2-(4,6-Dimethyl-1-benzo­furan-3-yl)acetic acid

Ramprasad, N.; Gowda, R.; Gowda, K.V.A.; Basanagouda, M.

doi:10.1107/S2414314616010324

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161032

https://doi.org/10.1107/S2414314616010324

Open

access

2-(4,6-Dimethyl-1-benzofuran-3-yl)acetic acid

N. Ramprasad,^a Ramakrishna Gowda,^b ^* K.V. Arjuna Gowda ^c and Mahantesha Basanagouda ^d

^aDepartment of Physics, Govt. First Grade College, Mulbagal, Kolar 563 131, Karnataka, India, ^bDepartment of Physics, Govt. College for Women, Kolar 563 101, Karnataka, India, ^cDepartment of Physics, Govt. College for Women, Mandya 571 401, India, and ^dDepartment of Chemistry, P.C. Jabin Science College, Hubli 580 031, Karnataka, India
^*Correspondence e-mail: rkgowdaphy@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 24 June 2016; accepted 25 June 2016; online 5 July 2016)

In the title compound, C₁₂H₁₂O₃, the dihedral angle between the planes of the carboxylic acid group and the benzofuran ring system (r.m.s. deviation = 0.012 Å) is 76.53 (10)°. In the crystal, carboxylic acid inversion dimers linked by pairs of O—H⋯O hydrogen bonds generate R₂²(8) loops. C—H⋯O interactions link the dimers into (101) sheets.

Keywords: crystal structure; benzofuran; hydrogen bonding.

CCDC reference: 1484420

Structure description

Carboxylic acids, such as arylalkanoic acids, exhibit anti-inflammatory, analgesic and antipyretic properties and have been in widespread clinical use for a number of years (Basanagouda et al., 2015 ). As part of our studies in this area, we now report the crystal structure of the title compound. All the bond lengths and angles are close to those observed for similar structures (Gowda et al., 2015 ; Ramprasad et al., 2016 ).

The X-ray structure of the title molecule (Fig. 1) reveals its non-planar nature; the plane of the acetic acid group makes a dihedral angle of 76.53 (10)° with that of the benzofuran ring system. The C9—C12 bond length [1.512 (3) Å] reflects the sp²(C1)—sp³(C12) hybridization of these atoms; this is also reflected in the C7—C11 bond length [1.497 (3) Å].

Figure 1
The molecular structure of the title compound, showing 40% probability displacement ellipsoids.

In the crystal, molecules are linked into carboxylic acid inversion dimers by pairs of O—H⋯O hydrogen bonds. The dimers are linked into (101) sheets by a very weak C—H⋯O hydrogen bond (Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O3ⁱ	0.93	2.58	3.328 (2)	137
O2—H2⋯O1ⁱⁱ	0.82	1.83	2.645 (2)	171
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z.

Figure 2
The crystal packing diagram of the title compound. The dotted lines indicate intermolecular hydrogen bonds. H atoms not involved in these interactions have been omitted for clarity.

Synthesis and crystallization

4-Bromomethyl-5,7-dimethylcoumarin (10 mM) was refluxed in 1 M NaOH (100 ml) for 2 h (the completion of the reaction was monitored by thin-layer chromatography). The reaction mixture was cooled, neutralized with 1 M HCl and the obtained product was filtered off and dried. Colourless blocks were obtained by recrystallization from an ethanol and ethyl acetate solvent mixture by slow evaporation (m.p. 442–443 K) (Basanagouda et al., 2015).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₂O₃
M_r	204.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.5048 (4), 4.8237 (2), 23.3395 (11)
β (°)	100.829 (2)
V (Å³)	1051.02 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.969, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	15929, 2056, 1581
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.129, 1.06
No. of reflections	2056
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.30
Computer programs: APEX2 and SAINT (Bruker, 2004), SIR92 (Altomare et al., 1994 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1484420

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314616010324/hb4062sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010324/hb4062Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010324/hb4062Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

2-(4,6-Dimethyl-1-benzofuran-3-yl)acetic acid top

Crystal data top

C₁₂H₁₂O₃	D_x = 1.291 Mg m⁻³
M_r = 204.22	Melting point = 433–432 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5048 (4) Å	Cell parameters from 4624 reflections
b = 4.8237 (2) Å	θ = 2.2–25.6°
c = 23.3395 (11) Å	µ = 0.09 mm⁻¹
β = 100.829 (2)°	T = 293 K
V = 1051.02 (8) Å³	Block, colourless
Z = 4	0.25 × 0.20 × 0.20 mm
F(000) = 432

Data collection top

Bruker axs kappa apex2 CCD diffractometer	2056 independent reflections
Radiation source: fine-focus sealed tube	1581 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and φ scan	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
T_min = 0.969, T_max = 0.992	k = −5→5
15929 measured reflections	l = −28→28

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0551P)² + 0.4386P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.129	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.27 e Å⁻³
2056 reflections	Δρ_min = −0.30 e Å⁻³
139 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.021 (3)

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.6178 (2)	−0.1293 (4)	0.07038 (8)	0.0483 (5)
C2	0.7035 (2)	−0.2388 (4)	0.12645 (9)	0.0544 (5)
H2A	0.6384	−0.2841	0.1525	0.065*
H2B	0.7501	−0.4093	0.1182	0.065*
C3	0.81502 (18)	−0.0435 (4)	0.15717 (8)	0.0431 (4)
C4	0.79779 (19)	0.1147 (4)	0.20245 (8)	0.0486 (5)
H4	0.7150	0.1145	0.2183	0.058*
C5	1.01240 (18)	0.2144 (4)	0.18824 (7)	0.0391 (4)
C6	0.95676 (17)	0.0184 (3)	0.14658 (7)	0.0384 (4)
C7	1.0429 (2)	−0.0704 (4)	0.10711 (8)	0.0458 (5)
C8	1.1781 (2)	0.0431 (4)	0.11406 (9)	0.0540 (5)
H8	1.2370	−0.0135	0.0886	0.065*
C9	1.23245 (19)	0.2375 (4)	0.15682 (9)	0.0519 (5)
C10	1.14744 (19)	0.3273 (4)	0.19488 (8)	0.0480 (5)
H10	1.1798	0.4580	0.2237	0.058*
C11	0.9921 (3)	−0.2776 (5)	0.06001 (9)	0.0667 (6)
H11A	0.9718	−0.4502	0.0773	0.100*
H11B	1.0651	−0.3056	0.0372	0.100*
H11C	0.9067	−0.2099	0.0353	0.100*
C12	1.3832 (2)	0.3480 (6)	0.16180 (13)	0.0832 (8)
H12A	1.4150	0.3199	0.1256	0.125*
H12B	1.4459	0.2517	0.1924	0.125*
H12C	1.3843	0.5425	0.1706	0.125*
O1	0.64980 (17)	0.0843 (4)	0.04769 (7)	0.0808 (6)
O2	0.50928 (17)	−0.2762 (4)	0.04947 (7)	0.0828 (6)
H2	0.4680	−0.2081	0.0187	0.124*
O3	0.91475 (13)	0.2772 (3)	0.22303 (5)	0.0484 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0459 (10)	0.0473 (11)	0.0473 (10)	−0.0099 (8)	−0.0028 (8)	0.0048 (8)
C2	0.0515 (11)	0.0519 (11)	0.0527 (11)	−0.0142 (9)	−0.0087 (9)	0.0131 (9)
C3	0.0398 (9)	0.0435 (10)	0.0413 (9)	−0.0045 (7)	−0.0040 (7)	0.0106 (8)
C4	0.0377 (9)	0.0612 (12)	0.0459 (10)	−0.0028 (8)	0.0053 (8)	0.0064 (9)
C5	0.0388 (9)	0.0427 (9)	0.0348 (8)	0.0014 (7)	0.0038 (7)	−0.0003 (7)
C6	0.0412 (9)	0.0356 (9)	0.0358 (8)	0.0002 (7)	0.0003 (7)	0.0050 (7)
C7	0.0576 (11)	0.0396 (10)	0.0392 (9)	0.0058 (8)	0.0068 (8)	0.0018 (8)
C8	0.0531 (11)	0.0596 (12)	0.0529 (11)	0.0104 (10)	0.0192 (9)	0.0045 (10)
C9	0.0405 (10)	0.0592 (12)	0.0555 (11)	−0.0007 (9)	0.0074 (8)	0.0084 (10)
C10	0.0423 (10)	0.0511 (11)	0.0471 (10)	−0.0067 (8)	−0.0005 (8)	−0.0018 (8)
C11	0.0917 (17)	0.0557 (13)	0.0519 (12)	0.0043 (12)	0.0110 (11)	−0.0118 (10)
C12	0.0465 (12)	0.108 (2)	0.0973 (19)	−0.0135 (13)	0.0180 (12)	0.0074 (16)
O1	0.0777 (11)	0.0734 (11)	0.0753 (11)	−0.0296 (9)	−0.0270 (8)	0.0324 (9)
O2	0.0786 (11)	0.0869 (12)	0.0666 (10)	−0.0386 (9)	−0.0284 (8)	0.0240 (9)
O3	0.0433 (7)	0.0587 (8)	0.0435 (7)	−0.0017 (6)	0.0089 (5)	−0.0080 (6)

Geometric parameters (Å, º) top

C1—O1	1.223 (2)	C7—C8	1.378 (3)
C1—O2	1.271 (2)	C7—C11	1.497 (3)
C1—C2	1.501 (3)	C8—C9	1.396 (3)
C2—C3	1.497 (2)	C8—H8	0.9300
C2—H2A	0.9700	C9—C10	1.378 (3)
C2—H2B	0.9700	C9—C12	1.512 (3)
C3—C4	1.338 (3)	C10—H10	0.9300
C3—C6	1.446 (2)	C11—H11A	0.9600
C4—O3	1.371 (2)	C11—H11B	0.9600
C4—H4	0.9300	C11—H11C	0.9600
C5—C10	1.376 (2)	C12—H12A	0.9600
C5—O3	1.377 (2)	C12—H12B	0.9600
C5—C6	1.388 (2)	C12—H12C	0.9600
C6—C7	1.409 (2)	O2—H2	0.8200

O1—C1—O2	123.60 (18)	C7—C8—C9	124.24 (18)
O1—C1—C2	122.38 (16)	C7—C8—H8	117.9
O2—C1—C2	114.02 (16)	C9—C8—H8	117.9
C3—C2—C1	114.56 (15)	C10—C9—C8	119.28 (17)
C3—C2—H2A	108.6	C10—C9—C12	120.1 (2)
C1—C2—H2A	108.6	C8—C9—C12	120.6 (2)
C3—C2—H2B	108.6	C5—C10—C9	116.77 (18)
C1—C2—H2B	108.6	C5—C10—H10	121.6
H2A—C2—H2B	107.6	C9—C10—H10	121.6
C4—C3—C6	105.86 (15)	C7—C11—H11A	109.5
C4—C3—C2	123.83 (17)	C7—C11—H11B	109.5
C6—C3—C2	130.31 (18)	H11A—C11—H11B	109.5
C3—C4—O3	113.03 (16)	C7—C11—H11C	109.5
C3—C4—H4	123.5	H11A—C11—H11C	109.5
O3—C4—H4	123.5	H11B—C11—H11C	109.5
C10—C5—O3	124.36 (16)	C9—C12—H12A	109.5
C10—C5—C6	124.98 (17)	C9—C12—H12B	109.5
O3—C5—C6	110.65 (15)	H12A—C12—H12B	109.5
C5—C6—C7	118.25 (16)	C9—C12—H12C	109.5
C5—C6—C3	105.41 (15)	H12A—C12—H12C	109.5
C7—C6—C3	136.34 (17)	H12B—C12—H12C	109.5
C8—C7—C6	116.47 (17)	C1—O2—H2	109.5
C8—C7—C11	121.12 (18)	C4—O3—C5	105.04 (14)
C6—C7—C11	122.41 (18)

O1—C1—C2—C3	9.8 (3)	C3—C6—C7—C8	−178.26 (18)
O2—C1—C2—C3	−169.37 (19)	C5—C6—C7—C11	−179.04 (16)
C1—C2—C3—C4	99.9 (2)	C3—C6—C7—C11	1.5 (3)
C1—C2—C3—C6	−80.0 (3)	C6—C7—C8—C9	−0.4 (3)
C6—C3—C4—O3	0.2 (2)	C11—C7—C8—C9	179.83 (19)
C2—C3—C4—O3	−179.76 (15)	C7—C8—C9—C10	−0.6 (3)
C10—C5—C6—C7	−1.2 (3)	C7—C8—C9—C12	179.1 (2)
O3—C5—C6—C7	−179.97 (15)	O3—C5—C10—C9	178.86 (16)
C10—C5—C6—C3	178.44 (17)	C6—C5—C10—C9	0.2 (3)
O3—C5—C6—C3	−0.37 (19)	C8—C9—C10—C5	0.6 (3)
C4—C3—C6—C5	0.13 (19)	C12—C9—C10—C5	−179.02 (19)
C2—C3—C6—C5	−179.96 (17)	C3—C4—O3—C5	−0.4 (2)
C4—C3—C6—C7	179.6 (2)	C10—C5—O3—C4	−178.36 (17)
C2—C3—C6—C7	−0.5 (3)	C6—C5—O3—C4	0.46 (19)
C5—C6—C7—C8	1.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3ⁱ	0.93	2.58	3.328 (2)	137
O2—H2···O1ⁱⁱ	0.82	1.83	2.645 (2)	171

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1, −y, −z.

Acknowledgements

MB thanks UGC–SWRO, Bangalore, for providing a Minor Research Project (reference No. 1415-MRP/14–15/KAKA067/UGC-SWRO, Diary No. 1709). The authors also thank the SAIF IIT Madras, Chennai, for the data collection.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Basanagouda, M., Narayanachar Majati, I. B., Mulimani, S. S., Sunnal, S. B., Nadiger, R. V., Ghanti, A. S., Gudageri, S. F., Naik, R. & Nayak, A. (2015). Synth. Commun. 45, 2195–2202. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gowda, R., Gowda, K. V. A., Reddy, M. K. & Basanagouda, M. (2015). Acta Cryst. E71, o1053–o1054. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ramprasad, N., Gowda, R., Gowda, K. V. A. & Basanagouda, M. (2016). IUCrData, 1, x160170. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.