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In the crystal structure of the title compound, phenyl(2,3,4-trihydroxyphenyl)methanone monohydrate, C13H10O4·H2O, two benzene rings are inclined at 44.6 (5)° to each other, and the carbonyl O atom of the benzoyl group lies nearly in the 2,3,4-trihydroxybenzene ring plane. 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 of the available hydrogen bonds and by stacking interactions between adjacent molecules.
Supporting information
CCDC reference: 185801
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.005 Å
- R factor = 0.043
- wR factor = 0.184
- Data-to-parameter ratio = 16.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
A pale-yellow needle crystal was obtained by slow evaporation from a 50%
methanol–water solution.
All H atoms were located from difference Fourier maps; their positions were
idealized and refined with a riding model. Restraints were applied to the H
atoms of the water molecule.
Data collection: MSC/AFC (Molecular Structure Corporation, Rigaku Corporation, 1999); cell refinement: MSC/AFC; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999) and DIRDIF94 (Beurskens et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Crystal data top
C13H10O4·H2O | F(000) = 1040.0 |
Mr = 248.23 | Dx = 1.412 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 33.365 (4) Å | θ = 11.3–13.2° |
b = 3.991 (2) Å | µ = 0.11 mm−1 |
c = 20.837 (3) Å | T = 296 K |
β = 122.679 (9)° | Needle, pale yellow |
V = 2335.5 (12) Å3 | 0.50 × 0.15 × 0.05 mm |
Z = 8 | |
Data collection top
Rigaku AFC-5R diffractometer | θmax = 27.5° |
ω–2θ scans | h = 0→42 |
3112 measured reflections | k = 0→5 |
2675 independent reflections | l = −27→22 |
1050 reflections with I > 2σ(I) | 3 standard reflections every 150 reflections |
Rint = 0.057 | intensity decay: 0.2% |
Refinement top
Refinement on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.184 | (Δ/σ)max < 0.001 |
S = 0.86 | Δρmax = 0.21 e Å−3 |
2675 reflections | Δρmin = −0.21 e Å−3 |
166 parameters | |
Crystal data top
C13H10O4·H2O | V = 2335.5 (12) Å3 |
Mr = 248.23 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.365 (4) Å | µ = 0.11 mm−1 |
b = 3.991 (2) Å | T = 296 K |
c = 20.837 (3) Å | 0.50 × 0.15 × 0.05 mm |
β = 122.679 (9)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.057 |
3112 measured reflections | 3 standard reflections every 150 reflections |
2675 independent reflections | intensity decay: 0.2% |
1050 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 166 parameters |
wR(F2) = 0.184 | H-atom parameters not refined |
S = 0.86 | Δρmax = 0.21 e Å−3 |
2675 reflections | Δρmin = −0.21 e Å−3 |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
O2 | 0.77764 (7) | −0.0444 (7) | 0.0854 (1) | 0.0573 (7) | |
O3 | 0.77694 (7) | 0.0804 (7) | 0.2131 (1) | 0.0516 (7) | |
O4 | 0.85390 (8) | 0.3741 (8) | 0.3361 (1) | 0.0630 (8) | |
O5 | 0.82160 (8) | 0.0127 (8) | 0.0167 (1) | 0.0649 (8) | |
O6 | 0.78910 (7) | −0.1207 (6) | −0.1346 (1) | 0.0506 (7) | |
C1 | 0.8571 (1) | 0.1898 (8) | 0.1432 (2) | 0.0374 (7) | |
C2 | 0.8166 (1) | 0.1023 (8) | 0.1447 (2) | 0.0377 (7) | |
C3 | 0.8156 (1) | 0.1609 (9) | 0.2096 (2) | 0.0385 (7) | |
C4 | 0.8537 (1) | 0.3130 (8) | 0.2722 (2) | 0.0403 (8) | |
C5 | 0.8930 (1) | 0.4161 (8) | 0.2705 (2) | 0.0448 (8) | |
C6 | 0.8946 (1) | 0.3544 (8) | 0.2077 (2) | 0.0407 (8) | |
C7 | 0.8582 (1) | 0.1151 (9) | 0.0762 (2) | 0.0442 (8) | |
C8 | 0.9027 (1) | 0.1483 (8) | 0.0752 (2) | 0.0388 (7) | |
C9 | 0.9462 (1) | 0.0318 (9) | 0.1340 (2) | 0.0459 (8) | |
C10 | 0.9856 (1) | 0.0469 (10) | 0.1289 (2) | 0.0544 (10) | |
C11 | 0.9818 (1) | 0.180 (1) | 0.0649 (2) | 0.060 (1) | |
C12 | 0.9386 (1) | 0.294 (1) | 0.0059 (2) | 0.060 (1) | |
C13 | 0.8988 (1) | 0.2783 (10) | 0.0100 (2) | 0.0510 (9) | |
H2 | 0.7804 | −0.0536 | 0.0487 | 0.0859* | |
H3 | 0.7604 | −0.0561 | 0.1796 | 0.0774* | |
H4 | 0.8323 | 0.2686 | 0.3347 | 0.0945* | |
H5 | 0.9180 | 0.5268 | 0.3122 | 0.0560* | |
H6 | 0.9211 | 0.4227 | 0.2072 | 0.0509* | |
H9 | 0.9489 | −0.0575 | 0.1774 | 0.0574* | |
H10 | 1.0148 | −0.0329 | 0.1687 | 0.0680* | |
H11 | 1.0085 | 0.1930 | 0.0616 | 0.0755* | |
H12 | 0.9361 | 0.3825 | −0.0374 | 0.0748* | |
H13 | 0.8696 | 0.3542 | −0.0304 | 0.0637* | |
H14 | 0.7766 | 0.0626 | −0.1581 | 0.0949* | |
H15 | 0.7997 | −0.0766 | −0.0880 | 0.0949* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.043 (1) | 0.096 (2) | 0.035 (1) | −0.020 (1) | 0.023 (1) | −0.019 (1) |
O3 | 0.044 (1) | 0.076 (2) | 0.044 (1) | −0.015 (1) | 0.030 (1) | −0.016 (1) |
O4 | 0.063 (2) | 0.095 (2) | 0.043 (1) | −0.026 (2) | 0.036 (1) | −0.025 (1) |
O5 | 0.047 (1) | 0.113 (2) | 0.036 (1) | −0.018 (2) | 0.024 (1) | −0.015 (1) |
O6 | 0.054 (1) | 0.068 (2) | 0.036 (1) | −0.005 (1) | 0.028 (1) | −0.005 (1) |
C1 | 0.039 (2) | 0.045 (2) | 0.030 (1) | 0.001 (2) | 0.020 (1) | 0.003 (1) |
C2 | 0.034 (2) | 0.047 (2) | 0.031 (1) | −0.001 (2) | 0.017 (1) | −0.001 (2) |
C3 | 0.035 (2) | 0.046 (2) | 0.037 (2) | 0.002 (2) | 0.021 (1) | 0.000 (2) |
C4 | 0.043 (2) | 0.047 (2) | 0.035 (1) | −0.003 (2) | 0.025 (1) | −0.006 (2) |
C5 | 0.043 (2) | 0.051 (2) | 0.037 (1) | −0.010 (2) | 0.020 (1) | −0.011 (2) |
C6 | 0.037 (2) | 0.047 (2) | 0.041 (2) | −0.007 (2) | 0.023 (1) | −0.003 (2) |
C7 | 0.045 (2) | 0.055 (2) | 0.033 (2) | −0.001 (2) | 0.022 (1) | 0.000 (2) |
C8 | 0.042 (2) | 0.045 (2) | 0.033 (1) | −0.005 (2) | 0.023 (1) | −0.006 (1) |
C9 | 0.052 (2) | 0.049 (2) | 0.042 (2) | −0.002 (2) | 0.028 (2) | −0.001 (2) |
C10 | 0.046 (2) | 0.063 (3) | 0.052 (2) | −0.002 (2) | 0.024 (2) | −0.009 (2) |
C11 | 0.055 (2) | 0.080 (3) | 0.062 (2) | −0.016 (2) | 0.043 (2) | −0.019 (2) |
C12 | 0.069 (2) | 0.075 (3) | 0.051 (2) | −0.016 (2) | 0.042 (2) | −0.003 (2) |
C13 | 0.056 (2) | 0.063 (2) | 0.038 (2) | −0.004 (2) | 0.028 (2) | 0.003 (2) |
Geometric parameters (Å, º) top
O2—C2 | 1.351 (3) | C5—C6 | 1.363 (6) |
O2—H2 | 0.820 | C5—H5 | 0.930 |
O3—C3 | 1.370 (5) | C6—H6 | 0.930 |
O3—H3 | 0.820 | C7—C8 | 1.500 (6) |
O4—C4 | 1.350 (5) | C8—C9 | 1.380 (4) |
O4—H4 | 0.820 | C8—C13 | 1.393 (6) |
O5—C7 | 1.250 (3) | C9—C10 | 1.377 (7) |
O6—H14 | 0.853 | C9—H9 | 0.930 |
O6—H15 | 0.854 | C10—C11 | 1.377 (6) |
C1—C2 | 1.411 (5) | C10—H10 | 0.930 |
C1—C6 | 1.409 (4) | C11—C12 | 1.371 (4) |
C1—C7 | 1.449 (5) | C11—H11 | 0.930 |
C2—C3 | 1.392 (5) | C12—C13 | 1.377 (7) |
C3—C4 | 1.375 (4) | C12—H12 | 0.930 |
C4—C5 | 1.393 (6) | C13—H13 | 0.930 |
| | | |
O2···O6i | 3.204 (4) | O3···O3iv | 3.545 (5) |
O2···O5i | 3.373 (3) | O3···O3v | 3.545 (5) |
O2···O2i | 3.416 (4) | O4···O6iii | 2.737 (4) |
O2···O5ii | 3.519 (3) | O4···C13vi | 3.382 (4) |
O3···O6i | 2.646 (3) | O4···C12vi | 3.385 (4) |
O3···O6ii | 2.879 (3) | O6···C3ii | 3.482 (4) |
O3···O6iii | 2.978 (4) | C1···C6vii | 3.559 (4) |
| | | |
C2—O2—H2 | 109.5 | O5—C7—C1 | 120.2 (4) |
C3—O3—H3 | 109.5 | O5—C7—C8 | 117.4 (3) |
C4—O4—H4 | 109.5 | C1—C7—C8 | 122.4 (2) |
H14—O6—H15 | 104.4 | C7—C8—C9 | 122.1 (3) |
C2—C1—C6 | 117.6 (3) | C7—C8—C13 | 118.3 (3) |
C2—C1—C7 | 119.5 (2) | C9—C8—C13 | 119.4 (4) |
C6—C1—C7 | 122.9 (3) | C8—C9—C10 | 120.5 (4) |
O2—C2—C1 | 123.3 (3) | C8—C9—H9 | 119.8 |
O2—C2—C3 | 116.4 (3) | C10—C9—H9 | 119.8 |
C1—C2—C3 | 120.3 (2) | C9—C10—C11 | 120.0 (3) |
O3—C3—C2 | 122.0 (2) | C9—C10—H10 | 120.0 |
O3—C3—C4 | 117.8 (3) | C11—C10—H10 | 120.0 |
C2—C3—C4 | 120.1 (3) | C10—C11—C12 | 119.9 (4) |
O4—C4—C3 | 121.8 (4) | C10—C11—H11 | 120.1 |
O4—C4—C5 | 117.9 (3) | C12—C11—H11 | 120.1 |
C3—C4—C5 | 120.4 (4) | C11—C12—C13 | 120.8 (4) |
C4—C5—C6 | 119.8 (3) | C11—C12—H12 | 119.6 |
C4—C5—H5 | 120.1 | C13—C12—H12 | 119.6 |
C6—C5—H5 | 120.1 | C8—C13—C12 | 119.5 (3) |
C1—C6—C5 | 121.6 (3) | C8—C13—H13 | 120.3 |
C1—C6—H6 | 119.2 | C12—C13—H13 | 120.2 |
C5—C6—H6 | 119.2 | | |
| | | |
O2—C2—C1—C6 | 177.4 (3) | C2—C1—C6—C5 | 2.5 (5) |
O2—C2—C1—C7 | −1.4 (5) | C2—C1—C7—C8 | −169.7 (3) |
O2—C2—C3—O3 | −1.2 (5) | C2—C3—C4—C5 | 1.4 (5) |
O2—C2—C3—C4 | −179.2 (3) | C3—C2—C1—C6 | −3.6 (5) |
O3—C3—C2—C1 | 179.8 (3) | C3—C2—C1—C7 | 177.6 (3) |
O3—C3—C4—O4 | 1.8 (5) | C3—C4—C5—C6 | −2.5 (5) |
O3—C3—C4—C5 | −176.7 (3) | C5—C6—C1—C7 | −178.8 (3) |
O4—C4—C3—C2 | 179.9 (3) | C6—C1—C7—C8 | 11.7 (5) |
O4—C4—C5—C6 | 178.9 (3) | C7—C8—C9—C10 | 175.7 (3) |
O5—C7—C1—C2 | 8.9 (5) | C7—C8—C13—C12 | −176.3 (3) |
O5—C7—C1—C6 | −169.8 (3) | C8—C9—C10—C11 | 0.3 (6) |
O5—C7—C8—C9 | −134.0 (4) | C8—C13—C12—C11 | 0.6 (6) |
O5—C7—C8—C13 | 41.1 (5) | C9—C8—C13—C12 | −1.1 (5) |
C1—C2—C3—C4 | 1.7 (5) | C9—C10—C11—C12 | −0.8 (6) |
C1—C6—C5—C4 | 0.5 (5) | C10—C9—C8—C13 | 0.7 (5) |
C1—C7—C8—C9 | 44.6 (5) | C10—C11—C12—C13 | 0.4 (6) |
C1—C7—C8—C13 | −140.3 (3) | C10—C11—C12—C13 | 0.4 (6) |
Symmetry codes: (i) −x+3/2, −y−1/2, −z; (ii) −x+3/2, −y+1/2, −z; (iii) x, −y, z+1/2; (iv) −x+3/2, y+1/2, −z+1/2; (v) −x+3/2, y−1/2, −z+1/2; (vi) x, −y+1, z+1/2; (vii) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O5 | 0.82 | 1.84 | 2.553 (3) | 145 |
O3—H3···O6i | 0.82 | 1.90 | 2.646 (3) | 152 |
O3—H3···O2 | 0.82 | 2.33 | 2.720 (3) | 110 |
O4—H4···O6iii | 0.82 | 1.96 | 2.737 (3) | 158 |
O4—H4···O3 | 0.82 | 2.31 | 2.726 (3) | 112 |
O6—H14···O3ii | 0.85 | 2.08 | 2.879 (4) | 156 |
O6—H15···O5 | 0.85 | 1.92 | 2.776 (3) | 178 |
Symmetry codes: (i) −x+3/2, −y−1/2, −z; (ii) −x+3/2, −y+1/2, −z; (iii) x, −y, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C13H10O4·H2O |
Mr | 248.23 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 33.365 (4), 3.991 (2), 20.837 (3) |
β (°) | 122.679 (9) |
V (Å3) | 2335.5 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.50 × 0.15 × 0.05 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3112, 2675, 1050 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.184, 0.86 |
No. of reflections | 2675 |
No. of parameters | 166 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.21, −0.21 |
Selected geometric parameters (Å, º) topO2—C2 | 1.351 (3) | C4—C5 | 1.393 (6) |
O3—C3 | 1.370 (5) | C5—C6 | 1.363 (6) |
O4—C4 | 1.350 (5) | C7—C8 | 1.500 (6) |
O5—C7 | 1.250 (3) | C8—C9 | 1.380 (4) |
C1—C2 | 1.411 (5) | C8—C13 | 1.393 (6) |
C1—C6 | 1.409 (4) | C9—C10 | 1.377 (7) |
C1—C7 | 1.449 (5) | C10—C11 | 1.377 (6) |
C2—C3 | 1.392 (5) | C11—C12 | 1.371 (4) |
C3—C4 | 1.375 (4) | C12—C13 | 1.377 (7) |
| | | |
C2—C1—C6 | 117.6 (3) | C1—C6—C5 | 121.6 (3) |
C2—C1—C7 | 119.5 (2) | O5—C7—C1 | 120.2 (4) |
C6—C1—C7 | 122.9 (3) | O5—C7—C8 | 117.4 (3) |
O2—C2—C1 | 123.3 (3) | C1—C7—C8 | 122.4 (2) |
O2—C2—C3 | 116.4 (3) | C7—C8—C9 | 122.1 (3) |
C1—C2—C3 | 120.3 (2) | C7—C8—C13 | 118.3 (3) |
O3—C3—C2 | 122.0 (2) | C9—C8—C13 | 119.4 (4) |
O3—C3—C4 | 117.8 (3) | C8—C9—C10 | 120.5 (4) |
C2—C3—C4 | 120.1 (3) | C9—C10—C11 | 120.0 (3) |
O4—C4—C3 | 121.8 (4) | C10—C11—C12 | 119.9 (4) |
O4—C4—C5 | 117.9 (3) | C11—C12—C13 | 120.8 (4) |
C3—C4—C5 | 120.4 (4) | C8—C13—C12 | 119.5 (3) |
C4—C5—C6 | 119.8 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O5 | 0.82 | 1.84 | 2.553 (3) | 145 |
O3—H3···O6i | 0.82 | 1.90 | 2.646 (3) | 152 |
O3—H3···O2 | 0.82 | 2.33 | 2.720 (3) | 110 |
O4—H4···O6ii | 0.82 | 1.96 | 2.737 (3) | 158 |
O4—H4···O3 | 0.82 | 2.31 | 2.726 (3) | 112 |
O6—H14···O3iii | 0.85 | 2.08 | 2.879 (4) | 156 |
O6—H15···O5 | 0.85 | 1.92 | 2.776 (3) | 178 |
Symmetry codes: (i) −x+3/2, −y−1/2, −z; (ii) x, −y, z+1/2; (iii) −x+3/2, −y+1/2, −z. |
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The title compound, (I), is a model compound of exifone (AdloneR), a drug which was launched in France for the treatment of cognitive disorders in the elderly. Exifone has three hydroxyl groups at positions 2,3,4- and three at positions 3',4',5'- on the two benzene rings of the molecule. It has demonstrated remarkable scavenger properties against free radicals; this may be an etiological factor, but it was withdrawn from the market because of its hepatotoxic effects (Largeron et al., 1995, 1998). The oxidation chemistry of exifone was studied to obtain information about the mechanism of the pharmacological action of exifone, and (I) was used as the starting material. In that study, the hydrogen bonding between the OH group at the 2-position of the 2,3,4-trihydroxyphenyl ring and the O atom of the carbonyl of the benzoyl group are supposed to be important for formation of a 1,4-benzoxazine derivative of compound (I). The authors noticed the strong intramolecular hydrogen bond reported in the crystal structures of 2-hydroxy-4-methoxybenzophenone (Liebich & Parthé, 1974) and 2,4-dihydroxybenzophenone (Liebich, 1979). We have been interested in the structural features of polyphenols, because some polyphenols, such as gallic acid (3,4,5-trihydroxybenzoic acid) and protocathecuic acid (3,4-dihydroxybenzoic acid), have anti-oxidative and antitumor activity (Isuzugawa et al., 2001; Sakaguchi et al., 1999; Satoh & Sakagami, 1997; Kawase et al., 1998). We aimed to determine the structure of (I), which is a polyphenol.
The molecular structure of compound (I) is shown in Fig. 1. The two benzene rings are inclined to each other, as indicated by the torsion angle of 44.6 (5)° for C1—C7—C8—C9, and the carbonyl O atom of the benzoyl group lies nearly in the trihydroxybenzene ring plane, as indicated by the torsion angle of 8.9 (5)° for O5—C7—C1—C2. All three hydroxyl groups form intra- and intermolecular hydrogen bonds involving the hydrate water molecule, as shown in Table 2. Considering the distances between the donor and the acceptor O atoms, the hydrogen bonding between the hydroxyl group at the 2-position and the O atom of the carbonyl of the benzoyl group seems to be the strongest. The distance of 2.555 Å agrees well with those of the corresponding hydrogen bond, of 2.55 Å in 2-hydroxy-4-methoxybenzophenones (Liebich & Parthé, 1974) and of 2.550 (4) Å in 2,4-dihydroxybenzophenone (Liebich, 1979). The presence of this strong intramolecular hydrogen bond in compound (I) may provide direct evidence for the hypothesis in the oxidation reaction of 2,3,4-trihydroxybenzophenone reported by Largeron et al. (1995, 1998). The hydroxyl groups at positions 3 and 4 are linked to the water O atom by bifurcated hydrogen bonds. The orientation of the three hydroxyl groups and the formation of intramolecular hydrogen bonds are similar to those observed in gallic acid (3,4,5-trihydroxybenzoic acid) (Okabe et al., 2001), propyl gallate (Okabe & Kyoyama, 2002) and octyl gallate (Jeffrey & Yeon, 1990). The hydrogen-bonding patterns observeded in this study may have a role in the biological activity or oxidation reactions of many antioxidative polyphenols. The crystal structure is stabilized by all of the available hydrogen bonds involving the water molecule and by stacking interactions between symmetry-related rings of adjacent molecules.