Methyl 2-(benzo­yloxy)benzoate

Naveen, P.; Naveen, S.; Zabiulla; Benaka Prasad, S.B.; Lokanath, N.K.; Khanum, S.A.; Warad, I.

doi:10.1107/S2414314616019349

organic compounds

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ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161934

https://doi.org/10.1107/S2414314616019349

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Methyl 2-(benzoyloxy)benzoate

P. Naveen,^a S. Naveen,^b Zabiulla,^a S. B. Benaka Prasad,^c N. K. Lokanath,^d Shaukath Ara Khanum ^a ^* and Ismail Warad ^e ^*

^aDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, ^bInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^cDepartment of Chemistry, School of Engineering and Technology, Jain University, Bengaluru 562 112, India, ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, and ^eDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: shaukathara@yahoo.co.in, khalil.i@najah.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 25 November 2016; accepted 3 December 2016; online 9 December 2016)

In the title compound, C₁₅H₁₂O₄, the arene rings are inclined at an angle of 65.97 (6)°. The pendant methyl ester substituent has an extended conformation. In the crystal, molecules are linked by C—H⋯π interactions, forming chains propagating along the b-axis direction. The chains are linked via offset π–π interactions [intercentroid distance = 3.640 (1) Å], forming sheets parallel to (10-1).

Keywords: crystal structure; benzoyloxybenzoate; C-H⋯π interactions; offset π-π interactions.

CCDC reference: 1485304

Structure description

Esters are a class of organic compounds which are of synthetic interest. Esters of salicylic acid such as acetyl salicylic acid (phenolic ester), phenyl salicylate and methyl salicylate (carboxylic esters) are widely used as drugs (Khanum et al., 2005 ). Methyl salicylate is a volatile organic compound which is used for the post-harvest treatment of fruits to protect them from chilling injury by protecting the cell wall of the lipid from oxidative affects. It is also used as an anaesthetic in aquaculture. The non-toxic effect of this ester has extended its utility as a flavoring agent in food and commercial products (Ozaki et al., 2015 ). The vast significance of such esters has enhanced the interest in exploring their structure–activity relationships and to search for esters as biological lead compounds. With these observations in mind, and as a part of our ongoing research on such molecules (Mohammed et al., 2016 ), we report here the synthesis and crystal structure of the title ester derivative.

The molecular structure of the title compound is shown in Fig. 1. The molecule is non-planar, the arene rings (C1–C6 and C8–C13) being inclined at a dihedral angle of 65.97 (6)°. The pendant methyl ester chain has an extended conformation, as indicated by the C15—O4—C14—C9 torsion angle of 179.46 (11)°, and lies in the plane of the C18–C13 benzene ring, subtending a dihedral angle of 3.97 (1)°.

Figure 1
The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids for the non-H atoms are drawn at the 50% probability level.

In the crystal, molecules are linked by C—H⋯π interactions, forming chains propagating along the b-axis direction (Table 1 and Fig. 2). The chains are linked via offset π–π interactions [Cg1⋯Cg1ⁱⁱ = 3.640 (1) Å; Cg1 is the centroid of the C1–C6 ring; interplanar distance = 3.403 (1) Å; slippage = 1.293 Å; symmetry code: (ii) −x, −y + 1, −z], forming sheets parallel to (10 $[\overline{1}]$ ); see Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯Cg2ⁱ	0.96	2.77	3.6021 (17)	137
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
A view along the b axis of the crystal packing of the title compound. The C—H⋯π interactions are illustrated as dashed lines (see Table 1

), and for clarity, only H atom H15A (grey ball) has been included.

Synthesis and crystallization

To a stirred solution of methyl 2-hydroxybenzoate (20 mmol) in dry dichloromethane (25 ml), triethylamine (42 mmol) was added at 0°C and stirred for 30 minutes. Benzoyl chloride (28 mmol) was then added dropwise and the resulting mixture stirred at room temperature. After the completion of the reaction, which was monitored by TLC, the organic layer was washed with 5% hydrochloric acid (3 × 15 ml), followed by distilled water (15 ml) and brine solution (10 ml. The solvent was dried over anhydrous sodium sulfate and evaporated under reduced pressure to obtain the title compound. The product obtained was further purified by recrystallization from ethanol. Yield: 87%, m.p 105–107°C.

IR (KBr, cm⁻¹): ν 3580–3660 (OH), 1670 (C=O), 1323 (O—CH₃). ¹H NMR (400 MHz, DMSO-d₆): δ 2.8 (s, 3H, CH₃), 7.1–8.1 (m, 4H, Ar—H), 11.5 (s, 1H, OH). LCMS (M⁺): (152). Analysis calculated for: C₈H₈O₃: C, 63.15; H, 5.30; found: C, 63.01; H, 5.26%.

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)	19.4344 (7), 8.5216 (3), 14.6195 (5)
β (°)	93.075 (2)
V (Å³)	2417.68 (15)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	0.85
Crystal size (mm)	0.29 × 0.27 × 0.25

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.790, 0.815
No. of measured, independent and observed [I > 2σ(I)] reflections	9409, 1986, 1830
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.584

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.05
No. of reflections	1986
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1485304

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616019349/sj4074sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019349/sj4074Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616019349/sj4074Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).

Methyl 2-(benzoyloxy)benzoate top

Crystal data top

C₁₅H₁₂O₄	F(000) = 1072
M_r = 256.25	D_x = 1.408 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 1830 reflections
a = 19.4344 (7) Å	θ = 4.6–64.3°
b = 8.5216 (3) Å	µ = 0.85 mm⁻¹
c = 14.6195 (5) Å	T = 296 K
β = 93.075 (2)°	Rectangle, white
V = 2417.68 (15) Å³	0.29 × 0.27 × 0.25 mm
Z = 8

Data collection top

Bruker X8 Proteum diffractometer	1986 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1830 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.036
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.3°, θ_min = 4.6°
φ and ω scans	h = −21→22
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −9→9
T_min = 0.790, T_max = 0.815	l = −17→16
9409 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0508P)² + 1.6772P] where P = (F_o² + 2F_c²)/3
1986 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

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
O1	0.16120 (5)	0.39065 (11)	0.10809 (6)	0.0220 (3)
O2	0.07331 (4)	0.34373 (11)	0.19949 (6)	0.0193 (3)
O3	0.16433 (5)	0.52333 (11)	0.30331 (7)	0.0247 (3)
O4	0.24143 (5)	0.39439 (11)	0.39470 (6)	0.0237 (3)
C1	0.06319 (7)	0.55993 (15)	0.09895 (8)	0.0172 (4)
C2	−0.00477 (7)	0.58022 (16)	0.12255 (9)	0.0185 (4)
C3	−0.04390 (7)	0.70056 (16)	0.08286 (9)	0.0204 (4)
C4	−0.01551 (7)	0.80070 (16)	0.02034 (9)	0.0221 (4)
C5	0.05259 (7)	0.78183 (16)	−0.00239 (9)	0.0226 (4)
C6	0.09183 (7)	0.66187 (16)	0.03662 (9)	0.0201 (4)
C7	0.10575 (7)	0.42714 (15)	0.13432 (8)	0.0174 (4)
C8	0.11023 (7)	0.21766 (16)	0.23893 (9)	0.0184 (4)
C9	0.16657 (7)	0.24064 (16)	0.30100 (9)	0.0185 (4)
C10	0.20047 (7)	0.10705 (16)	0.33598 (9)	0.0217 (4)
C11	0.17828 (8)	−0.04234 (17)	0.31165 (10)	0.0243 (4)
C12	0.12089 (7)	−0.06161 (17)	0.25246 (9)	0.0245 (4)
C13	0.08685 (7)	0.06899 (17)	0.21591 (9)	0.0217 (4)
C14	0.18925 (7)	0.40106 (16)	0.33073 (9)	0.0184 (4)
C15	0.26715 (8)	0.54508 (17)	0.42693 (10)	0.0265 (4)
H2	−0.02370	0.51340	0.16470	0.0220*
H3	−0.08930	0.71420	0.09820	0.0240*
H4	−0.04210	0.88080	−0.00650	0.0260*
H5	0.07170	0.84990	−0.04380	0.0270*
H6	0.13730	0.64890	0.02140	0.0240*
H10	0.23870	0.11880	0.37640	0.0260*
H11	0.20190	−0.12970	0.33510	0.0290*
H12	0.10520	−0.16180	0.23720	0.0290*
H13	0.04840	0.05650	0.17600	0.0260*
H15A	0.27720	0.60950	0.37550	0.0400*
H15B	0.30840	0.53000	0.46510	0.0400*
H15C	0.23290	0.59570	0.46160	0.0400*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0188 (5)	0.0254 (5)	0.0221 (5)	0.0031 (4)	0.0042 (4)	0.0022 (4)
O2	0.0170 (5)	0.0214 (5)	0.0195 (5)	0.0020 (4)	0.0019 (4)	0.0052 (4)
O3	0.0258 (5)	0.0213 (5)	0.0268 (5)	0.0038 (4)	−0.0006 (4)	−0.0003 (4)
O4	0.0239 (5)	0.0244 (5)	0.0224 (5)	−0.0029 (4)	−0.0035 (4)	0.0024 (4)
C1	0.0198 (7)	0.0171 (6)	0.0145 (6)	−0.0012 (5)	−0.0006 (5)	−0.0031 (5)
C2	0.0199 (7)	0.0193 (7)	0.0162 (6)	−0.0015 (5)	0.0008 (5)	−0.0012 (5)
C3	0.0189 (7)	0.0207 (7)	0.0215 (7)	0.0017 (5)	0.0001 (5)	−0.0037 (5)
C4	0.0280 (8)	0.0165 (7)	0.0214 (7)	0.0032 (6)	−0.0009 (5)	−0.0015 (5)
C5	0.0309 (8)	0.0172 (7)	0.0200 (7)	−0.0013 (6)	0.0037 (6)	0.0016 (5)
C6	0.0203 (7)	0.0204 (7)	0.0198 (7)	−0.0010 (5)	0.0034 (5)	−0.0027 (5)
C7	0.0182 (7)	0.0202 (7)	0.0136 (6)	−0.0030 (5)	−0.0004 (5)	−0.0008 (5)
C8	0.0180 (7)	0.0211 (7)	0.0166 (6)	0.0032 (5)	0.0050 (5)	0.0039 (5)
C9	0.0186 (7)	0.0215 (7)	0.0159 (6)	0.0013 (5)	0.0054 (5)	0.0030 (5)
C10	0.0197 (7)	0.0258 (7)	0.0197 (7)	0.0023 (6)	0.0024 (5)	0.0039 (5)
C11	0.0267 (8)	0.0211 (7)	0.0255 (7)	0.0037 (6)	0.0051 (6)	0.0058 (6)
C12	0.0297 (8)	0.0203 (7)	0.0239 (7)	−0.0042 (6)	0.0060 (6)	0.0006 (6)
C13	0.0216 (7)	0.0253 (7)	0.0184 (7)	−0.0022 (6)	0.0026 (5)	0.0021 (5)
C14	0.0163 (7)	0.0235 (7)	0.0157 (6)	0.0004 (6)	0.0047 (5)	0.0017 (5)
C15	0.0279 (8)	0.0272 (8)	0.0242 (7)	−0.0063 (6)	0.0001 (6)	−0.0021 (6)

Geometric parameters (Å, º) top

O1—C7	1.2039 (16)	C9—C14	1.4938 (19)
O2—C7	1.3693 (15)	C10—C11	1.384 (2)
O2—C8	1.3990 (16)	C11—C12	1.384 (2)
O3—C14	1.2083 (17)	C12—C13	1.387 (2)
O4—C14	1.3433 (16)	C2—H2	0.9300
O4—C15	1.4476 (17)	C3—H3	0.9300
C1—C2	1.3936 (19)	C4—H4	0.9300
C1—C6	1.3961 (18)	C5—H5	0.9300
C1—C7	1.4786 (18)	C6—H6	0.9300
C2—C3	1.3854 (19)	C10—H10	0.9300
C3—C4	1.3864 (19)	C11—H11	0.9300
C4—C5	1.3911 (19)	C12—H12	0.9300
C5—C6	1.3803 (19)	C13—H13	0.9300
C8—C9	1.3979 (19)	C15—H15A	0.9600
C8—C13	1.381 (2)	C15—H15B	0.9600
C9—C10	1.3984 (19)	C15—H15C	0.9600

C7—O2—C8	116.12 (10)	O4—C14—C9	111.33 (11)
C14—O4—C15	115.07 (11)	C1—C2—H2	120.00
C2—C1—C6	120.05 (12)	C3—C2—H2	120.00
C2—C1—C7	121.88 (12)	C2—C3—H3	120.00
C6—C1—C7	117.99 (12)	C4—C3—H3	120.00
C1—C2—C3	119.63 (12)	C3—C4—H4	120.00
C2—C3—C4	120.19 (13)	C5—C4—H4	120.00
C3—C4—C5	120.25 (13)	C4—C5—H5	120.00
C4—C5—C6	119.91 (12)	C6—C5—H5	120.00
C1—C6—C5	119.98 (12)	C1—C6—H6	120.00
O1—C7—O2	122.75 (11)	C5—C6—H6	120.00
O1—C7—C1	125.44 (12)	C9—C10—H10	119.00
O2—C7—C1	111.77 (11)	C11—C10—H10	119.00
O2—C8—C9	121.77 (12)	C10—C11—H11	120.00
O2—C8—C13	116.69 (12)	C12—C11—H11	120.00
C9—C8—C13	121.50 (13)	C11—C12—H12	120.00
C8—C9—C10	117.43 (12)	C13—C12—H12	120.00
C8—C9—C14	121.72 (12)	C8—C13—H13	120.00
C10—C9—C14	120.85 (12)	C12—C13—H13	120.00
C9—C10—C11	121.37 (13)	O4—C15—H15A	109.00
C10—C11—C12	119.94 (13)	O4—C15—H15B	109.00
C11—C12—C13	119.82 (13)	O4—C15—H15C	109.00
C8—C13—C12	119.88 (13)	H15A—C15—H15B	109.00
O3—C14—O4	122.79 (12)	H15A—C15—H15C	109.00
O3—C14—C9	125.86 (12)	H15B—C15—H15C	110.00

C8—O2—C7—O1	3.93 (17)	C4—C5—C6—C1	−0.2 (2)
C8—O2—C7—C1	−178.47 (10)	O2—C8—C9—C10	−179.43 (12)
C7—O2—C8—C9	72.72 (16)	O2—C8—C9—C14	1.8 (2)
C7—O2—C8—C13	−109.40 (13)	C13—C8—C9—C10	2.8 (2)
C15—O4—C14—O3	−1.61 (18)	C13—C8—C9—C14	−175.99 (13)
C15—O4—C14—C9	179.46 (11)	O2—C8—C13—C12	−179.96 (13)
C6—C1—C2—C3	0.90 (19)	C9—C8—C13—C12	−2.1 (2)
C7—C1—C2—C3	−175.76 (12)	C8—C9—C10—C11	−1.3 (2)
C2—C1—C6—C5	−0.68 (19)	C14—C9—C10—C11	177.47 (13)
C7—C1—C6—C5	176.11 (12)	C8—C9—C14—O3	−2.8 (2)
C2—C1—C7—O1	169.87 (13)	C8—C9—C14—O4	176.09 (12)
C2—C1—C7—O2	−7.66 (17)	C10—C9—C14—O3	178.45 (13)
C6—C1—C7—O1	−6.86 (19)	C10—C9—C14—O4	−2.66 (18)
C6—C1—C7—O2	175.62 (11)	C9—C10—C11—C12	−0.9 (2)
C1—C2—C3—C4	−0.3 (2)	C10—C11—C12—C13	1.6 (2)
C2—C3—C4—C5	−0.5 (2)	C11—C12—C13—C8	−0.2 (2)
C3—C4—C5—C6	0.8 (2)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···Cg2ⁱ	0.96	2.77	3.6021 (17)	137

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

Acknowledgements

The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility. PN gratefully acknowledges the financial support of the UGC MRP(S)-0551–13–14/KAMY013/UGC-SWRO. Zabiulla gratefully acknowledges the financial support provided by the Department of Science and Technology, New Delhi, under the INSPIRE-Fellowship scheme. SAK thankfully acknowledges the financial support provided by VGST, Bangalore, under the CISEE Programme.

References

Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Methyl 2-(benzo­yl­oxy)benzoate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

Methyl 2-(benzoyloxy)benzoate