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

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

doi:10.1107/S1600536808043274

organic compounds

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Volume 65| Part 2| February 2009| Page o231

doi:10.1107/S1600536808043274

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

Min Zhang,^a Ran-Zhe Lu,^a Lu-Na Han,^a Bin Wang ^a and Hai-Bo Wang ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No.5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 18 December 2008; accepted 19 December 2008; online 8 January 2009)

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

Related literature

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

Experimental

Crystal data

C₁₂H₁₅ClO₄
M_r = 258.69
Monoclinic, P 2₁ /c
a = 8.4980 (17) Å
b = 17.349 (4) Å
c = 8.8440 (18) Å
β = 106.46 (3)°
V = 1250.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.914, T_max = 0.970
2431 measured reflections
2274 independent reflections
1575 reflections with I > 2σ(I)
R_int = 0.048
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.176
S = 1.01
2274 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O2ⁱ	0.97	2.56	3.429 (6)	149
C2—H2A⋯O3ⁱⁱ	0.97	2.41	3.358 (6)	164
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks D, I. DOI: 10.1107/S1600536808043274/hk2602sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043274/hk2602Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
	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

C₁₂H₁₅ClO₄	F(000) = 544
M_r = 258.69	D_x = 1.374 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 384 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.4980 (17) Å	Cell parameters from 25 reflections
b = 17.349 (4) Å	θ = 10–13°
c = 8.8440 (18) Å	µ = 0.31 mm⁻¹
β = 106.46 (3)°	T = 294 K
V = 1250.5 (5) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1575 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 25.3°, θ_min = 2.4°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→20
T_min = 0.914, T_max = 0.970	l = −10→10
2431 measured reflections	3 standard reflections every 120 min
2274 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.050P)² + 3.3P] where P = (F_o² + 2F_c²)/3
2274 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₂H₁₅ClO₄	V = 1250.5 (5) Å³
M_r = 258.69	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4980 (17) Å	µ = 0.31 mm⁻¹
b = 17.349 (4) Å	T = 294 K
c = 8.8440 (18) Å	0.30 × 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)	R_int = 0.048
T_min = 0.914, T_max = 0.970	3 standard reflections every 120 min
2431 measured reflections	intensity decay: 1%
2274 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.01	Δρ_max = 0.35 e Å⁻³
2274 reflections	Δρ_min = −0.29 e Å⁻³
154 parameters

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

	x	y	z	U_iso*/U_eq
Cl	0.27901 (16)	0.58276 (8)	0.10729 (14)	0.0679 (4)
O1	0.3056 (3)	0.60776 (15)	0.5453 (3)	0.0480 (7)
O2	0.1798 (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)
C1	0.4233 (6)	0.5519 (3)	0.2872 (5)	0.0580 (12)
H1A	0.3693	0.5170	0.3424	0.070*
H1B	0.5119	0.5239	0.2627	0.070*
C2	0.4929 (5)	0.6187 (3)	0.3921 (5)	0.0554 (11)
H2A	0.5409	0.6546	0.3337	0.066*
H2B	0.5803	0.6000	0.4807	0.066*
C3	0.3697 (5)	0.6615 (2)	0.4548 (5)	0.0532 (11)
H3A	0.4223	0.7043	0.5207	0.064*
H3B	0.2819	0.6817	0.3684	0.064*
C4	0.1809 (5)	0.6315 (2)	0.6028 (4)	0.0401 (9)
C5	0.1190 (5)	0.7053 (2)	0.5911 (5)	0.0488 (10)
H5A	0.1656	0.7438	0.5444	0.059*
C6	−0.0123 (5)	0.7224 (2)	0.6489 (5)	0.0489 (10)
H6A	−0.0547	0.7722	0.6390	0.059*
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	−0.0638	0.5533	0.7811	0.048*
C9	0.1129 (4)	0.5731 (2)	0.6768 (4)	0.0378 (8)
C10	0.1078 (5)	0.4411 (2)	0.7422 (5)	0.0495 (10)
H10A	0.1631	0.3937	0.7342	0.074*
H10B	−0.0061	0.4366	0.6849	0.074*
H10C	0.1176	0.4517	0.8511	0.074*
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	−0.4308	0.5957	0.9646	0.101*
H12B	−0.5039	0.6531	0.8255	0.101*
H12C	−0.3865	0.6835	0.9846	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0710 (8)	0.0750 (8)	0.0547 (7)	0.0031 (6)	0.0130 (6)	0.0007 (6)
O1	0.0477 (16)	0.0459 (16)	0.0542 (17)	−0.0020 (12)	0.0206 (13)	0.0082 (13)
O2	0.0481 (16)	0.0364 (15)	0.0657 (19)	0.0022 (12)	0.0211 (14)	0.0077 (13)
O3	0.079 (2)	0.057 (2)	0.086 (2)	0.0270 (17)	0.037 (2)	0.0083 (18)
O4	0.0487 (17)	0.0563 (19)	0.074 (2)	0.0088 (14)	0.0267 (16)	−0.0028 (16)
C1	0.060 (3)	0.055 (3)	0.062 (3)	0.006 (2)	0.022 (2)	0.006 (2)
C2	0.048 (2)	0.063 (3)	0.057 (3)	−0.003 (2)	0.018 (2)	0.008 (2)
C3	0.059 (3)	0.044 (2)	0.054 (3)	−0.009 (2)	0.012 (2)	0.004 (2)
C4	0.041 (2)	0.043 (2)	0.036 (2)	−0.0010 (17)	0.0103 (16)	−0.0003 (16)
C5	0.063 (3)	0.034 (2)	0.050 (2)	−0.0083 (19)	0.016 (2)	−0.0017 (18)
C6	0.056 (3)	0.035 (2)	0.051 (2)	0.0081 (18)	0.006 (2)	−0.0028 (18)
C7	0.043 (2)	0.042 (2)	0.041 (2)	0.0039 (17)	0.0092 (17)	−0.0063 (17)
C8	0.039 (2)	0.040 (2)	0.040 (2)	−0.0037 (16)	0.0073 (16)	0.0028 (17)
C9	0.041 (2)	0.0330 (19)	0.040 (2)	0.0027 (16)	0.0114 (16)	−0.0013 (16)
C10	0.057 (3)	0.034 (2)	0.062 (3)	0.0011 (18)	0.023 (2)	0.0053 (19)
C11	0.054 (2)	0.042 (2)	0.043 (2)	0.0044 (19)	0.0058 (19)	−0.0037 (18)
C12	0.052 (3)	0.083 (4)	0.073 (3)	0.007 (2)	0.030 (2)	−0.014 (3)

Geometric parameters (Å, º) top

Cl—C1	1.794 (5)	C4—C5	1.378 (5)
O1—C3	1.433 (5)	C4—C9	1.415 (5)
O1—C4	1.362 (4)	C5—C6	1.385 (6)
O2—C9	1.355 (4)	C5—H5A	0.9300
O2—C10	1.420 (4)	C6—C7	1.394 (6)
O3—C11	1.201 (5)	C6—H6A	0.9300
O4—C11	1.336 (5)	C7—C8	1.390 (5)
O4—C12	1.429 (5)	C7—C11	1.478 (6)
C1—C2	1.498 (6)	C8—C9	1.377 (5)
C1—H1A	0.9700	C8—H8A	0.9300
C1—H1B	0.9700	C10—H10A	0.9600
C2—C3	1.512 (6)	C10—H10B	0.9600
C2—H2A	0.9700	C10—H10C	0.9600
C2—H2B	0.9700	C12—H12A	0.9600
C3—H3A	0.9700	C12—H12B	0.9600
C3—H3B	0.9700	C12—H12C	0.9600

C4—O1—C3	118.1 (3)	C5—C6—C7	120.5 (4)
C9—O2—C10	116.9 (3)	C5—C6—H6A	119.8
C11—O4—C12	117.1 (3)	C7—C6—H6A	119.8
Cl—C1—H1A	109.3	C8—C7—C6	118.9 (4)
Cl—C1—H1B	109.3	C8—C7—C11	122.7 (4)
C2—C1—Cl	111.6 (3)	C6—C7—C11	118.4 (4)
C2—C1—H1A	109.3	C9—C8—C7	121.6 (4)
C2—C1—H1B	109.3	C9—C8—H8A	119.2
H1A—C1—H1B	108.0	C7—C8—H8A	119.2
C1—C2—C3	114.5 (4)	O2—C9—C8	125.9 (3)
C1—C2—H2A	108.6	O2—C9—C4	115.4 (3)
C1—C2—H2B	108.6	C8—C9—C4	118.6 (3)
C3—C2—H2A	108.6	O2—C10—H10A	109.5
C3—C2—H2B	108.6	O2—C10—H10B	109.5
H2A—C2—H2B	107.6	H10A—C10—H10B	109.5
O1—C3—C2	107.3 (3)	O2—C10—H10C	109.5
O1—C3—H3A	110.3	H10A—C10—H10C	109.5
O1—C3—H3B	110.3	H10B—C10—H10C	109.5
C2—C3—H3A	110.3	O3—C11—O4	122.5 (4)
C2—C3—H3B	110.3	O3—C11—C7	125.4 (4)
H3A—C3—H3B	108.5	O4—C11—C7	112.1 (3)
O1—C4—C5	125.0 (3)	O4—C12—H12A	109.5
O1—C4—C9	114.8 (3)	O4—C12—H12B	109.5
C5—C4—C9	120.2 (4)	H12A—C12—H12B	109.5
C4—C5—C6	120.2 (4)	O4—C12—H12C	109.5
C4—C5—H5A	119.9	H12A—C12—H12C	109.5
C6—C5—H5A	119.9	H12B—C12—H12C	109.5

Cl—C1—C2—C3	65.9 (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—O1	60.5 (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—C9	173.8 (3)	C5—C4—C9—O2	178.2 (4)
O1—C4—C5—C6	177.6 (4)	O1—C4—C9—C8	−177.9 (3)
C9—C4—C5—C6	−1.3 (6)	C5—C4—C9—C8	1.2 (6)
C4—C5—C6—C7	1.1 (6)	C12—O4—C11—O3	0.8 (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—C9	0.6 (6)	C6—C7—C11—O3	3.4 (6)
C11—C7—C8—C9	178.5 (4)	C8—C7—C11—O4	5.6 (5)
C10—O2—C9—C8	0.6 (6)	C6—C7—C11—O4	−176.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.97	2.56	2.906 (5)	101
C1—H1B···O2ⁱ	0.97	2.56	3.429 (6)	149
C2—H2A···O3ⁱⁱ	0.97	2.41	3.358 (6)	164

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅ClO₄
M_r	258.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	8.4980 (17), 17.349 (4), 8.8440 (18)
β (°)	106.46 (3)
V (Å³)	1250.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.914, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	2431, 2274, 1575
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.176, 1.01
No. of reflections	2274
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.29

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.97	2.56	2.906 (5)	101.00
C1—H1B···O2ⁱ	0.97	2.56	3.429 (6)	149.00
C2—H2A···O3ⁱⁱ	0.97	2.41	3.358 (6)	164.00

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+3/2, z−1/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Knesl, P., Roeseling, D. & Jordis, U. (2006). Molecules, 11, 286–297. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 65| Part 2| February 2009| Page o231

doi:10.1107/S1600536808043274

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