Methyl 2-(benzo­yloxy)benzoate

Kumar, S.; Chandra; Dileep, C.S.; Mahendra, M.; Doreswamy, B.H.

doi:10.1107/S2414314616008671

organic compounds

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ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160867

doi:10.1107/S2414314616008671

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Methyl 2-(benzoyloxy)benzoate

Shamantha Kumar,^a Chandra,^b C. S. Dileep,^c M. Mahendra ^b and B. H. Doreswamy ^a ^*

^aDepartment of Physics, SJB Institute of Technology, Kengeri, Bangalore 560 060, India, ^bDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, and ^cDepartment of Physics, Vidyavardhaka College of Engineering, Mysore 570 002, India
^*Correspondence e-mail: mychandru.10@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 16 May 2016; accepted 30 May 2016; online 17 June 2016)

In the title compound, C₁₅H₁₂O₄, the dihedral angle between the two aryl rings is 68.19 (9)°. In the crystal, molecules are linked by C—H⋯π interactions forming chains along the b-axis direction. The chains are linked by offset π–π interactions [intercentroid distance = 3.6806 (14) Å], forming sheets lying parallel to (10-1).

Keywords: crystal structure; benzoate derivative; medicinal importance; C—H⋯π interactions; offset π–π interactions.

CCDC reference: 1482493

Structure description

Benzyl benzoate and its derivatives represent an interesting class of compounds, as they improve the stability and odour characteristics of products in which they are used as the main ingredients. Benzoate derivatives have drawn much attention because of their medicinal activities, such as anti-microbial (Ankersen et al., 1997 ) and anticancer (Revesz et al., 2004 ). In addition, a series of benzyloxybenzaldehyde derivatives were prepared and tested against the HL-60 cell line for anticancer activity (Lin et al., 2005 ). In view of the profound interest of these derivatives, we report herein on the synthesis and crystal structure of the title compound.

The molecular structure of the title compound is illustrated in Fig. 1. The dihedral angle between the benzene rings, C1–C6 and C10–C15, is 68.19 (9)°. The O9—C7=O8 group is almost coplanar with the aromatic ring C1–C6, with a dihedral angle of 8.11 (18)°, while it is inclined to the second benzene ring, C10–C15, by 74.8 (19) °. The O18—C16=O17 group is also almost coplanar with the benzene ring, C10–C15, to which it is attached with a dihedral angle of 5.1 (2)°.

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

There are no classical hydrogen bonds in the crystal structure. However, in the crystal, molecules are linked by C—H⋯π interactions, forming chains along the b axis direction (Table 1 and Fig. 2). The chains are linked by offset π–π interactions [Cg1⋯Cg1ⁱ = 3.6806 (14) Å, where Cg1 is the centroid of ring C1–C6, interplanar distance = 3.4792 (7) Å, slippage = 1.201 Å; symmetry code: (i) − x + 1, − y, − z + 2], forming sheets lying parallel to (10 $[\overline{1}]$ ); see Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19C⋯Cg2ⁱ	0.96	2.83	3.625 (3)	140
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view along the a axis of the crystal packing of the title compound. The C—H⋯π (see Table 1

) and π–π interactions are represented by dashed lines, and for clarity only H atom H19C (grey ball) is included.

Synthesis and crystallization

The solution of 2-hydroxybenzoic acid methyl ester (1.0 mmol) and benzoyl chloride (1.5 mmol) in pyridine was refluxed at 333 K. On completion of the reaction (monitored by TLC), the mixture was cooled to room temperature and pyridine was removed under reduced pressure. The residue obtained was dissolved in dichloromethane and washed with water. The separated organic layer was dried over anhydrous sodium sulfate and the solvent removed using a rotary evaporator. The crude product obtained was purified using silica gel column chromatography. Colourless block-like crystals were obtained by slow evaporation of a solution of the title compound in ethanol.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₂O₄
M_r	256.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	19.529 (5), 8.540 (2), 14.960 (4)
β (°)	93.334 (14)
V (Å³)	2490.8 (11)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	0.83
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6308, 2020, 1745
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.156, 1.19
No. of reflections	2020
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.28
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1482493

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616008671/su4050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616008671/su4050Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616008671/su4050Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Methyl 2-(benzoyloxy)benzoate top

Crystal data top

C₁₅H₁₂O₄	F(000) = 1072
M_r = 256.25	D_x = 1.367 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 2020 reflections
a = 19.529 (5) Å	θ = 4.5–65.1°
b = 8.540 (2) Å	µ = 0.83 mm⁻¹
c = 14.960 (4) Å	T = 296 K
β = 93.334 (14)°	Block, colourless
V = 2490.8 (11) Å³	0.30 × 0.25 × 0.20 mm
Z = 8

Data collection top

Bruker X8 Proteum diffractometer	1745 reflections with I > 2σ(I)
Radiation source: Bruker MicroStar microfocus rotating anode	R_int = 0.044
Helios multilayer optics monochromator	θ_max = 65.1°, θ_min = 4.5°
Detector resolution: 10.7 pixels mm^-1	h = −22→22
φ and ω scans	k = −10→9
6308 measured reflections	l = −11→17
2020 independent reflections

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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max = 0.002
2020 reflections	Δρ_max = 0.31 e Å⁻³
174 parameters	Δρ_min = −0.28 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: 0.0090 (9)

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs 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
O8	0.33968 (6)	0.10878 (15)	0.89122 (8)	0.0565 (5)
O9	0.42601 (6)	0.15246 (15)	0.80123 (8)	0.0492 (4)
O17	0.33585 (7)	−0.02518 (16)	0.69827 (10)	0.0652 (5)
O18	0.26162 (7)	0.10223 (16)	0.60645 (8)	0.0610 (5)
C1	0.43639 (8)	−0.06021 (19)	0.90068 (10)	0.0422 (5)
C2	0.50358 (8)	−0.0827 (2)	0.87647 (11)	0.0466 (5)
C3	0.54205 (9)	−0.2026 (2)	0.91535 (12)	0.0536 (6)
C4	0.51445 (10)	−0.2986 (2)	0.97716 (13)	0.0574 (6)
C5	0.44773 (10)	−0.2784 (2)	1.00044 (13)	0.0586 (6)
C6	0.40884 (9)	−0.1591 (2)	0.96259 (12)	0.0512 (6)
C7	0.39454 (8)	0.0715 (2)	0.86554 (10)	0.0434 (5)
C10	0.38930 (8)	0.2783 (2)	0.76212 (11)	0.0457 (5)
C11	0.41229 (10)	0.4253 (2)	0.78495 (12)	0.0558 (6)
C12	0.37880 (11)	0.5548 (2)	0.74854 (14)	0.0631 (7)
C13	0.32272 (11)	0.5356 (2)	0.68963 (14)	0.0617 (7)
C14	0.30113 (10)	0.3877 (2)	0.66520 (13)	0.0543 (6)
C15	0.33425 (8)	0.2550 (2)	0.70022 (11)	0.0455 (5)
C16	0.31208 (9)	0.0961 (2)	0.67047 (11)	0.0473 (6)
C19	0.23598 (12)	−0.0457 (3)	0.57343 (14)	0.0693 (7)
H2	0.52230	−0.01750	0.83450	0.0560*
H3	0.58690	−0.21840	0.89960	0.0640*
H4	0.54100	−0.37830	1.00370	0.0690*
H5	0.42910	−0.34530	1.04170	0.0700*
H6	0.36390	−0.14480	0.97850	0.0610*
H11	0.45030	0.43780	0.82480	0.0670*
H12	0.39420	0.65490	0.76380	0.0760*
H13	0.29940	0.62280	0.66630	0.0740*
H14	0.26370	0.37600	0.62450	0.0650*
H19A	0.27090	−0.09800	0.54210	0.1040*
H19B	0.19650	−0.02870	0.53330	0.1040*
H19C	0.22340	−0.10930	0.62280	0.1040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O8	0.0495 (7)	0.0643 (9)	0.0571 (8)	0.0116 (5)	0.0150 (6)	0.0101 (6)
O9	0.0422 (7)	0.0571 (7)	0.0485 (7)	0.0056 (5)	0.0048 (5)	0.0130 (5)
O17	0.0709 (9)	0.0517 (8)	0.0717 (9)	0.0106 (6)	−0.0062 (6)	−0.0001 (6)
O18	0.0625 (8)	0.0631 (9)	0.0558 (8)	−0.0080 (6)	−0.0089 (6)	0.0073 (6)
C1	0.0447 (9)	0.0429 (9)	0.0387 (8)	−0.0001 (7)	0.0006 (6)	−0.0036 (6)
C2	0.0464 (9)	0.0495 (10)	0.0441 (9)	0.0008 (7)	0.0032 (7)	0.0002 (7)
C3	0.0509 (10)	0.0502 (10)	0.0594 (10)	0.0083 (7)	0.0008 (8)	−0.0031 (8)
C4	0.0689 (12)	0.0417 (10)	0.0608 (11)	0.0090 (8)	−0.0029 (8)	0.0010 (8)
C5	0.0727 (12)	0.0450 (10)	0.0589 (11)	0.0017 (8)	0.0118 (9)	0.0065 (8)
C6	0.0534 (9)	0.0490 (10)	0.0521 (10)	0.0007 (7)	0.0099 (7)	0.0012 (7)
C7	0.0434 (9)	0.0495 (9)	0.0372 (8)	−0.0008 (7)	0.0015 (6)	0.0002 (6)
C10	0.0445 (9)	0.0522 (10)	0.0410 (9)	0.0046 (7)	0.0088 (7)	0.0090 (7)
C11	0.0576 (10)	0.0602 (11)	0.0495 (10)	−0.0071 (8)	0.0027 (8)	0.0056 (8)
C12	0.0763 (13)	0.0502 (11)	0.0636 (12)	−0.0069 (9)	0.0108 (10)	0.0053 (9)
C13	0.0671 (12)	0.0515 (11)	0.0670 (12)	0.0088 (9)	0.0093 (9)	0.0148 (9)
C14	0.0505 (10)	0.0572 (11)	0.0552 (11)	0.0046 (7)	0.0029 (8)	0.0135 (8)
C15	0.0440 (9)	0.0517 (10)	0.0415 (9)	0.0036 (7)	0.0086 (7)	0.0080 (7)
C16	0.0457 (9)	0.0554 (11)	0.0416 (9)	0.0030 (7)	0.0085 (7)	0.0053 (7)
C19	0.0731 (13)	0.0728 (13)	0.0614 (12)	−0.0175 (10)	−0.0019 (9)	−0.0053 (10)

Geometric parameters (Å, º) top

O8—C7	1.202 (2)	C12—C13	1.375 (3)
O9—C7	1.360 (2)	C13—C14	1.374 (3)
O9—C10	1.401 (2)	C14—C15	1.392 (2)
O17—C16	1.200 (2)	C15—C16	1.485 (2)
O18—C16	1.335 (2)	C2—H2	0.9300
O18—C19	1.436 (3)	C3—H3	0.9300
C1—C2	1.395 (2)	C4—H4	0.9300
C1—C6	1.385 (2)	C5—H5	0.9300
C1—C7	1.470 (2)	C6—H6	0.9300
C2—C3	1.379 (2)	C11—H11	0.9300
C3—C4	1.370 (3)	C12—H12	0.9300
C4—C5	1.379 (3)	C13—H13	0.9300
C5—C6	1.373 (3)	C14—H14	0.9300
C10—C11	1.370 (2)	C19—H19A	0.9600
C10—C15	1.392 (2)	C19—H19B	0.9600
C11—C12	1.381 (3)	C19—H19C	0.9600

C7—O9—C10	116.36 (13)	O18—C16—C15	111.69 (14)
C16—O18—C19	116.14 (15)	C1—C2—H2	120.00
C2—C1—C6	119.84 (15)	C3—C2—H2	120.00
C2—C1—C7	121.64 (14)	C2—C3—H3	120.00
C6—C1—C7	118.45 (14)	C4—C3—H3	120.00
C1—C2—C3	119.38 (15)	C3—C4—H4	120.00
C2—C3—C4	120.22 (16)	C5—C4—H4	120.00
C3—C4—C5	120.69 (17)	C4—C5—H5	120.00
C4—C5—C6	119.79 (17)	C6—C5—H5	120.00
C1—C6—C5	120.07 (16)	C1—C6—H6	120.00
O8—C7—O9	122.63 (15)	C5—C6—H6	120.00
O8—C7—C1	125.17 (15)	C10—C11—H11	120.00
O9—C7—C1	112.17 (13)	C12—C11—H11	120.00
O9—C10—C11	116.52 (15)	C11—C12—H12	120.00
O9—C10—C15	121.67 (15)	C13—C12—H12	120.00
C11—C10—C15	121.75 (16)	C12—C13—H13	120.00
C10—C11—C12	119.66 (17)	C14—C13—H13	120.00
C11—C12—C13	119.92 (17)	C13—C14—H14	119.00
C12—C13—C14	120.04 (17)	C15—C14—H14	119.00
C13—C14—C15	121.30 (18)	O18—C19—H19A	110.00
C10—C15—C14	117.26 (16)	O18—C19—H19B	109.00
C10—C15—C16	122.05 (15)	O18—C19—H19C	109.00
C14—C15—C16	120.68 (15)	H19A—C19—H19B	109.00
O17—C16—O18	122.51 (16)	H19A—C19—H19C	109.00
O17—C16—C15	125.81 (16)	H19B—C19—H19C	110.00

C10—O9—C7—O8	−3.4 (2)	C4—C5—C6—C1	0.5 (3)
C10—O9—C7—C1	178.57 (13)	O9—C10—C11—C12	179.64 (16)
C7—O9—C10—C11	107.89 (17)	C15—C10—C11—C12	2.5 (3)
C7—O9—C10—C15	−74.9 (2)	O9—C10—C15—C14	−180.00 (16)
C19—O18—C16—O17	1.2 (3)	O9—C10—C15—C16	−1.3 (2)
C19—O18—C16—C15	−179.50 (15)	C11—C10—C15—C14	−2.9 (3)
C6—C1—C2—C3	−0.7 (2)	C11—C10—C15—C16	175.71 (16)
C7—C1—C2—C3	176.19 (15)	C10—C11—C12—C13	−0.1 (3)
C2—C1—C6—C5	0.4 (3)	C11—C12—C13—C14	−1.7 (3)
C7—C1—C6—C5	−176.55 (16)	C12—C13—C14—C15	1.2 (3)
C2—C1—C7—O8	−170.75 (16)	C13—C14—C15—C10	1.1 (3)
C2—C1—C7—O9	7.2 (2)	C13—C14—C15—C16	−177.55 (18)
C6—C1—C7—O8	6.1 (3)	C10—C15—C16—O17	3.7 (3)
C6—C1—C7—O9	−175.94 (14)	C10—C15—C16—O18	−175.58 (15)
C1—C2—C3—C4	0.0 (3)	C14—C15—C16—O17	−177.75 (18)
C2—C3—C4—C5	0.9 (3)	C14—C15—C16—O18	3.0 (2)
C3—C4—C5—C6	−1.2 (3)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C10–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19C···Cg2ⁱ	0.96	2.83	3.625 (3)	140

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

Acknowledgements

The authors would like to thank the SJB Institute of Technology, Kengeri, Bangalore, for their support. MM would like to thank the UGC, New Delhi, Government of India, for awarding project F.41–920/2012(SR).

References

Ankersen, M., Peschke, B., Hansen, B. S. & Hansen, T. K. (1997). Bioorg. Med. Chem. Lett. 7, 1293–1298. CrossRef CAS Web of Science Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lin, C. F., Yang, J. S., Chang, C. Y., Kuo, S. C., Lee, M. R. & Huang, L. J. (2005). Bioorg. Med. Chem. 13, 1537–1544. CrossRef PubMed CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Revesz, L., Blum, E., Di Padova, E. T., Buhl, R., Feifel, H., Gram, P., Hiestand, U., Manning, U. & Rucklin, G. (2004). Bioorg. Med. Chem. Lett. 14, 3595–3599. CrossRef PubMed CAS 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

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