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The crystal structure determination of the title compound (also known as 7-hydr­oxy-4-methyl­coumarin), C10H8O3, has been reported previously [Shimizu, Kashino & Haisa (1975). Acta Cryst. B31, 1287-1292], but with incomplete crystallographic data. The present redetermination confirms the previous study, but with higher precision and full crystallographic data.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056085/ez2107sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056085/ez2107Isup2.hkl
Contains datablock I

CCDC reference: 616613

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.038
  • wR factor = 0.098
  • Data-to-parameter ratio = 7.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.99 Deg.
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.30 PLAT432_ALERT_2_C Short Inter X...Y Contact O3 .. C1 .. 2.99 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 24.99 From the CIF: _reflns_number_total 869 Count of symmetry unique reflns 870 Completeness (_total/calc) 99.89% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

7-Hydroxycoumarin derivatives have a broad range of biological activities, including as antioxidants (Sharma et al., 2005), and for the inhibition of acetylcholinesterase and monoamine oxidase (Rollinger et al.,2004; Brühlmann et al., 2001). The crystal structure of compound (I) has been reported previously, but with incomplete crystallographic data (Shimizu et al.,1975). We redetermined the crystal structure of compound (I), which we describe in this paper.

In the molecule of (I), the average C—C and C—O distances are 1.392 (4) Å and 1.371 (2) Å, respectively, slightly less than the previously reported values [1.40 Å and 1.373 Å; Shimizu et al. (1975)] (Fig. 1).

In the crystal packing of (I), the molecules are linked into a C22(16) chain by O—H···O hydrogen bonds (Bernstein et al., 1995) along the [0 0 1] direction (Fig. 2 and Table 1), with atom O3 acting as hydrogen-bond donor to atom O2 in the molecule at (-1/2 - x,-y,1/2 + z). The molecules are further linked by C—H···O hydrogen bonds, between atom C2 and atom O2 at (1/2 + x,1/2 - y,-z), forming a C22(8) chain along the [1 0 0] direction (Fig. 3 and Table 1),.

Related literature top

For the previously determined crystal structure, see: Shimizu et al. (1975). For related literature regarding the uses of 7-hydroxycoumarin derivatives, see: Brühlmann et al. (2001); Rollinger et al. (2004); Sharma et al. (2005). For related literature, see: Bernstein et al. (1995).

Experimental top

The reaction mixture containing resorcinol (1.10 g, 10 mmol), acetoacetic ester (1.3 ml, 10 mmol) and phosphoric acid (5.3 ml) was stirred at 343–353 K for 12 h, and then poured into water. The solid obtained was filtered off, washed with water and dried at room temperature. Colourless crystals of (I) suitable for X-ray structure analysis were obtained by slow evaporation of a solution of the crude product in acetone-petroleum benzine (1:1) over two weeks. (m. p. 463–465 K).

Refinement top

All H atoms were positioned geometrically and refined as riding on their parent atoms, with C—H = 0.96 Å, O—H = 0.82 Å, and Uiso(H)= 1.5Ueq(C,O) for methyl H atoms and hydroxy H atoms, and C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for all other H atoms. In the absence of significant anomalous scattering effects Friedel pairs have been merged.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I), viewed down the b axis, showing the formation of a [0 0 1] C22(16) chain built from O—H···O hydrogen bonds. For clarity, H atoms not involved in the motifs shown have been omitted. Dashed lines indicate hydrogen bonds [symmetry codes: (*)-1/2 - x,-y,1/2 + z; (#)-1/2 - x,-y,-1/2 + z; (&)x,y,1 + z].
[Figure 3] Fig. 3. Part of the crystal structure of (I), viewed down the b axis, showing the formation of a [1 0 0] C22(8) chain built from C—H···O hydrogen bonds. For clarity, H atoms not involved in the motifs shown have been omitted. Dashed lines indicate hydrogen bonds [symmetry codes: (*)1/2 + x,1/2 - y,-z; (#)-1/2 + x,1/2 - y,-z; (&)1 + x,y,z].
7-hydroxy-4-methyl-2H-1-Benzopyran-2-one top
Crystal data top
C10H8O3Dx = 1.432 Mg m3
Mr = 176.16Melting point: 463 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1640 reflections
a = 5.229 (3) Åθ = 2.3–25.2°
b = 11.875 (6) ŵ = 0.11 mm1
c = 13.161 (6) ÅT = 298 K
V = 817.3 (7) Å3Columnar, colourless
Z = 40.48 × 0.40 × 0.31 mm
F(000) = 368
Data collection top
Siemens SMART 1000 CCD area detector
diffractometer
869 independent reflections
Radiation source: fine-focus sealed tube732 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
ϕ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 65
Tmin = 0.951, Tmax = 0.968k = 1412
4236 measured reflectionsl = 1415
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)] = 0.038H-atom parameters constrained
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0516P)2 + 0.1639P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
869 reflectionsΔρmax = 0.20 e Å3
119 parametersΔρmin = 0.23 e Å3
0 restraintsAbsolute structure: Flack (1983), 565 Freidel pairs
Primary atom site location: structure-invariant direct methods
Crystal data top
C10H8O3V = 817.3 (7) Å3
Mr = 176.16Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.229 (3) ŵ = 0.11 mm1
b = 11.875 (6) ÅT = 298 K
c = 13.161 (6) Å0.48 × 0.40 × 0.31 mm
Data collection top
Siemens SMART 1000 CCD area detector
diffractometer
869 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
732 reflections with I > 2σ(I)
Tmin = 0.951, Tmax = 0.968Rint = 0.044
4236 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.08Δρmax = 0.20 e Å3
869 reflectionsΔρmin = 0.23 e Å3
119 parametersAbsolute structure: Flack (1983), 565 Freidel pairs
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
O10.0817 (4)0.08023 (15)0.22571 (13)0.0425 (5)
O20.1981 (4)0.10501 (18)0.06697 (14)0.0529 (6)
O30.1286 (5)0.02230 (17)0.57207 (14)0.0511 (6)
H30.00290.01880.56850.077*
C10.0515 (6)0.1327 (2)0.1341 (2)0.0391 (7)
C20.1438 (6)0.2161 (2)0.1257 (2)0.0416 (7)
H20.16370.25350.06410.050*
C30.3006 (6)0.2430 (2)0.2032 (2)0.0365 (7)
C40.2715 (5)0.1833 (2)0.2979 (2)0.0349 (7)
C50.4233 (6)0.1998 (2)0.3841 (2)0.0399 (7)
H50.55880.25040.38090.048*
C60.3779 (6)0.1437 (2)0.4730 (2)0.0420 (7)
H60.48440.15510.52860.050*
C70.1727 (6)0.0696 (2)0.4804 (2)0.0378 (7)
C80.0219 (6)0.0483 (2)0.3964 (2)0.0378 (7)
H80.11270.00270.40000.045*
C90.0750 (5)0.1044 (2)0.30701 (18)0.0343 (6)
C100.4971 (6)0.3342 (2)0.1934 (2)0.0484 (8)
H10A0.66100.30570.21370.073*
H10B0.45080.39650.23610.073*
H10C0.50530.35890.12400.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0424 (12)0.0494 (11)0.0358 (10)0.0115 (11)0.0033 (9)0.0021 (9)
O20.0535 (13)0.0650 (13)0.0402 (11)0.0092 (12)0.0113 (11)0.0009 (10)
O30.0579 (14)0.0548 (11)0.0405 (11)0.0058 (12)0.0015 (11)0.0087 (9)
C10.0398 (17)0.0432 (16)0.0342 (14)0.0004 (13)0.0010 (13)0.0000 (13)
C20.0458 (17)0.0428 (15)0.0361 (15)0.0024 (14)0.0051 (14)0.0037 (12)
C30.0359 (16)0.0343 (13)0.0391 (15)0.0002 (13)0.0080 (14)0.0027 (12)
C40.0305 (14)0.0368 (14)0.0373 (15)0.0006 (12)0.0034 (12)0.0059 (12)
C50.0341 (16)0.0413 (14)0.0444 (16)0.0075 (13)0.0003 (15)0.0042 (13)
C60.0375 (16)0.0482 (15)0.0402 (14)0.0017 (15)0.0049 (14)0.0043 (13)
C70.0389 (16)0.0370 (14)0.0376 (14)0.0034 (13)0.0048 (14)0.0007 (12)
C80.0352 (15)0.0371 (14)0.0411 (15)0.0038 (13)0.0019 (13)0.0007 (12)
C90.0324 (15)0.0366 (14)0.0340 (13)0.0001 (13)0.0021 (13)0.0044 (12)
C100.0506 (17)0.0442 (16)0.0505 (17)0.0077 (16)0.0058 (17)0.0018 (13)
Geometric parameters (Å, º) top
O1—C11.366 (3)C4—C51.399 (4)
O1—C91.378 (3)C5—C61.367 (4)
O2—C11.215 (3)C5—H50.9300
O3—C71.351 (3)C6—C71.391 (4)
O3—H30.8200C6—H60.9300
C1—C21.427 (4)C7—C81.381 (4)
C2—C31.346 (4)C8—C91.380 (4)
C2—H20.9300C8—H80.9300
C3—C41.443 (4)C10—H10A0.9600
C3—C101.498 (4)C10—H10B0.9600
C4—C91.396 (4)C10—H10C0.9600
C1—O1—C9121.4 (2)C5—C6—H6119.9
C7—O3—H3109.5C7—C6—H6119.9
O2—C1—O1116.5 (2)O3—C7—C8122.8 (3)
O2—C1—C2125.6 (3)O3—C7—C6117.2 (2)
O1—C1—C2117.9 (2)C8—C7—C6120.0 (2)
C3—C2—C1122.8 (2)C9—C8—C7118.6 (3)
C3—C2—H2118.6C9—C8—H8120.7
C1—C2—H2118.6C7—C8—H8120.7
C2—C3—C4118.2 (2)O1—C9—C8116.2 (2)
C2—C3—C10121.6 (2)O1—C9—C4120.7 (2)
C4—C3—C10120.1 (2)C8—C9—C4123.0 (2)
C9—C4—C5116.3 (2)C3—C10—H10A109.5
C9—C4—C3118.8 (2)C3—C10—H10B109.5
C5—C4—C3124.9 (2)H10A—C10—H10B109.5
C6—C5—C4121.8 (3)C3—C10—H10C109.5
C6—C5—H5119.1H10A—C10—H10C109.5
C4—C5—H5119.1H10B—C10—H10C109.5
C5—C6—C7120.2 (3)
C9—O1—C1—O2179.5 (2)C5—C6—C7—O3175.9 (3)
C9—O1—C1—C21.7 (4)C5—C6—C7—C83.2 (4)
O2—C1—C2—C3180.0 (3)O3—C7—C8—C9177.1 (3)
O1—C1—C2—C31.3 (4)C6—C7—C8—C91.9 (4)
C1—C2—C3—C41.1 (4)C1—O1—C9—C8178.3 (3)
C1—C2—C3—C10177.5 (3)C1—O1—C9—C40.4 (4)
C2—C3—C4—C93.1 (4)C7—C8—C9—O1179.9 (2)
C10—C3—C4—C9175.5 (2)C7—C8—C9—C41.2 (4)
C2—C3—C4—C5178.4 (3)C5—C4—C9—O1178.6 (2)
C10—C3—C4—C52.9 (4)C3—C4—C9—O12.9 (4)
C9—C4—C5—C61.4 (4)C5—C4—C9—C82.8 (4)
C3—C4—C5—C6177.1 (3)C3—C4—C9—C8175.8 (3)
C4—C5—C6—C71.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.821.892.712 (3)175
C2—H2···O2ii0.932.513.410 (4)162
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC10H8O3
Mr176.16
Crystal system, space groupOrthorhombic, P212121
Temperature (K)298
a, b, c (Å)5.229 (3), 11.875 (6), 13.161 (6)
V3)817.3 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.48 × 0.40 × 0.31
Data collection
DiffractometerSiemens SMART 1000 CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.951, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
4236, 869, 732
Rint0.044
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.098, 1.08
No. of reflections869
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.23
Absolute structureFlack (1983), 565 Freidel pairs

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.821.892.712 (3)175.3
C2—H2···O2ii0.932.513.410 (4)161.6
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y+1/2, z.
 

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