2,2′-[Biphenyl-2,2′-diylbis(­oxy)]diacetic acid monohydrate

Muhammad Rabnawaz; Qamar Ali; Muhammad Raza Shah; Kuldip Singh

doi:10.1107/S160053680802833X

. 2008 Sep 13;64(Pt 10):o1909. doi: 10.1107/S160053680802833X

2,2′-[Biphenyl-2,2′-diylbis(oxy)]diacetic acid monohydrate

Muhammad Rabnawaz ^a, Qamar Ali ^a, Muhammad Raza Shah ^a,^*, Kuldip Singh ^b

PMCID: PMC2959279 PMID: 21201118

Abstract

In the crystal structure of the title compound, C₁₆H₁₄O₆·H₂O, the dihedral angle between the benzene rings is 60.8 (3)°. Molecules are linked through a bifurcated O—H⋯O hydrogen bond, forming a zigzag chain along the b axis. The chains are further linked by O—H⋯O hydrogen bonds mediated by water molecules.

Related literature

For the crystal structures of related compounds, see: Ali, Hussain et al. (2008 ▶); Ali, Ibad et al. (2008 ▶); Ali, Shah & VanDerveer (2008 ▶); Ibad et al. (2008 ▶). For biological applications, see: Baudry et al. (2006 ▶); Kamoda et al. (2006 ▶); Litvinchuk et al. (2004 ▶); MacNeil & Decken (1999 ▶); Park (2000 ▶); Sisson et al. (2006 ▶).

Experimental

Crystal data

C₁₆H₁₄O₆·H₂O
M _r = 320.29
Monoclinic,
a = 13.7590 (17) Å
b = 6.7875 (9) Å
c = 16.446 (2) Å
β = 104.698 (2)°
V = 1485.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 150 (2) K
0.17 × 0.13 × 0.08 mm

Data collection

Bruker APEX 2000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.981, T _max = 0.991
10352 measured reflections
2612 independent reflections
1555 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.088
S = 0.85
2612 reflections
216 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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 datablocks I, global. DOI: 10.1107/S160053680802833X/is2319sup1.cif

e-64-o1909-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802833X/is2319Isup2.hkl

e-64-o1909-Isup2.hkl^{(128.3KB, hkl)}

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—H3⋯O5ⁱ	0.84	1.87	2.671 (2)	158
O3—H3⋯O4ⁱ	0.84	2.66	3.285 (2)	133
O6—H6⋯O7ⁱⁱ	0.84	1.76	2.584 (3)	165
O7—H7A⋯O2	0.833 (16)	2.30 (2)	2.958 (3)	136 (2)
O7—H7B⋯O1	0.820 (16)	2.50 (2)	3.153 (3)	138 (3)

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

Acknowledgments

The authors thanks the Organization for the Prohibition of Chemical Weapons and COMSTECH–ISECO for financial support.

supplementary crystallographic information

Comment

By virtue of their role as pharmacophore, the biphenyl structural motif is found to be an integral part of several important biologically active compounds (Kamoda et al., 2006). The biphenyl system have been extensively studied by X-ray crystallography (Ali, Hussain et al., 2008; Ali, Ibad et al., 2008; Ali, Shah & VanDerveer, 2008; Ibad et al., 2008) and their role have been elaborated in the domain of photophysics (Park, 2000). Our interest in the chemistry of biphenyl compounds stems from their use as starting material for the synthesis of oligo(p-phenylene)s (Sisson et al., 2006; Litvinchuk et al., 2004). The cylindrical self-assembly of suitably substituted oligo(p-phenylene)s result in the formation of functionalized pores (Baudry et al., 2006). We report now the synthesis and crystal structure of 2,2'-[biphenyl-2,2'-diylbis(oxy)]diacetic acid.

The dihedral angle between the planes of the benzene rings is 60.8 (3)°. The inter ring C6—C7 distance is 1.488 (3) Å, which compares well with the reported value (MacNeil & Decken 1999). The molecules of the title compound (Fig. 1) are interacting through intermolecular and intramolecular hydrogen bonding (Table 1) involving carbonyl and hydrogen of the type C═O···HO (Fig. 2). The intermolecular hydrogen bonding is mediated by water molecules (Fig. 2). The two carboxylic acid groups are oriented in the same directions (Fig. 1) due to hydrogen bonding contrary to its hydrazide (Ibad et al., 2008) and ester analogue (Ali, Hussain et al., 2008; Ali, Ibad et al., 2008; Ali, Shah & VanDerveer, 2008) where both carboxylic acids are oriented in different directions. The C14—O2 and C16—O5 distances in the title compound are 1.207 (5) and 1.194 (5) Å, respectively, typical of double bonds (Ibad et al., 2008). The OCH₂COOH substituent are having torsion angle 165.3 (4)° (C13—O1—C1—C6) and 178.6 (4)° (C15—O4—C12—C7) with respect to phenyl rings.

Experimental

The title compound 1 was synthesized in two steps. In the first step tert-butyl 2-({2'-[2-(tert-butoxy)-2-oxoethoxy][1,1'-biphenyl]-2- yl}oxy) acetate (compound 2) was prepared and in the second step the tert-butyl group was removed to obtain the title compound 1. The experimental procedure of the both steps is presented below. 1. Synthesis of tert-butyl 2-({2'-[2-(tert-butoxy)-2-oxoethoxy][1,1'-biphenyl] -2- yl}oxy)acetate 2: K₂CO₃ (414 mg, 3 mmol) and 2,2'-dihydroxybiphenyl (186 mg, 1 mmol) in 15 ml of acetone were stirred for 10 minutes, followed by addition of tertiary butyl bromoacetate (371 mg, 3 mmol). The reaction mixture was stirred at room temperature for three hours. Solvent was evaporated under reduced pressure and the residue was dissolved in a mixture of water (50 ml) and dichloromethane (50 ml). The aqueous layer was extracted three times with dichloromethane.The combined organic phases were evaporated under reduced pressure and the solid residue was dissolved in hot hexane and slow evaporation of hot hexane give us colorless crystals (736 mg) in 80% yield. 2. Synthesis of 2,2'-[biphenyl-2,2'-diylbis(oxy)]diacetic acid 1: 500 mg (1.2 mmol) of was dissolved in 10 ml of dichloromethane and 5 ml of TFA was added to the stirred solution. The reaction was monitor with thin layer chromatography (hexane:choroform 2:8) after each 10 minutes of interval. After 30 minutes the starting material disappeared. All the TFA and solvent were removed through freeze drying and the solid residue was dissolved in methanol, slow evaporation of methanol at room temperature yielded colorless crystals (310 mg, 85%).