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Acta Cryst. (2009). E65, o231    [ doi:10.1107/S1600536808043274 ]

Methyl 4-(3-chloropropoxy)-3-methoxybenzoate

M. Zhang, R.-Z. Lu, L.-N. Han, B. Wang and H.-B. Wang

Abstract top

In the title compound, C12H15ClO4, the molecules are linked by C-H...O interactions.

Comment top

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

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C4-C9) is, of course, planar. The intramolecular C-H···O hydrogen bond (Table 1) results in the formation of a five-membered ring B (O1/C1-C3/H1A), having envelope conformation with C2 atom displaced by -0.668 (3) Å from the plane of the other ring atoms.

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

Related literature top

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

Experimental top

For the preparation of the title compound, methyl 3-methoxy-4-hydroxybenzoate (55 mmol), 1-bromo-3-chloropropane (165 mmol) and potassium carbonate (275 mmol) were mixed with DMF (60 ml), and then the mixture was heated to reflux for 2 h. Reaction progress was monitored by TLC. After cooling and filtration, the title compound was obtained (yield; 93.7%, m.p. 384 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution.

Refinement top

H atoms were positioned geometrically, with C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
Methyl 4-(3-chloropropoxy)-3-methoxybenzoate top
Crystal data top
C12H15ClO4F(000) = 544
Mr = 258.69Dx = 1.374 Mg m−3
Monoclinic, P21/cMelting point: 384 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.4980 (17) ÅCell parameters from 25 reflections
b = 17.349 (4) Åθ = 10–13°
c = 8.8440 (18) ŵ = 0.31 mm−1
β = 106.46 (3)°T = 294 K
V = 1250.5 (5) Å3Block, colorless
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1575 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
graphiteθmax = 25.3°, θmin = 2.4°
ω/2θ scansh = 0→10
Absorption correction: ψ scan
(North et al., 1968)		k = 0→20
Tmin = 0.914, Tmax = 0.970l = −10→10
2431 measured reflections3 standard reflections every 120 min
2274 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.050P)2 + 3.3P]
where P = (Fo2 + 2Fc2)/3
2274 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.35 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C12H15ClO4V = 1250.5 (5) Å3
Mr = 258.69Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.4980 (17) ŵ = 0.31 mm−1
b = 17.349 (4) ÅT = 294 K
c = 8.8440 (18) Å0.30 × 0.20 × 0.10 mm
β = 106.46 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1575 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.048
Tmin = 0.914, Tmax = 0.970θmax = 25.3°
2431 measured reflections3 standard reflections every 120 min
2274 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.068H-atom parameters constrained
wR(F2) = 0.176Δρmax = 0.35 e Å−3
S = 1.01Δρmin = −0.29 e Å−3
2274 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.27901 (16)0.58276 (8)0.10729 (14)0.0679 (4)
O10.3056 (3)0.60776 (15)0.5453 (3)0.0480 (7)
O20.1798 (3)0.50211 (15)0.6779 (3)0.0491 (7)
O3−0.2908 (4)0.74808 (19)0.7610 (4)0.0711 (10)
O4−0.2715 (3)0.62804 (17)0.8531 (4)0.0578 (8)
C10.4233 (6)0.5519 (3)0.2872 (5)0.0580 (12)
H1A0.36930.51700.34240.070*
H1B0.51190.52390.26270.070*
C20.4929 (5)0.6187 (3)0.3921 (5)0.0554 (11)
H2A0.54090.65460.33370.066*
H2B0.58030.60000.48070.066*
C30.3697 (5)0.6615 (2)0.4548 (5)0.0532 (11)
H3A0.42230.70430.52070.064*
H3B0.28190.68170.36840.064*
C40.1809 (5)0.6315 (2)0.6028 (4)0.0401 (9)
C50.1190 (5)0.7053 (2)0.5911 (5)0.0488 (10)
H5A0.16560.74380.54440.059*
C6−0.0123 (5)0.7224 (2)0.6489 (5)0.0489 (10)
H6A−0.05470.77220.63900.059*
C7−0.0814 (5)0.6657 (2)0.7216 (4)0.0424 (9)
C8−0.0174 (5)0.5915 (2)0.7335 (4)0.0404 (9)
H8A−0.06380.55330.78110.048*
C90.1129 (4)0.5731 (2)0.6768 (4)0.0378 (8)
C100.1078 (5)0.4411 (2)0.7422 (5)0.0495 (10)
H10A0.16310.39370.73420.074*
H10B−0.00610.43660.68490.074*
H10C0.11760.45170.85110.074*
C11−0.2236 (5)0.6865 (2)0.7781 (5)0.0478 (10)
C12−0.4095 (6)0.6411 (3)0.9117 (6)0.0670 (14)
H12A−0.43080.59570.96460.101*
H12B−0.50390.65310.82550.101*
H12C−0.38650.68350.98460.101*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0710 (8)0.0750 (8)0.0547 (7)0.0031 (6)0.0130 (6)0.0007 (6)
O10.0477 (16)0.0459 (16)0.0542 (17)−0.0020 (12)0.0206 (13)0.0082 (13)
O20.0481 (16)0.0364 (15)0.0657 (19)0.0022 (12)0.0211 (14)0.0077 (13)
O30.079 (2)0.057 (2)0.086 (2)0.0270 (17)0.037 (2)0.0083 (18)
O40.0487 (17)0.0563 (19)0.074 (2)0.0088 (14)0.0267 (16)−0.0028 (16)
C10.060 (3)0.055 (3)0.062 (3)0.006 (2)0.022 (2)0.006 (2)
C20.048 (2)0.063 (3)0.057 (3)−0.003 (2)0.018 (2)0.008 (2)
C30.059 (3)0.044 (2)0.054 (3)−0.009 (2)0.012 (2)0.004 (2)
C40.041 (2)0.043 (2)0.036 (2)−0.0010 (17)0.0103 (16)−0.0003 (16)
C50.063 (3)0.034 (2)0.050 (2)−0.0083 (19)0.016 (2)−0.0017 (18)
C60.056 (3)0.035 (2)0.051 (2)0.0081 (18)0.006 (2)−0.0028 (18)
C70.043 (2)0.042 (2)0.041 (2)0.0039 (17)0.0092 (17)−0.0063 (17)
C80.039 (2)0.040 (2)0.040 (2)−0.0037 (16)0.0073 (16)0.0028 (17)
C90.041 (2)0.0330 (19)0.040 (2)0.0027 (16)0.0114 (16)−0.0013 (16)
C100.057 (3)0.034 (2)0.062 (3)0.0011 (18)0.023 (2)0.0053 (19)
C110.054 (2)0.042 (2)0.043 (2)0.0044 (19)0.0058 (19)−0.0037 (18)
C120.052 (3)0.083 (4)0.073 (3)0.007 (2)0.030 (2)−0.014 (3)
Geometric parameters (Å, °) top
Cl—C11.794 (5)C4—C51.378 (5)
O1—C31.433 (5)C4—C91.415 (5)
O1—C41.362 (4)C5—C61.385 (6)
O2—C91.355 (4)C5—H5A0.9300
O2—C101.420 (4)C6—C71.394 (6)
O3—C111.201 (5)C6—H6A0.9300
O4—C111.336 (5)C7—C81.390 (5)
O4—C121.429 (5)C7—C111.478 (6)
C1—C21.498 (6)C8—C91.377 (5)
C1—H1A0.9700C8—H8A0.9300
C1—H1B0.9700C10—H10A0.9600
C2—C31.512 (6)C10—H10B0.9600
C2—H2A0.9700C10—H10C0.9600
C2—H2B0.9700C12—H12A0.9600
C3—H3A0.9700C12—H12B0.9600
C3—H3B0.9700C12—H12C0.9600
C4—O1—C3118.1 (3)C5—C6—C7120.5 (4)
C9—O2—C10116.9 (3)C5—C6—H6A119.8
C11—O4—C12117.1 (3)C7—C6—H6A119.8
Cl—C1—H1A109.3C8—C7—C6118.9 (4)
Cl—C1—H1B109.3C8—C7—C11122.7 (4)
C2—C1—Cl111.6 (3)C6—C7—C11118.4 (4)
C2—C1—H1A109.3C9—C8—C7121.6 (4)
C2—C1—H1B109.3C9—C8—H8A119.2
H1A—C1—H1B108.0C7—C8—H8A119.2
C1—C2—C3114.5 (4)O2—C9—C8125.9 (3)
C1—C2—H2A108.6O2—C9—C4115.4 (3)
C1—C2—H2B108.6C8—C9—C4118.6 (3)
C3—C2—H2A108.6O2—C10—H10A109.5
C3—C2—H2B108.6O2—C10—H10B109.5
H2A—C2—H2B107.6H10A—C10—H10B109.5
O1—C3—C2107.3 (3)O2—C10—H10C109.5
O1—C3—H3A110.3H10A—C10—H10C109.5
O1—C3—H3B110.3H10B—C10—H10C109.5
C2—C3—H3A110.3O3—C11—O4122.5 (4)
C2—C3—H3B110.3O3—C11—C7125.4 (4)
H3A—C3—H3B108.5O4—C11—C7112.1 (3)
O1—C4—C5125.0 (3)O4—C12—H12A109.5
O1—C4—C9114.8 (3)O4—C12—H12B109.5
C5—C4—C9120.2 (4)H12A—C12—H12B109.5
C4—C5—C6120.2 (4)O4—C12—H12C109.5
C4—C5—H5A119.9H12A—C12—H12C109.5
C6—C5—H5A119.9H12B—C12—H12C109.5
Cl—C1—C2—C365.9 (4)C10—O2—C9—C4−176.1 (3)
C4—O1—C3—C2−174.3 (3)C7—C8—C9—O2−177.5 (4)
C1—C2—C3—O160.5 (5)C7—C8—C9—C4−0.9 (6)
C3—O1—C4—C5−5.2 (6)O1—C4—C9—O2−0.9 (5)
C3—O1—C4—C9173.8 (3)C5—C4—C9—O2178.2 (4)
O1—C4—C5—C6177.6 (4)O1—C4—C9—C8−177.9 (3)
C9—C4—C5—C6−1.3 (6)C5—C4—C9—C81.2 (6)
C4—C5—C6—C71.1 (6)C12—O4—C11—O30.8 (6)
C5—C6—C7—C8−0.7 (6)C12—O4—C11—C7−179.4 (3)
C5—C6—C7—C11−178.7 (4)C8—C7—C11—O3−174.5 (4)
C6—C7—C8—C90.6 (6)C6—C7—C11—O33.4 (6)
C11—C7—C8—C9178.5 (4)C8—C7—C11—O45.6 (5)
C10—O2—C9—C80.6 (6)C6—C7—C11—O4−176.5 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O10.972.562.906 (5)101
C1—H1B···O2i0.972.563.429 (6)149
C2—H2A···O3ii0.972.413.358 (6)164
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O10.972.562.906 (5)101
C1—H1B···O2i0.972.563.429 (6)149
C2—H2A···O3ii0.972.413.358 (6)164
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+3/2, z−1/2.
Acknowledgements top

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references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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