Methyl 5-chloro-2-hydr­oxy-3-(4-methoxy­phen­yl)-4,6-dimethyl­benzoate

Muhammad Adeel; Irshad Ali; Peter Langer; Alexander Villinger

doi:10.1107/S1600536809031614

. 2009 Aug 19;65(Pt 9):o2176. doi: 10.1107/S1600536809031614

Methyl 5-chloro-2-hydroxy-3-(4-methoxyphenyl)-4,6-dimethylbenzoate

Muhammad Adeel ^a,^*, Irshad Ali ^a, Peter Langer ^b,^c, Alexander Villinger ^b

PMCID: PMC2969919 PMID: 21577582

Abstract

In the title compound, C₁₇H₁₇ClO₄, the dihedral angle between the mean planes of the two benzene rings is 65.92 (5)°. The methyl ester group lies within the ring plane [deviations of O atoms from the plane = −0.051 (2) and 0.151 (2) Å] due to an intramolecular O—H⋯O hydrogen bond. In the crystal, molecules are held together by rather weak non-classical intermolecular C—H⋯O hydrogen bonds, resulting in dimeric units about inversion centers, forming eight- and ten-membered ring systems as R ₂ ²(8) and R ₂ ²(10) motifs.

Related literature

For the pharmacological relevance of 3-arylsalicylates, see: Buchanan et al. (1997 ▶); Huang et al. (1999 ▶); Lin, Lin & Kuo (1997 ▶); Lin, Wu & Kuo (1997 ▶). For the synthesis, see: Adeel et al. (2009 ▶); For hydrogen-bond motifs, see: Bernstein et al. (1994 ▶).

Experimental

Crystal data

C₁₇H₁₇ClO₄
M _r = 320.76
Triclinic,
a = 6.534 (4) Å
b = 9.574 (6) Å
c = 12.694 (8) Å
α = 97.420 (15)°
β = 100.56 (2)°
γ = 96.042 (14)°
V = 767.3 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 173 K
0.55 × 0.27 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.868, T _max = 0.997
14947 measured reflections
3964 independent reflections
3091 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.125
S = 1.09
3964 reflections
207 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031614/pv2189sup1.cif

e-65-o2176-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031614/pv2189Isup2.hkl

e-65-o2176-Isup2.hkl^{(190.3KB, 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
O1—H1⋯O2	0.94 (2)	1.63 (2)	2.5061 (18)	153 (2)
C10—H10A⋯Cl1	0.98	2.45	3.003 (2)	115
C9—H9A⋯O2ⁱ	0.98	2.73	3.242 (3)	113
C15—H15⋯O4ⁱⁱ	0.95	2.50	3.437 (2)	170

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

Acknowledgments

Financial support for MA from the Higher Education Commission of Pakistan (HEC) under the IPFP programe is gratefully acknowledged.

supplementary crystallographic information

Comment

Functionalized biaryls containing a 3-arylsalicylate substructure occur in a variety of pharmacologically relevant natural products. The simple biaryls cynandione A—C have been isolated from many plant sources and show a considerable in vitro activity against hepatocytes, human bladder carcinoma T-24 cells, epidermoid carcinoma KB cells, and human hepatoma PLC/PRF/5 cells. For data on the pharmacological relevance of 3-arylsalicylates, see: Buchanan et al., (1997), Huang et al., (1999), Lin, Lin & Kuo (1997) and Lin, Wu & Kuo (1997). The sterically encumbered and functionalized biaryl, the title compound (I), was synthesized from 4-(4-methoxyphenyl)-1,3-bis(trimethylsilyloxy)-1,3-butadiene which is not readily available by other methods. In this paper, the crystal structure of (I) has been presented.

In the title compound (Fig. 1), the the dihedral angle between the mean planes of the two benzene rings is 65.92 (5)°. The methoxy group and the methylester group lie within the planes of the benzene rings to which they are bonded (deviation from mean planes: O2, -0.051 (2); O3, 0.151 (2); (??), 0.143 (2) Å; the torsion angles are: C2—C3—C8—O2 -174.47 (12) and C17—O4—C14—C15 -176.38 (12)°). There is an intramolecular hydrogen bond between the hydroxyl group and the carbonyl O atom of the methylester group. There are weak intramolecular interactions of the types C—H···O between atom O3 of the ester group and the adjacent methyl group (C10) and C—H···Cl between Cl1 and the adjacent methyl groups (C7/C10).

In the crystal structure, the molecules of (I) are held together by rather weak intermolecular C—H···O type non-classical hydrogen bonds resulting in dimeric units about inversion centers, forming eight and ten membered ring systems which may be described in terms of graph set notations (Bernstein et al. 1994) as R₂²(8) and R₂²(10) motifs for the hydrogen bonds: C15–H15···O4ⁱⁱ and C9–H9A···O2ⁱ, respectively (details are given in Table 1 and Figure 2); leading to a zigzag chain arrangement.

Experimental

The title compound was prepared according to a previously published procedure (Adeel et al., 2009) using 3-chloro-4-trimethylsiloxy-pent-3-en-2-one (450 mg, 2.2 mmol), 4-(4-methoxyphenyl)-1,3-bis(silyloxy)-1,3-diene (806 mg, 2.2 mmol), and TiCl₄ (0.241 ml, 2.2 mmol). (I) was isolated as a colourless crystalline solid. Re-crystallization from a saturated dichloromethane/methanol (9:1) solution at ambient temperature gave colourless crystals suitable for crystallographic studies.