organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

7-Hy­dr­oxy-4-(hy­dr­oxy­meth­yl)coumarin

aDepartment of Chemistry, Taiyuan Normal University, Taiyuan 030031, People's Republic of China
*Correspondence e-mail: dongjinlong20123@163.com

Edited by J. Simpson, University of Otago, New Zealand (Received 7 April 2016; accepted 11 April 2016; online 15 April 2016)

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.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

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[Cherng, J.-M., Chiang, W. & Chiang, L.-C. (2008). Food Chem. 106, 944-950.]; Nawrot-Modranka et al., 2007[Nawrot-Modranka, J., Nawrot, E. & Graczyk, J. (2007). Eur. J. Med. Chem. 42, 891-891.]; Nakagawa-Goto et al., 2007[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.]). 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[Jiang, H., Zou, H., Xia, P. & Zhang, Q. (2008). Chin. J. Struct. Chem. 27, 1423-1426.]). 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[link]), 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[Jiang, H., Zou, H., Xia, P. & Zhang, Q. (2008). Chin. J. Struct. Chem. 27, 1423-1426.]). In the crystal, adjacent mol­ecules are aggregated into a three-dimensional supra­molecular network by O—H⋯O hydrogen bonds (Table 1[link] and Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}].
[Figure 1]
Figure 1
The mol­ecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
[Figure 2]
Figure 2
Part of the crystal structure, viewed along a, with hydrogen bonds drawn as dashed lines.

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 chromatography 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 refinement details are summarized in Table 2[link].

Table 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)
V3) 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.])
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−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 and SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Structural data


Experimental top

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 chromatography 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%).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2.

Structure description top

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).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure, viewed along a, with hydrogen bonds drawn as dashed lines.
7-Hydroxy-4-(hydroxymethyl)-2-oxo-2H-chromene top
Crystal data top
C10H8O4F(000) = 800
Mr = 192.16Dx = 1.442 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2954 reflections
a = 13.217 (10) Åθ = 3.0–26.6°
b = 9.831 (7) ŵ = 0.11 mm1
c = 13.627 (9) ÅT = 296 K
V = 1771 (2) Å3Block, colorless
Z = 80.33 × 0.30 × 0.30 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1543 independent reflections
Radiation source: fine-focus sealed tube1273 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
φ and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1510
Tmin = 0.964, Tmax = 0.967k = 1111
9109 measured reflectionsl = 1216
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-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 reflectionsΔρmax = 0.15 e Å3
130 parametersΔρmin = 0.13 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0102 (14)
Crystal data top
C10H8O4V = 1771 (2) Å3
Mr = 192.16Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 13.217 (10) ŵ = 0.11 mm1
b = 9.831 (7) ÅT = 296 K
c = 13.627 (9) Å0.33 × 0.30 × 0.30 mm
Data collection top
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 = 0.967Rint = 0.027
9109 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.078H-atom parameters constrained
S = 1.01Δρmax = 0.15 e Å3
1543 reflectionsΔρmin = 0.13 e Å3
130 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.37748 (11)0.30023 (12)0.36743 (8)0.0518 (4)
H10.32890.29620.33010.078*
O20.50816 (9)0.10367 (10)0.65278 (7)0.0422 (3)
O30.58112 (10)0.01787 (12)0.78346 (8)0.0520 (4)
O40.27929 (10)0.28639 (10)0.74612 (8)0.0453 (3)
H40.32190.34590.73770.068*
C10.36957 (14)0.20140 (15)0.43601 (11)0.0400 (4)
C20.29307 (14)0.10429 (16)0.43439 (11)0.0435 (4)
H20.24540.10510.38420.052*
C30.28770 (14)0.00731 (16)0.50660 (11)0.0417 (4)
H30.23600.05680.50480.050*
C40.35857 (13)0.00311 (14)0.58290 (10)0.0348 (4)
C50.43436 (12)0.10092 (15)0.58148 (10)0.0355 (4)
C70.51031 (14)0.00963 (16)0.72671 (11)0.0406 (4)
C80.43095 (14)0.08943 (15)0.72989 (11)0.0399 (4)
H80.42990.15200.78110.048*
C90.35823 (13)0.09497 (14)0.66163 (10)0.0357 (4)
C100.27631 (14)0.20065 (15)0.66317 (11)0.0413 (4)
H10A0.21120.15530.66120.050*
H10B0.28200.25610.60450.050*
C110.44128 (14)0.19958 (15)0.50994 (11)0.0407 (4)
H110.49310.26360.51130.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0544 (9)0.0540 (7)0.0471 (7)0.0047 (6)0.0053 (6)0.0131 (5)
O20.0395 (7)0.0415 (6)0.0456 (6)0.0050 (5)0.0093 (5)0.0024 (5)
O30.0456 (8)0.0535 (7)0.0569 (7)0.0042 (6)0.0191 (6)0.0042 (5)
O40.0475 (9)0.0418 (7)0.0465 (6)0.0018 (5)0.0060 (5)0.0042 (5)
C10.0449 (11)0.0395 (9)0.0356 (8)0.0042 (7)0.0035 (7)0.0004 (6)
C20.0475 (11)0.0458 (9)0.0373 (8)0.0010 (8)0.0084 (7)0.0019 (7)
C30.0437 (11)0.0398 (8)0.0416 (8)0.0042 (8)0.0051 (7)0.0036 (6)
C40.0366 (10)0.0322 (8)0.0356 (8)0.0030 (7)0.0010 (7)0.0045 (6)
C50.0322 (9)0.0378 (8)0.0366 (8)0.0040 (7)0.0021 (7)0.0051 (6)
C70.0396 (11)0.0385 (9)0.0438 (9)0.0038 (7)0.0052 (8)0.0027 (7)
C80.0422 (11)0.0359 (8)0.0416 (8)0.0014 (7)0.0023 (7)0.0003 (6)
C90.0367 (10)0.0324 (8)0.0380 (8)0.0041 (7)0.0018 (7)0.0063 (6)
C100.0404 (11)0.0399 (9)0.0437 (8)0.0013 (7)0.0025 (7)0.0002 (7)
C110.0385 (11)0.0394 (9)0.0441 (8)0.0024 (7)0.0022 (7)0.0003 (7)
Geometric parameters (Å, º) top
O1—C11.3521 (18)C3—H30.9300
O1—H10.8200C4—C51.389 (2)
O2—C71.3676 (19)C4—C91.442 (2)
O2—C51.377 (2)C5—C111.378 (2)
O3—C71.217 (2)C7—C81.432 (3)
O4—C101.4106 (19)C8—C91.339 (2)
O4—H40.8200C8—H80.9300
C1—C111.383 (2)C9—C101.501 (2)
C1—C21.391 (3)C10—H10A0.9700
C2—C31.372 (2)C10—H10B0.9700
C2—H20.9300C11—H110.9300
C3—C41.400 (2)
C1—O1—H1109.5O3—C7—O2116.05 (15)
C7—O2—C5121.41 (13)O3—C7—C8126.12 (15)
C10—O4—H4109.5O2—C7—C8117.83 (14)
O1—C1—C11117.37 (15)C9—C8—C7122.18 (15)
O1—C1—C2122.58 (15)C9—C8—H8118.9
C11—C1—C2120.05 (15)C7—C8—H8118.9
C3—C2—C1120.22 (15)C8—C9—C4119.16 (15)
C3—C2—H2119.9C8—C9—C10122.45 (14)
C1—C2—H2119.9C4—C9—C10118.38 (14)
C2—C3—C4121.23 (16)O4—C10—C9113.87 (14)
C2—C3—H3119.4O4—C10—H10A108.8
C4—C3—H3119.4C9—C10—H10A108.8
C5—C4—C3116.87 (14)O4—C10—H10B108.8
C5—C4—C9118.39 (14)C9—C10—H10B108.8
C3—C4—C9124.74 (15)H10A—C10—H10B107.7
O2—C5—C11115.99 (14)C5—C11—C1118.60 (15)
O2—C5—C4120.98 (13)C5—C11—H11120.7
C11—C5—C4123.03 (15)C1—C11—H11120.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O3i0.821.882.696 (2)179
O1—H1···O4ii0.821.832.654 (2)180
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x+1/2, y, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O3i0.821.882.696 (2)179.2
O1—H1···O4ii0.821.832.654 (2)179.6
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x+1/2, y, z1/2.

Experimental details

Crystal data
Chemical formulaC10H8O4
Mr192.16
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)13.217 (10), 9.831 (7), 13.627 (9)
V3)1771 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.33 × 0.30 × 0.30
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.964, 0.967
No. of measured, independent and
observed [I > 2σ(I)] reflections
9109, 1543, 1273
Rint0.027
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.078, 1.01
No. of reflections1543
No. of parameters130
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCherng, J.-M., Chiang, W. & Chiang, L.-C. (2008). Food Chem. 106, 944–950.  Web of Science CrossRef CAS Google Scholar
First citationJiang, H., Zou, H., Xia, P. & Zhang, Q. (2008). Chin. J. Struct. Chem. 27, 1423–1426.  CAS Google Scholar
First citationNakagawa-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
First citationNawrot-Modranka, J., Nawrot, E. & Graczyk, J. (2007). Eur. J. Med. Chem. 42, 891–891.  CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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