4,4′-[p-Phenyl­enebis(­oxy)]dibutanoic acid

Zhi Li

doi:10.1107/S1600536811036828

. 2011 Sep 17;67(Pt 10):o2654. doi: 10.1107/S1600536811036828

4,4′-[p-Phenylenebis(oxy)]dibutanoic acid

Zhi Li ^a,^*

PMCID: PMC3201374 PMID: 22065827

Abstract

The complete molecule of the title compound, C₁₄H₁₈O₆, has a center of inversion at the centroid of the benzene ring and the asymmetric unit contains one half-molecule. The conformation of the side chain is anti [C—C—C—C = −171.40 (17)°]. In the crystal, pairs of head-to-head carboxylic acid O—H⋯O hydrogen bonds link the molecules into infinite zigzag chains propagating along [130]. Weak C—H⋯π interactions between adjacent chains expand the structure into a layered network in the ac plane.

Related literature

For general background to phenoxyacetic acid derivatives, see: Yada (1959 ▶); Zheng et al. (2007 ▶); Deng et al. (2010 ▶); Xiong et al. (2010 ▶); Fu et al. (2011 ▶). For related structures of multidentate O-donor ligands such as benzene-1,4-dioxydiacetic acid and benzene-1,4-dioxydibutanoic acid, see: Dai et al. (2009 ▶); Zhu et al. (2008 ▶); Li et al. (2010 ▶); Yang et al. (2010 ▶); Zhao (2011 ▶). For the synthesis of the title compound, see: Zhang et al. (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₄H₁₈O₆
M _r = 282.28
Triclinic,
a = 4.8389 (11) Å
b = 6.6300 (15) Å
c = 11.406 (3) Å
α = 83.067 (5)°
β = 81.249 (5)°
γ = 71.095 (4)°
V = 341.16 (13) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.21 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.978, T _max = 0.981
1861 measured reflections
1170 independent reflections
1025 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.162
S = 1.02
1170 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036828/hb6398sup1.cif

e-67-o2654-sup1.cif^{(13.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036828/hb6398Isup2.hkl

e-67-o2654-Isup2.hkl^{(57.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036828/hb6398Isup3.cml

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

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

Cg1 is the centroid of the C5–C7/C5′–C7′ ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.85	2.668 (3)	174
C4—H4B⋯Cg1ⁱⁱ	0.97	2.89	3.703 (3)	142

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The author thanks Beijing Jiaotong University for financial support.

supplementary crystallographic information

Comment

Compounds of the phenoxyacetic acid and their derivatives have good herbicidal activity and become excellent plant growth regulators (Yada, 1959; Zheng et al., 2007; Deng et al., 2010; Xiong et al., 2010; Fu et al., 2011). Also, the two phenoxyacetate moieties have versatile flexiable bonding fashions to metal ions and easily forms coordination polymers (Dai et al., 2009; Zhu et al., 2008; Li et al., 2010; Yang et al., 2010; Zhao et al., 2011). Benzene-1,4-dioxydibutanoic acid is an interesting dicarboxylate ligand and its cobalt polymer has been reported by Zhao et al. 2011. To further investigate this family of ligands, the title compound, (I), was synthesized and its structure was confirmed by X-ray diffraction. X-ray diffraction analysis reveals that the asymmetric unit of the title compound contains one half-molecule and has a crystallographic inversion center at the centroid of the benzene ring (Fig. 1). The benzene-connected portions of the alkoxy substituents lie almost coplanar with the C3–C4–O3–C5 torsion angle of 176.81 (16)°. In the molecule of (I) (Fig. 1) the bond lengths are within normal ranges (Allen et al., 1987). The C1—O2, C4—O3 and C5—O3 bond length of 1.287 (3), 1.428 (2) and 1.375 (2) Å, respectively, indicate the presence of typical single bonds. Whereas the C1–O1 [1.221 (3) Å] bond lengths correspond to a typical C═O bond.

In the crystal structure, it is noteworthy that pairs of intermolecular O—H···O hydrogen bonds link head-to-tail the molecules into infinite 1 d chains along the [1 3 0] direction (Fig. 2). Neighboring 1 d chains are in turn interacting with each other through C—H···π stacking interactions with the H···π distances of 2.89 (3) Å to form infinite stacks along b axis, thus leading to an interwoven two dimensional network held together by O—H···O interactions and C—H···π stacking (Fig. 3).

Experimental

Reagents and solvents were of commercially available quality. The title compound was synthesized according to the method of Zhang et al. 2009. To a solution of p-dihydroxybenzene (0.01 mol) in acetonitrile (50 ml), anhydrous potassium carbonate (0.02 mol) and ethyl 4-bromobutanoate (0.01 mol) were mixed. The mixture solution was refluxed for 6 h and filtered. The filtrate was evaporated under reduced pressure and the solid product was dissolved in water/ethanol (1:2 v/v), then sodium hydroxide (0.02 mol) was added. The solution was refluxed for another 24 h, then acidified with dilute HCl. The crude product was separated by filtration and crystals of the title compound were prepared by recrystallization from a mixture of water and ethanol (1:1 v/v).