organic compounds
7-Hydroxy-4-(hydroxymethyl)coumarin
aDepartment of Chemistry, Taiyuan Normal University, Taiyuan 030031, People's Republic of China
*Correspondence e-mail: dongjinlong20123@163.com
In the title compound, C10H8O4, the almost planar coumarin ring system (r.m.s. deviation = 0.0216 Å from the plane through all 11 non-H atoms of the system) has hydroxymethyl and hydroxyl substituents at the 4- and 7-positions, respectively. In the crystal, two classical O—H⋯O hydrogen bonds generate a three-dimensional network structure.
Keywords: crystal structure; coumarin; hydrogen bond.
CCDC reference: 1473298
Structure description
The design and synthesis of coumarin derivatives have attracted considerable attention because of their diverse pharmaceutical applications, including antivirus, anti-HIV and anti-neoplasm activities (Cherng et al., 2008; Nawrot-Modranka et al., 2007; Nakagawa-Goto et al., 2007). In 2008, Zhang and co-workers described the preparation of 3-(p-methoxyphenyl)-4-hydroxymethyl-6-bromo-7-hydroxycoumarin co-crystallized from methanol (Jiang et al., 2008). It is well known that variations in substituent groups can alter the biological properties and we have therefore synthesized the title coumarin derivative and report its structure here.
In the title coumarin derivative (Fig. 1), the C1–C5/C11 and O2/C4/C5/C7C9 rings are inclined to one another at an angle of 0.77 (4)°. The C10 and O4 atoms of the hydroxymethyl and the O1 atom of the hydroxyl substituent all lie close to the plane of the ring system with a maximum deviation of 0.055 (1) Å for O4. Bond lengths and angles observed here are closely similar to those found for 3-(p-methoxyphenyl)-4-hydroxymethyl-6-bromo-7-hydroxycoumarin (Jiang et al., 2008). In the crystal, adjacent molecules are aggregated into a three-dimensional supramolecular network by O—H⋯O hydrogen bonds (Table 1 and Fig. 2).
Synthesis and crystallization
Freshly prepared acetyl chloride (1.10 g, 14.02 mmol) was added dropwise to a mixture of 1-(2,4-dihydroxyphenyl)-2- chloroethanone (1.03 g, 5.61 mmol) and K2CO3 (7.73 g, 56.1 mmol) in acetonitrile (70 ml). The mixture was filtered after refluxing for 6 h. The filtrate was neutralized with 2M HCl and extracted with ethyl acetate. The organic layer was washed with Na2CO3 (aq.) and water, dried over anhydrous Na2SO4 and concentrated under reduced pressure to yield a yellow oil. The crude product was purified by to give the title compound as white solid. Colorless crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of this solid in methanol at room temperature for 5 days (yield 0.51 g, 45%).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1473298
10.1107/S2414314616005988/sj4022sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616005988/sj4022Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616005988/sj4022Isup3.cml
Freshly prepared acetyl chloride (1.10 g, 14.02 mmol) was added dropwise to a mixture of 1-(2,4-dihydroxyphenyl)-2- chloroethanone (1.03 g, 5.61 mmol) and K2CO3 (7.73 g, 56.1 mmol) in acetonitrile (70 ml). The mixture was filtered after refluxing for 6 h. The filtrate was neutralized with 2M HCl and extracted with ethyl acetate. The organic layer was washed with Na2CO3 (aq.) and water, dried over anhydrous Na2SO4 and concentrated under reduced pressure to yield a yellow oil. The crude product was purified by
to give the title compound as white solid. Colorless crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of this solid in methanol at room temperature for 5 days (yield 0.51 g, 44.58%).The design and synthesis of coumarin derivatives have attracted considerable attention because of their diverse pharmaceutical applications, including antivirus, anti-HIV and anti-neoplasm activities (Cherng et al., 2008; Nawrot-Modranka et al., 2007; Nakagawa-Goto et al., 2007). In 2008, Zhang and co-workers described the preparation of 3-(p-methoxyphenyl)-4-hydroxymethyl-6-bromo-7-hydroxycoumarin co-crystallized from methanol (Jiang et al., 2008). It is well known that variations in substituent groups can alter the biological properties and we have therefore synthesized the title coumarin derivative and report its structure here.
In the title coumarin derivative, the C1–C5/C11 and O2/C4/C5/C7C9 rings are inclined to one another at an angle of 0.77 (4)°. The C10 and O4 atoms of the hydroxymethyl and the O1 atom of the hydroxyl substituent all lie close to the plane of the ring system with a maximum deviation of 0.055 (1) Å for O4. Bond lengths and angles observed here are closely similar to those found for 3-(p-methoxyphenyl)-4-hydroxymethyl-6-bromo-7-hydroxycoumarin (Jiang et al., 2008). In the crystal, adjacent molecules are aggregated into a three-dimensional supramolecular network by O—H···O hydrogen bonds (Table 1 and Fig. 2).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. | |
Fig. 2. Part of the crystal structure, viewed along a, with hydrogen bonds drawn as dashed lines. |
C10H8O4 | F(000) = 800 |
Mr = 192.16 | Dx = 1.442 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2954 reflections |
a = 13.217 (10) Å | θ = 3.0–26.6° |
b = 9.831 (7) Å | µ = 0.11 mm−1 |
c = 13.627 (9) Å | T = 296 K |
V = 1771 (2) Å3 | Block, colorless |
Z = 8 | 0.33 × 0.30 × 0.30 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1543 independent reflections |
Radiation source: fine-focus sealed tube | 1273 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
φ and ω scans | θmax = 25.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→10 |
Tmin = 0.964, Tmax = 0.967 | k = −11→11 |
9109 measured reflections | l = −12→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0246P)2 + 0.7759P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
1543 reflections | Δρmax = 0.15 e Å−3 |
130 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0102 (14) |
C10H8O4 | V = 1771 (2) Å3 |
Mr = 192.16 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.217 (10) Å | µ = 0.11 mm−1 |
b = 9.831 (7) Å | T = 296 K |
c = 13.627 (9) Å | 0.33 × 0.30 × 0.30 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1543 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1273 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.967 | Rint = 0.027 |
9109 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.15 e Å−3 |
1543 reflections | Δρmin = −0.13 e Å−3 |
130 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.37748 (11) | 0.30023 (12) | 0.36743 (8) | 0.0518 (4) | |
H1 | 0.3289 | 0.2962 | 0.3301 | 0.078* | |
O2 | 0.50816 (9) | 0.10367 (10) | 0.65278 (7) | 0.0422 (3) | |
O3 | 0.58112 (10) | 0.01787 (12) | 0.78346 (8) | 0.0520 (4) | |
O4 | 0.27929 (10) | −0.28639 (10) | 0.74612 (8) | 0.0453 (3) | |
H4 | 0.3219 | −0.3459 | 0.7377 | 0.068* | |
C1 | 0.36957 (14) | 0.20140 (15) | 0.43601 (11) | 0.0400 (4) | |
C2 | 0.29307 (14) | 0.10429 (16) | 0.43439 (11) | 0.0435 (4) | |
H2 | 0.2454 | 0.1051 | 0.3842 | 0.052* | |
C3 | 0.28770 (14) | 0.00731 (16) | 0.50660 (11) | 0.0417 (4) | |
H3 | 0.2360 | −0.0568 | 0.5048 | 0.050* | |
C4 | 0.35857 (13) | 0.00311 (14) | 0.58290 (10) | 0.0348 (4) | |
C5 | 0.43436 (12) | 0.10092 (15) | 0.58148 (10) | 0.0355 (4) | |
C7 | 0.51031 (14) | 0.00963 (16) | 0.72671 (11) | 0.0406 (4) | |
C8 | 0.43095 (14) | −0.08943 (15) | 0.72989 (11) | 0.0399 (4) | |
H8 | 0.4299 | −0.1520 | 0.7811 | 0.048* | |
C9 | 0.35823 (13) | −0.09497 (14) | 0.66163 (10) | 0.0357 (4) | |
C10 | 0.27631 (14) | −0.20065 (15) | 0.66317 (11) | 0.0413 (4) | |
H10A | 0.2112 | −0.1553 | 0.6612 | 0.050* | |
H10B | 0.2820 | −0.2561 | 0.6045 | 0.050* | |
C11 | 0.44128 (14) | 0.19958 (15) | 0.50994 (11) | 0.0407 (4) | |
H11 | 0.4931 | 0.2636 | 0.5113 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0544 (9) | 0.0540 (7) | 0.0471 (7) | −0.0047 (6) | −0.0053 (6) | 0.0131 (5) |
O2 | 0.0395 (7) | 0.0415 (6) | 0.0456 (6) | −0.0050 (5) | −0.0093 (5) | 0.0024 (5) |
O3 | 0.0456 (8) | 0.0535 (7) | 0.0569 (7) | −0.0042 (6) | −0.0191 (6) | 0.0042 (5) |
O4 | 0.0475 (9) | 0.0418 (7) | 0.0465 (6) | 0.0018 (5) | 0.0060 (5) | 0.0042 (5) |
C1 | 0.0449 (11) | 0.0395 (9) | 0.0356 (8) | 0.0042 (7) | 0.0035 (7) | 0.0004 (6) |
C2 | 0.0475 (11) | 0.0458 (9) | 0.0373 (8) | −0.0010 (8) | −0.0084 (7) | −0.0019 (7) |
C3 | 0.0437 (11) | 0.0398 (8) | 0.0416 (8) | −0.0042 (8) | −0.0051 (7) | −0.0036 (6) |
C4 | 0.0366 (10) | 0.0322 (8) | 0.0356 (8) | 0.0030 (7) | 0.0010 (7) | −0.0045 (6) |
C5 | 0.0322 (9) | 0.0378 (8) | 0.0366 (8) | 0.0040 (7) | −0.0021 (7) | −0.0051 (6) |
C7 | 0.0396 (11) | 0.0385 (9) | 0.0438 (9) | 0.0038 (7) | −0.0052 (8) | −0.0027 (7) |
C8 | 0.0422 (11) | 0.0359 (8) | 0.0416 (8) | 0.0014 (7) | −0.0023 (7) | 0.0003 (6) |
C9 | 0.0367 (10) | 0.0324 (8) | 0.0380 (8) | 0.0041 (7) | 0.0018 (7) | −0.0063 (6) |
C10 | 0.0404 (11) | 0.0399 (9) | 0.0437 (8) | −0.0013 (7) | −0.0025 (7) | −0.0002 (7) |
C11 | 0.0385 (11) | 0.0394 (9) | 0.0441 (8) | −0.0024 (7) | 0.0022 (7) | −0.0003 (7) |
O1—C1 | 1.3521 (18) | C3—H3 | 0.9300 |
O1—H1 | 0.8200 | C4—C5 | 1.389 (2) |
O2—C7 | 1.3676 (19) | C4—C9 | 1.442 (2) |
O2—C5 | 1.377 (2) | C5—C11 | 1.378 (2) |
O3—C7 | 1.217 (2) | C7—C8 | 1.432 (3) |
O4—C10 | 1.4106 (19) | C8—C9 | 1.339 (2) |
O4—H4 | 0.8200 | C8—H8 | 0.9300 |
C1—C11 | 1.383 (2) | C9—C10 | 1.501 (2) |
C1—C2 | 1.391 (3) | C10—H10A | 0.9700 |
C2—C3 | 1.372 (2) | C10—H10B | 0.9700 |
C2—H2 | 0.9300 | C11—H11 | 0.9300 |
C3—C4 | 1.400 (2) | ||
C1—O1—H1 | 109.5 | O3—C7—O2 | 116.05 (15) |
C7—O2—C5 | 121.41 (13) | O3—C7—C8 | 126.12 (15) |
C10—O4—H4 | 109.5 | O2—C7—C8 | 117.83 (14) |
O1—C1—C11 | 117.37 (15) | C9—C8—C7 | 122.18 (15) |
O1—C1—C2 | 122.58 (15) | C9—C8—H8 | 118.9 |
C11—C1—C2 | 120.05 (15) | C7—C8—H8 | 118.9 |
C3—C2—C1 | 120.22 (15) | C8—C9—C4 | 119.16 (15) |
C3—C2—H2 | 119.9 | C8—C9—C10 | 122.45 (14) |
C1—C2—H2 | 119.9 | C4—C9—C10 | 118.38 (14) |
C2—C3—C4 | 121.23 (16) | O4—C10—C9 | 113.87 (14) |
C2—C3—H3 | 119.4 | O4—C10—H10A | 108.8 |
C4—C3—H3 | 119.4 | C9—C10—H10A | 108.8 |
C5—C4—C3 | 116.87 (14) | O4—C10—H10B | 108.8 |
C5—C4—C9 | 118.39 (14) | C9—C10—H10B | 108.8 |
C3—C4—C9 | 124.74 (15) | H10A—C10—H10B | 107.7 |
O2—C5—C11 | 115.99 (14) | C5—C11—C1 | 118.60 (15) |
O2—C5—C4 | 120.98 (13) | C5—C11—H11 | 120.7 |
C11—C5—C4 | 123.03 (15) | C1—C11—H11 | 120.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.82 | 1.88 | 2.696 (2) | 179 |
O1—H1···O4ii | 0.82 | 1.83 | 2.654 (2) | 180 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1/2, −y, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.82 | 1.88 | 2.696 (2) | 179.2 |
O1—H1···O4ii | 0.82 | 1.83 | 2.654 (2) | 179.6 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1/2, −y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H8O4 |
Mr | 192.16 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 13.217 (10), 9.831 (7), 13.627 (9) |
V (Å3) | 1771 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.33 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.964, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9109, 1543, 1273 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.078, 1.01 |
No. of reflections | 1543 |
No. of parameters | 130 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.13 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
Financial support from the Science and Technology project of Shanxi Province (No. 20110321044) is gratefully acknowledged.
References
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cherng, J.-M., Chiang, W. & Chiang, L.-C. (2008). Food Chem. 106, 944–950. Web of Science CrossRef CAS Google Scholar
Jiang, H., Zou, H., Xia, P. & Zhang, Q. (2008). Chin. J. Struct. Chem. 27, 1423–1426. CAS Google Scholar
Nakagawa-Goto, K., Yamada, K., Nakamura, S., Chen, T. H., Chiang, P. C., Bastow, K. F., Wang, S. C., Spohn, B., Hung, M. C., Lee, F. Y., Lee, F. C. & Lee, K. H. (2007). Bioorg. Med. Chem. Lett. 17, 5204–5209. Web of Science PubMed CAS Google Scholar
Nawrot-Modranka, J., Nawrot, E. & Graczyk, J. (2007). Eur. J. Med. Chem. 42, 891–891. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.