2-[4-(Carb­oxy­meth­yl)phen­oxy]acetic acid

Abstract

The title compound, C₁₀H₁₀O₅, was obtained by the reaction of 4-hy­droxy­phenyl­acetic acid with chloro­acetic acid. In the crystal, the mol­ecules form a three-dimensional network by way of inter­molecular O—H⋯O hydrogen bonding.

Related literature

For applications of metal-organic frameworks with carb­oxy­lic acid ligands, see: Kuppler et al. (2009) ▶; Jahan et al. (2010 ▶); Armelao et al. (2010 ▶); Yashima et al. (2009 ▶). The title compound was obtained by the reaction of 4-hy­droxy­phenyl­acetic (Gracin et al., 2005 ▶) and chloro­acetic acid (Sandhu et al., 1991 ▶).

Experimental

Crystal data

• C₁₀H₁₀O₅

• M _r = 210.18

• Orthorhombic,

• a = 5.4640 (2) Å

• b = 10.7798 (5) Å

• c = 16.2550 (7) Å

• V = 957.43 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.12 mm⁻¹

• T = 296 K

• 0.42 × 0.38 × 0.31 mm

Data collection

• Bruker APEXII area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.95, T _max = 0.96

• 11814 measured reflections

• 1315 independent reflections

• 1162 reflections with I > 2σ(I)

• R _int = 0.049

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.099

• S = 1.07

• 1315 reflections

• 136 parameters

• H-atom parameters constrained

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4i	0.82	1.81	2.617 (2)	168
O5—H5⋯O1ii	0.82	1.85	2.666 (2)	171

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Various aromatic carboxylic acid ligands are being used in designing versatile metal-organic frameworks (MOFs) having potential applications (Kuppler et al., 2009; Jahan et al., 2010; Armelao et al., 2010; Yashima et al., 2009). In present work, we report the synthesis and single crystal structure of a new aromatic dicarboxylic acid ligand namely 4-carboxymethoxy phenylacetic acid (I) containing two flexible carboxylic acid groups, obtained by the reaction of 4-hydroxyphenylacetic (Gracin et al., 2005) and chloroacetic acid (Sandhu et al., 1991).

The molecular structure of the title compound is presented in Fig.1. The carboxymethoxy group is almost parallel to the benzene ring with a dihedral angle of 11.4 (1)° between the two least-squares planes,while the acetic acid unit is almost perpendicular to the benzene ring, making a dihedral angle of 72.4 (2)°.In addtion, the moleculars were linked by the intermolecular O—H···O hydrogen bonding forming a three-dimensional network (Fig.2).

Experimental

The solution of 4-hydroxyphenylacetic acid (1.522 g, 10.0 mmol) in water (10 ml) neutralized with NaOH (0.8 g, 20 mmol) was added to a 1:1 mixture of chloroacetic acid (3.78 g, 40 mmol) and NaOH (1.600 g, 40 mmol) with stirring to adjust the pH value of the mixture to ca 11 and refluxed at 90 ⁰C for 3 h. The pH value was adjusted to 2–3 with concentrated hydrochloric acid. While cooling the mixture to room temperature, a white precipitate was appeared rapidly. The solid was filtrated, washed by water. Single crystals suitable for X-ray diffraction were obtained in the mother liquid after evaporation within a few days.

Refinement

The Flack parameter could not be refined to an acceptable value as the title compound is a poor anomalous scatterer even after using MOVE command in Shelxl97. Therefore, the Friedel oppostites were merged (using MERG 3 command in Shelxl97) and Flack parameter is not reported. H-atoms were positioned geometrically and included in the refinement using a riding-model approximation [aromatic C–H = 0.93 Å, aliphatic C–H = 0.97 Å, O–H = 0.82 Å] with U_iso(H) = 1.2U_eq(C,O).

Figures

Fig. 1.

View of the molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

A packing diagram of (I), the hydrogen bonds are depicted as green dashed lines.

Crystal data

C10H10O5	F(000) = 440
Mr = 210.18	Dx = 1.458 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6173 reflections
a = 5.4640 (2) Å	θ = 2.3–27.7°
b = 10.7798 (5) Å	µ = 0.12 mm−1
c = 16.2550 (7) Å	T = 296 K
V = 957.43 (7) Å3	Block, colourless
Z = 4	0.42 × 0.38 × 0.31 mm

Data collection

Bruker APEXII area-detector diffractometer	1315 independent reflections
Radiation source: fine-focus sealed tube	1162 reflections with I > 2σ(I)
graphite	Rint = 0.049
phi and ω scans	θmax = 27.7°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.95, Tmax = 0.96	k = −13→14
11814 measured reflections	l = −20→21

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0425P)2 + 0.2342P] where P = (Fo2 + 2Fc2)/3
1315 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.19 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.4626 (4)	0.67278 (16)	0.64905 (10)	0.0651 (5)
O2	0.7484 (4)	0.79234 (17)	0.59564 (10)	0.0645 (5)
H2	0.7132	0.8367	0.6349	0.077*
O3	0.4929 (3)	0.51339 (14)	0.52607 (9)	0.0489 (4)
O4	0.8002 (3)	0.06923 (15)	0.22690 (11)	0.0536 (4)
O5	0.6100 (4)	−0.00299 (16)	0.33749 (9)	0.0589 (5)
H5	0.7257	−0.0515	0.3374	0.071*
C1	0.6127 (4)	0.6927 (2)	0.59700 (12)	0.0440 (5)
C2	0.6695 (4)	0.6081 (2)	0.52593 (12)	0.0443 (5)
H2A	0.6632	0.6538	0.4746	0.053*
H2B	0.8320	0.5731	0.5320	0.053*
C3	0.4856 (4)	0.43389 (19)	0.46020 (12)	0.0401 (4)
C4	0.2906 (4)	0.3526 (2)	0.45967 (13)	0.0449 (5)
H4A	0.1741	0.3559	0.5013	0.054*
C5	0.2681 (4)	0.2661 (2)	0.39733 (13)	0.0467 (5)
H5A	0.1357	0.2119	0.3972	0.056*
C6	0.4405 (4)	0.2592 (2)	0.33498 (12)	0.0427 (5)
C7	0.6354 (4)	0.3416 (2)	0.33640 (13)	0.0457 (5)
H7A	0.7520	0.3381	0.2948	0.055*
C8	0.6606 (4)	0.4294 (2)	0.39878 (12)	0.0445 (5)
H8A	0.7925	0.4839	0.3991	0.053*
C9	0.4187 (4)	0.1613 (2)	0.26811 (13)	0.0502 (5)
H9A	0.2651	0.1171	0.2741	0.060*
H9B	0.4198	0.2009	0.2145	0.060*
C10	0.6279 (4)	0.07182 (19)	0.27412 (13)	0.0431 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0757 (12)	0.0593 (11)	0.0602 (9)	−0.0208 (10)	0.0218 (10)	−0.0149 (8)
O2	0.0736 (12)	0.0572 (10)	0.0627 (10)	−0.0251 (10)	0.0144 (10)	−0.0129 (8)
O3	0.0598 (9)	0.0426 (8)	0.0444 (7)	−0.0102 (8)	0.0096 (8)	−0.0050 (6)
O4	0.0479 (8)	0.0490 (9)	0.0639 (9)	0.0009 (8)	0.0033 (8)	0.0069 (8)
O5	0.0625 (10)	0.0639 (10)	0.0503 (8)	0.0177 (10)	0.0026 (8)	0.0099 (8)
C1	0.0475 (11)	0.0409 (10)	0.0437 (10)	−0.0063 (10)	−0.0009 (10)	0.0025 (9)
C2	0.0446 (11)	0.0461 (11)	0.0423 (10)	−0.0056 (10)	0.0009 (10)	0.0003 (9)
C3	0.0448 (10)	0.0376 (9)	0.0378 (9)	0.0010 (9)	0.0000 (9)	0.0026 (8)
C4	0.0447 (11)	0.0452 (11)	0.0448 (10)	−0.0008 (10)	0.0034 (10)	0.0012 (9)
C5	0.0435 (11)	0.0452 (11)	0.0515 (11)	−0.0016 (10)	−0.0029 (10)	0.0017 (9)
C6	0.0436 (11)	0.0428 (10)	0.0416 (9)	0.0092 (10)	−0.0067 (9)	0.0012 (8)
C7	0.0436 (11)	0.0512 (12)	0.0422 (10)	0.0051 (10)	0.0030 (9)	0.0011 (9)
C8	0.0412 (10)	0.0465 (11)	0.0457 (10)	−0.0023 (10)	0.0002 (9)	0.0018 (9)
C9	0.0493 (12)	0.0541 (12)	0.0473 (11)	0.0129 (11)	−0.0122 (10)	−0.0060 (10)
C10	0.0455 (11)	0.0389 (10)	0.0451 (10)	0.0010 (10)	−0.0084 (10)	−0.0040 (9)

Geometric parameters (Å, °)

O1—C1	1.198 (3)	C4—C5	1.383 (3)
O2—C1	1.305 (3)	C4—H4A	0.9300
O2—H2	0.8200	C5—C6	1.386 (3)
O3—C3	1.372 (2)	C5—H5A	0.9300
O3—C2	1.405 (3)	C6—C7	1.387 (3)
O4—C10	1.215 (3)	C6—C9	1.519 (3)
O5—C10	1.312 (3)	C7—C8	1.394 (3)
O5—H5	0.8200	C7—H7A	0.9300
C1—C2	1.504 (3)	C8—H8A	0.9300
C2—H2A	0.9700	C9—C10	1.499 (3)
C2—H2B	0.9700	C9—H9A	0.9700
C3—C4	1.380 (3)	C9—H9B	0.9700
C3—C8	1.383 (3)
C1—O2—H2	109.5	C6—C5—H5A	119.6
C3—O3—C2	118.19 (16)	C5—C6—C7	118.39 (19)
C10—O5—H5	109.5	C5—C6—C9	120.5 (2)
O1—C1—O2	123.3 (2)	C7—C6—C9	121.11 (19)
O1—C1—C2	125.1 (2)	C6—C7—C8	121.5 (2)
O2—C1—C2	111.64 (18)	C6—C7—H7A	119.2
O3—C2—C1	107.31 (17)	C8—C7—H7A	119.2
O3—C2—H2A	110.3	C3—C8—C7	118.7 (2)
C1—C2—H2A	110.3	C3—C8—H8A	120.6
O3—C2—H2B	110.3	C7—C8—H8A	120.6
C1—C2—H2B	110.3	C10—C9—C6	109.89 (17)
H2A—C2—H2B	108.5	C10—C9—H9A	109.7
O3—C3—C4	115.09 (18)	C6—C9—H9A	109.7
O3—C3—C8	124.41 (19)	C10—C9—H9B	109.7
C4—C3—C8	120.47 (19)	C6—C9—H9B	109.7
C3—C4—C5	120.1 (2)	H9A—C9—H9B	108.2
C3—C4—H4A	119.9	O4—C10—O5	122.6 (2)
C5—C4—H4A	119.9	O4—C10—C9	124.4 (2)
C4—C5—C6	120.8 (2)	O5—C10—C9	112.97 (19)
C4—C5—H5A	119.6
C3—O3—C2—C1	171.19 (18)	C5—C6—C7—C8	0.3 (3)
O1—C1—C2—O3	8.2 (3)	C9—C6—C7—C8	−178.2 (2)
O2—C1—C2—O3	−171.83 (18)	O3—C3—C8—C7	178.09 (19)
C2—O3—C3—C4	−172.77 (18)	C4—C3—C8—C7	0.2 (3)
C2—O3—C3—C8	9.3 (3)	C6—C7—C8—C3	−0.2 (3)
O3—C3—C4—C5	−178.35 (19)	C5—C6—C9—C10	−114.2 (2)
C8—C3—C4—C5	−0.3 (3)	C7—C6—C9—C10	64.2 (3)
C3—C4—C5—C6	0.4 (3)	C6—C9—C10—O4	−106.1 (2)
C4—C5—C6—C7	−0.3 (3)	C6—C9—C10—O5	72.4 (2)
C4—C5—C6—C9	178.15 (19)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4i	0.82	1.81	2.617 (2)	168
O5—H5···O1ii	0.82	1.85	2.666 (2)	171

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