Methyl 4-benz­yloxy-2-hy­droxy­benzoate

Palakshamurthy, B.S.; Srinivasa, H.T.; Kumar, V.; Sreenivasa, S.; Devarajegowda, H.C.

doi:10.1107/S1600536812046491

organic compounds

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Volume 68| Part 12| December 2012| Page o3382

doi:10.1107/S1600536812046491

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Methyl 4-benzyloxy-2-hydroxybenzoate

B. S. Palakshamurthy,^a H. T. Srinivasa,^b Vijith Kumar,^c S. Sreenivasa ^d and H. C. Devarajegowda ^a ^*

^aDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India, ^bRaman Research Institute, C. V. Raman Avenue, Sadashivanagar, Bangalore 560 080, Karnataka, India, ^cSoild State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^dDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur 572 103, Karnataka, India
^*Correspondence e-mail: devarajegowda@yahoo.com

(Received 4 November 2012; accepted 10 November 2012; online 17 November 2012)

In the title compound, C₁₅H₁₄O₄, the dihedral angle between the benzene rings is 67.18 (8)°. The C_a—C_m—O—C_a (a = aromatic and m = methylene) torsion angle is 172.6 (3)° and an intramolecular O—H⋯O hydrogen bond generates an S(6) ring. In the crystal, molecules are linked by C—H⋯O hydrogen bonds into zigzag chains propagating in [001] and C—H⋯π interactions also occur.

Related literature

For general background to benzyloxybenzoates, see: Pifferi et al. (1977 ); Ghosh et al. (2008 ). For related structures and further synthetic details, see: Tangdenpaisal et al. (2009 ); Kashi et al. (2010 ).

Experimental

Crystal data

C₁₅H₁₄O₄
M_r = 258.26
Triclinic, $[P \overline 1]$
a = 5.7731 (10) Å
b = 7.9855 (14) Å
c = 14.046 (3) Å
α = 89.490 (6)°
β = 80.111 (5)°
γ = 87.210 (6)°
V = 637.16 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.24 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.977, T_max = 0.983
12770 measured reflections
2231 independent reflections
1679 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.129
S = 1.07
2231 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.82	1.89	2.6133 (17)	146
C19—H19C⋯O2ⁱ	0.96	2.54	3.469 (3)	163
C11—H11A⋯Cg1ⁱⁱ	0.97	2.78	3.5991 (19)	143
C13—H13⋯Cg1ⁱⁱⁱ	0.93	2.95	3.7324 (19)	142
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z; (iii) -x+1, -y, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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, 2012); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046491/hb6982sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046491/hb6982Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046491/hb6982Isup3.cml

checkCIF report

Comment top

Protected benzyloxyphenols and benzyloxybenzoates are an important class of compounds for the syntheses of pharmaceuticals, natural products and polymers (Pifferi et al., 1977). In particular, Methyl 4-(benzyloxy)-2-hydroxybenzoates are essential components of various types of liquid crystals and materials science (Ghosh et al., 2008), also will play an important role in synthesizing rod shaped liquid crystal which exhibits monotropic nematic mesophase (Kashi et al., 2010). Solid supported reagents have been employed for the protection and deprotection process frequently in organic synthesis particularly for title compound (Tangdenpaisal et al., 2009).

The asymmetric unit of the title compound is shown in Fig. 1. The dihedral angle between the least-squares planes of the two benzene rings (C5–C10) and (C12–C17) is 67.18 (8)°. The crystal structure is characterized by intermolecular C19—H19···O2 and intramolecular O2—H2···O3 hydrogen bonding and also features C11—H11A···C_g(1) (C5–C10) and C13—H13···C_g(1) (C5–C10) (Table 1) interactions.

Related literature top

For general background to benzyloxybenzoates, see: Pifferi et al. (1977); Ghosh et al. (2008). For related structures and further synthetic details, see: Tangdenpaisal et al. (2009); Kashi et al. (2010).

Experimental top

A mixture of methyl 2,4-dihydroxybenzoate (1 mmol) and benzylchloride (1.2 mmol) anhydrous potassium carbonate (1.5 mmol) in methyethylketone was refluxed for 12hrs. After completion of reaction, the reaction mixture was extracted into chloroform washed with water dried over anhydrous sodium sulfate. On removal of organic solvent offered crude white solid, which was purified by column chromatography on silica gel (60–120 mesh size) using 5% ethyl acetate in hexane as an eluent. Finaly the title compound was recrystallized from pure ethanol to yield colourless plates.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The packing of molecules.

Methyl 4-benzyloxy-2-hydroxybenzoate top

Crystal data top

C₁₅H₁₄O₄	Z = 2
M_r = 258.26	F(000) = 272
Triclinic, P1	D_x = 1.346 Mg m⁻³
Hall symbol: -P 1	Melting point: 377 K
a = 5.7731 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9855 (14) Å	Cell parameters from 2231 reflections
c = 14.046 (3) Å	θ = 2.6–25.0°
α = 89.490 (6)°	µ = 0.10 mm⁻¹
β = 80.111 (5)°	T = 293 K
γ = 87.210 (6)°	Plate, colourless
V = 637.16 (19) Å³	0.24 × 0.22 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2231 independent reflections
Radiation source: fine-focus sealed tube	1679 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −6→6
T_min = 0.977, T_max = 0.983	k = −9→9
12770 measured reflections	l = −16→16

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.0713P)² + 0.0386P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2231 reflections	Δρ_max = 0.17 e Å⁻³
173 parameters	Δρ_min = −0.15 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: 0.069 (9)

Crystal data top

C₁₅H₁₄O₄	γ = 87.210 (6)°
M_r = 258.26	V = 637.16 (19) Å³
Triclinic, P1	Z = 2
a = 5.7731 (10) Å	Mo Kα radiation
b = 7.9855 (14) Å	µ = 0.10 mm⁻¹
c = 14.046 (3) Å	T = 293 K
α = 89.490 (6)°	0.24 × 0.22 × 0.18 mm
β = 80.111 (5)°

Data collection top

Bruker SMART CCD diffractometer	2231 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	1679 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.983	R_int = 0.053
12770 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.07	Δρ_max = 0.17 e Å⁻³
2231 reflections	Δρ_min = −0.15 e Å⁻³
173 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O1	0.3228 (2)	0.20059 (14)	0.10019 (7)	0.0518 (4)
O2	0.1364 (2)	0.41392 (14)	0.42117 (8)	0.0574 (4)
H2	0.1856	0.4109	0.4726	0.086*
O3	0.4189 (2)	0.31994 (16)	0.54049 (8)	0.0605 (4)
O4	0.7269 (2)	0.14432 (15)	0.48726 (8)	0.0568 (4)
C5	−0.0453 (3)	0.2119 (2)	−0.06754 (12)	0.0516 (5)
H5	−0.1633	0.1609	−0.0253	0.062*
C6	−0.0486 (3)	0.2107 (2)	−0.16596 (12)	0.0579 (5)
H6	−0.1693	0.1600	−0.1893	0.069*
C7	0.1252 (3)	0.2840 (2)	−0.22893 (12)	0.0563 (5)
H7	0.1224	0.2838	−0.2949	0.068*
C8	0.3032 (3)	0.3575 (2)	−0.19423 (12)	0.0578 (5)
H8	0.4226	0.4063	−0.2368	0.069*
C9	0.3056 (3)	0.3594 (2)	−0.09595 (12)	0.0549 (5)
H9	0.4271	0.4097	−0.0730	0.066*
C10	0.1305 (3)	0.2876 (2)	−0.03155 (11)	0.0443 (4)
C11	0.1266 (3)	0.2994 (2)	0.07531 (11)	0.0534 (5)
H11A	0.1366	0.4154	0.0935	0.064*
H11B	−0.0197	0.2585	0.1101	0.064*
C12	0.3616 (3)	0.21291 (19)	0.19290 (10)	0.0406 (4)
C13	0.5597 (3)	0.1217 (2)	0.21350 (11)	0.0477 (4)
H13	0.6521	0.0552	0.1662	0.057*
C14	0.6165 (3)	0.1310 (2)	0.30389 (11)	0.0471 (4)
H14	0.7493	0.0707	0.3171	0.057*
C15	0.4801 (3)	0.22901 (18)	0.37723 (10)	0.0400 (4)
C16	0.2802 (3)	0.31707 (18)	0.35554 (11)	0.0406 (4)
C17	0.2211 (3)	0.30868 (19)	0.26383 (11)	0.0433 (4)
H17	0.0875	0.3674	0.2503	0.052*
C18	0.5349 (3)	0.23696 (19)	0.47507 (11)	0.0444 (4)
C19	0.7991 (4)	0.1564 (2)	0.58079 (13)	0.0637 (5)
H19A	0.9378	0.0855	0.5817	0.096*
H19B	0.6749	0.1213	0.6303	0.096*
H19C	0.8323	0.2704	0.5922	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0604 (7)	0.0624 (7)	0.0333 (6)	0.0172 (6)	−0.0155 (5)	−0.0058 (5)
O2	0.0632 (8)	0.0671 (8)	0.0402 (7)	0.0173 (6)	−0.0085 (6)	−0.0148 (5)
O3	0.0718 (9)	0.0731 (8)	0.0362 (7)	0.0062 (7)	−0.0110 (6)	−0.0084 (6)
O4	0.0628 (8)	0.0695 (8)	0.0423 (7)	0.0048 (6)	−0.0230 (6)	−0.0020 (6)
C5	0.0496 (10)	0.0602 (10)	0.0461 (10)	−0.0027 (8)	−0.0109 (8)	0.0012 (8)
C6	0.0567 (11)	0.0682 (12)	0.0534 (11)	0.0005 (9)	−0.0229 (9)	−0.0096 (9)
C7	0.0670 (12)	0.0686 (11)	0.0345 (9)	0.0143 (9)	−0.0164 (8)	−0.0038 (8)
C8	0.0580 (11)	0.0699 (12)	0.0427 (10)	−0.0022 (9)	−0.0012 (8)	0.0039 (8)
C9	0.0491 (10)	0.0693 (12)	0.0484 (10)	−0.0070 (9)	−0.0130 (8)	−0.0057 (8)
C10	0.0454 (9)	0.0522 (9)	0.0358 (8)	0.0082 (7)	−0.0114 (7)	−0.0019 (7)
C11	0.0523 (10)	0.0702 (11)	0.0378 (9)	0.0136 (8)	−0.0127 (8)	−0.0024 (8)
C12	0.0471 (9)	0.0443 (9)	0.0312 (8)	0.0008 (7)	−0.0095 (7)	−0.0004 (6)
C13	0.0510 (10)	0.0563 (10)	0.0340 (8)	0.0119 (8)	−0.0060 (7)	−0.0059 (7)
C14	0.0457 (9)	0.0555 (10)	0.0401 (9)	0.0090 (8)	−0.0102 (7)	0.0008 (7)
C15	0.0446 (9)	0.0425 (8)	0.0333 (8)	−0.0026 (7)	−0.0077 (7)	0.0009 (6)
C16	0.0464 (9)	0.0393 (8)	0.0346 (8)	0.0000 (7)	−0.0035 (7)	−0.0026 (6)
C17	0.0452 (9)	0.0459 (9)	0.0396 (9)	0.0057 (7)	−0.0115 (7)	−0.0001 (7)
C18	0.0507 (10)	0.0461 (9)	0.0377 (9)	−0.0071 (8)	−0.0094 (7)	0.0026 (7)
C19	0.0778 (13)	0.0748 (12)	0.0459 (10)	−0.0062 (10)	−0.0311 (9)	0.0036 (9)

Geometric parameters (Å, º) top

O1—C12	1.3638 (17)	C9—H9	0.9300
O1—C11	1.4393 (19)	C10—C11	1.501 (2)
O2—C16	1.3509 (18)	C11—H11A	0.9700
O2—H2	0.8200	C11—H11B	0.9700
O3—C18	1.2198 (19)	C12—C17	1.382 (2)
O4—C18	1.337 (2)	C12—C13	1.397 (2)
O4—C19	1.4502 (19)	C13—C14	1.368 (2)
C5—C10	1.376 (2)	C13—H13	0.9300
C5—C6	1.386 (2)	C14—C15	1.403 (2)
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.369 (3)	C15—C16	1.399 (2)
C6—H6	0.9300	C15—C18	1.465 (2)
C7—C8	1.369 (3)	C16—C17	1.391 (2)
C7—H7	0.9300	C17—H17	0.9300
C8—C9	1.383 (2)	C19—H19A	0.9600
C8—H8	0.9300	C19—H19B	0.9600
C9—C10	1.379 (2)	C19—H19C	0.9600

C12—O1—C11	116.82 (12)	O1—C12—C17	124.30 (14)
C16—O2—H2	109.5	O1—C12—C13	115.41 (14)
C18—O4—C19	116.31 (14)	C17—C12—C13	120.29 (14)
C10—C5—C6	120.76 (17)	C14—C13—C12	119.41 (15)
C10—C5—H5	119.6	C14—C13—H13	120.3
C6—C5—H5	119.6	C12—C13—H13	120.3
C7—C6—C5	120.18 (16)	C13—C14—C15	121.85 (15)
C7—C6—H6	119.9	C13—C14—H14	119.1
C5—C6—H6	119.9	C15—C14—H14	119.1
C8—C7—C6	119.67 (16)	C16—C15—C14	117.79 (14)
C8—C7—H7	120.2	C16—C15—C18	119.60 (14)
C6—C7—H7	120.2	C14—C15—C18	122.57 (14)
C7—C8—C9	120.09 (17)	O2—C16—C17	116.75 (14)
C7—C8—H8	120.0	O2—C16—C15	122.45 (14)
C9—C8—H8	120.0	C17—C16—C15	120.81 (14)
C10—C9—C8	120.92 (16)	C12—C17—C16	119.83 (14)
C10—C9—H9	119.5	C12—C17—H17	120.1
C8—C9—H9	119.5	C16—C17—H17	120.1
C5—C10—C9	118.37 (15)	O3—C18—O4	122.01 (14)
C5—C10—C11	121.05 (16)	O3—C18—C15	124.12 (15)
C9—C10—C11	120.52 (15)	O4—C18—C15	113.87 (14)
O1—C11—C10	109.23 (13)	O4—C19—H19A	109.5
O1—C11—H11A	109.8	O4—C19—H19B	109.5
C10—C11—H11A	109.8	H19A—C19—H19B	109.5
O1—C11—H11B	109.8	O4—C19—H19C	109.5
C10—C11—H11B	109.8	H19A—C19—H19C	109.5
H11A—C11—H11B	108.3	H19B—C19—H19C	109.5

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	1.89	2.6133 (17)	146
C19—H19C···O2ⁱ	0.96	2.54	3.469 (3)	163
C11—H11A···Cg1ⁱⁱ	0.97	2.78	3.5991 (19)	143
C13—H13···Cg1ⁱⁱⁱ	0.93	2.95	3.7324 (19)	142

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z; (iii) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄O₄
M_r	258.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.7731 (10), 7.9855 (14), 14.046 (3)
α, β, γ (°)	89.490 (6), 80.111 (5), 87.210 (6)
V (Å³)	637.16 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.24 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.977, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	12770, 2231, 1679
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.129, 1.07
No. of reflections	2231
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	1.89	2.6133 (17)	146
C19—H19C···O2ⁱ	0.96	2.54	3.469 (3)	163
C11—H11A···Cg1ⁱⁱ	0.97	2.78	3.5991 (19)	143
C13—H13···Cg1ⁱⁱⁱ	0.93	2.95	3.7324 (19)	142

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z; (iii) −x+1, −y, −z.

Acknowledgements

The authors thank to Professor T. N. Guru Row, Soild State and Structural Chemistry Unit, Indian Institute of Science, Bangalore and G. B. Sadananda, Department of Studies and Research in Physics, U.C.S. Tumkur University, Tumkur, for their help and suggestions.

References

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