Isopropyl 3,4,5-trihy­droxy­benzoate

Lan, W.; Shen, X.-J.; Xiao, C.-N.; Wang, S.-X.; Zheng, X.-H.

doi:10.1107/S1600536812004278

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o650

doi:10.1107/S1600536812004278

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Isopropyl 3,4,5-trihydroxybenzoate

Wei Lan,^a Xu-Ji Shen,^a Chao-Ni Xiao,^a Shi-Xiang Wang ^a and Xiao-Hui Zheng ^a,^b ^*

^aCollege of Life Sciences, Northwest University, Xi'an 710069, People's Republic of China, and ^bResource Biology and Biotechnology in Western China, Ministry of Education Key Laboratory of Northwest University, Xi'an 710069, People's Republic of China
^*Correspondence e-mail: zhengxh@nwu.edu.cn

(Received 24 January 2012; accepted 1 February 2012; online 10 February 2012)

In the title compound, C₁₀H₁₂O₅, the dihedral angle between the benzene ring is almost coplanar with the attached C(O)—O—C group [dihedral angle = 0.32 (15)°]. In the crystal, two intermolecular O—H⋯O hydrogen bonds make R₄⁴(26) ring mofits.

Related literature

For the properties of isopropyl gallate, see: Calheiros et al. (2008 ); Morais et al. (2010 ). For the synthesis method, see: Christiansen (1926 ); Li et al. (2001 ). For the hydrogen-bonding pattern, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₂O₅
M_r = 212.20
Monoclinic, P 2₁ /c
a = 19.148 (6) Å
b = 4.7030 (15) Å
c = 11.571 (4) Å
β = 90.159 (5)°
V = 1042.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.31 × 0.29 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.967, T_max = 0.977
5181 measured reflections
2055 independent reflections
1589 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.132
S = 1.05
2055 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.82	2.00	2.772 (2)	158
O3—H3⋯O4ⁱⁱ	0.82	1.93	2.742 (2)	173
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812004278/mw2052sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004278/mw2052Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004278/mw2052Isup3.cml

checkCIF report

Comment top

Pharmacological studies indicate the title compound, (I), has antioxidant, anti-apoptotic and anti-platelet activities suggesting it could be a new drug with therapeutic effects on cardiovascular or cerebrovascular diseases. (Calheiros et al., 2008; Morais et al., 2010).

The structure of the title compound, (I), is shown in Fig. 1. In the crystal, two intermolecular O—H···O hydrogen bonds make R₄⁴(26) ring mofits (Bernstein et al., 1995) which links the molecules into one-dimensional chains along [001] (Fig. 2).

Related literature top

For the properties of isopropyl gallate, see: Calheiros et al. (2008); Morais et al. (2010). For the synthesis method, see: Christiansen (1926); Li et al. (2001). For the hydrogen-bonding pattern, see: Bernstein et al. (1995).

Experimental top

0.01M p-toluenesulfonic acid in 2-propanol was added to a solution of 0.1M gallic acid in 500 ml of 2-propanol at room temperature. After being stirred and refluxed for 16 h, the solvent was removed under reduced pressure and the residue was extracted three times with ethyl acetate and filtered. The filtrate was washed successively with dilute saturated aqueous NaHCO₃ solution, saturated aqueous NaCl solution, dried over MgSO₄ and was evaporated to dryness. The crude product was purified by chromatography (SiO₂; elution with petroleum ether and ethyl acetate, 5:1 v/v). Yield 36%. (Christiansen, 1926; Li et al., 2001).

X-ray quality crystals were obtained from a solution of the title compound in acetone and toluene at room temperature. Spectroscopic analysis: IR (KBr, cm^-1): 3499, 2971, 2922, 2957, 1677, 1609, 1671, 1613, 1541, 1449, 1327, 1252, 1165, 1111, 1026, 979; ¹H NMR (DMSO, δ, p.p.m.): 9.126(s, 3 H), 6.946(s, 2 H), 5.014—5.055(m, 1 H), 1.274 (s, 3H), 1.264 (s, 3 H).

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

Figures top

	Fig. 1. The molecular structure of (I) with the atom numbering scheme, showing displacement ellipsoids at the 30% probability level.
	Fig. 2. The packing of (I) viewed down the a axis with O—H···O hydrogen bonds shown as dashed lines.

Isopropyl 3,4,5-trihydroxybenzoate top

Crystal data top

C₁₀H₁₂O₅	F(000) = 448
M_r = 212.20	D_x = 1.353 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 396(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 19.148 (6) Å	Cell parameters from 1697 reflections
b = 4.7030 (15) Å	θ = 3.5–25.7°
c = 11.571 (4) Å	µ = 0.11 mm⁻¹
β = 90.159 (5)°	T = 296 K
V = 1042.0 (6) Å³	Block, colourless
Z = 4	0.31 × 0.29 × 0.21 mm

Data collection top

Bruker APEXII CCD diffractometer	2055 independent reflections
Radiation source: fine-focus sealed tube	1589 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 26.1°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→23
T_min = 0.967, T_max = 0.977	k = −5→5
5181 measured reflections	l = −14→12

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0778P)² + 0.0222P] where P = (F_o² + 2F_c²)/3
2055 reflections	(Δ/σ)_max < 0.001
141 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₀H₁₂O₅	V = 1042.0 (6) Å³
M_r = 212.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 19.148 (6) Å	µ = 0.11 mm⁻¹
b = 4.7030 (15) Å	T = 296 K
c = 11.571 (4) Å	0.31 × 0.29 × 0.21 mm
β = 90.159 (5)°

Data collection top

Bruker APEXII CCD diffractometer	2055 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1589 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.977	R_int = 0.033
5181 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
2055 reflections	Δρ_min = −0.18 e Å⁻³
141 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	0.46197 (5)	−0.0043 (2)	0.24204 (10)	0.0447 (3)
H1	0.4823	−0.1535	0.2275	0.067*
O2	0.45282 (6)	−0.3102 (3)	0.04068 (10)	0.0478 (3)
H2	0.4449	−0.3814	−0.0227	0.072*
O3	0.34242 (6)	−0.2621 (3)	−0.09898 (9)	0.0485 (4)
H3	0.3094	−0.2187	−0.1407	0.073*
O4	0.23999 (6)	0.5891 (3)	0.25056 (9)	0.0462 (4)
O5	0.18797 (6)	0.4562 (3)	0.08655 (10)	0.0476 (4)
C1	0.35320 (8)	0.2096 (3)	0.20035 (12)	0.0349 (4)
H1A	0.3564	0.3109	0.2692	0.042*
C2	0.40505 (7)	0.0233 (3)	0.17032 (13)	0.0337 (4)
C3	0.40050 (7)	−0.1299 (3)	0.06846 (12)	0.0341 (4)
C4	0.34216 (8)	−0.0952 (3)	−0.00283 (12)	0.0339 (4)
C5	0.29047 (8)	0.0934 (3)	0.02583 (12)	0.0354 (4)
H5	0.2522	0.1181	−0.0227	0.042*
C6	0.29573 (7)	0.2479 (3)	0.12825 (12)	0.0329 (4)
C7	0.24087 (8)	0.4472 (3)	0.16310 (13)	0.0356 (4)
C8	0.13112 (9)	0.6509 (4)	0.10811 (16)	0.0549 (5)
H8	0.1488	0.8212	0.1473	0.066*
C9	0.10338 (12)	0.7293 (5)	−0.0096 (2)	0.0821 (8)
H9A	0.1394	0.8223	−0.0530	0.123*
H9B	0.0643	0.8552	−0.0012	0.123*
H9C	0.0888	0.5603	−0.0495	0.123*
C10	0.07847 (11)	0.5047 (6)	0.1831 (2)	0.0847 (8)
H10A	0.0618	0.3367	0.1448	0.127*
H10B	0.0400	0.6308	0.1974	0.127*
H10C	0.0999	0.4529	0.2552	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0373 (6)	0.0438 (7)	0.0530 (7)	0.0058 (5)	−0.0220 (5)	−0.0060 (5)
O2	0.0415 (7)	0.0523 (8)	0.0495 (7)	0.0136 (6)	−0.0065 (5)	−0.0082 (6)
O3	0.0558 (7)	0.0553 (8)	0.0344 (6)	0.0150 (6)	−0.0117 (5)	−0.0108 (5)
O4	0.0429 (7)	0.0565 (8)	0.0391 (7)	0.0089 (5)	−0.0089 (5)	−0.0104 (5)
O5	0.0350 (6)	0.0611 (8)	0.0467 (7)	0.0134 (5)	−0.0145 (5)	−0.0123 (5)
C1	0.0370 (8)	0.0361 (9)	0.0315 (8)	−0.0020 (7)	−0.0077 (6)	−0.0006 (6)
C2	0.0293 (7)	0.0349 (9)	0.0369 (8)	−0.0032 (6)	−0.0097 (6)	0.0038 (6)
C3	0.0322 (8)	0.0332 (8)	0.0370 (8)	0.0027 (6)	−0.0023 (6)	0.0043 (6)
C4	0.0367 (8)	0.0376 (9)	0.0274 (7)	0.0000 (6)	−0.0028 (6)	0.0007 (6)
C5	0.0333 (8)	0.0428 (9)	0.0300 (8)	0.0003 (6)	−0.0087 (6)	0.0030 (6)
C6	0.0308 (7)	0.0370 (9)	0.0310 (8)	−0.0003 (6)	−0.0044 (6)	0.0033 (6)
C7	0.0331 (8)	0.0429 (9)	0.0308 (8)	−0.0013 (7)	−0.0069 (6)	0.0018 (7)
C8	0.0375 (9)	0.0619 (13)	0.0653 (12)	0.0159 (9)	−0.0152 (8)	−0.0146 (10)
C9	0.0632 (13)	0.0969 (19)	0.0860 (16)	0.0249 (13)	−0.0316 (11)	0.0047 (13)
C10	0.0523 (13)	0.120 (2)	0.0817 (16)	0.0100 (13)	0.0083 (11)	−0.0198 (14)

Geometric parameters (Å, º) top

O1—C2	1.3741 (16)	C4—C5	1.371 (2)
O1—H1	0.8200	C5—C6	1.394 (2)
O2—C3	1.3519 (18)	C5—H5	0.9300
O2—H2	0.8200	C6—C7	1.465 (2)
O3—C4	1.3616 (19)	C8—C10	1.499 (3)
O3—H3	0.8200	C8—C9	1.506 (3)
O4—C7	1.2122 (19)	C8—H8	0.9800
O5—C7	1.3443 (17)	C9—H9A	0.9600
O5—C8	1.445 (2)	C9—H9B	0.9600
C1—C2	1.370 (2)	C9—H9C	0.9600
C1—C6	1.3909 (19)	C10—H10A	0.9600
C1—H1A	0.9300	C10—H10B	0.9600
C2—C3	1.384 (2)	C10—H10C	0.9600
C3—C4	1.397 (2)

C2—O1—H1	109.5	O4—C7—O5	121.38 (14)
C3—O2—H2	109.5	O4—C7—C6	126.39 (13)
C4—O3—H3	109.5	O5—C7—C6	112.22 (13)
C7—O5—C8	118.22 (13)	O5—C8—C10	108.52 (18)
C2—C1—C6	120.23 (14)	O5—C8—C9	105.25 (16)
C2—C1—H1A	119.9	C10—C8—C9	113.57 (18)
C6—C1—H1A	119.9	O5—C8—H8	109.8
C1—C2—O1	118.78 (13)	C10—C8—H8	109.8
C1—C2—C3	120.34 (13)	C9—C8—H8	109.8
O1—C2—C3	120.86 (14)	C8—C9—H9A	109.5
O2—C3—C2	118.96 (12)	C8—C9—H9B	109.5
O2—C3—C4	121.67 (13)	H9A—C9—H9B	109.5
C2—C3—C4	119.37 (14)	C8—C9—H9C	109.5
O3—C4—C5	125.10 (13)	H9A—C9—H9C	109.5
O3—C4—C3	114.24 (14)	H9B—C9—H9C	109.5
C5—C4—C3	120.66 (13)	C8—C10—H10A	109.5
C4—C5—C6	119.51 (13)	C8—C10—H10B	109.5
C4—C5—H5	120.2	H10A—C10—H10B	109.5
C6—C5—H5	120.2	C8—C10—H10C	109.5
C1—C6—C5	119.86 (14)	H10A—C10—H10C	109.5
C1—C6—C7	118.98 (13)	H10B—C10—H10C	109.5
C5—C6—C7	121.15 (13)

C6—C1—C2—O1	178.39 (14)	C2—C1—C6—C5	0.8 (2)
C6—C1—C2—C3	−0.5 (2)	C2—C1—C6—C7	179.57 (13)
C1—C2—C3—O2	179.39 (13)	C4—C5—C6—C1	0.0 (2)
O1—C2—C3—O2	0.6 (2)	C4—C5—C6—C7	−178.73 (13)
C1—C2—C3—C4	−0.7 (2)	C8—O5—C7—O4	3.0 (2)
O1—C2—C3—C4	−179.53 (13)	C8—O5—C7—C6	−178.08 (14)
O2—C3—C4—O3	1.6 (2)	C1—C6—C7—O4	0.5 (2)
C2—C3—C4—O3	−178.31 (14)	C5—C6—C7—O4	179.19 (16)
O2—C3—C4—C5	−178.57 (14)	C1—C6—C7—O5	−178.35 (13)
C2—C3—C4—C5	1.5 (2)	C5—C6—C7—O5	0.4 (2)
O3—C4—C5—C6	178.66 (14)	C7—O5—C8—C10	−87.29 (19)
C3—C4—C5—C6	−1.2 (2)	C7—O5—C8—C9	150.82 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	2.00	2.772 (2)	158
O3—H3···O4ⁱⁱ	0.82	1.93	2.742 (2)	173

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂O₅
M_r	212.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	19.148 (6), 4.7030 (15), 11.571 (4)
β (°)	90.159 (5)
V (Å³)	1042.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.31 × 0.29 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.967, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	5181, 2055, 1589
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.132, 1.05
No. of reflections	2055
No. of parameters	141
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.820	1.996	2.772 (2)	158
O3—H3···O4ⁱⁱ	0.820	1.927	2.742 (2)	173

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2.

Acknowledgements

The authors are grateful for financial support from the Higher Specialized Research Fund for the Doctoral Program (grant Nos. 20106101120024 and 20106101110001) and the Important Science and Technology Specific Innovative Projects Program of Shannxi Province (grant No. 2010ZDKG-46).

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