3,4,5-Trihy­droxy­benzoic acid

Hirun, N.; Saithong, S.; Pakawatchai, C.; Tantishaiyakul, V.

doi:10.1107/S1600536811007471

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o787

doi:10.1107/S1600536811007471

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3,4,5-Trihydroxybenzoic acid

Namon Hirun,^a Saowanit Saithong,^b Chaveng Pakawatchai ^b and Vimon Tantishaiyakul ^a ^*

^aDepartment of Pharmaceutical Chemistry, Faculty of Pharmaceutical Sciences, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand, and ^bDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: vimon.t@psu.ac.th

(Received 10 February 2011; accepted 28 February 2011; online 5 March 2011)

In the title compound, C₇H₆O₅, the three hydroxy groups on the ring are oriented in the same direction. There are two intramolecular O—H⋯O hydrogen bonds in the ring. In the crystal, there are several intermolecular O—H⋯O hydrogen bonds and a short contact of 2.7150 (18) Å between the O atoms of the para-OH groups of adjacent molecules.

Related literature

For the biological activity of the title compound, see: Gomes et al. (2003 ); Priscilla & Prince (2009 ); Lu et al. (2010 ). For the structure of gallic acid monohydrate, see: Okabe et al. (2001 ); Jiang et al. (2000 ); Billes et al. (2007 ).

Experimental

Crystal data

C₇H₆O₅
M_r = 170.12
Monoclinic, C 2/c
a = 25.629 (2) Å
b = 4.9211 (4) Å
c = 11.2217 (9) Å
β = 106.251 (1)°
V = 1358.77 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.30 × 0.19 × 0.11 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.916, T_max = 1.000
7171 measured reflections
1254 independent reflections
1172 reflections with I > 2s(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.091
S = 1.06
1254 reflections
121 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.82 (1)	2.19 (2)	2.6625 (14)	117 (1)
O3—H3⋯O2	0.82 (1)	2.35 (2)	2.7464 (14)	110 (1)
O1—H1⋯O5ⁱ	0.84 (1)	1.89 (2)	2.7324 (13)	176 (2)
O3—H3⋯O3ⁱⁱ	0.82 (1)	2.04 (2)	2.8167 (9)	157 (2)
O4—H4⋯O5ⁱⁱⁱ	0.85 (2)	1.81 (2)	2.6570 (13)	175 (2)
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 2003); 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 Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811007471/fj2397sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007471/fj2397Isup2.hkl

checkCIF report

Comment top

Gallic acid, 3,4,5-trihydroxybenzoic acid, has been reported to have various biological activities such as antioxidant, antimutagenic, anticarcinogenic, antihyperglycemic and cardioprotective effects (Gomes et al., 2003; Priscilla & Prince, 2009; Lu et al., 2010). It has been shown that the activity of polyphenolic compounds, including gallic acid, is dependent on their structural characteristics (Gomes et al., 2003). Thus, the investigation of its crystal structure is important for a better understanding of its biological functions. Recently, different crystal structures of gallic acid monohydrate have been reported (Jiang et al., 2000; Okabe et al., 2001; Billes et al., 2007). Here, for the first time, the crystal structure of anhydrous gallic acid (I) was determined. The molecular structure of I is planar [Fig.1]. All the H atoms of the three hydroxy groups are oriented in the same direction.

The intra-hydrogen bonds are found between these hydroxy groups, O2···O1 = 2.6625 (14) and O3···O2 = 2.7464 (14)Å [Table.1]. This agrees with the report of Okabe et al. (2001). However, this orientation is inconsistent with those described by Billes et al. (2007) and Jiang et al. (2000), in which one H atom of the hydroxy group is oriented in the opposite direction to the others. The dissimilarity between I and the gallic acid monohydrate structure reported by Okabe is the different orientation of their carboxyl groups in relation to the direction of the three hydroxy groups.

The inter-hydrogen bonds in the crystal packing of I are found between oxygen atoms,O3···O3ⁱⁱ [2.8167 (9) Å, symmetry code (ii): 1/2 - x, y + 1/2 - z - 1/2], O1···O5ⁱ [2.7324 (13) Å, symmetry code (i): x, -y + 1, z + 1/2] and O4···O5ⁱⁱⁱ [2.6570 (13) Å, symmetry code (iii): -x + 1, -y, -z] [Table 1]. Moreover, the short contact between the oxygen of the hydroxy groups of the adjacent molecule is observed, O2···O2^vi [2.7150 (18) Å, symmetry code (vi): 1/2 - x, 2.5 - y, -z]. All intra- and intermolecular interactions including short contacts are depicted in Fig. 2 and the packing interactions as plotted down the b axis are shown in Fig. 3.

Related literature top

For the biological activity of the title compound, see: Gomes et al. (2003); Priscilla & Prince (2009); Lu et al. (2010). For the structure of gallic acid monohydrate, see: Okabe et al. (2001); Jiang et al. (2000); Billes et al. (2007).

Experimental top

Gallic acid monohydrate was obtained from Fluka Chemie GmbH (Buchs, Switzerland). The anhydrous gallic acid crystals for this X-ray structure study were obtained by dissolving gallic acid monohydrate in diethyl ether followed by a slow evaporation of the solvent.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of I with thermal ellipsoids plotted at the 30% probability level.
	Fig. 2. The intra- and inter hydrogen bonds of I are shown. Symmetry code: i = x, 1 - y, 1/2 + z; ii = 1/2 - x, 1/2 + y, z - 1/2; iii = 1 - x, -y, -z; iv = x, 1 - y, z - 1/2; v = 1/2 - x, y - 1/2, -z - 1/2; vi = 1/2 - x, 2.5 - y, -z.
	Fig. 3. The packing interactions plotted down the b axis.

3,4,5-Trihydroxybenzoic acid top

Crystal data top

C₇H₆O₅	F(000) = 704
M_r = 170.12	D_x = 1.663 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3476 reflections
a = 25.629 (2) Å	θ = 3.3–28.1°
b = 4.9211 (4) Å	µ = 0.15 mm⁻¹
c = 11.2217 (9) Å	T = 293 K
β = 106.251 (1)°	Hexagon, colourless
V = 1358.77 (19) Å³	0.30 × 0.19 × 0.11 mm
Z = 8

Data collection top

Bruker APEX CCD area-detector diffractometer	1254 independent reflections
Radiation source: fine-focus sealed tube	1172 reflections with I > 2s(I)
Graphite monochromator	R_int = 0.022
Frames, each covering 0.3 ° in ω scans	θ_max = 25.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −30→30
T_min = 0.916, T_max = 1.000	k = −5→5
7171 measured reflections	l = −13→13

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.054P)² + 0.7476P] where P = (F_o² + 2F_c²)/3
1254 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.16 e Å⁻³
4 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₇H₆O₅	V = 1358.77 (19) Å³
M_r = 170.12	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.629 (2) Å	µ = 0.15 mm⁻¹
b = 4.9211 (4) Å	T = 293 K
c = 11.2217 (9) Å	0.30 × 0.19 × 0.11 mm
β = 106.251 (1)°

Data collection top

Bruker APEX CCD area-detector diffractometer	1254 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1172 reflections with I > 2s(I)
T_min = 0.916, T_max = 1.000	R_int = 0.022
7171 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	4 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.16 e Å⁻³
1254 reflections	Δρ_min = −0.21 e Å⁻³
121 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 > 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
C1	0.40390 (5)	0.4849 (2)	−0.00701 (11)	0.0251 (3)
C2	0.40861 (5)	0.6475 (3)	0.09733 (11)	0.0267 (3)
H2A	0.4380	0.6271	0.1674	0.032*
C3	0.36900 (5)	0.8389 (3)	0.09502 (11)	0.0256 (3)
C4	0.32438 (5)	0.8667 (2)	−0.00919 (11)	0.0249 (3)
C5	0.32041 (5)	0.7058 (2)	−0.11289 (11)	0.0247 (3)
C6	0.36006 (5)	0.5156 (3)	−0.11223 (12)	0.0262 (3)
H6A	0.3575	0.4083	−0.1819	0.031*
C7	0.44558 (5)	0.2786 (2)	−0.00657 (11)	0.0262 (3)
O1	0.36873 (4)	1.0116 (2)	0.18952 (9)	0.0367 (3)
H1	0.3935 (6)	0.969 (4)	0.2539 (15)	0.044*
O2	0.28434 (4)	1.0485 (2)	−0.01206 (10)	0.0352 (3)
H2	0.2920 (6)	1.127 (3)	0.0553 (13)	0.042*
O3	0.27680 (4)	0.7268 (2)	−0.21619 (9)	0.0334 (3)
H3	0.2610 (7)	0.872 (3)	−0.2151 (16)	0.040*
O4	0.48474 (4)	0.2647 (2)	0.09722 (9)	0.0392 (3)
H4	0.5076 (7)	0.143 (3)	0.0928 (17)	0.047*
O5	0.44465 (4)	0.12950 (19)	−0.09537 (8)	0.0314 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0237 (6)	0.0240 (6)	0.0263 (6)	0.0027 (5)	0.0050 (5)	0.0020 (5)
C2	0.0244 (6)	0.0292 (7)	0.0234 (6)	0.0041 (5)	0.0015 (5)	0.0025 (5)
C3	0.0284 (6)	0.0248 (6)	0.0230 (6)	0.0007 (5)	0.0062 (5)	0.0000 (5)
C4	0.0224 (6)	0.0219 (6)	0.0301 (7)	0.0036 (5)	0.0070 (5)	0.0028 (5)
C5	0.0214 (6)	0.0236 (6)	0.0254 (6)	−0.0008 (5)	0.0005 (5)	0.0018 (5)
C6	0.0260 (6)	0.0252 (6)	0.0256 (6)	0.0021 (5)	0.0042 (5)	−0.0027 (5)
C7	0.0238 (6)	0.0264 (7)	0.0263 (6)	0.0028 (5)	0.0037 (5)	0.0014 (5)
O1	0.0420 (6)	0.0387 (6)	0.0251 (5)	0.0130 (4)	0.0020 (4)	−0.0060 (4)
O2	0.0309 (5)	0.0345 (6)	0.0369 (5)	0.0131 (4)	0.0038 (4)	−0.0051 (4)
O3	0.0265 (5)	0.0293 (5)	0.0346 (5)	0.0063 (4)	−0.0074 (4)	−0.0050 (4)
O4	0.0332 (5)	0.0433 (6)	0.0324 (5)	0.0189 (4)	−0.0054 (4)	−0.0078 (4)
O5	0.0292 (5)	0.0322 (5)	0.0289 (5)	0.0101 (4)	0.0019 (4)	−0.0037 (4)

Geometric parameters (Å, º) top

C1—C6	1.3918 (17)	C5—O3	1.3706 (14)
C1—C2	1.3951 (18)	C5—C6	1.3800 (18)
C1—C7	1.4726 (17)	C6—H6A	0.9300
C2—C3	1.3796 (18)	C7—O5	1.2325 (15)
C2—H2A	0.9300	C7—O4	1.3093 (15)
C3—O1	1.3606 (15)	O1—H1	0.844 (14)
C3—C4	1.3949 (17)	O2—H2	0.821 (14)
C4—O2	1.3551 (15)	O3—H3	0.824 (14)
C4—C5	1.3874 (18)	O4—H4	0.850 (15)

C6—C1—C2	120.64 (11)	O3—C5—C4	121.15 (11)
C6—C1—C7	119.36 (11)	C6—C5—C4	120.10 (11)
C2—C1—C7	120.00 (11)	C5—C6—C1	119.77 (12)
C3—C2—C1	119.02 (11)	C5—C6—H6A	120.1
C3—C2—H2A	120.5	C1—C6—H6A	120.1
C1—C2—H2A	120.5	O5—C7—O4	121.64 (11)
O1—C3—C2	125.17 (11)	O5—C7—C1	123.91 (11)
O1—C3—C4	114.22 (11)	O4—C7—C1	114.45 (11)
C2—C3—C4	120.60 (11)	C3—O1—H1	110.2 (12)
O2—C4—C5	118.66 (11)	C4—O2—H2	107.7 (12)
O2—C4—C3	121.50 (11)	C5—O3—H3	109.9 (12)
C5—C4—C3	119.85 (11)	C7—O4—H4	110.8 (12)
O3—C5—C6	118.73 (11)

C6—C1—C2—C3	0.27 (19)	O2—C4—C5—C6	−178.95 (11)
C7—C1—C2—C3	−179.80 (11)	C3—C4—C5—C6	1.06 (19)
C1—C2—C3—O1	−179.47 (12)	O3—C5—C6—C1	−178.09 (11)
C1—C2—C3—C4	1.08 (19)	C4—C5—C6—C1	0.28 (19)
O1—C3—C4—O2	−1.25 (18)	C2—C1—C6—C5	−0.96 (19)
C2—C3—C4—O2	178.26 (11)	C7—C1—C6—C5	179.12 (11)
O1—C3—C4—C5	178.74 (11)	C6—C1—C7—O5	0.77 (19)
C2—C3—C4—C5	−1.75 (19)	C2—C1—C7—O5	−179.16 (12)
O2—C4—C5—O3	−0.62 (18)	C6—C1—C7—O4	−179.37 (11)
C3—C4—C5—O3	179.39 (11)	C2—C1—C7—O4	0.70 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82 (1)	2.19 (2)	2.6625 (14)	117 (1)
O3—H3···O2	0.82 (1)	2.35 (2)	2.7464 (14)	110 (1)
O1—H1···O5ⁱ	0.84 (1)	1.89 (2)	2.7324 (13)	176 (2)
O3—H3···O3ⁱⁱ	0.82 (1)	2.04 (2)	2.8167 (9)	157 (2)
O4—H4···O5ⁱⁱⁱ	0.85 (2)	1.81 (2)	2.6570 (13)	175 (2)

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

Experimental details

Crystal data
Chemical formula	C₇H₆O₅
M_r	170.12
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	25.629 (2), 4.9211 (4), 11.2217 (9)
β (°)	106.251 (1)
V (Å³)	1358.77 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.30 × 0.19 × 0.11

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.916, 1.000
No. of measured, independent and observed [I > 2s(I)] reflections	7171, 1254, 1172
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.091, 1.06
No. of reflections	1254
No. of parameters	121
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.821 (14)	2.191 (16)	2.6625 (14)	116.6 (14)
O3—H3···O2	0.824 (14)	2.353 (16)	2.7464 (14)	110.0 (14)
O1—H1···O5ⁱ	0.844 (14)	1.890 (15)	2.7324 (13)	175.5 (17)
O3—H3···O3ⁱⁱ	0.824 (14)	2.040 (15)	2.8167 (9)	157.0 (16)
O4—H4···O5ⁱⁱⁱ	0.850 (15)	1.809 (15)	2.6570 (13)	175.0 (18)

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

Acknowledgements

This work was supported by the Thailand Research Fund through the Royal Golden Jubilee PhD Program under grant No. PHD/0259/2549, the Prince of Songkla University under grant No. PHA520036S and the National Research University Project of Thailand's Office of the Higher Education Commission.

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