2-Hy­droxy­ethyl 4-hy­droxy­benzoate

Jeyalaxmi, M.; Jagadeesan, G.; Arulmoli, J.; Singh, D.R.; Aravindhan, S.

doi:10.1107/S1600536810054516

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o442

doi:10.1107/S1600536810054516

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2-Hydroxyethyl 4-hydroxybenzoate

M. Jeyalaxmi,^a G. Jagadeesan,^a J. Arulmoli,^b D. Roop Singh ^b and S. Aravindhan ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bDepartment of Chemistry, Presidency College, Chennai 600 005, India
^*Correspondence e-mail: aravindhanpresidency@gmail.com

(Received 17 December 2010; accepted 28 December 2010; online 22 January 2011)

In the title compound, C₉H₁₀O₄, the dihedral angle between the benzene ring and the –CO₂ unit is 11.93 (8)° and the conformation of the 2-hydroxyethyl side chain is gauche [O—C—C—O = −71.91 (17)°]. In the crystal, molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For background to the properties of esters of 4-hydroxybenzoic acid, see: Kadokawa et al. (2002 ).

Experimental

Crystal data

C₉H₁₀O₄
M_r = 182.17
Triclinic, P 1
a = 4.4235 (10) Å
b = 5.6850 (17) Å
c = 8.7050 (17) Å
α = 80.819 (13)°
β = 79.943 (14)°
γ = 81.804 (14)°
V = 211.30 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.978, T_max = 0.982
3761 measured reflections
1767 independent reflections
1609 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.088
S = 1.06
1767 reflections
126 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4ⁱ	0.86 (3)	1.87 (3)	2.7204 (19)	169 (2)
O4—H4A⋯O2ⁱⁱ	0.75 (3)	2.15 (3)	2.8970 (18)	170 (3)
C9—H9A⋯O2ⁱⁱⁱ	0.97	2.51	3.322 (2)	141
Symmetry codes: (i) x-1, y+1, z-1; (ii) x, y-1, z; (iii) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054516/hb5779sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810054516/hb5779Isup2.hkl

checkCIF report

Comment top

The ORTEP diagram of the title compound, (I), shown in Fig.1 indicates that the aromatic ring is in a plane and the ester group attached to it maintains near planarity with it which is defined by the torsion angles C5—C6—C7—O2 (166.91°), C5—C6—C7—O3 (-12.81°).

Though the C6—C7 is a single bond (1.468 Å) and the possibility of free rotation is high at that connectivity, the planarity exerted by the ester group may be purely because of crystal packing.

The torsion angle O3—C8—C9—O4 is -71.09° which makes the ethyl hydroxy O4 to assume the syn-clinal conformation with respect to the carboxy O3. Such a conformation instead of anti conformation may be due to crystal packing of the molecules which makes them compactly stacked to one another.

The crystal packing (Fig.2) shows the presence of inter-molecular hydrogen bonding. The phenolic oxygen (O1) forms a strong intermolecular hydrogen bond (O1—H1A···O4) with the D···A distance of 2.720 Å and the D—H···A angle of 169°. The ethanolic O4 donates the hydrogen to symmetrically related carbonyl O2 to form intermolecular hydrogen bond (O4—H4A···O2) with the D···A distance of 2.897 Å and the D—H···A angle of 170°. The carbon (C9) atom forms a weak intermolecular hydrogen bond (C9—H9A···O2) with the D···A distance of 3.392 Å and the D—H···A angle is 140.8°. All these three hydrogen bonds are exisiting between a given molecule and three different symmetry related molecules (x - 1, +y + 1, +z - 1 x, +y - 1, +z and x + 1, +y - 1, +z respectively). This multiple hydrogen bonding network makes the well defined crystal packing.

Related literature top

For background to the properties of esters of 4-hydroxybenzoic acid, see: Kadokawa et al. (2002).

Experimental top

An ethanolic solution of 3-methyl-1-phenyl-4-acetylpyrazolin-5-ol (0.432 g, 2 mmol) and 2-aminoethanol (0.122 g, 2mmoL) were taken in a round bottom flask and refluxed for 4 h. The solid product was filtered and washed with cold ethanol. The product obtained was pure by TLC and NMR spectroscopy. However, the product was further purified by re-crystallization from ethanol and dried under vacuum. The compound was crystallized by slow evaporation technique using methanol as solvent at room temperature to yield colourless blocks of (I).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.
	Fig. 2. Crystal packing diagram. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

2-Hydroxyethyl 4-hydroxybenzoate top

Crystal data top

C₉H₁₀O₄	Z = 1
M_r = 182.17	F(000) = 96
Triclinic, P1	D_x = 1.432 Mg m⁻³
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.4235 (10) Å	Cell parameters from 1767 reflections
b = 5.6850 (17) Å	θ = 2.4–28.3°
c = 8.7050 (17) Å	µ = 0.11 mm⁻¹
α = 80.819 (13)°	T = 293 K
β = 79.943 (14)°	Block, colourless
γ = 81.804 (14)°	0.20 × 0.20 × 0.20 mm
V = 211.30 (9) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	1767 independent reflections
Radiation source: fine-focus sealed tube	1609 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −5→5
T_min = 0.978, T_max = 0.982	k = −7→7
3761 measured reflections	l = −11→10

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0532P)² + 0.0112P] where P = (F_o² + 2F_c²)/3
1767 reflections	(Δ/σ)_max < 0.001
126 parameters	Δρ_max = 0.21 e Å⁻³
3 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₉H₁₀O₄	γ = 81.804 (14)°
M_r = 182.17	V = 211.30 (9) Å³
Triclinic, P1	Z = 1
a = 4.4235 (10) Å	Mo Kα radiation
b = 5.6850 (17) Å	µ = 0.11 mm⁻¹
c = 8.7050 (17) Å	T = 293 K
α = 80.819 (13)°	0.20 × 0.20 × 0.20 mm
β = 79.943 (14)°

Data collection top

Bruker SMART APEXII CCD diffractometer	1767 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1609 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.982	R_int = 0.018
3761 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	3 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.21 e Å⁻³
1767 reflections	Δρ_min = −0.14 e Å⁻³
126 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
O1	0.5796 (3)	0.5763 (2)	0.61019 (14)	0.0532 (3)
O2	1.0292 (3)	0.7852 (2)	1.22266 (15)	0.0481 (3)
O3	1.1612 (2)	0.38911 (18)	1.22823 (13)	0.0413 (3)
O4	1.2540 (3)	−0.0314 (2)	1.46819 (18)	0.0527 (3)
C1	0.7231 (4)	0.7899 (3)	0.96121 (18)	0.0389 (4)
H1	0.6776	0.9251	1.0126	0.047*
C2	0.6084 (4)	0.7891 (3)	0.82391 (19)	0.0416 (4)
H2	0.4835	0.9223	0.7836	0.050*
C3	0.6800 (3)	0.5888 (2)	0.74610 (16)	0.0383 (4)
C4	0.8620 (4)	0.3879 (3)	0.80814 (19)	0.0441 (4)
H4	0.9092	0.2533	0.7562	0.053*
C5	0.9712 (4)	0.3888 (3)	0.94576 (17)	0.0406 (4)
H5	1.0900	0.2534	0.9878	0.049*
C6	0.9064 (3)	0.5905 (2)	1.02359 (17)	0.0346 (3)
C7	1.0346 (3)	0.6029 (3)	1.16625 (17)	0.0342 (3)
C8	1.3041 (4)	0.3878 (3)	1.36534 (18)	0.0385 (3)
H8A	1.1488	0.4292	1.4532	0.046*
H8B	1.4522	0.5040	1.3436	0.046*
C9	1.4636 (4)	0.1408 (3)	1.4041 (2)	0.0447 (4)
H9A	1.5896	0.0912	1.3092	0.054*
H9B	1.6004	0.1443	1.4793	0.054*
H1A	0.471 (6)	0.706 (5)	0.577 (3)	0.058 (6)*
H4A	1.190 (5)	−0.062 (4)	1.401 (3)	0.056 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0782 (9)	0.0440 (7)	0.0442 (7)	0.0023 (6)	−0.0365 (6)	−0.0051 (5)
O2	0.0672 (8)	0.0375 (6)	0.0458 (6)	0.0033 (5)	−0.0264 (5)	−0.0130 (4)
O3	0.0587 (7)	0.0341 (5)	0.0368 (6)	−0.0018 (4)	−0.0256 (5)	−0.0055 (4)
O4	0.0742 (8)	0.0404 (6)	0.0511 (8)	−0.0043 (5)	−0.0365 (6)	−0.0024 (5)
C1	0.0488 (9)	0.0333 (8)	0.0360 (8)	0.0007 (6)	−0.0148 (6)	−0.0057 (6)
C2	0.0505 (9)	0.0336 (7)	0.0414 (8)	0.0019 (6)	−0.0188 (7)	−0.0010 (6)
C3	0.0498 (9)	0.0376 (8)	0.0306 (8)	−0.0064 (6)	−0.0173 (7)	−0.0003 (6)
C4	0.0631 (10)	0.0324 (7)	0.0415 (9)	−0.0008 (7)	−0.0219 (7)	−0.0081 (6)
C5	0.0553 (9)	0.0320 (8)	0.0375 (9)	0.0018 (6)	−0.0223 (7)	−0.0034 (6)
C6	0.0410 (8)	0.0324 (7)	0.0323 (8)	−0.0061 (6)	−0.0106 (6)	−0.0035 (6)
C7	0.0381 (8)	0.0357 (8)	0.0305 (7)	−0.0026 (6)	−0.0116 (6)	−0.0041 (6)
C8	0.0488 (9)	0.0385 (8)	0.0330 (7)	−0.0008 (6)	−0.0209 (6)	−0.0075 (6)
C9	0.0508 (9)	0.0426 (8)	0.0443 (9)	0.0060 (6)	−0.0247 (7)	−0.0080 (6)

Geometric parameters (Å, º) top

O1—C3	1.3494 (19)	C3—C4	1.392 (2)
O1—H1A	0.86 (3)	C4—C5	1.369 (2)
O2—C7	1.211 (2)	C4—H4	0.9300
O3—C7	1.3357 (17)	C5—C6	1.394 (2)
O3—C8	1.4436 (18)	C5—H5	0.9300
O4—C9	1.426 (2)	C6—C7	1.468 (2)
O4—H4A	0.75 (3)	C8—C9	1.494 (2)
C1—C2	1.379 (2)	C8—H8A	0.9700
C1—C6	1.390 (2)	C8—H8B	0.9700
C1—H1	0.9300	C9—H9A	0.9700
C2—C3	1.387 (2)	C9—H9B	0.9700
C2—H2	0.9300

C3—O1—H1A	112.3 (16)	C1—C6—C5	119.03 (13)
C7—O3—C8	115.86 (12)	C1—C6—C7	118.75 (13)
C9—O4—H4A	107.0 (19)	C5—C6—C7	122.18 (12)
C2—C1—C6	120.59 (14)	O2—C7—O3	123.00 (14)
C2—C1—H1	119.7	O2—C7—C6	124.52 (13)
C6—C1—H1	119.7	O3—C7—C6	112.48 (12)
C1—C2—C3	119.71 (14)	O3—C8—C9	107.48 (12)
C1—C2—H2	120.1	O3—C8—H8A	110.2
C3—C2—H2	120.1	C9—C8—H8A	110.2
O1—C3—C2	123.02 (14)	O3—C8—H8B	110.2
O1—C3—C4	116.90 (13)	C9—C8—H8B	110.2
C2—C3—C4	120.08 (13)	H8A—C8—H8B	108.5
C5—C4—C3	119.84 (14)	O4—C9—C8	113.01 (14)
C5—C4—H4	120.1	O4—C9—H9A	109.0
C3—C4—H4	120.1	C8—C9—H9A	109.0
C4—C5—C6	120.74 (13)	O4—C9—H9B	109.0
C4—C5—H5	119.6	C8—C9—H9B	109.0
C6—C5—H5	119.6	H9A—C9—H9B	107.8

C6—C1—C2—C3	−0.9 (2)	C4—C5—C6—C7	−176.35 (15)
C1—C2—C3—O1	−179.07 (13)	C8—O3—C7—O2	−2.2 (2)
C1—C2—C3—C4	1.2 (2)	C8—O3—C7—C6	177.51 (12)
O1—C3—C4—C5	−179.98 (15)	C1—C6—C7—O2	−10.8 (2)
C2—C3—C4—C5	−0.3 (2)	C5—C6—C7—O2	166.91 (15)
C3—C4—C5—C6	−1.0 (3)	C1—C6—C7—O3	169.50 (13)
C2—C1—C6—C5	−0.4 (2)	C5—C6—C7—O3	−12.81 (18)
C2—C1—C6—C7	177.41 (14)	C7—O3—C8—C9	−173.21 (12)
C4—C5—C6—C1	1.3 (2)	O3—C8—C9—O4	−71.91 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4ⁱ	0.86 (3)	1.87 (3)	2.7204 (19)	169 (2)
O4—H4A···O2ⁱⁱ	0.75 (3)	2.15 (3)	2.8970 (18)	170 (3)
C9—H9A···O2ⁱⁱⁱ	0.97	2.51	3.322 (2)	141

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀O₄
M_r	182.17
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.4235 (10), 5.6850 (17), 8.7050 (17)
α, β, γ (°)	80.819 (13), 79.943 (14), 81.804 (14)
V (Å³)	211.30 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.978, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	3761, 1767, 1609
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.088, 1.06
No. of reflections	1767
No. of parameters	126
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.14

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4ⁱ	0.86 (3)	1.87 (3)	2.7204 (19)	169 (2)
O4—H4A···O2ⁱⁱ	0.75 (3)	2.15 (3)	2.8970 (18)	170 (3)
C9—H9A···O2ⁱⁱⁱ	0.97	2.51	3.322 (2)	141

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

Acknowledgements

SA thanks the UGC, India, for financial support.

References

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