Methyl 4-(3-chloro­prop­oxy)benzoate

Shi, Y.-B.; Liu, K.-K.; Xia, S.; He, F.-F.; Wang, H.-B.

doi:10.1107/S1600536811011093

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1052

doi:10.1107/S1600536811011093

Open

access

Methyl 4-(3-chloropropoxy)benzoate

Ya-Bin Shi,^a,^b Ke-Ke Liu,^a,^b Song Xia,^a,^b Fei-Fei He ^a,^b and Hai-Bo Wang ^a ^*

^aCollege of Food Science and Light Industry, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege 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 9 March 2011; accepted 25 March 2011; online 7 April 2011)

In the crystal structure of the title compound, C₁₁H₁₃ClO₃, intermolecular C—H⋯O hydrogen bonds link the molecules into zigzag chains along the c axis.

Related literature

The title compound is an intermediate in the synthesis of 4-(3-(dibutylamino)propoxy)benzoyl chloride, which in turn is a useful pharmaceutical intermediate that can be used to prepare dronedarone [systematic name N-(2-butyl-3-(p-(3-(dibutylamino)propoxy)benzoyl)-5-benzofuranyl)methanesulfonamide]. For background to the biological activity of dronedarone and the preparation of the title compound, see: Jaseer et al. (2010 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₃ClO₃
M_r = 228.66
Monoclinic, P 2₁ /n
a = 6.2400 (12) Å
b = 10.611 (2) Å
c = 17.189 (3) Å
β = 100.35 (3)°
V = 1119.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 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 = 0.909, T_max = 0.968
4391 measured reflections
2063 independent reflections
1470 reflections with I > 2σ(I)
R_int = 0.045
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.132
S = 1.00
2063 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O2ⁱ	0.97	2.45	3.351 (3)	154
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS; 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011093/sj5116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011093/sj5116Isup2.hkl

checkCIF report

Comment top

The title compound, methyl 4-(3-chloropropoxy)benzoate, is a useful pharmaceutical intermediate in the preparation of precursors to dronedarone. (Jaseer et al., 2010).

We report here in the crystal structure of the title compound, methyl 2-amino-5-chlorobenzoate. In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal structure, intermolecular C-H1A···O2 hydrogen bonds link the molecules into zig-zag chains along the c axis, to form a stable structure (Fig. 2).

Related literature top

For background to the biological activity of dronedarone and the preparation of the title compound, see: Jaseer et al. (2010). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, methyl 4-(3-chloropropoxy)benzoate was prepared by a literature method (Jaseer et al. 2010). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I) viewed down the b axis. Hydrogen bond are drawn as dashed lines.

Methyl 4-(3-chloropropoxy)benzoate top

Crystal data top

C₁₁H₁₃ClO₃	F(000) = 480
M_r = 228.66	D_x = 1.357 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 328 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.2400 (12) Å	Cell parameters from 25 reflections
b = 10.611 (2) Å	θ = 9–14°
c = 17.189 (3) Å	µ = 0.33 mm⁻¹
β = 100.35 (3)°	T = 293 K
V = 1119.6 (4) Å³	Block, colourless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1470 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 25.4°, θ_min = 2.3°
ω/2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
T_min = 0.909, T_max = 0.968	l = −20→20
4391 measured reflections	3 standard reflections every 200 reflections
2063 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.132	w = 1/[σ²(F_o²) + (0.078P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2063 reflections	Δρ_max = 0.24 e Å⁻³
137 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (3)

Crystal data top

C₁₁H₁₃ClO₃	V = 1119.6 (4) Å³
M_r = 228.66	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2400 (12) Å	µ = 0.33 mm⁻¹
b = 10.611 (2) Å	T = 293 K
c = 17.189 (3) Å	0.30 × 0.20 × 0.10 mm
β = 100.35 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1470 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.045
T_min = 0.909, T_max = 0.968	3 standard reflections every 200 reflections
4391 measured reflections	intensity decay: 1%
2063 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.00	Δρ_max = 0.24 e Å⁻³
2063 reflections	Δρ_min = −0.19 e Å⁻³
137 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	0.18566 (11)	0.25211 (6)	0.23318 (4)	0.0652 (3)
O1	0.6595 (3)	0.50541 (15)	0.39148 (9)	0.0564 (5)
C1	0.3616 (4)	0.3834 (2)	0.26514 (16)	0.0607 (7)
H1A	0.3635	0.4397	0.2208	0.073*
H1B	0.3046	0.4298	0.3056	0.073*
O2	1.0386 (3)	0.94288 (18)	0.62662 (11)	0.0759 (6)
C2	0.5887 (4)	0.3415 (2)	0.29744 (15)	0.0580 (6)
H2A	0.6463	0.2964	0.2566	0.070*
H2B	0.5861	0.2838	0.3410	0.070*
O3	1.3033 (3)	0.92169 (16)	0.55628 (10)	0.0597 (5)
C3	0.7360 (4)	0.4500 (2)	0.32576 (14)	0.0560 (6)
H3A	0.8847	0.4207	0.3418	0.067*
H3B	0.7328	0.5115	0.2838	0.067*
C4	0.7766 (3)	0.5999 (2)	0.43188 (13)	0.0455 (5)
C5	0.6944 (4)	0.6495 (2)	0.49502 (14)	0.0536 (6)
H5A	0.5652	0.6180	0.5071	0.064*
C6	0.8022 (4)	0.7447 (2)	0.53971 (14)	0.0520 (6)
H6A	0.7446	0.7779	0.5816	0.062*
C7	0.9978 (3)	0.7924 (2)	0.52298 (12)	0.0444 (5)
C8	1.0772 (4)	0.7424 (2)	0.45955 (13)	0.0494 (6)
H8A	1.2066	0.7736	0.4475	0.059*
C9	0.9695 (4)	0.6480 (2)	0.41406 (13)	0.0520 (6)
H9A	1.0253	0.6162	0.3714	0.062*
C10	1.1089 (4)	0.8931 (2)	0.57411 (13)	0.0488 (5)
C11	1.4283 (4)	1.0149 (2)	0.60542 (15)	0.0660 (7)
H11A	1.5645	1.0279	0.5881	0.099*
H11B	1.4553	0.9864	0.6593	0.099*
H11C	1.3485	1.0927	0.6017	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0545 (4)	0.0718 (5)	0.0679 (4)	−0.0158 (3)	0.0069 (3)	−0.0037 (3)
O1	0.0519 (10)	0.0640 (11)	0.0561 (9)	−0.0138 (8)	0.0172 (8)	−0.0071 (8)
C1	0.0523 (14)	0.0559 (14)	0.0691 (16)	−0.0074 (12)	−0.0018 (12)	0.0098 (12)
O2	0.0740 (13)	0.0836 (13)	0.0768 (12)	−0.0177 (10)	0.0311 (11)	−0.0280 (10)
C2	0.0509 (14)	0.0593 (14)	0.0628 (14)	0.0006 (11)	0.0079 (12)	−0.0079 (11)
O3	0.0512 (10)	0.0704 (11)	0.0576 (10)	−0.0181 (8)	0.0101 (8)	−0.0101 (8)
C3	0.0453 (13)	0.0651 (15)	0.0586 (14)	−0.0031 (11)	0.0121 (11)	−0.0075 (11)
C4	0.0407 (12)	0.0467 (12)	0.0490 (12)	−0.0051 (10)	0.0080 (10)	0.0032 (10)
C5	0.0455 (13)	0.0605 (14)	0.0592 (13)	−0.0101 (11)	0.0214 (11)	−0.0004 (12)
C6	0.0490 (13)	0.0584 (14)	0.0524 (13)	−0.0049 (11)	0.0195 (11)	−0.0010 (11)
C7	0.0389 (11)	0.0507 (12)	0.0428 (11)	0.0003 (10)	0.0054 (9)	0.0071 (10)
C8	0.0380 (12)	0.0580 (13)	0.0538 (13)	−0.0081 (11)	0.0128 (10)	0.0027 (11)
C9	0.0447 (13)	0.0645 (14)	0.0501 (12)	−0.0056 (11)	0.0172 (10)	−0.0036 (11)
C10	0.0445 (13)	0.0535 (13)	0.0478 (12)	−0.0042 (11)	0.0068 (10)	0.0072 (10)
C11	0.0602 (16)	0.0682 (17)	0.0667 (16)	−0.0193 (14)	0.0035 (13)	−0.0076 (13)

Geometric parameters (Å, º) top

Cl—C1	1.798 (2)	C4—C5	1.385 (3)
O1—C4	1.356 (3)	C4—C9	1.391 (3)
O1—C3	1.430 (3)	C5—C6	1.370 (3)
C1—C2	1.494 (3)	C5—H5A	0.9300
C1—H1A	0.9700	C6—C7	1.398 (3)
C1—H1B	0.9700	C6—H6A	0.9300
O2—C10	1.195 (3)	C7—C8	1.382 (3)
C2—C3	1.499 (3)	C7—C10	1.476 (3)
C2—H2A	0.9700	C8—C9	1.370 (3)
C2—H2B	0.9700	C8—H8A	0.9300
O3—C10	1.338 (3)	C9—H9A	0.9300
O3—C11	1.436 (3)	C11—H11A	0.9600
C3—H3A	0.9700	C11—H11B	0.9600
C3—H3B	0.9700	C11—H11C	0.9600

C4—O1—C3	118.88 (17)	C6—C5—H5A	119.8
C2—C1—Cl	111.69 (17)	C4—C5—H5A	119.8
C2—C1—H1A	109.3	C5—C6—C7	120.7 (2)
Cl—C1—H1A	109.3	C5—C6—H6A	119.7
C2—C1—H1B	109.3	C7—C6—H6A	119.7
Cl—C1—H1B	109.3	C8—C7—C6	118.3 (2)
H1A—C1—H1B	107.9	C8—C7—C10	123.4 (2)
C1—C2—C3	112.2 (2)	C6—C7—C10	118.3 (2)
C1—C2—H2A	109.2	C9—C8—C7	121.5 (2)
C3—C2—H2A	109.2	C9—C8—H8A	119.3
C1—C2—H2B	109.2	C7—C8—H8A	119.3
C3—C2—H2B	109.2	C8—C9—C4	119.8 (2)
H2A—C2—H2B	107.9	C8—C9—H9A	120.1
C10—O3—C11	116.09 (19)	C4—C9—H9A	120.1
O1—C3—C2	107.46 (19)	O2—C10—O3	123.0 (2)
O1—C3—H3A	110.2	O2—C10—C7	125.0 (2)
C2—C3—H3A	110.2	O3—C10—C7	112.1 (2)
O1—C3—H3B	110.2	O3—C11—H11A	109.5
C2—C3—H3B	110.2	O3—C11—H11B	109.5
H3A—C3—H3B	108.5	H11A—C11—H11B	109.5
O1—C4—C5	116.15 (19)	O3—C11—H11C	109.5
O1—C4—C9	124.5 (2)	H11A—C11—H11C	109.5
C5—C4—C9	119.4 (2)	H11B—C11—H11C	109.5
C6—C5—C4	120.4 (2)

Cl—C1—C2—C3	−178.88 (17)	C10—C7—C8—C9	179.4 (2)
C4—O1—C3—C2	174.81 (19)	C7—C8—C9—C4	−0.5 (3)
C1—C2—C3—O1	65.1 (3)	O1—C4—C9—C8	−178.9 (2)
C3—O1—C4—C5	−179.9 (2)	C5—C4—C9—C8	0.8 (3)
C3—O1—C4—C9	−0.1 (3)	C11—O3—C10—O2	1.4 (3)
O1—C4—C5—C6	179.5 (2)	C11—O3—C10—C7	−177.2 (2)
C9—C4—C5—C6	−0.2 (3)	C8—C7—C10—O2	175.7 (2)
C4—C5—C6—C7	−0.7 (4)	C6—C7—C10—O2	−4.4 (4)
C5—C6—C7—C8	1.0 (3)	C8—C7—C10—O3	−5.7 (3)
C5—C6—C7—C10	−178.8 (2)	C6—C7—C10—O3	174.1 (2)
C6—C7—C8—C9	−0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2ⁱ	0.97	2.45	3.351 (3)	154

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃ClO₃
M_r	228.66
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.2400 (12), 10.611 (2), 17.189 (3)
β (°)	100.35 (3)
V (Å³)	1119.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
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	0.909, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	4391, 2063, 1470
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.132, 1.00
No. of reflections	2063
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2ⁱ	0.97	2.45	3.351 (3)	154

Symmetry code: (i) x−1/2, −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. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 EXPRESS. Enraf-Nonius, Delft. The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Jaseer, E. A., Prasad, D. J. C. & Sekar, G. (2010). Tetrahedron. 66, 2077–2082. CrossRef 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. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1052

doi:10.1107/S1600536811011093

Open

access