Methyl 4-(3-chloro­prop­oxy)benzoate

Abstract

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,

• a = 6.2400 (12) Å

• b = 10.611 (2) Å

• c = 17.189 (3) Å

• β = 100.35 (3)°

• V = 1119.6 (4) ų

• 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[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 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

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 ▶).

Supplementary Material

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
C1—H1A⋯O2i	0.97	2.45	3.351 (3)	154

Symmetry code: (i) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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

Figures

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.

Crystal data

C11H13ClO3	F(000) = 480
Mr = 228.66	Dx = 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

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

Refinement

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(Fo2) + (0.078P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2063 reflections	Δρmax = 0.24 e Å−3
137 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

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