7-Hy­droxy-4-(hy­droxy­meth­yl)coumarin

Bai, J.-H.; Dong, J.-L.

doi:10.1107/S2414314616005988

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160598

doi:10.1107/S2414314616005988

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7-Hydroxy-4-(hydroxymethyl)coumarin

Jun-Hua Bai ^a and Jin-Long Dong ^a ^*

^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.

Keywords: crystal structure; coumarin; hydrogen bond.

CCDC reference: 1473298

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Chemical scheme

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).

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

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.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₈O₄
M_r	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 )
T_min, T_max	0.964, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	9109, 1543, 1273
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.13
Computer programs: SMART and SAINT (Bruker, 2007 ), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1473298

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616005988/sj4022sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616005988/sj4022Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616005988/sj4022Isup3.cml

checkCIF report

Experimental top

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

	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.

7-Hydroxy-4-(hydroxymethyl)-2-oxo-2H-chromene top

Crystal data top

C₁₀H₈O₄	F(000) = 800
M_r = 192.16	D_x = 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

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1543 independent reflections
Radiation source: fine-focus sealed tube	1273 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→10
T_min = 0.964, T_max = 0.967	k = −11→11
9109 measured reflections	l = −12→16

Refinement top

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(F_o²) + (0.0246P)² + 0.7759P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1543 reflections	Δρ_max = 0.15 e Å⁻³
130 parameters	Δρ_min = −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)

Crystal data top

C₁₀H₈O₄	V = 1771 (2) Å³
M_r = 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

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)
T_min = 0.964, T_max = 0.967	R_int = 0.027
9109 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.01	Δρ_max = 0.15 e Å⁻³
1543 reflections	Δρ_min = −0.13 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.964, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	9109, 1543, 1273
R_int	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
Δρ_max, Δρ_min (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

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