Methyl 2-[(2-methyl­phen­oxy)meth­yl]benzoate

Isloor, A.M.; Sankappa Rai, U.; Shetty, P.; Gerber, T.; Hosten, E.; Betz, R.

doi:10.1107/S1600536812005995

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o728

doi:10.1107/S1600536812005995

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Methyl 2-[(2-methylphenoxy)methyl]benzoate

Arun M. Isloor,^a U. Sankappa Rai,^b Prakash Shetty,^c Thomas Gerber,^d Eric Hosten ^d and Richard Betz ^d ^*

^aOrganic Electronics Division, Department of Chemistry, National Institute of Technology - Karnataka, Surathkal, Mangalore 575 025, India, ^bDepartment of Chemistry, Manipal Institute of Technology, Manipal University, Manipal, India, ^cDepartment of Printing Engineering, Manipal Institute of Technology, Manipal University, Manipal, India, and ^dNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth, 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 7 February 2012; accepted 10 February 2012; online 17 February 2012)

In the title methylbenzoate compound, C₁₆H₁₆O₃, the molecule is essentially planar (r.m.s. of all fitted non-H atoms = 0.0370 Å); the dihedral angle between the phenyl rings is 2.30 (7)°. Apart from a C—H⋯π interaction, no marked intermolecular contacts are obvious.

Related literature

For the pharmaceutical background to methylbenzoate derivatives, see: Orlek et al. (1991 ); Ankersen et al. (1997 ); Andersen et al. (1996 ).

Experimental

Crystal data

C₁₆H₁₆O₃
M_r = 256.29
Monoclinic, C 2/c
a = 31.6873 (13) Å
b = 6.5389 (2) Å
c = 13.8746 (6) Å
β = 111.716 (2)°
V = 2670.79 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.51 × 0.12 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.956, T_max = 0.996
12273 measured reflections
3320 independent reflections
2295 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.108
S = 1.03
3320 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C25—H25⋯Cg1ⁱ	0.95	2.72	3.5461 (15)	146
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{3\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005995/tk5056sup1.cif

Supporting information file. DOI: 10.1107/S1600536812005995/tk5056Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005995/tk5056Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812005995/tk5056Isup4.cml

checkCIF report

Comment top

Methyl 3-[(2-methylphenoxy)methyl]benzoate derivatives are extensively studied in medicinal chemistry as they are important intermediates for many pharmaceutical products. Methyl 3-[(2-methylphenoxy)methyl]benzoate derivatives are mainly used as antifungal (Orlek et al., 1991) and antimicrobial (Ankersen et al., 1997), diuretic, anticancer and antianaphylactic (Andersen et al., 1996) agents. In view of the biological importance of the benzoate derivatives, we hereby report the crystal structure of the title compound.

The central part of the molecule, which is comprised of two connected phenyl rings, is essentially planar (r.m.s. of all fitted non-H atoms = 0.0370 Å). The least-squares planes defined by the respective C atoms of the two phenyl groups enclose an angle of 2.30 (7)° (Fig. 1).

In the crystal, a C—H···π interaction is apparent whose metrical details are summarized in Table 1. No other interatomic contacts less than the sum of van der Waals radii are observed. A view of the crystal packing for the title compound is shown in Fig. 2.

Related literature top

For the pharmaceutical background to methylbenzoate derivatives, see: Orlek et al. (1991); Ankersen et al. (1997); Andersen et al. (1996).

Experimental top

To a stirred solution of 2-methyphenol (1 g, 0.009 mol) in acetonitrile (20 ml) was added potassium carbonate (2.5 g, 0.018 mol) and methyl 3-(bromomethyl) benzoate (2.1 g, 0.009 mol) drop-wise. The reaction mixture was heated to reflux for 2 h. Mass analysis of the crude reaction mixture confirmed the completion of the reaction. Afterwards, the reaction mixture was concentrated and the residue was purified by column chromatography to get title compound, which was recrystallized using acetone to get single crystals. Yield: 88% (m.p. 412–414 K).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
	Fig. 2. Molecular packing of the title compound, viewed along [010] (anisotropic displacement ellipsoids drawn at 50% probability level).

Methyl 2-[(2-methylphenoxy)methyl]benzoate top

Crystal data top

C₁₆H₁₆O₃	F(000) = 1088
M_r = 256.29	D_x = 1.275 Mg m⁻³
Monoclinic, C2/c	Melting point = 412–414 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 31.6873 (13) Å	Cell parameters from 4067 reflections
b = 6.5389 (2) Å	θ = 2.8–28.1°
c = 13.8746 (6) Å	µ = 0.09 mm⁻¹
β = 111.716 (2)°	T = 200 K
V = 2670.79 (18) Å³	Platelet, colourless
Z = 8	0.51 × 0.12 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	3320 independent reflections
Radiation source: fine-focus sealed tube	2295 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −39→42
T_min = 0.956, T_max = 0.996	k = −8→7
12273 measured reflections	l = −18→18

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0475P)² + 1.0316P] where P = (F_o² + 2F_c²)/3
3320 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₆H₁₆O₃	V = 2670.79 (18) Å³
M_r = 256.29	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 31.6873 (13) Å	µ = 0.09 mm⁻¹
b = 6.5389 (2) Å	T = 200 K
c = 13.8746 (6) Å	0.51 × 0.12 × 0.05 mm
β = 111.716 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3320 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	2295 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.996	R_int = 0.022
12273 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
3320 reflections	Δρ_min = −0.19 e Å⁻³
174 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.10397 (3)	0.81204 (14)	0.13302 (7)	0.0379 (2)
O2	0.18815 (3)	0.10731 (15)	0.06203 (7)	0.0413 (3)
O3	0.20550 (3)	0.42927 (15)	0.11449 (9)	0.0479 (3)
C1	0.04466 (5)	1.1075 (2)	0.14318 (12)	0.0452 (4)
H1A	0.0273	1.1996	0.1703	0.068*
H1B	0.0330	0.9679	0.1401	0.068*
H1C	0.0416	1.1517	0.0734	0.068*
C2	0.13423 (4)	0.6661 (2)	0.11746 (10)	0.0317 (3)
H2A	0.1505	0.5918	0.1830	0.038*
H2B	0.1570	0.7366	0.0962	0.038*
C3	0.17758 (4)	0.3033 (2)	0.06884 (9)	0.0305 (3)
C4	0.23538 (5)	0.0547 (3)	0.11380 (13)	0.0519 (4)
H4A	0.2394	−0.0923	0.1064	0.078*
H4B	0.2451	0.0893	0.1876	0.078*
H4C	0.2537	0.1312	0.0826	0.078*
C11	0.12341 (4)	0.96097 (19)	0.20588 (10)	0.0311 (3)
C12	0.09376 (5)	1.1127 (2)	0.21316 (10)	0.0331 (3)
C13	0.11164 (5)	1.2669 (2)	0.28589 (11)	0.0410 (3)
H13	0.0921	1.3722	0.2919	0.049*
C14	0.15703 (5)	1.2712 (2)	0.34969 (12)	0.0443 (4)
H14	0.1684	1.3778	0.3991	0.053*
C15	0.18555 (5)	1.1203 (2)	0.34109 (11)	0.0411 (3)
H15	0.2168	1.1230	0.3845	0.049*
C16	0.16901 (5)	0.9642 (2)	0.26944 (10)	0.0359 (3)
H16	0.1888	0.8597	0.2639	0.043*
C21	0.10746 (4)	0.51750 (19)	0.03453 (9)	0.0282 (3)
C22	0.06136 (4)	0.5484 (2)	−0.02189 (10)	0.0339 (3)
H22	0.0466	0.6644	−0.0074	0.041*
C23	0.03669 (5)	0.4130 (2)	−0.09866 (10)	0.0385 (3)
H23	0.0054	0.4375	−0.1368	0.046*
C24	0.05731 (5)	0.2426 (2)	−0.12015 (10)	0.0390 (3)
H24	0.0403	0.1505	−0.1733	0.047*
C25	0.10285 (4)	0.2062 (2)	−0.06413 (10)	0.0337 (3)
H25	0.1170	0.0877	−0.0781	0.040*
C26	0.12814 (4)	0.34252 (19)	0.01282 (9)	0.0277 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0334 (5)	0.0333 (5)	0.0417 (5)	0.0048 (4)	0.0079 (4)	−0.0104 (4)
O2	0.0333 (5)	0.0335 (5)	0.0489 (6)	0.0078 (4)	0.0056 (4)	−0.0051 (4)
O3	0.0302 (5)	0.0371 (6)	0.0677 (7)	−0.0025 (4)	0.0078 (5)	−0.0114 (5)
C1	0.0420 (8)	0.0468 (9)	0.0476 (9)	0.0138 (7)	0.0173 (7)	0.0052 (7)
C2	0.0307 (7)	0.0269 (7)	0.0362 (7)	0.0029 (5)	0.0110 (5)	−0.0033 (5)
C3	0.0329 (7)	0.0299 (7)	0.0300 (6)	0.0020 (6)	0.0130 (5)	0.0000 (5)
C4	0.0368 (8)	0.0470 (9)	0.0628 (10)	0.0142 (7)	0.0077 (7)	−0.0014 (8)
C11	0.0378 (7)	0.0256 (6)	0.0311 (7)	−0.0001 (5)	0.0143 (6)	−0.0008 (5)
C12	0.0406 (7)	0.0290 (7)	0.0353 (7)	0.0037 (6)	0.0205 (6)	0.0058 (5)
C13	0.0552 (9)	0.0293 (7)	0.0485 (8)	0.0044 (7)	0.0308 (7)	−0.0012 (6)
C14	0.0562 (9)	0.0367 (8)	0.0461 (8)	−0.0092 (7)	0.0259 (7)	−0.0124 (6)
C15	0.0407 (8)	0.0407 (8)	0.0426 (8)	−0.0100 (7)	0.0164 (6)	−0.0080 (6)
C16	0.0365 (7)	0.0319 (7)	0.0401 (7)	0.0007 (6)	0.0149 (6)	−0.0037 (6)
C21	0.0310 (6)	0.0264 (6)	0.0275 (6)	−0.0008 (5)	0.0111 (5)	0.0021 (5)
C22	0.0329 (7)	0.0340 (7)	0.0348 (7)	0.0043 (6)	0.0127 (6)	−0.0004 (6)
C23	0.0277 (7)	0.0465 (9)	0.0370 (7)	0.0007 (6)	0.0070 (6)	−0.0014 (6)
C24	0.0355 (7)	0.0434 (8)	0.0345 (7)	−0.0056 (6)	0.0088 (6)	−0.0103 (6)
C25	0.0354 (7)	0.0325 (7)	0.0341 (7)	−0.0006 (6)	0.0140 (6)	−0.0050 (6)
C26	0.0293 (6)	0.0275 (6)	0.0273 (6)	−0.0014 (5)	0.0113 (5)	0.0010 (5)

Geometric parameters (Å, º) top

O1—C11	1.3744 (15)	C12—C13	1.3901 (19)
O1—C2	1.4251 (15)	C13—C14	1.382 (2)
O2—C3	1.3367 (16)	C13—H13	0.9500
O2—C4	1.4419 (16)	C14—C15	1.373 (2)
O3—C3	1.2034 (15)	C14—H14	0.9500
C1—C12	1.4988 (19)	C15—C16	1.3856 (19)
C1—H1A	0.9800	C15—H15	0.9500
C1—H1B	0.9800	C16—H16	0.9500
C1—H1C	0.9800	C21—C22	1.3933 (17)
C2—C21	1.5049 (17)	C21—C26	1.4054 (18)
C2—H2A	0.9900	C22—C23	1.3836 (19)
C2—H2B	0.9900	C22—H22	0.9500
C3—C26	1.4910 (17)	C23—C24	1.379 (2)
C4—H4A	0.9800	C23—H23	0.9500
C4—H4B	0.9800	C24—C25	1.3832 (19)
C4—H4C	0.9800	C24—H24	0.9500
C11—C16	1.3869 (18)	C25—C26	1.3940 (17)
C11—C12	1.3954 (18)	C25—H25	0.9500

C11—O1—C2	116.26 (10)	C14—C13—H13	119.1
C3—O2—C4	115.77 (11)	C12—C13—H13	119.1
C12—C1—H1A	109.5	C15—C14—C13	119.48 (13)
C12—C1—H1B	109.5	C15—C14—H14	120.3
H1A—C1—H1B	109.5	C13—C14—H14	120.3
C12—C1—H1C	109.5	C14—C15—C16	120.37 (14)
H1A—C1—H1C	109.5	C14—C15—H15	119.8
H1B—C1—H1C	109.5	C16—C15—H15	119.8
O1—C2—C21	109.13 (10)	C15—C16—C11	119.72 (13)
O1—C2—H2A	109.9	C15—C16—H16	120.1
C21—C2—H2A	109.9	C11—C16—H16	120.1
O1—C2—H2B	109.9	C22—C21—C26	118.21 (11)
C21—C2—H2B	109.9	C22—C21—C2	120.87 (12)
H2A—C2—H2B	108.3	C26—C21—C2	120.92 (11)
O3—C3—O2	122.60 (12)	C23—C22—C21	121.06 (13)
O3—C3—C26	125.65 (12)	C23—C22—H22	119.5
O2—C3—C26	111.75 (11)	C21—C22—H22	119.5
O2—C4—H4A	109.5	C24—C23—C22	120.37 (12)
O2—C4—H4B	109.5	C24—C23—H23	119.8
H4A—C4—H4B	109.5	C22—C23—H23	119.8
O2—C4—H4C	109.5	C23—C24—C25	119.80 (12)
H4A—C4—H4C	109.5	C23—C24—H24	120.1
H4B—C4—H4C	109.5	C25—C24—H24	120.1
O1—C11—C16	123.80 (12)	C24—C25—C26	120.31 (13)
O1—C11—C12	115.25 (12)	C24—C25—H25	119.8
C16—C11—C12	120.95 (12)	C26—C25—H25	119.8
C13—C12—C11	117.63 (13)	C25—C26—C21	120.22 (11)
C13—C12—C1	122.21 (13)	C25—C26—C3	118.98 (11)
C11—C12—C1	120.15 (12)	C21—C26—C3	120.77 (11)
C14—C13—C12	121.85 (13)

C11—O1—C2—C21	−179.15 (10)	O1—C2—C21—C26	−172.01 (11)
C4—O2—C3—O3	0.5 (2)	C26—C21—C22—C23	−1.23 (19)
C4—O2—C3—C26	179.87 (12)	C2—C21—C22—C23	179.57 (12)
C2—O1—C11—C16	−6.01 (19)	C21—C22—C23—C24	0.7 (2)
C2—O1—C11—C12	174.45 (11)	C22—C23—C24—C25	0.5 (2)
O1—C11—C12—C13	179.82 (11)	C23—C24—C25—C26	−1.0 (2)
C16—C11—C12—C13	0.3 (2)	C24—C25—C26—C21	0.4 (2)
O1—C11—C12—C1	−0.95 (18)	C24—C25—C26—C3	−177.54 (12)
C16—C11—C12—C1	179.49 (13)	C22—C21—C26—C25	0.69 (18)
C11—C12—C13—C14	−0.4 (2)	C2—C21—C26—C25	179.89 (12)
C1—C12—C13—C14	−179.57 (13)	C22—C21—C26—C3	178.60 (11)
C12—C13—C14—C15	0.4 (2)	C2—C21—C26—C3	−2.21 (18)
C13—C14—C15—C16	−0.3 (2)	O3—C3—C26—C25	158.37 (14)
C14—C15—C16—C11	0.2 (2)	O2—C3—C26—C25	−20.99 (16)
O1—C11—C16—C15	−179.72 (12)	O3—C3—C26—C21	−19.6 (2)
C12—C11—C16—C15	−0.2 (2)	O2—C3—C26—C21	161.08 (11)
O1—C2—C21—C22	7.17 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25···Cg1ⁱ	0.95	2.72	3.5461 (15)	146

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆O₃
M_r	256.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	31.6873 (13), 6.5389 (2), 13.8746 (6)
β (°)	111.716 (2)
V (Å³)	2670.79 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.51 × 0.12 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2010)
T_min, T_max	0.956, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	12273, 3320, 2295
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.108, 1.03
No. of reflections	3320
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25···Cg1ⁱ	0.95	2.72	3.5461 (15)	146

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

Acknowledgements

AMI is grateful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India, for a Young Scientist award.

References

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