Gallic acid monohydrate

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organic papers

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Nobuo Okabeet al. C₇H₆O₅H₂O DOI: 10.1107/S1600536801012041 Acta Cryst.(2001). E57, o764±o766 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Gallic acid monohydrate

Nobuo Okabe,* Hasuyo Kyoyama and Misato Suzuki

Faculty of Pharmaceutical Sciences, Kinki University, Kokawae 3-4-1, Higashiosaka, Osaka 577-8502, Japan

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 296 K

Mean(C±C) = 0.005 AÊ

Rfactor = 0.049

wRfactor = 0.188

Data-to-parameter ratio = 15.0

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

In the crystal structure of the title compound, 3,4,5-tri-hydroxybenzoic acid monohydrate, C7H6O5H2O, the gallic

acid molecule is essentially planar and has two intramolecular hydrogen bonds between hydroxyl groups. The H atoms of the three hydroxyl groups are oriented in the same direction around the ring, and form intra- and intermolecular hydrogen bonds. The crystal structure is stabilized by all available intermolecular hydrogen bonds, including also those involving the water molecule.

Comment

Gallic acid, 3,4,5-trihydroxybenzoic acid, is a naturally occur-ring plant phenol which has antitumor and anti-oxidative activity. It induces apotosis in the human myelogenous leukemic cell line (Sakaguchiet al., 1999; Satoh & Sakagami, 1997). Therefore the determination of its crystal structure is important for the structural clari®cation of its biological function. Recently the crystal structure was determined in a monohydrate form by Jiang et al. (2000). We have now determined its structure as a different monohydrated form, (I).

The molecular structure of (I) is essentially planar, as shown in Fig. 1. In the molecule, all the H atoms of the three hydroxyl groups are oriented in the same direction around the ring, forming two intramolecular hydrogen bonds between a pair of hydroxyl groups at positions 3 and 4, and at positions 4 and 5. The hydroxyl groups at positions 3 and 4 are also linked to the water-O atom and to the hydroxyl-O atom of a neighbouring molecule by a bifurcated hydrogen bond. This hydrogen-bonding scheme is different from that reported by Jianget al.

(2000), in which only one intramolecular hydrogen bond is present, and one of the three H atoms of the hydroxyl groups is oriented in the reverse direction to the others. Furthermore, a hydrogen bond is formed between the carboxyl groups in the

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previous structure, but this interaction is not present in the structure reported here. All of the possible hydrogen bonds are present as either intra- or intermolecular interactions, as shown in Table 2. The two different crystal structures and hydrogen-bonding schemes observed for gallic acid mono-hydrate may have a role in the biological function of this compound.

Experimental

The crystal was obtained by slow evaporation of an ethanol solution.

Crystal data C7H6O5H2O

Mr= 188.13

Monoclinic,P2=n a= 14.15 (1) AÊ

b= 3.622 (9) AÊ

c= 15.028 (10) AÊ

= 97.52 (7)

V= 764 (1) AÊ3

Z= 4

Dx= 1.636 Mg mÿ3

MoKradiation Cell parameters from 18

re¯ections

= 10.0±14.3

= 0.15 mmÿ1

T= 296.2 K Needle, colorless 0.500.100.03 mm Data collection

Rigaku AFC-5Rdiffractometer

!±2scans

Absorption correction: none 2109 measured re¯ections 1766 independent re¯ections 764 re¯ections withI> 2(I)

Rint= 0.040

max= 27.5

h= 0!18

k=ÿ4!0

l=ÿ19!19 3 standard re¯ections

every 150 re¯ections intensity decay: 0.1% Re®nement

Re®nement onF2

R[F2_{> 2}₍_F2_{)] = 0.049}

wR(F2_{) = 0.188}

S= 0.91 1766 re¯ections 118 parameters

H-atom parameters not re®ned

w= 1/[2₍_F

o2) + (0.1P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.31 e AÊÿ3 min=ÿ0.31 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

O1ÐC7 1.317 (5)

O2ÐC7 1.203 (5)

O3ÐC3 1.373 (4)

O4ÐC4 1.370 (4)

O5ÐC5 1.372 (4)

C1ÐC2 1.396 (5)

C1ÐC6 1.380 (5)

C1ÐC7 1.487 (5)

C2ÐC3 1.376 (4)

C3ÐC4 1.391 (5)

C4ÐC5 1.390 (5)

C5ÐC6 1.377 (4)

C2ÐC1ÐC6 119.7 (3)

C2ÐC1ÐC7 122.2 (3)

C6ÐC1ÐC7 118.0 (3)

C1ÐC2ÐC3 119.3 (3)

O3ÐC3ÐC2 119.8 (3)

O3ÐC3ÐC4 119.2 (3)

C2ÐC3ÐC4 121.0 (3)

O4ÐC4ÐC3 117.4 (3)

O4ÐC4ÐC5 123.2 (3)

C3ÐC4ÐC5 119.3 (3)

O5ÐC5ÐC4 116.8 (3)

O5ÐC5ÐC6 124.0 (3)

C4ÐC5ÐC6 119.6 (3)

C1ÐC6ÐC5 121.0 (3)

O1ÐC7ÐO2 122.6 (3)

O1ÐC7ÐC1 113.5 (3)

O2ÐC7ÐC1 123.8 (3)

O1ÐC7ÐC1ÐC2 2.7 (5)

O1ÐC7ÐC1ÐC6 178.6 (3)

O2ÐC7ÐC1ÐC2 ÿ175.3 (4)

O2ÐC7ÐC1ÐC6 0.2 (6)

O3ÐC3ÐC2ÐC1 ÿ179.0 (3)

O3ÐC3ÐC4ÐO4 ÿ0.2 (5)

O3ÐC3ÐC4ÐC5 179.0 (3)

O4ÐC4ÐC3ÐC2 ÿ177.3 (3)

O4ÐC4ÐC5ÐO5 0.9 (5)

O4ÐC4ÐC5ÐC6 178.9 (4)

O5ÐC5ÐC4ÐC3 ÿ178.9 (3)

O5ÐC5ÐC6ÐC1 177.2 (3)

C1ÐC2ÐC3ÐC4 ÿ1.9 (6)

C2ÐC1ÐC6ÐC5 1.4 (6)

C2ÐC3ÐC4ÐC5 1.8 (6)

C3ÐC2ÐC1ÐC6 0.3 (6)

C3ÐC2ÐC1ÐC7 175.7 (4)

C5ÐC6ÐC1ÐC7 ÿ174.2 (4)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O3ÐH3 O4 0.850 2.328 2.692 (8) 106.3

O4ÐH4 O5 0.945 2.306 2.752 (8) 108.9

O3ÐH3 O6i _0.850 _1.949 _{2.770 (4)} _161.6

O4ÐH4 O5ii _0.945 _1.907 _{2.767 (8)} _150.0

O5ÐH5 O2iii _0.851 _1.878 _{2.729 (4)} _177.7

O6ÐH7 O4ii _0.820 _2.182 _{2.977 (4)} _163.8

O6ÐH8 O3iv _0.812 _1.941 _{2.747 (4)} _170.9

O1ÐH1 O6iii _0.830 _1.859 _{2.686 (4)} _174.2

Symmetry codes: (i)1

2ÿx;yÿ1;21ÿz; (ii)12ÿx;y;12ÿz; (iii) 1ÿx;1ÿy;1ÿz; (iv) 1

2x;ÿy;zÿ12.

All H atoms were located from difference Fourier maps and were not re®ned.

Data collection: MSC /AFC Diffractometer Control Software

(Molecular Structure Corporation & Rigaku Corporation, 1999); cell re®nement:MSC/AFC Diffractometer Control Software; data reduc-tion: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 1999); program(s) used to solve structure:SIR88 (Burla

et al., 1989) andDIRDIF(Beurskenset al., 1992); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:

ORTEPII (Johnson, 1976); software used to prepare material for publication:TEXSAN.

References

Beurskens, P. T., Admiraal, G., Beurskens, G., Bosman, W. P., Garcia-Granda, S., Gould, R. O., Smith, J. M. M. & Smykalla, C. (1992).DIRDIF.University of Nijmegen, The Netherlands.

Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Spagna, R. & Viterbo, D. (1989).J. Appl. Cryst.22, 389±403.

Johnson, C. K. (1976).ORTEPII. Oak Ridge National Laboratory, Tennessee, USA.

Acta Cryst.(2001). E57, o764±o766 Nobuo Okabeet al. C₇H₆O₅H₂O

o765

organic papers

Figure 1

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organic papers

o766

Nobuo Okabeet al. C₇H₆O₅H₂O Acta Cryst.(2001). E57, o764±o766 Molecular Structure Corporation & Rigaku Corporation (1999).MSC/AFC

Diffractometer Control SoftwareandTEXSAN(Version 1.10). MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA, and Rigaku, 3-9-12 Akishima, Tokyo, Japan.

Jiang, R.-W., Ming, D.-S., But, P. H. P. & Mak, T. C. W. (2000).Acta Cryst.C56, 594±595.

Satoh, K. & Sakagami, H. (1997).Anticancer Res.17, 2181±2184.

Sakaguchi, N., Inoue, M., Isuzugawa, K., Ogihara, Y. & Hosaka, K. (1999).

Biol. Pharm. Bull.22, 471±475.

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supporting information

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Acta Cryst. (2001). E57, o764–o766

supporting information

Acta Cryst. (2001). E57, o764–o766 [doi:10.1107/S1600536801012041]

Gallic acid monohydrate

Nobuo Okabe, Hasuyo Kyoyama and Misato Suzuki

S1. Comment

Gallic acid, 3,4,5-trihydroxybenzoic acid, is a naturally occurring plant phenol which has antitumor and anti-oxidative

activity. It induces apotosis in the human myelogenenous leukemic cell line (Sakaguchi et al., 1999; Satoh & Sakagami,

1997). Therefore the determination of its crystal structure is important for the structural clarification of its biological

function. For this reason, we intended to analyse its crystal structure. Recently, this was determined in a monohydrate

form by Jiang et al. (2000). We have mow determined its structure as a different monohydrated form, (I).

The molecular structure of (I) is essentially planar as shown in Fig. 1. In the molecule, all the H atoms of the three

hydroxyl groups are oriented in the same direction around the ring, forming two intramolecular hydrogen bonds between

a pair of hydroxyl groups at positions 3 and 4, and at positions 4 and 5. The hydroxyl groups at positions 3 and 4 are also

linked to the water-O atom and to the hydroxyl-O atom of a neighbouring molecule by a bifurcated hydrogen bond. This

hydrogen-bonding scheme is different from that reported by Jiant et al. (2000), in which only one intramolecular

hydrogen bond is present, and one of the three H atoms of the hydroxyl groups is oriented in the reverse direction to the

others. Furthermore, a hydrogen bond is formed between the carboxyl groups in the previous structure, but this

interaction is not present in the structure reported here. All of the possible hydrogen bonds are present as either intra- or

intermolecular interactions, as shown in Table 2. The two different crystal structures and hydrogen-bonding schemes

observed for gallic acid monohydrate may have a role in the biological function of this compound.

S2. Experimental

The crystal was obtained by slow evaporation of an ethanol solution.

S3. Refinement

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[image:5.610.133.438.95.332.2]

Acta Cryst. (2001). E57, o764–o766 Figure 1

ORTEPII (Johnson, 1976) drawing of the title compound with the atomic numbering scheme. Ellipsoids for non-H atoms

correspond to 50% probability.

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Crystal data

C7H6O5·H2O Mr = 188.13

Monoclinic, P2/n a = 14.15 (1) Å

b = 3.622 (9) Å

c = 15.028 (10) Å

β = 97.52 (7)°

V = 764 (1) Å3 Z = 4

F(000) = 392.0

Dx = 1.636 Mg m−3

Mo Kα radiation, λ = 0.7107 Å Cell parameters from 18 reflections

θ = 10.0–14.3°

µ = 0.15 mm−1 T = 296 K Needle, colorless 0.50 × 0.10 × 0.03 mm

Data collection

Rigaku AFC-5R diffractometer

ω–2θ scans

2109 measured reflections 1766 independent reflections 764 reflections with I > 2σ(I)

Rint = 0.040

θmax = 27.5°, θmin = 4° h = 0→18

k = −4→0

l = −19→19

3 standard reflections every 150 reflections intensity decay: 0.1%

Refinement

Refinement on F2 R[F2_{> 2}_σ₍_F2_{)] = 0.049} wR(F2_{) = 0.188} S = 0.91

1766 reflections 118 parameters

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Acta Cryst. (2001). E57, o764–o766 w = 1/[σ2₍_F

o2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 0.31 e Å−3 Δρmin = −0.31 e Å−3

Special details

Refinement. Refinement using reflections with F2_{> -10.0}_σ₍_F2_{). The weighted}_R_{-factor (}_wR_{) and goodness of fit (}_S_{) are} based on F2_._R_{-factor (gt) are based on}_F_{. The threshold expression of}_F2_{> 2.0}_σ₍_F2_{) is used only for calculating}_R_-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

O1 0.3779 (2) 0.2043 (9) 0.7302 (2) 0.0449 (8) O2 0.4899 (2) 0.4049 (9) 0.6523 (2) 0.0447 (9) O3 0.1018 (2) −0.1394 (8) 0.5049 (2) 0.0338 (7) O4 0.1550 (2) 0.0075 (8) 0.3430 (2) 0.0334 (7) O5 0.3351 (2) 0.2679 (8) 0.3286 (2) 0.0336 (7) O6 0.5102 (2) 0.4879 (8) 0.1313 (2) 0.0370 (7) C1 0.3455 (2) 0.175 (1) 0.5732 (2) 0.0243 (8) C2 0.2535 (2) 0.044 (1) 0.5784 (2) 0.0253 (8) C3 0.1931 (2) −0.0162 (10) 0.5004 (2) 0.0230 (8) C4 0.2207 (2) 0.0606 (10) 0.4172 (2) 0.0228 (8) C5 0.3126 (2) 0.191 (1) 0.4124 (2) 0.0248 (8) C6 0.3740 (2) 0.243 (1) 0.4905 (2) 0.0264 (8) C7 0.4124 (3) 0.272 (1) 0.6544 (2) 0.0280 (9)

H1 0.4126 0.2858 0.7748 0.0464*

H2 0.2292 −0.0105 0.6347 0.0464*

H3 0.0777 −0.2436 0.4565 0.0464*

H4 0.1808 0.0710 0.2901 0.0464*

H5 0.3893 0.3730 0.3331 0.0473*

H6 0.4346 0.3306 0.4847 0.0464*

H7 0.4673 0.3675 0.1493 0.0556*

H8 0.5347 0.3636 0.0958 0.0556*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2001). E57, o764–o766

C7 0.027 (2) 0.031 (2) 0.025 (2) −0.003 (2) 0.001 (1) −0.001 (2)

Geometric parameters (Å, º)

O1—C7 1.317 (5) O6—H8 0.812

O1—H1 0.830 C1—C2 1.396 (5)

O2—C7 1.203 (5) C1—C6 1.380 (5)

O3—C3 1.373 (4) C1—C7 1.487 (5)

O3—H3 0.850 C2—C3 1.376 (4)

O4—C4 1.370 (4) C2—H2 0.975

O4—H4 0.945 C3—C4 1.391 (5)

O5—C5 1.372 (4) C4—C5 1.390 (5)

O5—H5 0.851 C5—C6 1.377 (4)

O6—H7 0.820 C6—H6 0.929

O1···O6i _{2.686 (4)} _O3···O6v _{2.769 (4)}

O1···O2ii _{3.576 (5)} _O3···O3vi _{3.039 (5)}

O2···O5i _{2.718 (4)} _O3···C3ii _{3.432 (5)}

O2···O6i _{3.275 (9)} _O4···O5vii _{2.772 (4)}

O2···C6i _{3.321 (5)} _O4···O6vii _{2.977 (4)}

O2···C7iii _{3.325 (5)} _O5···C5iii _{3.602 (10)} O2···C5i _{3.410 (5)} _O6···O3viii _{2.747 (4)} O2···C1iii _{3.569 (5)} _O6···O4vii _{2.977 (4)} O3···O6iv _{2.747 (4)}

C7—O1—H1 112.7 C2—C3—C4 121.0 (3)

C3—O3—H3 112.3 O4—C4—C3 117.4 (3)

C4—O4—H4 110.6 O4—C4—C5 123.2 (3)

C5—O5—H5 109.5 C3—C4—C5 119.3 (3)

H7—O6—H8 108.7 O5—C5—C4 116.8 (3)

C2—C1—C6 119.7 (3) O5—C5—C6 124.0 (3)

C2—C1—C7 122.2 (3) C4—C5—C6 119.6 (3)

C6—C1—C7 118.0 (3) C1—C6—C5 121.0 (3)

C1—C2—C3 119.3 (3) C1—C6—H6 121.8

C1—C2—H2 123.7 C5—C6—H6 117.2

C3—C2—H2 117.0 O1—C7—O2 122.6 (3)

O3—C3—C2 119.8 (3) O1—C7—C1 113.5 (3)

O3—C3—C4 119.2 (3) O2—C7—C1 123.8 (3)

O1—C7—C1—C2 2.7 (5) O5—C5—C4—C3 −178.9 (3)

O1—C7—C1—C6 178.6 (3) O5—C5—C6—C1 177.2 (3) O2—C7—C1—C2 −175.3 (4) C1—C2—C3—C4 −1.9 (6)

O2—C7—C1—C6 0.2 (6) C1—C6—C5—C4 −1.5 (6)

O3—C3—C2—C1 −179.0 (3) C2—C1—C6—C5 1.4 (6)

O3—C3—C4—O4 −0.2 (5) C2—C3—C4—C5 1.8 (6)

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Acta Cryst. (2001). E57, o764–o766

O4—C4—C5—O5 0.9 (5) C3—C4—C5—C6 −0.1 (6)

O4—C4—C5—C6 178.9 (4) C5—C6—C1—C7 −174.2 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x−1/2, −y, z+1/2; (v) −x+1/2, y−1, −z+1/2; (vi) −x, −y, −z+1; (vii) −x+1/2, y, −z+1/2; (viii) x+1/2, −y, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O3—H3···O4 0.850 2.328 2.692 (8) 106.3

O4—H4···O5 0.945 2.306 2.752 (8) 108.9

O3—H3···O6v _0.850 _1.949 _{2.770 (4)} _161.6

O4—H4···O5vii _0.945 _1.907 _{2.767 (8)} _150.0

O5—H5···O2i _0.851 _1.878 _{2.729 (4)} _177.7

O6—H7···O4vii _0.820 _2.182 _{2.977 (4)} _163.8

O6—H8···O3viii _0.812 _1.941 _{2.747 (4)} _170.9

O1—H1···O6i _0.830 _1.859 _{2.686 (4)} _174.2