4,4′-[(5-Carb­oxy-1,3-phenyl­ene)bis­(­oxy)]dibenzoic acid

Chao Du; Wei Wu; Ge Tian

doi:10.1107/S1600536812012275

. 2012 Mar 31;68(Pt 4):o1243. doi: 10.1107/S1600536812012275

4,4′-[(5-Carboxy-1,3-phenylene)bis(oxy)]dibenzoic acid

Chao Du ^a, Wei Wu ^b, Ge Tian ^c,^*

PMCID: PMC3344173 PMID: 22606176

Abstract

In the title compound, C₂₁H₁₄O₈, the central benzene ring makes dihedral angles of 77.8 (6) and 75.9 (5)° with the outer benzene rings. In the crystal, molecules are linked by O—H⋯O hydrogen bonds involving carboxyl groups, forming one-dimensional ladders. Two-dimensional layers are formed by interpenetration of these one-dimensional ladders.

Related literature

For general background, see: Moulton & Zaworotko,(2001 ▶); Kitagawa et al.,(2001 ▶); Lee et al.,(2009 ▶); Robin & Fromm, (2006 ▶). For the preparation of title compound, see: Neogi et al.(2009 ▶). For related structares, see: Lama et al.(2010 ▶); Pan et al. (2007 ▶).

Experimental

Crystal data

C₂₁H₁₄O₈
M _r = 394.32
Monoclinic,
a = 17.235 (3) Å
b = 13.419 (3) Å
c = 15.586 (3) Å
β = 96.24 (3)°
V = 3583.3 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.33 × 0.29 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.316, T _max = 0.622
16922 measured reflections
4073 independent reflections
2862 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.121
S = 1.09
4073 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXP97 (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812012275/bq2343sup1.cif

e-68-o1243-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012275/bq2343Isup2.hkl

e-68-o1243-Isup2.hkl^{(199.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812012275/bq2343Isup3.cml

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
O3—H6⋯O4ⁱ	0.82	1.87	2.6919 (16)	176.4
O6—H3⋯O8ⁱⁱ	0.82	1.85	2.6615 (18)	169.9
O7—H8⋯O5ⁱⁱⁱ	0.82	1.82	2.6307 (18)	167.2

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

Acknowledgments

The authors thank the National Natural Science Foundation of China.

supplementary crystallographic information

Comment

As a new kind of functional molecular materials, metal-organic frameworks have received extensive attention for their potential applications in gas storage, catalysis, optoelectronics, sensors, magnetism, luminescence, porous materials and so on. (Moulton & Zaworotko, 2001; Kitagawa et al., 2001; Lee et al., 2009). Organic molecules with O– and N-donors can be used as organic linkers in these coordination polymers (Robin & Fromm, 2006). In fact, there are many organic ligands which are linked by ether bond (Lama et al. 2010; Pan et al., 2007). Here, we report the crystal structure of the title compound.

In the crystal structure, two benzene rings, β(composed of C₈—C₁₃) and γ (composed of C₁₅—C₂₀) are connected to the center ring (α, composed of C₁—C₆) by ether bond. The dihedral angle between α and β is 77.8 (6)°, and between α and γ is 75.9 (5)° (Fig. 1). Strong intermolecular O—H···O hydrogen bonds are formed between the carboxylic acid groups of neighboring molecules (Table 1), which link the molecules to one-dimensional supra-molecular ladder (Fig. 2). The interpenetration among the one-dimensional molecular ladders which are parallel produce two-dimensional layer (Fig. 3).

Experimental

The title compound was synthesized by a modified literature method (Neogi et al.2009). Methyl 3,5-dihydroxylbenzoate (1.68 g,10 mmol) was dissolved in DMF (50 ml). To this solution was added K₂CO₃ (7 g,51 mmol) and 4-fluorobenzonitrile (2.4 g,20 mmol). The mixture was heated under reflux for 2 days. The resulting solution was poured in 250 ml ice-cold water and kept over-night. The yellow compound was filtered and washed several times with water. The yellow compound (3.73 g, 10 mmol) was allowed to reflux with 6 N NaOH solution (50 ml) for 12 h, cooled to room temperature and acidified with HCl (6 N). Colorless crystalline product was obtained and isolated by filtration, washed with water and dried in vacuum. Zn(NO₃)₂ (0.075 g,0.25 mmol), 4,4'-(5-carboxy-1,3-phenylene)bis(oxy)dibenzoic acid (0.098 g,0.25 mmol), were mixed in water (5 ml). The mixture were placed in a 25 ml Teflon-lined stainless steel autoclave and heated autogenously under pressure for 2 d at 393 K. After cooling to room temperature, the block-shaped colourless crystals were obtained.