Isopropyl 3,4-dihy­droxy­benzoate

Shen, X.-J.; Zhang, Q.-Z.; Wang, S.-X.; Zhang, Y.-J.; Zheng, X.-H.

doi:10.1107/S1600536811044965

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3233

https://doi.org/10.1107/S1600536811044965

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Isopropyl 3,4-dihydroxybenzoate

Xu-Ji Shen,^a Qun-Zheng Zhang,^b Shi-Xiang Wang,^a Ya-Jun Zhang ^a and Xiao-Hui Zheng ^c ^*

^aCollege of Life Sciences, Northwest University, Xi'an 710069, People's Republic of China, ^bCollege of Chemistry & Chemical Engineering, Xian Shiyou University, Xi'an 710065, People's Republic of China, and ^cCollege of Life Sciences and Key Laboratory of Resource Biology and Biotechnology in Western China, Ministry of Education, Northwest University, Xi'an 710069, People's Republic of China
^*Correspondence e-mail: zhengxh@nwu.edu.cn

(Received 19 September 2011; accepted 27 October 2011; online 9 November 2011)

In the crystal structure of the title compound, C₁₀H₁₂O₄, O—H⋯O hydrogen bonds incorporating R₂²(10) and R₂²(14) motifs link molecules into chains along [1 $[\overline{1}]$ 0]. An intramolecular O—H⋯O hydrogen bond is also observed.

Related literature

The title compound is a derivative of protocatechuic acid (3,4-dihydroxybenzoic acid). For the properties of esters of protocatechuic acid, see: Shizuka et al. (2004 ); Yun-Choi et al. (1996 ); Robert et al. (1986 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₂O₄
M_r = 196.20
Triclinic, $[P \overline 1]$
a = 5.8485 (12) Å
b = 9.1844 (17) Å
c = 9.9834 (19) Å
α = 72.629 (3)°
β = 80.547 (3)°
γ = 78.980 (3)°
V = 499.06 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.37 × 0.25 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
2520 measured reflections
1745 independent reflections
1289 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.133
S = 1.04
1745 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4ⁱ	0.82	2.15	2.844 (2)	142
O3—H3⋯O4	0.82	2.28	2.720 (2)	115
O4—H4⋯O2ⁱⁱ	0.82	1.93	2.747 (2)	175
Symmetry codes: (i) -x+1, -y-1, -z; (ii) -x, -y, -z.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811044965/lh5339sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811044965/lh5339Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811044965/lh5339Isup3.cml

checkCIF report

Comment top

Esters of protocatechuic acid has been shown to have, a DPPH radical scavenging ability, anti-thrombotic activity, and can act as inhibitors of the sn-glycerol-3-phosphate oxidase of Trypanosoma brucei brucei (Shizuka et al., 2004; Yun-Choi et al., 1996; Robert et al., 1986).

The molecular structure of the title compound (I) is shown in Fig. 1. Intramolecular O—H···O hydrogen bonds form R²₂(10) and R²₂(14) motifs (Bernstein et al., 1995). In the crystal, intermolecular O—H···O hydrogen bonds link molecules into chains propagating along [110] (see Fig. 2).

Related literature top

The title compound is a derivative of protocatechuic acid (3,4-dihydroxybenzoic acid). For the properties of esters of protocatechuic acid, see: Shizuka et al. (2004); Yun-Choi et al. (1996); Robert et al. (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

To a solution of 0.1M protocatechuic acid in 500 ml of 2-propanol at room temperature, 0.01M TsOH in 2-propanol was added. After the solution had been allowed to stir and reflux for 16 h, the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate three times and filtered. The filtrate was washed successively with dilute saturated aqueous NaHCO₃ solution, saturated aqueous NaCl, dried over MgSO₄, and evaporated. The crude product was purified by chromatography (SiO₂; elution with petroleum ether-acetoacetate, 6:1 v/v). Yield 30%. X-ray quality crystals were grown from a solution of the title compound in acetone and toluene at room temperature. Spectroscopic analysis: IR(KBr, χm^-1): 3458, 3314, 2985, 2957, 1677, 1609, 1531, 1445, 1378, 1347, 1299, 1238, 1165, 1101; ¹H NMR (DMSO, δ, p.p.m.): 9.539 (s, 1 H), 9.536 (s, 1 H), 7.363—7.366(d, 1 H), 7.299—7.316 (dd, 1 H), 6.804—7.818 (d, 1 H), 5.037—5.079(m, 1 H), 1.285 (s, 3 H), 1.275 (s, 3 H).

Structure description top

The title compound is a derivative of protocatechuic acid (3,4-dihydroxybenzoic acid). For the properties of esters of protocatechuic acid, see: Shizuka et al. (2004); Yun-Choi et al. (1996); Robert et al. (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995).

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: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I) with Hydrogen bonds shown as dashed lines.

Isopropyl 3,4-dihydroxybenzoate top

Crystal data top

C₁₀H₁₂O₄	Z = 2
M_r = 196.20	F(000) = 208
Triclinic, P1	D_x = 1.306 Mg m⁻³
Hall symbol: -P 1	Melting point: 407(1) K
a = 5.8485 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1844 (17) Å	Cell parameters from 666 reflections
c = 9.9834 (19) Å	θ = 2.4–24.2°
α = 72.629 (3)°	µ = 0.10 mm⁻¹
β = 80.547 (3)°	T = 296 K
γ = 78.980 (3)°	Needle, colorless
V = 499.06 (17) Å³	0.37 × 0.25 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	1289 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.012
Graphite monochromator	θ_max = 25.1°, θ_min = 2.2°
φ and ω scans	h = −6→6
2520 measured reflections	k = −10→10
1745 independent reflections	l = −9→11

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0685P)² + 0.037P] where P = (F_o² + 2F_c²)/3
1745 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₀H₁₂O₄	γ = 78.980 (3)°
M_r = 196.20	V = 499.06 (17) Å³
Triclinic, P1	Z = 2
a = 5.8485 (12) Å	Mo Kα radiation
b = 9.1844 (17) Å	µ = 0.10 mm⁻¹
c = 9.9834 (19) Å	T = 296 K
α = 72.629 (3)°	0.37 × 0.25 × 0.15 mm
β = 80.547 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1289 reflections with I > 2σ(I)
2520 measured reflections	R_int = 0.012
1745 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.04	Δρ_max = 0.13 e Å⁻³
1745 reflections	Δρ_min = −0.23 e Å⁻³
131 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	0.2571 (2)	0.15042 (14)	0.29888 (13)	0.0554 (4)
O2	−0.0069 (2)	0.13603 (15)	0.16625 (15)	0.0666 (5)
O3	0.7691 (2)	−0.42927 (15)	0.09653 (16)	0.0672 (5)
H3	0.7088	−0.4623	0.0452	0.101*
O4	0.3545 (3)	−0.32701 (15)	−0.01531 (15)	0.0667 (5)
H4	0.2461	−0.2741	−0.0586	0.100*
C1	−0.0633 (5)	0.2409 (3)	0.4524 (3)	0.0925 (9)
H1A	−0.1650	0.1839	0.4288	0.139*
H1B	−0.1541	0.3308	0.4754	0.139*
H1C	0.0143	0.1771	0.5321	0.139*
C2	0.2856 (5)	0.3780 (3)	0.3562 (3)	0.0811 (7)
H2A	0.3599	0.3182	0.4385	0.122*
H2B	0.2030	0.4736	0.3715	0.122*
H2C	0.4024	0.3988	0.2762	0.122*
C3	0.1158 (4)	0.2893 (2)	0.3288 (2)	0.0605 (6)
H3A	0.0369	0.3511	0.2462	0.073*
C4	0.1778 (3)	0.0861 (2)	0.21617 (18)	0.0471 (5)
C5	0.3358 (3)	−0.05140 (19)	0.19011 (18)	0.0436 (4)
C6	0.2685 (3)	−0.12546 (19)	0.10392 (18)	0.0463 (5)
H6	0.1255	−0.0895	0.0673	0.056*
C7	0.4099 (3)	−0.25143 (19)	0.07177 (18)	0.0469 (5)
C8	0.6225 (3)	−0.3068 (2)	0.12786 (19)	0.0485 (5)
C9	0.6887 (3)	−0.2345 (2)	0.2151 (2)	0.0553 (5)
H9	0.8301	−0.2720	0.2534	0.066*
C10	0.5479 (3)	−0.1072 (2)	0.2463 (2)	0.0521 (5)
H10	0.5949	−0.0590	0.3047	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0583 (9)	0.0500 (8)	0.0628 (8)	0.0063 (6)	−0.0190 (7)	−0.0256 (6)
O2	0.0620 (9)	0.0635 (9)	0.0807 (10)	0.0197 (7)	−0.0336 (8)	−0.0342 (8)
O3	0.0612 (9)	0.0555 (8)	0.0889 (11)	0.0185 (7)	−0.0253 (8)	−0.0338 (7)
O4	0.0740 (11)	0.0547 (8)	0.0803 (10)	0.0211 (7)	−0.0381 (8)	−0.0354 (8)
C1	0.0704 (16)	0.107 (2)	0.116 (2)	−0.0091 (14)	0.0063 (15)	−0.0656 (18)
C2	0.0992 (19)	0.0651 (14)	0.0901 (17)	−0.0163 (13)	−0.0072 (14)	−0.0374 (13)
C3	0.0705 (14)	0.0491 (11)	0.0651 (13)	0.0111 (10)	−0.0207 (11)	−0.0265 (10)
C4	0.0507 (11)	0.0447 (10)	0.0442 (10)	−0.0008 (8)	−0.0102 (8)	−0.0110 (8)
C5	0.0439 (10)	0.0397 (9)	0.0434 (10)	−0.0011 (8)	−0.0072 (8)	−0.0077 (8)
C6	0.0433 (10)	0.0438 (10)	0.0492 (10)	0.0045 (8)	−0.0136 (8)	−0.0115 (8)
C7	0.0518 (11)	0.0398 (10)	0.0491 (10)	0.0002 (8)	−0.0119 (8)	−0.0133 (8)
C8	0.0461 (11)	0.0407 (10)	0.0540 (11)	0.0027 (8)	−0.0091 (8)	−0.0101 (8)
C9	0.0452 (11)	0.0516 (11)	0.0684 (13)	0.0057 (9)	−0.0203 (9)	−0.0166 (9)
C10	0.0521 (11)	0.0488 (11)	0.0580 (11)	−0.0020 (9)	−0.0159 (9)	−0.0172 (9)

Geometric parameters (Å, º) top

O1—C4	1.330 (2)	C2—H2B	0.9600
O1—C3	1.464 (2)	C2—H2C	0.9600
O2—C4	1.215 (2)	C3—H3A	0.9800
O3—C8	1.361 (2)	C4—C5	1.479 (2)
O3—H3	0.8200	C5—C6	1.386 (2)
O4—C7	1.372 (2)	C5—C10	1.389 (3)
O4—H4	0.8200	C6—C7	1.377 (2)
C1—C3	1.497 (3)	C6—H6	0.9300
C1—H1A	0.9600	C7—C8	1.391 (3)
C1—H1B	0.9600	C8—C9	1.380 (3)
C1—H1C	0.9600	C9—C10	1.381 (3)
C2—C3	1.502 (3)	C9—H9	0.9300
C2—H2A	0.9600	C10—H10	0.9300

C4—O1—C3	118.03 (14)	O2—C4—O1	123.08 (16)
C8—O3—H3	109.5	O2—C4—C5	123.18 (17)
C7—O4—H4	109.5	O1—C4—C5	113.73 (15)
C3—C1—H1A	109.5	C6—C5—C10	119.21 (16)
C3—C1—H1B	109.5	C6—C5—C4	117.83 (16)
H1A—C1—H1B	109.5	C10—C5—C4	122.95 (17)
C3—C1—H1C	109.5	C7—C6—C5	121.01 (16)
H1A—C1—H1C	109.5	C7—C6—H6	119.5
H1B—C1—H1C	109.5	C5—C6—H6	119.5
C3—C2—H2A	109.5	O4—C7—C6	123.48 (16)
C3—C2—H2B	109.5	O4—C7—C8	116.86 (15)
H2A—C2—H2B	109.5	C6—C7—C8	119.66 (16)
C3—C2—H2C	109.5	O3—C8—C9	119.09 (16)
H2A—C2—H2C	109.5	O3—C8—C7	121.41 (16)
H2B—C2—H2C	109.5	C9—C8—C7	119.49 (16)
O1—C3—C1	108.46 (17)	C8—C9—C10	120.90 (17)
O1—C3—C2	105.88 (17)	C8—C9—H9	119.6
C1—C3—C2	113.43 (18)	C10—C9—H9	119.6
O1—C3—H3A	109.7	C9—C10—C5	119.73 (18)
C1—C3—H3A	109.7	C9—C10—H10	120.1
C2—C3—H3A	109.7	C5—C10—H10	120.1

C4—O1—C3—C1	85.7 (2)	C5—C6—C7—C8	0.8 (3)
C4—O1—C3—C2	−152.21 (17)	O4—C7—C8—O3	0.6 (3)
C3—O1—C4—O2	−0.9 (3)	C6—C7—C8—O3	−178.80 (16)
C3—O1—C4—C5	178.76 (15)	O4—C7—C8—C9	179.39 (17)
O2—C4—C5—C6	0.3 (3)	C6—C7—C8—C9	0.0 (3)
O1—C4—C5—C6	−179.44 (15)	O3—C8—C9—C10	178.19 (17)
O2—C4—C5—C10	179.34 (18)	C7—C8—C9—C10	−0.6 (3)
O1—C4—C5—C10	−0.4 (3)	C8—C9—C10—C5	0.5 (3)
C10—C5—C6—C7	−1.0 (3)	C6—C5—C10—C9	0.3 (3)
C4—C5—C6—C7	178.12 (15)	C4—C5—C10—C9	−178.72 (17)
C5—C6—C7—O4	−178.53 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4ⁱ	0.82	2.15	2.844 (2)	142
O3—H3···O4	0.82	2.28	2.720 (2)	115
O4—H4···O2ⁱⁱ	0.82	1.93	2.747 (2)	175

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂O₄
M_r	196.20
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.8485 (12), 9.1844 (17), 9.9834 (19)
α, β, γ (°)	72.629 (3), 80.547 (3), 78.980 (3)
V (Å³)	499.06 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.37 × 0.25 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2520, 1745, 1289
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.133, 1.04
No. of reflections	1745
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.23

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4ⁱ	0.820	2.150	2.844 (2)	142.27
O3—H3···O4	0.820	2.276	2.720 (2)	114.47
O4—H4···O2ⁱⁱ	0.820	1.929	2.747 (2)	175.23

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

Acknowledgements

The authors are grateful for financial support from the National Natural Sciences Foundation of China (grant No. 20875074), the Higher Specialized Research Fund for the Doctoral Program (grant Nos. 20106101110001 and 20106101120024), the Important Science & Technology Specific Projects of the Innovative Program of Shannxi Province (grant No. 2010ZDKG-46) and the Scientific Research Foundation for PhDs of Xi'an Shiyou University (grant No. 2011BS004).

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