4-[3-(Bromo­meth­yl)benz­yloxy]-3-methoxy­benzaldehyde

Wei, J.-J.; Jin, L.; Zhou, C.-H.; Zhang, Y.-Y.

doi:10.1107/S1600536810011347

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o987

doi:10.1107/S1600536810011347

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4-[3-(Bromomethyl)benzyloxy]-3-methoxybenzaldehyde

Jin-Jian Wei,^a Lei Jin,^b Cheng-He Zhou ^a ^* and Yi-Yi Zhang ^a

^aLaboratory of Bioorganic & Medicinal Chemistry, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China, and ^bSchool of Pharmaceutical Sciences, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: zhouch@swu.edu.cn

(Received 21 March 2010; accepted 25 March 2010; online 31 March 2010)

In the title compound, C₁₆H₁₅BrO₃, the dihedral angle between the mean planes of the two benzene rings is 76.64 (2)°. In the crystal structure, there are weak π–π stacking interactions, with a centroid–centroid distance of 3.724 (3) Å, as well as an intermolecular C⋯Br distance [3.495 (2) Å] which is slightly less than the sum of the van der Waals radii for these atoms.

Related literature

For the applications of related compounds, see: Chen et al. (2001 ); Demestre et al. (2009 ); Liao et al. (2003 ); Xia & Hu (2004 ). For a related structure, see: Jin et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₅BrO₃
M_r = 335.19
Monoclinic, P 2₁ /c
a = 14.275 (3) Å
b = 11.791 (2) Å
c = 8.7315 (17) Å
β = 95.671 (3)°
V = 1462.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.82 mm⁻¹
T = 298 K
0.08 × 0.08 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick,1996 ) T_min = 0.798, T_max = 0.845
7566 measured reflections
2777 independent reflections
2014 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.150
S = 1.07
2777 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810011347/lh5019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810011347/lh5019Isup2.hkl

checkCIF report

Comment top

Vanillin (4-hydroxy-3-methoxybenzaldehyde) and its derivatives are important medicinal intermediates which are extensively employed to prepare bioactive compounds such as anti-hypertension compounds, diureses and deodorisers (Chen, et al., 2001; Demestre, et al., 2009; Liao, et al., 2003; Xia, et al., 2004). Recently, our research has been focused on the development of vanillin-derived azole drugs, and a nitroimidazole derivative has been reported (Jin, et al., 2009). Herein we report the crystal structure of the title compound a potential intermediate for the synthesis of azole antifungal agents.

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the mean planes of the two benzene rings is 76.64 (2)°. In the crystal structure, there are weak π–π stacking interactions where Cg···Cg(-x,2-y,1-z) = 3.724 (3)Å [Cg is the centroid of the C2-C7 ring] as well as an intermolecular C13···Br1(-x+1, 0.5+y, 2.5-z) distance [3.495 (2)Å] which is slightly less than the sum of the van der Waals radii for these atoms.

Related literature top

For the applications of related compounds, see: Chen et al. (2001); Demestre et al. (2009); Liao et al. (2003); Xia et al. (2004). For a related structure, see: Jin et al. (2009).

Experimental top

A suspension of 4-hyhydroxy-3-methoxybenzaldehyde (200 mg, 1.31 mmol) and anhydrous potassium carbonate (200 mg, 1.45 mmol, 1.2 equiv) in CH₃CN (10 ml) was stirred for 30 min at 338 K, and then tetrabutyl ammonium iodide (TBAI, 5 mg) and 1,3-bis(bromomethyl)benzene (1 g, 3.78 mmol) were added. The resulting mixture was stirred for 5–7 h at 348–353 K (monitored by TLC, eluent, ethyl acetate/petroleum, V/V, 5/1). After the reaction solvent was evaporated under reduced pressure, water (10 mL) was added. The mixture was extracted with chloroform (3×10 ml). The organic layer was collected, dried over anhydrous Na₂SO₄and evaporated under reduced pressure to give the crude product, which was purified by silica gel column chromatography (eluent, ethyl acetate/petroleum, V/V, 5/1) to afford the title compound (I). Single crystals were grown by slow evaporation of a solution of (I) in an ethyl acetate and petroleum mixture at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

4-[3-(Bromomethyl)benzyloxy]-3-methoxybenzaldehyde top

Crystal data top

C₁₆H₁₅BrO₃	F(000) = 680
M_r = 335.19	D_x = 1.522 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2434 reflections
a = 14.275 (3) Å	θ = 2.3–24.0°
b = 11.791 (2) Å	µ = 2.82 mm⁻¹
c = 8.7315 (17) Å	T = 298 K
β = 95.671 (3)°	Block, colourless
V = 1462.5 (5) Å³	0.08 × 0.08 × 0.06 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2777 independent reflections
Radiation source: fine-focus sealed tube	2014 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	h = −17→17
T_min = 0.798, T_max = 0.845	k = −14→14
7566 measured reflections	l = −10→5

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0765P)² + 1.2302P] where P = (F_o² + 2F_c²)/3
2777 reflections	(Δ/σ)_max = 0.001
182 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₆H₁₅BrO₃	V = 1462.5 (5) Å³
M_r = 335.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.275 (3) Å	µ = 2.82 mm⁻¹
b = 11.791 (2) Å	T = 298 K
c = 8.7315 (17) Å	0.08 × 0.08 × 0.06 mm
β = 95.671 (3)°

Data collection top

Bruker SMART CCD diffractometer	2777 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	2014 reflections with I > 2σ(I)
T_min = 0.798, T_max = 0.845	R_int = 0.031
7566 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.07	Δρ_max = 0.85 e Å⁻³
2777 reflections	Δρ_min = −0.35 e Å⁻³
182 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 > σ(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
Br1	0.58913 (3)	0.68699 (4)	1.13810 (7)	0.0709 (3)
C1	−0.0081 (3)	1.0150 (5)	0.1918 (5)	0.0559 (11)
H1	−0.0372	0.9491	0.1526	0.067*
C2	0.0624 (3)	1.0028 (4)	0.3238 (5)	0.0450 (9)
C3	0.1048 (3)	1.0973 (3)	0.3971 (5)	0.0437 (9)
H3	0.0915	1.1693	0.3572	0.052*
C4	0.1657 (3)	1.0851 (3)	0.5270 (4)	0.0409 (9)
C5	0.1854 (3)	0.9748 (3)	0.5878 (5)	0.0411 (9)
C6	0.1453 (3)	0.8818 (4)	0.5123 (5)	0.0483 (10)
H6	0.1598	0.8093	0.5493	0.058*
C7	0.0832 (3)	0.8959 (4)	0.3805 (5)	0.0492 (10)
H7	0.0556	0.8328	0.3305	0.059*
C8	0.1941 (3)	1.2830 (4)	0.5499 (6)	0.0532 (11)
H8A	0.2168	1.2873	0.4502	0.080*
H8B	0.2278	1.3363	0.6180	0.080*
H8C	0.1282	1.3007	0.5412	0.080*
C9	0.2625 (3)	0.8629 (3)	0.7868 (5)	0.0561 (12)
H9A	0.2991	0.8176	0.7216	0.067*
H9B	0.2040	0.8234	0.7983	0.067*
C10	0.3167 (3)	0.8807 (3)	0.9420 (5)	0.0446 (10)
C11	0.4120 (3)	0.8598 (3)	0.9632 (5)	0.0482 (10)
H11	0.4430	0.8359	0.8802	0.058*
C12	0.4628 (3)	0.8737 (3)	1.1059 (5)	0.0486 (10)
C13	0.4153 (4)	0.9079 (3)	1.2281 (5)	0.0576 (12)
H13	0.4481	0.9167	1.3247	0.069*
C14	0.3197 (3)	0.9293 (4)	1.2093 (6)	0.0581 (12)
H14	0.2886	0.9527	1.2925	0.070*
C15	0.2709 (3)	0.9158 (3)	1.0667 (6)	0.0530 (11)
H15	0.2065	0.9303	1.0537	0.064*
C16	0.5658 (3)	0.8494 (4)	1.1234 (7)	0.0683 (14)
H16A	0.5948	0.8865	1.2153	0.082*
H16B	0.5942	0.8798	1.0356	0.082*
O1	−0.0319 (2)	1.1038 (3)	0.1288 (4)	0.0668 (9)
O2	0.2083 (2)	1.1717 (2)	0.6096 (3)	0.0501 (7)
O3	0.2435 (2)	0.9726 (2)	0.7192 (3)	0.0516 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0595 (3)	0.0524 (3)	0.0992 (5)	0.0119 (2)	0.0002 (3)	0.0131 (3)
C1	0.056 (3)	0.067 (3)	0.045 (3)	−0.005 (2)	0.003 (2)	−0.007 (2)
C2	0.040 (2)	0.056 (2)	0.040 (2)	−0.0003 (18)	0.0050 (18)	−0.003 (2)
C3	0.047 (2)	0.041 (2)	0.044 (2)	0.0044 (17)	0.0074 (19)	0.0016 (19)
C4	0.041 (2)	0.039 (2)	0.043 (2)	0.0013 (16)	0.0025 (18)	−0.0020 (18)
C5	0.041 (2)	0.040 (2)	0.042 (2)	0.0006 (16)	0.0021 (18)	−0.0009 (18)
C6	0.053 (2)	0.038 (2)	0.053 (3)	0.0029 (18)	0.004 (2)	0.0008 (19)
C7	0.049 (2)	0.048 (2)	0.050 (2)	−0.0055 (19)	0.002 (2)	−0.010 (2)
C8	0.063 (3)	0.039 (2)	0.055 (3)	0.0037 (19)	−0.007 (2)	0.000 (2)
C9	0.071 (3)	0.033 (2)	0.061 (3)	0.005 (2)	−0.011 (2)	0.007 (2)
C10	0.052 (2)	0.0263 (18)	0.054 (3)	0.0026 (16)	0.001 (2)	0.0082 (18)
C11	0.051 (2)	0.036 (2)	0.058 (3)	0.0052 (18)	0.008 (2)	0.006 (2)
C12	0.051 (2)	0.0295 (19)	0.064 (3)	0.0006 (17)	−0.002 (2)	0.009 (2)
C13	0.083 (3)	0.034 (2)	0.052 (3)	−0.001 (2)	−0.011 (2)	0.003 (2)
C14	0.072 (3)	0.039 (2)	0.064 (3)	0.001 (2)	0.016 (3)	−0.003 (2)
C15	0.050 (2)	0.033 (2)	0.075 (3)	0.0017 (18)	0.005 (2)	0.001 (2)
C16	0.058 (3)	0.046 (3)	0.098 (4)	−0.002 (2)	−0.009 (3)	0.013 (3)
O1	0.063 (2)	0.078 (2)	0.055 (2)	0.0041 (18)	−0.0122 (16)	0.0038 (19)
O2	0.0631 (18)	0.0365 (15)	0.0474 (17)	−0.0004 (13)	−0.0112 (14)	0.0001 (12)
O3	0.0621 (18)	0.0359 (14)	0.0536 (18)	0.0014 (13)	−0.0108 (15)	0.0060 (13)

Geometric parameters (Å, º) top

Br1—C16	1.946 (5)	C8—H8C	0.9600
C1—O1	1.216 (6)	C9—O3	1.437 (5)
C1—C2	1.460 (6)	C9—C10	1.508 (6)
C1—H1	0.9300	C9—H9A	0.9700
C2—C7	1.376 (6)	C9—H9B	0.9700
C2—C3	1.393 (6)	C10—C11	1.376 (6)
C3—C4	1.367 (6)	C10—C15	1.388 (6)
C3—H3	0.9300	C11—C12	1.388 (6)
C4—O2	1.358 (5)	C11—H11	0.9300
C4—C5	1.422 (5)	C12—C13	1.380 (6)
C5—O3	1.348 (5)	C12—C16	1.492 (6)
C5—C6	1.375 (6)	C13—C14	1.381 (7)
C6—C7	1.392 (6)	C13—H13	0.9300
C6—H6	0.9300	C14—C15	1.375 (7)
C7—H7	0.9300	C14—H14	0.9300
C8—O2	1.420 (5)	C15—H15	0.9300
C8—H8A	0.9600	C16—H16A	0.9700
C8—H8B	0.9600	C16—H16B	0.9700

O1—C1—C2	125.6 (4)	O3—C9—H9B	110.2
O1—C1—H1	117.2	C10—C9—H9B	110.2
C2—C1—H1	117.2	H9A—C9—H9B	108.5
C7—C2—C3	120.0 (4)	C11—C10—C15	118.9 (4)
C7—C2—C1	118.7 (4)	C11—C10—C9	120.6 (4)
C3—C2—C1	121.2 (4)	C15—C10—C9	120.4 (4)
C4—C3—C2	120.6 (4)	C10—C11—C12	121.4 (4)
C4—C3—H3	119.7	C10—C11—H11	119.3
C2—C3—H3	119.7	C12—C11—H11	119.3
O2—C4—C3	125.2 (4)	C13—C12—C11	118.4 (4)
O2—C4—C5	115.3 (3)	C13—C12—C16	122.2 (5)
C3—C4—C5	119.5 (4)	C11—C12—C16	119.4 (4)
O3—C5—C6	125.8 (4)	C12—C13—C14	121.1 (4)
O3—C5—C4	114.7 (3)	C12—C13—H13	119.4
C6—C5—C4	119.5 (4)	C14—C13—H13	119.4
C5—C6—C7	120.1 (4)	C15—C14—C13	119.6 (4)
C5—C6—H6	119.9	C15—C14—H14	120.2
C7—C6—H6	119.9	C13—C14—H14	120.2
C2—C7—C6	120.3 (4)	C14—C15—C10	120.6 (4)
C2—C7—H7	119.9	C14—C15—H15	119.7
C6—C7—H7	119.9	C10—C15—H15	119.7
O2—C8—H8A	109.5	C12—C16—Br1	110.9 (3)
O2—C8—H8B	109.5	C12—C16—H16A	109.5
H8A—C8—H8B	109.5	Br1—C16—H16A	109.5
O2—C8—H8C	109.5	C12—C16—H16B	109.5
H8A—C8—H8C	109.5	Br1—C16—H16B	109.5
H8B—C8—H8C	109.5	H16A—C16—H16B	108.1
O3—C9—C10	107.6 (3)	C4—O2—C8	117.4 (3)
O3—C9—H9A	110.2	C5—O3—C9	116.2 (3)
C10—C9—H9A	110.2

O1—C1—C2—C7	−178.7 (4)	C15—C10—C11—C12	−0.4 (6)
O1—C1—C2—C3	4.6 (7)	C9—C10—C11—C12	−178.8 (4)
C7—C2—C3—C4	−1.3 (6)	C10—C11—C12—C13	0.8 (6)
C1—C2—C3—C4	175.4 (4)	C10—C11—C12—C16	179.7 (4)
C2—C3—C4—O2	−177.8 (4)	C11—C12—C13—C14	−0.8 (6)
C2—C3—C4—C5	−0.3 (6)	C16—C12—C13—C14	−179.7 (4)
O2—C4—C5—O3	0.2 (5)	C12—C13—C14—C15	0.3 (6)
C3—C4—C5—O3	−177.6 (3)	C13—C14—C15—C10	0.1 (6)
O2—C4—C5—C6	179.9 (4)	C11—C10—C15—C14	−0.1 (6)
C3—C4—C5—C6	2.1 (6)	C9—C10—C15—C14	178.3 (4)
O3—C5—C6—C7	177.3 (4)	C13—C12—C16—Br1	100.3 (5)
C4—C5—C6—C7	−2.5 (6)	C11—C12—C16—Br1	−78.6 (5)
C3—C2—C7—C6	1.0 (6)	C3—C4—O2—C8	−5.1 (6)
C1—C2—C7—C6	−175.8 (4)	C5—C4—O2—C8	177.3 (4)
C5—C6—C7—C2	0.9 (6)	C6—C5—O3—C9	−1.7 (6)
O3—C9—C10—C11	−104.6 (4)	C4—C5—O3—C9	178.0 (3)
O3—C9—C10—C15	77.0 (5)	C10—C9—O3—C5	−172.1 (3)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅BrO₃
M_r	335.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.275 (3), 11.791 (2), 8.7315 (17)
β (°)	95.671 (3)
V (Å³)	1462.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.82
Crystal size (mm)	0.08 × 0.08 × 0.06

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick,1996)
T_min, T_max	0.798, 0.845
No. of measured, independent and observed [I > 2σ(I)] reflections	7566, 2777, 2014
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.150, 1.07
No. of reflections	2777
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.35

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We thank Southwest University (SWUB2006018, XSGX0602 and SWUF2007023) and the Natural Science Foundation of Chongqing (2007BB5369) for financial support.

References

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