Methyl 4′,5-dichloro-2-hy­droxy-4,6-dimethyl­biphenyl-3-carboxyl­ate

Muhammad Adeel; Peter Langer; Martin Hein; Helmut Reinke

doi:10.1107/S1600536812012676

. 2012 Mar 28;68(Pt 4):o1224. doi: 10.1107/S1600536812012676

Methyl 4′,5-dichloro-2-hydroxy-4,6-dimethylbiphenyl-3-carboxylate

Muhammad Adeel ^a,^*, Peter Langer ^b, Martin Hein ^b, Helmut Reinke ^c

PMCID: PMC3344157 PMID: 22606160

Abstract

In the title compound, C₁₆H₁₄Cl₂O₃, the dihedral angle between the mean planes of the two benzene rings is 55.30 (5)°. The methyl ester group lies within the ring plane due to an intramolecular O—H⋯O hydrogen bond [maximum deviation from the C₈O₂ mean plane is 0.0383 (13) Å]. In the crystal, molecules are held together by rather weak C—H⋯O hydrogen bonds.

Related literature

For pharmacological relevance of salicylates and the synthesis of the title compound, see: Adeel, Rashid et al. (2009 ▶). For related structures, see: Adeel, Ali et al. (2009 ▶); Adeel, Langer et al. (2011 ▶).

Experimental

Crystal data

C₁₆H₁₄Cl₂O₃
M _r = 325.19
Monoclinic,
a = 4.0956 (5) Å
b = 13.3066 (17) Å
c = 13.3656 (16) Å
β = 92.711 (7)°
V = 727.59 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 173 K
0.65 × 0.50 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.758, T _max = 0.973
9311 measured reflections
3754 independent reflections
3331 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.074
S = 1.04
3754 reflections
197 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 1569 Friedel pairs
Flack parameter: 0.05 (5)

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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) I, global. DOI: 10.1107/S1600536812012676/pv2517sup1.cif

e-68-o1224-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012676/pv2517Isup2.hkl

e-68-o1224-Isup2.hkl^{(180.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812012676/pv2517Isup3.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—H3O⋯O1	0.77 (3)	1.80 (3)	2.523 (2)	156 (3)
C12—H12⋯O3ⁱ	0.95	2.53	3.306 (2)	139

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Higher Education Commission of Pakistan (HEC) under the resource grant programe and the World University Service, Deutsches Kommitee, is gratefully acknowledged.

supplementary crystallographic information

Comment

Functionalized biaryls containing a 3-arylsalicylate substructure occur in a variety of pharmacologically relevant natural products (Adeel, Rashid & et al., 2009). A sterically encumbered and functionalized biaryl, the title compound, was synthesized from 4-(4-methoxyphenyl)-1,3-bis(trimethylsilyloxy)-1,3-butadiene. In this paper, the crystal structure of the title compound has been presented.

In the title compound (Fig. 1), the dihedral angle between the mean planes of the two benzene rings is 55.30 (5)°. The methyl ester group lies within the ring plane due to an intramolecular O—H···O hydrogen bond; the maximum deviation of any atom from the mean-plane of atoms C1–C8/O1/O2 is 0.0383 (13) Å for C2. In the crystal, molecules are held together by rather weak intermolecular C—H···O hydrogen bonds along the a-axis (Fig. 2 & Table 1).

Experimental

The title compound was prepared according to a previously published procedure (Adeel, Rashid et al., 2009) using 3-(Silyloxy)-2-en-1-ones (332 mg, 1.65 mmol), 1,3-bis(silyl enol ethers) (612 mg, 1.65 mmol) and TiCl₄ (0.18 ml, 1.65 mmol) in CH₂Cl₂ (4 mL). The title compound was isolated as a colorless prisms; (190 mg, 40%, m.p. = 367–369 K). Crystallization from a saturated dichloromethane/methanol (9:1) solution at ambient temperature gave colourless crystals suitable for X-ray crystallographic studies.