Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056085/ez2107sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056085/ez2107Isup2.hkl |
CCDC reference: 616613
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).
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.
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).
C10H8O3 | Dx = 1.432 Mg m−3 |
Mr = 176.16 | Melting point: 463 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1640 reflections |
a = 5.229 (3) Å | θ = 2.3–25.2° |
b = 11.875 (6) Å | µ = 0.11 mm−1 |
c = 13.161 (6) Å | T = 298 K |
V = 817.3 (7) Å3 | Columnar, colourless |
Z = 4 | 0.48 × 0.40 × 0.31 mm |
F(000) = 368 |
Siemens SMART 1000 CCD area detector diffractometer | 869 independent reflections |
Radiation source: fine-focus sealed tube | 732 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→5 |
Tmin = 0.951, Tmax = 0.968 | k = −14→12 |
4236 measured reflections | l = −14→15 |
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)] = 0.038 | H-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 reflections | Δρmax = 0.20 e Å−3 |
119 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 565 Freidel pairs |
Primary atom site location: structure-invariant direct methods |
C10H8O3 | V = 817.3 (7) Å3 |
Mr = 176.16 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.229 (3) Å | µ = 0.11 mm−1 |
b = 11.875 (6) Å | T = 298 K |
c = 13.161 (6) Å | 0.48 × 0.40 × 0.31 mm |
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 = 0.968 | Rint = 0.044 |
4236 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.20 e Å−3 |
869 reflections | Δρmin = −0.23 e Å−3 |
119 parameters | Absolute structure: Flack (1983), 565 Freidel pairs |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.0817 (4) | 0.08023 (15) | 0.22571 (13) | 0.0425 (5) | |
O2 | −0.1981 (4) | 0.10501 (18) | 0.06697 (14) | 0.0529 (6) | |
O3 | 0.1286 (5) | 0.02230 (17) | 0.57207 (14) | 0.0511 (6) | |
H3 | 0.0029 | −0.0188 | 0.5685 | 0.077* | |
C1 | −0.0515 (6) | 0.1327 (2) | 0.1341 (2) | 0.0391 (7) | |
C2 | 0.1438 (6) | 0.2161 (2) | 0.1257 (2) | 0.0416 (7) | |
H2 | 0.1637 | 0.2535 | 0.0641 | 0.050* | |
C3 | 0.3006 (6) | 0.2430 (2) | 0.2032 (2) | 0.0365 (7) | |
C4 | 0.2715 (5) | 0.1833 (2) | 0.2979 (2) | 0.0349 (7) | |
C5 | 0.4233 (6) | 0.1998 (2) | 0.3841 (2) | 0.0399 (7) | |
H5 | 0.5588 | 0.2504 | 0.3809 | 0.048* | |
C6 | 0.3779 (6) | 0.1437 (2) | 0.4730 (2) | 0.0420 (7) | |
H6 | 0.4844 | 0.1551 | 0.5286 | 0.050* | |
C7 | 0.1727 (6) | 0.0696 (2) | 0.4804 (2) | 0.0378 (7) | |
C8 | 0.0219 (6) | 0.0483 (2) | 0.3964 (2) | 0.0378 (7) | |
H8 | −0.1127 | −0.0027 | 0.4000 | 0.045* | |
C9 | 0.0750 (5) | 0.1044 (2) | 0.30701 (18) | 0.0343 (6) | |
C10 | 0.4971 (6) | 0.3342 (2) | 0.1934 (2) | 0.0484 (8) | |
H10A | 0.6610 | 0.3057 | 0.2137 | 0.073* | |
H10B | 0.4508 | 0.3965 | 0.2361 | 0.073* | |
H10C | 0.5053 | 0.3589 | 0.1240 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0424 (12) | 0.0494 (11) | 0.0358 (10) | −0.0115 (11) | −0.0033 (9) | 0.0021 (9) |
O2 | 0.0535 (13) | 0.0650 (13) | 0.0402 (11) | −0.0092 (12) | −0.0113 (11) | −0.0009 (10) |
O3 | 0.0579 (14) | 0.0548 (11) | 0.0405 (11) | −0.0058 (12) | −0.0015 (11) | 0.0087 (9) |
C1 | 0.0398 (17) | 0.0432 (16) | 0.0342 (14) | 0.0004 (13) | −0.0010 (13) | 0.0000 (13) |
C2 | 0.0458 (17) | 0.0428 (15) | 0.0361 (15) | −0.0024 (14) | 0.0051 (14) | 0.0037 (12) |
C3 | 0.0359 (16) | 0.0343 (13) | 0.0391 (15) | 0.0002 (13) | 0.0080 (14) | −0.0027 (12) |
C4 | 0.0305 (14) | 0.0368 (14) | 0.0373 (15) | 0.0006 (12) | 0.0034 (12) | −0.0059 (12) |
C5 | 0.0341 (16) | 0.0413 (14) | 0.0444 (16) | −0.0075 (13) | 0.0003 (15) | −0.0042 (13) |
C6 | 0.0375 (16) | 0.0482 (15) | 0.0402 (14) | −0.0017 (15) | −0.0049 (14) | −0.0043 (13) |
C7 | 0.0389 (16) | 0.0370 (14) | 0.0376 (14) | 0.0034 (13) | 0.0048 (14) | 0.0007 (12) |
C8 | 0.0352 (15) | 0.0371 (14) | 0.0411 (15) | −0.0038 (13) | 0.0019 (13) | −0.0007 (12) |
C9 | 0.0324 (15) | 0.0366 (14) | 0.0340 (13) | −0.0001 (13) | −0.0021 (13) | −0.0044 (12) |
C10 | 0.0506 (17) | 0.0442 (16) | 0.0505 (17) | −0.0077 (16) | 0.0058 (17) | 0.0018 (13) |
O1—C1 | 1.366 (3) | C4—C5 | 1.399 (4) |
O1—C9 | 1.378 (3) | C5—C6 | 1.367 (4) |
O2—C1 | 1.215 (3) | C5—H5 | 0.9300 |
O3—C7 | 1.351 (3) | C6—C7 | 1.391 (4) |
O3—H3 | 0.8200 | C6—H6 | 0.9300 |
C1—C2 | 1.427 (4) | C7—C8 | 1.381 (4) |
C2—C3 | 1.346 (4) | C8—C9 | 1.380 (4) |
C2—H2 | 0.9300 | C8—H8 | 0.9300 |
C3—C4 | 1.443 (4) | C10—H10A | 0.9600 |
C3—C10 | 1.498 (4) | C10—H10B | 0.9600 |
C4—C9 | 1.396 (4) | C10—H10C | 0.9600 |
C1—O1—C9 | 121.4 (2) | C5—C6—H6 | 119.9 |
C7—O3—H3 | 109.5 | C7—C6—H6 | 119.9 |
O2—C1—O1 | 116.5 (2) | O3—C7—C8 | 122.8 (3) |
O2—C1—C2 | 125.6 (3) | O3—C7—C6 | 117.2 (2) |
O1—C1—C2 | 117.9 (2) | C8—C7—C6 | 120.0 (2) |
C3—C2—C1 | 122.8 (2) | C9—C8—C7 | 118.6 (3) |
C3—C2—H2 | 118.6 | C9—C8—H8 | 120.7 |
C1—C2—H2 | 118.6 | C7—C8—H8 | 120.7 |
C2—C3—C4 | 118.2 (2) | O1—C9—C8 | 116.2 (2) |
C2—C3—C10 | 121.6 (2) | O1—C9—C4 | 120.7 (2) |
C4—C3—C10 | 120.1 (2) | C8—C9—C4 | 123.0 (2) |
C9—C4—C5 | 116.3 (2) | C3—C10—H10A | 109.5 |
C9—C4—C3 | 118.8 (2) | C3—C10—H10B | 109.5 |
C5—C4—C3 | 124.9 (2) | H10A—C10—H10B | 109.5 |
C6—C5—C4 | 121.8 (3) | C3—C10—H10C | 109.5 |
C6—C5—H5 | 119.1 | H10A—C10—H10C | 109.5 |
C4—C5—H5 | 119.1 | H10B—C10—H10C | 109.5 |
C5—C6—C7 | 120.2 (3) | ||
C9—O1—C1—O2 | 179.5 (2) | C5—C6—C7—O3 | −175.9 (3) |
C9—O1—C1—C2 | −1.7 (4) | C5—C6—C7—C8 | 3.2 (4) |
O2—C1—C2—C3 | 180.0 (3) | O3—C7—C8—C9 | 177.1 (3) |
O1—C1—C2—C3 | 1.3 (4) | C6—C7—C8—C9 | −1.9 (4) |
C1—C2—C3—C4 | 1.1 (4) | C1—O1—C9—C8 | 178.3 (3) |
C1—C2—C3—C10 | −177.5 (3) | C1—O1—C9—C4 | −0.4 (4) |
C2—C3—C4—C9 | −3.1 (4) | C7—C8—C9—O1 | −179.9 (2) |
C10—C3—C4—C9 | 175.5 (2) | C7—C8—C9—C4 | −1.2 (4) |
C2—C3—C4—C5 | 178.4 (3) | C5—C4—C9—O1 | −178.6 (2) |
C10—C3—C4—C5 | −2.9 (4) | C3—C4—C9—O1 | 2.9 (4) |
C9—C4—C5—C6 | −1.4 (4) | C5—C4—C9—C8 | 2.8 (4) |
C3—C4—C5—C6 | 177.1 (3) | C3—C4—C9—C8 | −175.8 (3) |
C4—C5—C6—C7 | −1.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.82 | 1.89 | 2.712 (3) | 175 |
C2—H2···O2ii | 0.93 | 2.51 | 3.410 (4) | 162 |
Symmetry codes: (i) −x−1/2, −y, z+1/2; (ii) x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H8O3 |
Mr | 176.16 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 5.229 (3), 11.875 (6), 13.161 (6) |
V (Å3) | 817.3 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.48 × 0.40 × 0.31 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.951, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4236, 869, 732 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.098, 1.08 |
No. of reflections | 869 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.23 |
Absolute structure | Flack (1983), 565 Freidel pairs |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.82 | 1.89 | 2.712 (3) | 175.3 |
C2—H2···O2ii | 0.93 | 2.51 | 3.410 (4) | 161.6 |
Symmetry codes: (i) −x−1/2, −y, z+1/2; (ii) x+1/2, −y+1/2, −z. |
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),.