Crystal structure of 2-(5-meth­oxy-1-benzo­furan-3-yl)acetic acid

Abstract

The benzo­furan residue in the title compound, C₁₁H₁₀O₄, is essentially planar (the r.m.s. deviation for the nine non-H atoms = 0.011 Å). While the meth­oxy group is coplanar with the fused ring system [C—C—O—C torsion angle = 3.1 (3)°], the acetic acid residue occupies a position almost prime [C—C—C—C = 77.0 (2)°]. In the crystal, centrosymmetrically related mol­ecules are linked by O—H⋯O hydrogen bonds to form eight-membered {⋯HOCO}₂ synthons. The dimeric aggregates assemble into supra­molecular layers in the ab plane via benzene-C—H⋯O(ring) inter­actions.

Related literature  

For a related structures and background to benzo­furans and their applications, see: Dawood (2013 ▸); Khanam & Shamsuzzaman (2015 ▸); Radadiya & Shah (2015 ▸); Naik et al. (2015 ▸); Nevagi et al. (2015 ▸). For the synthesis, see: Basanagouda et al. (2015 ▸).

Experimental  

Crystal data  

• C₁₁H₁₀O₄

• M _r = 206.19

• Monoclinic,

• a = 5.8096 (3) Å

• b = 13.2034 (5) Å

• c = 12.5738 (6) Å

• β = 97.641 (3)°

• V = 955.93 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 296 K

• 0.35 × 0.30 × 0.25 mm

Data collection  

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T _min = 0.961, T _max = 0.979

• 12813 measured reflections

• 2094 independent reflections

• 1621 reflections with I > 2σ(I)

• R _int = 0.024

Refinement  

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.110

• S = 1.12

• 2094 reflections

• 137 parameters

• H-atom parameters constrained

• Δρ_max = 0.22 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (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 (Bruno et al., 2002 ▸); software used to prepare material for publication: SHELXL2014.

Supplementary Material

CCDC reference: 1401314

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2i	0.82	1.82	2.6357 (17)	174
C2—H2⋯O4ii	0.93	2.55	3.4629 (19)	169

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

S1. Comment

Benzofuran scaffolds have drawn considerable attention due to their physiological and chemotherapeutic properties as well as their widespread occurrence in nature. They display potent biological properties including antihyperglycemic, analgesic, antiparasitic, antimicrobial, antitumor and kinase inhibitor activities (Dawood, 2013; Khanam & Shamsuzzaman, 2015; Radadiya & Shah, 2015; Naik et al. 2015; Nevagi et al. 2015). In addition, substituted benzofurans find application such as fluorescent sensors, oxidant, antioxidants and brightening agents. The derivatives of 2,3-dihydro-benzofuranyl-3-acetic acid have been reported to be potent, selective and orally bioavailable G protein-coupled receptor 40 (GPR40) and free fatty acid receptor 1 agonists (FFA1) (Basanagouda et al., 2015). A perspective view of the molecule is shown in Fig. 1 and geomtric data for the intermolecular interactions are listed in Table 1.

S2. Experimental

6-Methoxy-4-bromomethylcoumarin (10 mM) was refluxed in 1 M NaOH (100 ml) for 2 h (monitored by TLC). 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 ethanol and ethyl acetate mixture by slow evaporation.

S3. Refinement

The carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_equiv(C). The oxygen-bound H-atom was also placed in a calculated position (O—H = 0.82 Å) with U_iso(H) set to 1.5U_equiv(O).

Figures

Fig. 1.

Molecular structure of the title compound showing atom labelling and 40% probability displacement ellipsoids.

Crystal data

C11H10O4	Dx = 1.433 Mg m−3
Mr = 206.19	Melting point: 413 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.8096 (3) Å	Cell parameters from 5229 reflections
b = 13.2034 (5) Å	θ = 2.2–28.6°
c = 12.5738 (6) Å	µ = 0.11 mm−1
β = 97.641 (3)°	T = 296 K
V = 955.93 (8) Å3	Block, colourless
Z = 4	0.35 × 0.30 × 0.25 mm
F(000) = 432

Data collection

Bruker Kappa APEXII CCD diffractometer	2094 independent reflections
Radiation source: fine-focus sealed tube	1621 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω and φ scan	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −7→7
Tmin = 0.961, Tmax = 0.979	k = −16→16
12813 measured reflections	l = −16→16

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.0364P)2 + 0.4069P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.110	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 0.22 e Å−3
2094 reflections	Δρmin = −0.16 e Å−3
137 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.017 (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
C1	0.4010 (3)	0.61606 (13)	0.80077 (14)	0.0432 (4)
C2	0.2178 (3)	0.67578 (12)	0.82316 (13)	0.0389 (4)
H2	0.1770	0.6787	0.8922	0.047*
C3	0.0964 (3)	0.73116 (11)	0.74025 (12)	0.0349 (4)
C4	0.1631 (3)	0.72515 (13)	0.63818 (13)	0.0398 (4)
C5	0.3460 (3)	0.66724 (14)	0.61521 (14)	0.0477 (5)
H5	0.3882	0.6653	0.5464	0.057*
C6	0.4647 (3)	0.61208 (14)	0.69782 (15)	0.0479 (5)
H6	0.5890	0.5716	0.6848	0.057*
C7	0.7098 (4)	0.50545 (17)	0.8728 (2)	0.0646 (6)
H7A	0.7685	0.4733	0.9394	0.097*
H7B	0.6680	0.4547	0.8190	0.097*
H7C	0.8272	0.5488	0.8506	0.097*
C8	−0.0997 (3)	0.79821 (12)	0.73082 (13)	0.0378 (4)
C9	−0.1369 (3)	0.82596 (14)	0.62760 (14)	0.0476 (4)
H9	−0.2559	0.8692	0.5995	0.057*
C10	−0.2391 (3)	0.82719 (13)	0.81742 (14)	0.0421 (4)
H10A	−0.2708	0.7666	0.8566	0.051*
H10B	−0.3869	0.8541	0.7845	0.051*
C11	−0.1270 (3)	0.90353 (12)	0.89552 (13)	0.0367 (4)
O1	−0.2484 (2)	0.92135 (9)	0.97334 (10)	0.0491 (4)
H1	−0.1813	0.9636	1.0141	0.074*
O2	0.0578 (2)	0.94412 (10)	0.88700 (10)	0.0514 (4)
O3	0.5123 (3)	0.56354 (12)	0.88677 (12)	0.0665 (4)
O4	0.0193 (2)	0.78381 (10)	0.56745 (9)	0.0503 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0431 (9)	0.0419 (9)	0.0459 (10)	−0.0026 (7)	0.0101 (8)	−0.0053 (7)
C2	0.0428 (9)	0.0434 (9)	0.0328 (8)	−0.0051 (7)	0.0133 (7)	−0.0068 (7)
C3	0.0381 (8)	0.0356 (8)	0.0329 (8)	−0.0099 (7)	0.0113 (6)	−0.0089 (6)
C4	0.0456 (9)	0.0428 (9)	0.0325 (8)	−0.0113 (7)	0.0114 (7)	−0.0072 (7)
C5	0.0537 (11)	0.0543 (10)	0.0394 (9)	−0.0101 (9)	0.0218 (8)	−0.0140 (8)
C6	0.0464 (10)	0.0477 (10)	0.0535 (11)	−0.0024 (8)	0.0215 (8)	−0.0139 (8)
C7	0.0515 (12)	0.0578 (12)	0.0832 (15)	0.0092 (10)	0.0038 (11)	−0.0052 (11)
C8	0.0383 (9)	0.0399 (8)	0.0360 (8)	−0.0087 (7)	0.0075 (7)	−0.0069 (7)
C9	0.0477 (10)	0.0514 (10)	0.0439 (10)	−0.0038 (8)	0.0065 (8)	−0.0018 (8)
C10	0.0363 (9)	0.0472 (9)	0.0438 (9)	−0.0026 (7)	0.0093 (7)	−0.0071 (7)
C11	0.0408 (9)	0.0362 (8)	0.0349 (8)	0.0018 (7)	0.0118 (7)	−0.0002 (6)
O1	0.0558 (8)	0.0503 (7)	0.0461 (7)	−0.0115 (6)	0.0248 (6)	−0.0119 (6)
O2	0.0507 (8)	0.0599 (8)	0.0476 (7)	−0.0158 (6)	0.0207 (6)	−0.0172 (6)
O3	0.0661 (9)	0.0760 (10)	0.0590 (9)	0.0257 (8)	0.0144 (7)	0.0081 (7)
O4	0.0604 (8)	0.0598 (8)	0.0322 (6)	−0.0064 (6)	0.0114 (6)	−0.0009 (5)

Geometric parameters (Å, º)

C1—O3	1.372 (2)	C7—H7A	0.9600
C1—C2	1.383 (2)	C7—H7B	0.9600
C1—C6	1.394 (2)	C7—H7C	0.9600
C2—C3	1.387 (2)	C8—C9	1.338 (2)
C2—H2	0.9300	C8—C10	1.491 (2)
C3—C4	1.391 (2)	C9—O4	1.374 (2)
C3—C8	1.435 (2)	C9—H9	0.9300
C4—C5	1.371 (2)	C10—C11	1.495 (2)
C4—O4	1.375 (2)	C10—H10A	0.9700
C5—C6	1.377 (3)	C10—H10B	0.9700
C5—H5	0.9300	C11—O2	1.217 (2)
C6—H6	0.9300	C11—O1	1.3014 (18)
C7—O3	1.410 (2)	O1—H1	0.8200
O3—C1—C2	115.00 (15)	O3—C7—H7C	109.5
O3—C1—C6	123.86 (17)	H7A—C7—H7C	109.5
C2—C1—C6	121.13 (17)	H7B—C7—H7C	109.5
C1—C2—C3	118.41 (15)	C9—C8—C3	105.85 (15)
C1—C2—H2	120.8	C9—C8—C10	127.22 (17)
C3—C2—H2	120.8	C3—C8—C10	126.89 (15)
C2—C3—C4	119.14 (15)	C8—C9—O4	112.94 (17)
C2—C3—C8	134.93 (14)	C8—C9—H9	123.5
C4—C3—C8	105.92 (15)	O4—C9—H9	123.5
C5—C4—O4	126.81 (15)	C8—C10—C11	114.92 (14)
C5—C4—C3	123.03 (17)	C8—C10—H10A	108.5
O4—C4—C3	110.16 (15)	C11—C10—H10A	108.5
C4—C5—C6	117.44 (15)	C8—C10—H10B	108.5
C4—C5—H5	121.3	C11—C10—H10B	108.5
C6—C5—H5	121.3	H10A—C10—H10B	107.5
C5—C6—C1	120.83 (17)	O2—C11—O1	123.98 (15)
C5—C6—H6	119.6	O2—C11—C10	123.47 (14)
C1—C6—H6	119.6	O1—C11—C10	112.55 (14)
O3—C7—H7A	109.5	C11—O1—H1	109.5
O3—C7—H7B	109.5	C1—O3—C7	118.88 (16)
H7A—C7—H7B	109.5	C9—O4—C4	105.13 (13)
O3—C1—C2—C3	−179.94 (15)	C4—C3—C8—C9	0.53 (18)
C6—C1—C2—C3	0.7 (3)	C2—C3—C8—C10	−1.0 (3)
C1—C2—C3—C4	−0.3 (2)	C4—C3—C8—C10	178.12 (15)
C1—C2—C3—C8	178.71 (17)	C3—C8—C9—O4	−0.6 (2)
C2—C3—C4—C5	−0.5 (2)	C10—C8—C9—O4	−178.15 (15)
C8—C3—C4—C5	−179.78 (15)	C9—C8—C10—C11	−105.9 (2)
C2—C3—C4—O4	178.93 (14)	C3—C8—C10—C11	77.0 (2)
C8—C3—C4—O4	−0.33 (17)	C8—C10—C11—O2	4.0 (3)
O4—C4—C5—C6	−178.48 (16)	C8—C10—C11—O1	−175.80 (15)
C3—C4—C5—C6	0.9 (3)	C2—C1—O3—C7	−176.25 (17)
C4—C5—C6—C1	−0.4 (3)	C6—C1—O3—C7	3.1 (3)
O3—C1—C6—C5	−179.65 (17)	C8—C9—O4—C4	0.38 (19)
C2—C1—C6—C5	−0.3 (3)	C5—C4—O4—C9	179.42 (17)
C2—C3—C8—C9	−178.54 (18)	C3—C4—O4—C9	−0.01 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.82	1.82	2.6357 (17)	174
C2—H2···O4ii	0.93	2.55	3.4629 (19)	169

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