4-Bromo-2-(dieth­oxy­meth­yl)phenyl benzoate

Sharmila, P.; Suresh Kumar, C.; Maheshwaran, S.; Narasimhan, S.; Aravindhan, S.

doi:10.1107/S1600536813006351

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o553

doi:10.1107/S1600536813006351

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4-Bromo-2-(diethoxymethyl)phenyl benzoate

P. Sharmila,^a C. Suresh Kumar,^b S. Maheshwaran,^b S. Narasimhan ^b and S. Aravindhan ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bAsthagiri Herbal Research Foundation, Perungudi, Chennai 600 096, India
^*Correspondence e-mail: aravindhanpresidency@gmail.com

(Received 17 February 2013; accepted 5 March 2013; online 16 March 2013)

In the title compound, C₁₈H₁₉BrO₄, the aromatic rings enclose a dihedral angle of 81.9 (7)°. There are no short directional contacts in the crystal structure.

Related literature

For the biological activity of ester derivatives, see: Bi et al. (2012 ); Bartzatt et al. (2004 ); Anadu et al. (2006 ).

Experimental

Crystal data

C₁₈H₁₉BrO₄
M_r = 379.24
Triclinic, $[P \overline 1]$
a = 8.2662 (8) Å
b = 9.6378 (10) Å
c = 11.6224 (13) Å
α = 99.927 (5)°
β = 93.700 (5)°
γ = 101.178 (5)°
V = 890.16 (16) Å³
Z = 2
Mo Kα radiation
μ = 2.33 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2004 ) T_min = 0.497, T_max = 0.594
16152 measured reflections
4493 independent reflections
3037 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.085
S = 1.01
4493 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); 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, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813006351/bt6892sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006351/bt6892Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813006351/bt6892Isup3.cml

checkCIF report

Comment top

Ester derivatives of many compounds exhibit a variety of pharmacological properties, for example anticancer, antitumor and antimicrobial activities (Anadu et al., 2006; Bi et al., 2012; Bartzatt et al., 2004). In view of their importance, the title compound was synthesized and we report herein on its crystal structure.

In the title molecule (Fig. 1) the two aromatic rings enclose a dihedral angle of 98.1 (7)°. The molecular conformation is stabilized by C-H···O contacts. The crystals packing, on the other hand, shows no short contacts.

A packing diagram of the molecule is shown in Fig. 2.

Related literature top

For the biological activity of ester derivatives, see: Bi et al. (2012); Bartzatt et al. (2004); Anadu et al. (2006).

Experimental top

A solution of 4-Bromo-2-diethoxymethyl-phenol (0.03 mol) in chloroform (100 ml) was cooled and Benzoyl chlorides (0.03 mol) was added dropwise followed by addition of triethyl amine (0.03 mol). Then, the reaction was stirred at room temperature for 3 h. The reaction mixture was quenched with water and the chloroform layer was separated. The combined chloroform layer was washed with 5% NaOH solution followed by water wash and dried with anhydrous sodium sulfate, concentrated under reduced pressure. The obtained solid was crystallized in a mixture of Methanol:Chloroform.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); 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, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. Crystal packing of the title compound viewed along the b axis. For the sake of clarity, H atoms have been omitted.

4-Bromo-2-(diethoxymethyl)phenyl benzoate top

Crystal data top

C₁₈H₁₉BrO₄	Z = 2
M_r = 379.24	F(000) = 388
Triclinic, P1	D_x = 1.415 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2662 (8) Å	Cell parameters from 8834 reflections
b = 9.6378 (10) Å	θ = 2.1–31.2°
c = 11.6224 (13) Å	µ = 2.33 mm⁻¹
α = 99.927 (5)°	T = 293 K
β = 93.700 (5)°	Block, colourless
γ = 101.178 (5)°	0.35 × 0.30 × 0.25 mm
V = 890.16 (16) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	4493 independent reflections
Radiation source: fine-focus sealed tube	3037 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and ϕ scan	θ_max = 28.6°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker 2004)	h = −10→11
T_min = 0.497, T_max = 0.594	k = −12→12
16152 measured reflections	l = −14→15

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0325P)² + 0.2669P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
4493 reflections	Δρ_max = 0.46 e Å⁻³
209 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0293 (17)

Crystal data top

C₁₈H₁₉BrO₄	γ = 101.178 (5)°
M_r = 379.24	V = 890.16 (16) Å³
Triclinic, P1	Z = 2
a = 8.2662 (8) Å	Mo Kα radiation
b = 9.6378 (10) Å	µ = 2.33 mm⁻¹
c = 11.6224 (13) Å	T = 293 K
α = 99.927 (5)°	0.35 × 0.30 × 0.25 mm
β = 93.700 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	4493 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2004)	3037 reflections with I > 2σ(I)
T_min = 0.497, T_max = 0.594	R_int = 0.035
16152 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.01	Δρ_max = 0.46 e Å⁻³
4493 reflections	Δρ_min = −0.42 e Å⁻³
209 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
C1	1.0177 (3)	0.1162 (2)	0.14518 (19)	0.0568 (5)
H1	1.0276	0.2024	0.1179	0.068*
C2	1.1551 (3)	0.0569 (3)	0.1588 (2)	0.0668 (6)
H2	1.2575	0.1035	0.1415	0.080*
C3	1.1409 (3)	−0.0706 (3)	0.1979 (2)	0.0686 (6)
H3	1.2335	−0.1108	0.2067	0.082*
C4	0.9906 (3)	−0.1388 (2)	0.2238 (2)	0.0657 (6)
H4	0.9814	−0.2257	0.2500	0.079*
C5	0.8522 (3)	−0.0800 (2)	0.21151 (19)	0.0560 (5)
H5	0.7504	−0.1266	0.2299	0.067*
C6	0.8660 (2)	0.0487 (2)	0.17159 (16)	0.0446 (4)
C7	0.7144 (3)	0.1076 (2)	0.16072 (17)	0.0476 (5)
C8	0.6138 (2)	0.3097 (2)	0.12700 (17)	0.0454 (4)
C9	0.4947 (3)	0.2747 (2)	0.03277 (18)	0.0530 (5)
H9	0.5006	0.2030	−0.0306	0.064*
C10	0.3663 (3)	0.3469 (2)	0.03332 (19)	0.0553 (5)
H10	0.2848	0.3249	−0.0298	0.066*
C11	0.3603 (2)	0.4517 (2)	0.12799 (18)	0.0495 (5)
C12	0.4820 (2)	0.4902 (2)	0.22060 (17)	0.0477 (5)
H12	0.4769	0.5639	0.2827	0.057*
C13	0.6130 (2)	0.4189 (2)	0.22129 (17)	0.0440 (4)
C14	0.7505 (2)	0.4552 (2)	0.32109 (18)	0.0487 (5)
H14	0.8563	0.4704	0.2868	0.058*
C15	0.8756 (3)	0.6431 (3)	0.4779 (2)	0.0728 (7)
H15A	0.9786	0.6372	0.4438	0.087*
H15B	0.8675	0.5876	0.5402	0.087*
C16	0.8736 (4)	0.7952 (3)	0.5262 (2)	0.0831 (8)
H16A	0.9657	0.8344	0.5850	0.125*
H16B	0.7720	0.8003	0.5607	0.125*
H16C	0.8819	0.8497	0.4642	0.125*
C17	0.5999 (3)	0.3033 (3)	0.4376 (2)	0.0698 (6)
H17A	0.5091	0.2600	0.3771	0.084*
H17B	0.5723	0.3875	0.4843	0.084*
C18	0.6251 (4)	0.1991 (4)	0.5128 (3)	0.1005 (10)
H18A	0.5260	0.1717	0.5494	0.151*
H18B	0.7155	0.2424	0.5721	0.151*
H18C	0.6501	0.1153	0.4657	0.151*
O1	0.57904 (18)	0.05021 (16)	0.17780 (15)	0.0657 (4)
O2	0.74639 (16)	0.23833 (14)	0.12732 (12)	0.0502 (3)
O3	0.74890 (16)	0.34407 (15)	0.38518 (12)	0.0535 (3)
O4	0.73826 (17)	0.58602 (15)	0.38984 (13)	0.0578 (4)
Br1	0.17952 (3)	0.54626 (3)	0.13035 (2)	0.07463 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0560 (12)	0.0532 (12)	0.0665 (14)	0.0203 (10)	0.0098 (10)	0.0140 (10)
C2	0.0549 (13)	0.0715 (16)	0.0812 (16)	0.0235 (12)	0.0154 (12)	0.0195 (13)
C3	0.0660 (15)	0.0711 (16)	0.0759 (16)	0.0377 (13)	0.0041 (12)	0.0085 (13)
C4	0.0794 (17)	0.0487 (12)	0.0752 (15)	0.0271 (12)	0.0037 (12)	0.0142 (11)
C5	0.0601 (13)	0.0463 (12)	0.0606 (13)	0.0147 (10)	0.0032 (10)	0.0044 (10)
C6	0.0501 (11)	0.0403 (10)	0.0418 (10)	0.0145 (8)	0.0012 (8)	−0.0010 (8)
C7	0.0491 (11)	0.0401 (10)	0.0499 (11)	0.0116 (9)	0.0018 (9)	−0.0028 (9)
C8	0.0437 (10)	0.0399 (10)	0.0541 (12)	0.0137 (8)	0.0050 (8)	0.0073 (9)
C9	0.0616 (13)	0.0442 (11)	0.0495 (12)	0.0127 (10)	−0.0018 (10)	−0.0005 (9)
C10	0.0558 (12)	0.0502 (12)	0.0557 (12)	0.0102 (10)	−0.0116 (10)	0.0062 (10)
C11	0.0440 (10)	0.0445 (11)	0.0608 (13)	0.0146 (8)	−0.0032 (9)	0.0096 (9)
C12	0.0469 (10)	0.0429 (10)	0.0517 (11)	0.0150 (8)	−0.0022 (9)	0.0007 (9)
C13	0.0402 (9)	0.0417 (10)	0.0495 (11)	0.0105 (8)	−0.0001 (8)	0.0058 (8)
C14	0.0423 (10)	0.0471 (11)	0.0551 (12)	0.0118 (8)	−0.0024 (9)	0.0052 (9)
C15	0.0678 (15)	0.0647 (15)	0.0731 (16)	0.0076 (12)	−0.0277 (12)	−0.0026 (12)
C16	0.0846 (18)	0.0742 (17)	0.0724 (17)	0.0070 (14)	−0.0140 (14)	−0.0166 (13)
C17	0.0651 (15)	0.0801 (17)	0.0676 (15)	0.0161 (13)	0.0103 (12)	0.0209 (13)
C18	0.104 (2)	0.092 (2)	0.116 (2)	0.0156 (18)	0.0205 (19)	0.0523 (19)
O1	0.0468 (8)	0.0520 (9)	0.0981 (12)	0.0104 (7)	0.0066 (8)	0.0144 (8)
O2	0.0469 (7)	0.0433 (7)	0.0639 (9)	0.0181 (6)	0.0090 (6)	0.0086 (6)
O3	0.0459 (7)	0.0551 (8)	0.0607 (8)	0.0136 (6)	−0.0023 (6)	0.0135 (7)
O4	0.0532 (8)	0.0498 (8)	0.0622 (9)	0.0137 (6)	−0.0156 (7)	−0.0073 (7)
Br1	0.05575 (16)	0.07410 (19)	0.0983 (2)	0.03299 (12)	−0.00794 (12)	0.01173 (14)

Geometric parameters (Å, º) top

C1—C6	1.375 (3)	C11—Br1	1.8944 (19)
C1—C2	1.380 (3)	C12—C13	1.391 (3)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.368 (3)	C13—C14	1.515 (3)
C2—H2	0.9300	C14—O4	1.397 (2)
C3—C4	1.366 (3)	C14—O3	1.405 (2)
C3—H3	0.9300	C14—H14	0.9800
C4—C5	1.382 (3)	C15—O4	1.432 (2)
C4—H4	0.9300	C15—C16	1.480 (3)
C5—C6	1.385 (3)	C15—H15A	0.9700
C5—H5	0.9300	C15—H15B	0.9700
C6—C7	1.480 (3)	C16—H16A	0.9600
C7—O1	1.193 (2)	C16—H16B	0.9600
C7—O2	1.364 (2)	C16—H16C	0.9600
C8—C9	1.374 (3)	C17—O3	1.427 (3)
C8—C13	1.384 (3)	C17—C18	1.475 (4)
C8—O2	1.402 (2)	C17—H17A	0.9700
C9—C10	1.377 (3)	C17—H17B	0.9700
C9—H9	0.9300	C18—H18A	0.9600
C10—C11	1.370 (3)	C18—H18B	0.9600
C10—H10	0.9300	C18—H18C	0.9600
C11—C12	1.374 (3)

C6—C1—C2	120.4 (2)	C8—C13—C12	117.63 (17)
C6—C1—H1	119.8	C8—C13—C14	119.86 (16)
C2—C1—H1	119.8	C12—C13—C14	122.51 (17)
C3—C2—C1	120.1 (2)	O4—C14—O3	113.44 (17)
C3—C2—H2	120.0	O4—C14—C13	107.35 (15)
C1—C2—H2	120.0	O3—C14—C13	112.85 (15)
C4—C3—C2	120.0 (2)	O4—C14—H14	107.6
C4—C3—H3	120.0	O3—C14—H14	107.6
C2—C3—H3	120.0	C13—C14—H14	107.6
C3—C4—C5	120.6 (2)	O4—C15—C16	109.0 (2)
C3—C4—H4	119.7	O4—C15—H15A	109.9
C5—C4—H4	119.7	C16—C15—H15A	109.9
C4—C5—C6	119.5 (2)	O4—C15—H15B	109.9
C4—C5—H5	120.2	C16—C15—H15B	109.9
C6—C5—H5	120.2	H15A—C15—H15B	108.3
C1—C6—C5	119.40 (18)	C15—C16—H16A	109.5
C1—C6—C7	123.17 (18)	C15—C16—H16B	109.5
C5—C6—C7	117.43 (19)	H16A—C16—H16B	109.5
O1—C7—O2	122.72 (18)	C15—C16—H16C	109.5
O1—C7—C6	125.59 (19)	H16A—C16—H16C	109.5
O2—C7—C6	111.68 (17)	H16B—C16—H16C	109.5
C9—C8—C13	122.30 (17)	O3—C17—C18	108.7 (2)
C9—C8—O2	120.00 (17)	O3—C17—H17A	110.0
C13—C8—O2	117.64 (16)	C18—C17—H17A	110.0
C8—C9—C10	119.24 (18)	O3—C17—H17B	110.0
C8—C9—H9	120.4	C18—C17—H17B	110.0
C10—C9—H9	120.4	H17A—C17—H17B	108.3
C11—C10—C9	119.18 (18)	C17—C18—H18A	109.5
C11—C10—H10	120.4	C17—C18—H18B	109.5
C9—C10—H10	120.4	H18A—C18—H18B	109.5
C10—C11—C12	121.75 (18)	C17—C18—H18C	109.5
C10—C11—Br1	118.92 (14)	H18A—C18—H18C	109.5
C12—C11—Br1	119.33 (15)	H18B—C18—H18C	109.5
C11—C12—C13	119.83 (18)	C7—O2—C8	115.71 (15)
C11—C12—H12	120.1	C14—O3—C17	115.33 (16)
C13—C12—H12	120.1	C14—O4—C15	112.95 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2	0.93	2.42	2.740 (3)	100
C12—H12···O4	0.93	2.38	2.699 (2)	100
C17—H17B···O4	0.97	2.58	2.905 (3)	100

Experimental details

Crystal data
Chemical formula	C₁₈H₁₉BrO₄
M_r	379.24
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.2662 (8), 9.6378 (10), 11.6224 (13)
α, β, γ (°)	99.927 (5), 93.700 (5), 101.178 (5)
V (Å³)	890.16 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.33
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker 2004)
T_min, T_max	0.497, 0.594
No. of measured, independent and observed [I > 2σ(I)] reflections	16152, 4493, 3037
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.085, 1.01
No. of reflections	4493
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.42

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2	0.93	2.42	2.740 (3)	100
C12—H12···O4	0.93	2.38	2.699 (2)	100
C17—H17B···O4	0.97	2.58	2.905 (3)	100

Acknowledgements

SA thanks the UGC, India, for financial support

References

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