Methyl 4-(3-chloro­prop­oxy)-5-meth­oxy-2-nitro­benzoate

Min Zhang; Ran-zhe Lu; Lu-na Han; Wen-bin Wei; Hai-bo Wang

doi:10.1107/S1600536809009076

. 2009 Mar 19;65(Pt 4):o781. doi: 10.1107/S1600536809009076

Methyl 4-(3-chloropropoxy)-5-methoxy-2-nitrobenzoate

Min Zhang ^a,^b, Ran-zhe Lu ^a,^b, Lu-na Han ^a,^b, Wen-bin Wei ^a,^b, Hai-bo Wang ^a,^*

PMCID: PMC2969097 PMID: 21582506

Abstract

The asymmetric unit of the title compound, C₁₂H₁₄ClNO₆, contains two crystallographically independent molecules, in which the benzene rings are oriented at a dihedral angle of 9.12 (3)°. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For general background, see: Knesl et al. (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₄ClNO₆
M _r = 303.69
Monoclinic,
a = 23.150 (5) Å
b = 15.013 (3) Å
c = 8.0700 (16) Å
β = 93.42 (3)°
V = 2799.7 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.916, T _max = 0.943
5208 measured reflections
5096 independent reflections
2874 reflections with I > 2σ(I)
R _int = 0.038
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.162
S = 1.03
5096 reflections
362 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009076/hk2642sup1.cif

e-65-0o781-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009076/hk2642Isup2.hkl

e-65-0o781-Isup2.hkl^{(248.8KB, 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
C10—H10B⋯O4ⁱ	0.97	2.58	3.336 (7)	135
C13—H13B⋯O9ⁱⁱ	0.96	2.41	3.211 (6)	141
C21—H21A⋯O5ⁱⁱⁱ	0.96	2.48	3.243 (5)	136
C24—H24A⋯O9^iv	0.97	2.59	3.276 (6)	128

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

supplementary crystallographic information

Comment

As part of our ongoing studies on quinazoline derivatives (Knesl et al., 2006), we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound contains two crystallographically independent molecules (Fig. 1), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C3-C8) and A' (C15-C20) are, of course, planar and they are oriented at a dihedral angle of A/A' = 9.12 (3)°.

In the crystal structure, weak intermolecular C-H···O hydrogen bonds (Table 1) link the molecules into a three dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, a solution of methyl 4-(3-chloro- propoxy)-3-methoxybenzoate (19 mmol) in acetic acid (20 ml) was added dropwise to nitric acid (98%, 4.5 ml) at 273-278 K. The mixture was stirred for 1 h at room temperature, and then for 2 h at 323 K. After the reaction was completed, the reaction mixture was poured into ice/water (130 ml), and then extracted with trichloromethane (20 ml). The combined organic phases were collected, washed with saturated sodium bicarbonate (20 ml), brine (20 ml), dried (Na₂SO₄) and decolorized (charcoal). Trichloromethane was then removed under reduced pressure to give a yellow oil, which was crystallized from ethyl acetate/petroleum ether to afford the product as light yellow crystals (m.p. 337 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.