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

Abstract

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,

• a = 8.4980 (17) Å

• b = 17.349 (4) Å

• c = 8.8440 (18) Å

• β = 106.46 (3)°

• V = 1250.5 (5) ų

• 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[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 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

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 ▶).

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—H1B⋯O2i	0.97	2.56	3.429 (6)	149
C2—H2A⋯O3ii	0.97	2.41	3.358 (6)	164

Symmetry codes: (i) ; (ii) .

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.

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.

Experimental

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

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 U_iso(H) = xU_eq(C), 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. Hydrogen bond is shown as dashed line.

Fig. 2.

A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H15ClO4	F(000) = 544
Mr = 258.69	Dx = 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

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

Refinement

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(Fo2) + (0.050P)2 + 3.3P] where P = (Fo2 + 2Fc2)/3
2274 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.29 e Å−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	0.27901 (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 (Ų)

	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, °)

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, °)

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.