—C9	0.1 (2)
C11—O1—C2—C1	89.4 (3)	C8—S1—C10—C11	179.4 (3)
C1—C2—C3—C4	−2.9 (5)	C2—O1—C11—O2	6.7 (4)
O1—C2—C3—C4	−177.9 (3)	C2—O1—C11—C10	−173.6 (2)
C2—C3—C4—C5	1.0 (5)	C9—C10—C11—O2	2.8 (5)
C3—C4—C5—C6	1.3 (5)	S1—C10—C11—O2	−176.5 (2)
C2—C1—C6—C5	−0.2 (4)	C9—C10—C11—O1	−176.9 (3)
C13—C1—C6—C5	−179.2 (3)	S1—C10—C11—O1	3.8 (4)
C4—C5—C6—C1	−1.7 (5)	C6—C1—C13—O3	148.3 (3)
C9—C7—C8—C12	−177.5 (4)	C2—C1—C13—O3	−30.7 (4)
C9—C7—C8—S1	0.3 (4)	C6—C1—C13—C14	−31.5 (4)
C10—S1—C8—C7	−0.2 (2)	C2—C1—C13—C14	149.6 (3)