Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106017409/fa3017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106017409/fa3017Isup2.hkl |
CCDC reference: 612465
The title compound was extracted from the fruit of Kilmeyera pumila Pohl (family Guttiferae) using conventional methods of extraction and chromatography on silica gel, eluting with what solvent? (de Abreu e Silva, 1987). The purified powder of compound (I) which was obtained was re-crystallized from a solution in acetone by slow evaporation at room temperature.
Since the most electron-rich atom is O, the absolute structure could not be determined using the diffraction data. Therefore, Friedel pairs were averaged before refinement. All H atoms were positioned stereochemically and were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C or O) or 1.5Ueq(C(aromatic)] using a riding model, with C—H = 0.93–0.97 Å and O—H = 0.82 Å.
Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
C25H24O5 | F(000) = 856 |
Mr = 404.44 | Dx = 1.302 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 5698 reflections |
a = 16.727 (1) Å | θ = 2.9–27.5° |
b = 14.152 (1) Å | µ = 0.09 mm−1 |
c = 8.718 (1) Å | T = 150 K |
β = 90.79 (1)° | Prism, pale yellow |
V = 2063.5 (3) Å3 | 0.35 × 0.12 × 0.10 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 2350 independent reflections |
Radiation source: fine-focus sealed tube | 1799 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.065 |
Detector resolution: 9 pixels mm-1 | θmax = 27.4°, θmin = 3.7° |
ϕ scans and ω scans with κ offsets | h = −21→21 |
Absorption correction: multi-scan (Blessing, 1995) | k = −16→18 |
Tmin = 0.950, Tmax = 0.985 | l = −11→10 |
9028 measured reflections |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0542P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.105 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.22 e Å−3 |
2350 reflections | Δρmin = −0.24 e Å−3 |
271 parameters |
C25H24O5 | V = 2063.5 (3) Å3 |
Mr = 404.44 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 16.727 (1) Å | µ = 0.09 mm−1 |
b = 14.152 (1) Å | T = 150 K |
c = 8.718 (1) Å | 0.35 × 0.12 × 0.10 mm |
β = 90.79 (1)° |
Nonius KappaCCD area-detector diffractometer | 2350 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1799 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.985 | Rint = 0.065 |
9028 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 2 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
2350 reflections | Δρmin = −0.24 e Å−3 |
271 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.30704 (17) | −0.0962 (2) | 0.9510 (3) | 0.0254 (6) | |
C2 | 0.24896 (17) | −0.0427 (2) | 0.8756 (3) | 0.0283 (7) | |
H2 | 0.2628 | −0.0056 | 0.792 | 0.034* | |
C3 | 0.17039 (19) | −0.0443 (2) | 0.9248 (4) | 0.0344 (7) | |
H3 | 0.132 | −0.0077 | 0.8746 | 0.041* | |
C4 | 0.1488 (2) | −0.0999 (2) | 1.0474 (4) | 0.0360 (8) | |
H4 | 0.0961 | −0.101 | 1.0796 | 0.043* | |
C5 | 0.20644 (19) | −0.1540 (2) | 1.1224 (3) | 0.0327 (7) | |
H5 | 0.1922 | −0.1914 | 1.2054 | 0.039* | |
C6 | 0.28525 (18) | −0.1528 (2) | 1.0742 (3) | 0.0277 (6) | |
H6 | 0.3235 | −0.1897 | 1.1242 | 0.033* | |
C7 | 0.38952 (17) | −0.0996 (2) | 0.8893 (3) | 0.0234 (6) | |
C8 | 0.42125 (18) | −0.1849 (2) | 0.8550 (3) | 0.0298 (7) | |
H8 | 0.3951 | −0.239 | 0.8884 | 0.036* | |
C9 | 0.49349 (19) | −0.1960 (2) | 0.7694 (3) | 0.0323 (7) | |
C10 | 0.50012 (17) | −0.0261 (2) | 0.7534 (3) | 0.0245 (6) | |
C11 | 0.43399 (16) | −0.0156 (2) | 0.8481 (3) | 0.0234 (6) | |
C12 | 0.41675 (15) | 0.0771 (2) | 0.8968 (3) | 0.0226 (6) | |
C13 | 0.45746 (16) | 0.1581 (2) | 0.8387 (3) | 0.0227 (6) | |
C14 | 0.52295 (17) | 0.1396 (2) | 0.7400 (3) | 0.0230 (6) | |
C15 | 0.54405 (17) | 0.0491 (2) | 0.6946 (3) | 0.0247 (6) | |
C16 | 0.60621 (17) | 0.0374 (2) | 0.5814 (3) | 0.0299 (7) | |
H16 | 0.6134 | −0.0206 | 0.5335 | 0.036* | |
C17 | 0.65279 (18) | 0.1102 (2) | 0.5466 (3) | 0.0347 (7) | |
H17 | 0.6887 | 0.1054 | 0.4666 | 0.042* | |
C18 | 0.64724 (17) | 0.2000 (2) | 0.6369 (3) | 0.0307 (7) | |
C19 | 0.66477 (19) | 0.2882 (3) | 0.5444 (4) | 0.0401 (8) | |
H19A | 0.6602 | 0.3428 | 0.6089 | 0.06* | |
H19B | 0.6272 | 0.2929 | 0.4605 | 0.06* | |
H19C | 0.718 | 0.2846 | 0.5052 | 0.06* | |
C20 | 0.7011 (2) | 0.1941 (3) | 0.7785 (4) | 0.0395 (8) | |
H20A | 0.6975 | 0.2519 | 0.8356 | 0.059* | |
H20B | 0.7554 | 0.1845 | 0.7477 | 0.059* | |
H20C | 0.6845 | 0.1423 | 0.8415 | 0.059* | |
C21 | 0.42774 (17) | 0.2520 (2) | 0.8787 (3) | 0.0261 (6) | |
C22 | 0.45446 (18) | 0.3410 (2) | 0.7984 (4) | 0.0309 (7) | |
H22A | 0.4612 | 0.3272 | 0.6904 | 0.037* | |
H22B | 0.5062 | 0.3596 | 0.8399 | 0.037* | |
C23 | 0.39661 (19) | 0.4244 (2) | 0.8135 (4) | 0.0355 (7) | |
H23 | 0.3808 | 0.4296 | 0.921 | 0.043* | |
C24 | 0.4393 (2) | 0.5154 (3) | 0.7681 (5) | 0.0535 (10) | |
H24A | 0.486 | 0.5238 | 0.8319 | 0.08* | |
H24B | 0.4039 | 0.5682 | 0.7813 | 0.08* | |
H24C | 0.4548 | 0.5116 | 0.6627 | 0.08* | |
C25 | 0.3222 (2) | 0.4096 (3) | 0.7157 (4) | 0.0455 (9) | |
H25A | 0.296 | 0.3525 | 0.7469 | 0.068* | |
H25B | 0.3368 | 0.4046 | 0.6099 | 0.068* | |
H25C | 0.2867 | 0.4622 | 0.7284 | 0.068* | |
O1 | 0.36031 (12) | 0.08751 (15) | 1.0027 (2) | 0.0274 (5) | |
H1 | 0.355 | 0.1438 | 1.0228 | 0.041* | |
O2 | 0.37608 (12) | 0.26023 (15) | 0.9796 (2) | 0.0336 (5) | |
O3 | 0.56437 (11) | 0.21496 (16) | 0.6873 (2) | 0.0291 (5) | |
O4 | 0.52670 (12) | −0.11352 (14) | 0.7105 (2) | 0.0288 (5) | |
O5 | 0.52657 (14) | −0.26898 (16) | 0.7374 (3) | 0.0444 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0273 (15) | 0.0222 (16) | 0.0267 (14) | −0.0028 (12) | 0.0008 (12) | −0.0003 (11) |
C2 | 0.0248 (15) | 0.0266 (16) | 0.0335 (16) | −0.0030 (12) | 0.0031 (12) | 0.0058 (12) |
C3 | 0.0255 (16) | 0.0336 (18) | 0.0439 (18) | −0.0008 (14) | −0.0006 (13) | −0.0012 (13) |
C4 | 0.0302 (16) | 0.040 (2) | 0.0384 (16) | −0.0084 (15) | 0.0099 (13) | −0.0079 (15) |
C5 | 0.0391 (18) | 0.0328 (18) | 0.0265 (15) | −0.0119 (15) | 0.0066 (13) | −0.0025 (12) |
C6 | 0.0317 (16) | 0.0282 (17) | 0.0232 (13) | −0.0037 (13) | −0.0018 (12) | 0.0015 (12) |
C7 | 0.0267 (15) | 0.0215 (16) | 0.0221 (13) | 0.0000 (12) | −0.0012 (11) | 0.0009 (11) |
C8 | 0.0293 (16) | 0.0257 (17) | 0.0344 (16) | −0.0014 (14) | −0.0014 (13) | −0.0004 (12) |
C9 | 0.0319 (17) | 0.0274 (18) | 0.0377 (17) | 0.0011 (14) | −0.0027 (13) | −0.0065 (13) |
C10 | 0.0256 (15) | 0.0257 (17) | 0.0222 (14) | 0.0031 (12) | −0.0026 (11) | −0.0053 (11) |
C11 | 0.0234 (15) | 0.0253 (17) | 0.0214 (14) | 0.0021 (12) | 0.0004 (12) | 0.0003 (11) |
C12 | 0.0209 (15) | 0.0281 (17) | 0.0188 (13) | −0.0025 (12) | 0.0028 (11) | 0.0001 (11) |
C13 | 0.0232 (15) | 0.0239 (16) | 0.0208 (13) | −0.0010 (12) | −0.0013 (11) | 0.0020 (10) |
C14 | 0.0194 (14) | 0.0305 (16) | 0.0191 (13) | −0.0044 (13) | −0.0012 (10) | 0.0016 (11) |
C15 | 0.0225 (14) | 0.0290 (17) | 0.0226 (13) | −0.0013 (12) | −0.0008 (11) | −0.0033 (11) |
C16 | 0.0259 (16) | 0.0382 (19) | 0.0255 (14) | −0.0020 (13) | 0.0048 (12) | −0.0070 (12) |
C17 | 0.0284 (16) | 0.048 (2) | 0.0278 (14) | −0.0041 (15) | 0.0091 (12) | −0.0044 (14) |
C18 | 0.0246 (15) | 0.0404 (19) | 0.0274 (16) | −0.0076 (14) | 0.0086 (12) | −0.0012 (13) |
C19 | 0.0353 (19) | 0.048 (2) | 0.0370 (17) | −0.0111 (16) | 0.0092 (14) | 0.0036 (15) |
C20 | 0.0339 (18) | 0.045 (2) | 0.0393 (17) | −0.0058 (15) | −0.0027 (14) | −0.0043 (14) |
C21 | 0.0228 (14) | 0.0265 (16) | 0.0290 (15) | 0.0001 (13) | 0.0005 (12) | −0.0007 (12) |
C22 | 0.0272 (15) | 0.0283 (18) | 0.0372 (16) | −0.0027 (14) | 0.0017 (12) | 0.0010 (13) |
C23 | 0.0344 (18) | 0.0269 (18) | 0.0453 (19) | 0.0008 (14) | 0.0014 (15) | 0.0027 (13) |
C24 | 0.052 (2) | 0.029 (2) | 0.079 (3) | 0.0004 (18) | −0.0005 (19) | 0.0095 (18) |
C25 | 0.039 (2) | 0.037 (2) | 0.060 (2) | 0.0072 (16) | 0.0006 (16) | 0.0027 (16) |
O1 | 0.0284 (11) | 0.0258 (12) | 0.0283 (10) | −0.0009 (9) | 0.0092 (8) | −0.0031 (8) |
O2 | 0.0332 (12) | 0.0283 (13) | 0.0396 (11) | 0.0021 (10) | 0.0116 (9) | −0.0010 (9) |
O3 | 0.0241 (11) | 0.0317 (12) | 0.0317 (11) | −0.0054 (9) | 0.0088 (8) | 0.0023 (8) |
O4 | 0.0249 (11) | 0.0263 (12) | 0.0353 (11) | 0.0015 (9) | 0.0029 (9) | −0.0059 (9) |
O5 | 0.0387 (14) | 0.0283 (14) | 0.0664 (16) | 0.0071 (12) | 0.0065 (11) | −0.0104 (12) |
C1—C2 | 1.390 (4) | C16—C17 | 1.329 (4) |
C1—C6 | 1.392 (4) | C16—H16 | 0.93 |
C1—C7 | 1.488 (4) | C17—C18 | 1.499 (5) |
C2—C3 | 1.388 (4) | C17—H17 | 0.93 |
C2—H2 | 0.93 | C18—O3 | 1.475 (3) |
C3—C4 | 1.379 (5) | C18—C19 | 1.516 (5) |
C3—H3 | 0.93 | C18—C20 | 1.520 (4) |
C4—C5 | 1.388 (5) | C19—H19A | 0.96 |
C4—H4 | 0.93 | C19—H19B | 0.96 |
C5—C6 | 1.389 (4) | C19—H19C | 0.96 |
C5—H5 | 0.93 | C20—H20A | 0.96 |
C6—H6 | 0.93 | C20—H20B | 0.96 |
C7—C8 | 1.354 (4) | C20—H20C | 0.96 |
C7—C11 | 1.451 (4) | C21—O2 | 1.247 (3) |
C8—C9 | 1.438 (4) | C21—C22 | 1.512 (4) |
C8—H8 | 0.93 | C22—C23 | 1.533 (4) |
C9—O5 | 1.207 (4) | C22—H22A | 0.97 |
C9—O4 | 1.393 (4) | C22—H22B | 0.97 |
C10—O4 | 1.368 (3) | C23—C25 | 1.513 (5) |
C10—C15 | 1.394 (4) | C23—C24 | 1.528 (5) |
C10—C11 | 1.397 (4) | C23—H23 | 0.98 |
C11—C12 | 1.410 (4) | C24—H24A | 0.96 |
C12—O1 | 1.338 (3) | C24—H24B | 0.96 |
C12—C13 | 1.429 (4) | C24—H24C | 0.96 |
C13—C14 | 1.426 (4) | C25—H25A | 0.96 |
C13—C21 | 1.463 (4) | C25—H25B | 0.96 |
C14—O3 | 1.356 (3) | C25—H25C | 0.96 |
C14—C15 | 1.388 (4) | O1—H1 | 0.82 |
C15—C16 | 1.453 (4) | ||
C2—C1—C6 | 119.3 (2) | C18—C17—H17 | 120.1 |
C2—C1—C7 | 119.5 (2) | O3—C18—C17 | 110.1 (2) |
C6—C1—C7 | 120.9 (3) | O3—C18—C19 | 103.3 (3) |
C3—C2—C1 | 120.2 (3) | C17—C18—C19 | 113.9 (2) |
C3—C2—H2 | 119.9 | O3—C18—C20 | 108.4 (2) |
C1—C2—H2 | 119.9 | C17—C18—C20 | 109.8 (3) |
C4—C3—C2 | 120.5 (3) | C19—C18—C20 | 111.1 (3) |
C4—C3—H3 | 119.8 | C18—C19—H19A | 109.5 |
C2—C3—H3 | 119.8 | C18—C19—H19B | 109.5 |
C3—C4—C5 | 119.5 (3) | H19A—C19—H19B | 109.5 |
C3—C4—H4 | 120.2 | C18—C19—H19C | 109.5 |
C5—C4—H4 | 120.2 | H19A—C19—H19C | 109.5 |
C4—C5—C6 | 120.4 (3) | H19B—C19—H19C | 109.5 |
C4—C5—H5 | 119.8 | C18—C20—H20A | 109.5 |
C6—C5—H5 | 119.8 | C18—C20—H20B | 109.5 |
C5—C6—C1 | 120.0 (3) | H20A—C20—H20B | 109.5 |
C5—C6—H6 | 120 | C18—C20—H20C | 109.5 |
C1—C6—H6 | 120 | H20A—C20—H20C | 109.5 |
C8—C7—C11 | 118.2 (2) | H20B—C20—H20C | 109.5 |
C8—C7—C1 | 118.5 (3) | O2—C21—C13 | 119.6 (3) |
C11—C7—C1 | 122.9 (3) | O2—C21—C22 | 117.4 (3) |
C7—C8—C9 | 123.1 (3) | C13—C21—C22 | 122.9 (2) |
C7—C8—H8 | 118.4 | C21—C22—C23 | 114.3 (2) |
C9—C8—H8 | 118.4 | C21—C22—H22A | 108.7 |
O5—C9—O4 | 116.4 (3) | C23—C22—H22A | 108.7 |
O5—C9—C8 | 127.2 (3) | C21—C22—H22B | 108.7 |
O4—C9—C8 | 116.3 (3) | C23—C22—H22B | 108.7 |
O4—C10—C15 | 114.5 (2) | H22A—C22—H22B | 107.6 |
O4—C10—C11 | 121.4 (3) | C25—C23—C24 | 110.8 (3) |
C15—C10—C11 | 124.1 (3) | C25—C23—C22 | 111.1 (3) |
C10—C11—C12 | 116.4 (3) | C24—C23—C22 | 109.2 (3) |
C10—C11—C7 | 118.2 (3) | C25—C23—H23 | 108.6 |
C12—C11—C7 | 125.5 (2) | C24—C23—H23 | 108.6 |
O1—C12—C11 | 117.3 (2) | C22—C23—H23 | 108.6 |
O1—C12—C13 | 120.1 (3) | C23—C24—H24A | 109.5 |
C11—C12—C13 | 122.6 (2) | C23—C24—H24B | 109.5 |
C14—C13—C12 | 116.1 (3) | H24A—C24—H24B | 109.5 |
C14—C13—C21 | 125.2 (3) | C23—C24—H24C | 109.5 |
C12—C13—C21 | 118.6 (2) | H24A—C24—H24C | 109.5 |
O3—C14—C15 | 119.8 (2) | H24B—C24—H24C | 109.5 |
O3—C14—C13 | 117.4 (3) | C23—C25—H25A | 109.5 |
C15—C14—C13 | 122.8 (3) | C23—C25—H25B | 109.5 |
C14—C15—C10 | 117.5 (2) | H25A—C25—H25B | 109.5 |
C14—C15—C16 | 119.1 (3) | C23—C25—H25C | 109.5 |
C10—C15—C16 | 123.3 (3) | H25A—C25—H25C | 109.5 |
C17—C16—C15 | 119.6 (3) | H25B—C25—H25C | 109.5 |
C17—C16—H16 | 120.2 | C12—O1—H1 | 109.5 |
C15—C16—H16 | 120.2 | C14—O3—C18 | 118.4 (2) |
C16—C17—C18 | 119.8 (3) | C10—O4—C9 | 121.6 (2) |
C16—C17—H17 | 120.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.82 | 1.73 | 2.467 (3) | 149 |
C4—H4···O5i | 0.93 | 2.58 | 3.234 (4) | 128 |
C19—H19B···O5ii | 0.96 | 2.58 | 3.523 (4) | 168 |
C20—H20A···Cgiii | 0.96 | 2.60 | 3.534 (3) | 165 |
Symmetry codes: (i) x−1/2, −y−1/2, z+1/2; (ii) x, −y, z−1/2; (iii) x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C25H24O5 |
Mr | 404.44 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 150 |
a, b, c (Å) | 16.727 (1), 14.152 (1), 8.718 (1) |
β (°) | 90.79 (1) |
V (Å3) | 2063.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.950, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9028, 2350, 1799 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.105, 1.02 |
No. of reflections | 2350 |
No. of parameters | 271 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.24 |
Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
C9—O5 | 1.207 (4) | C15—C16 | 1.453 (4) |
C9—O4 | 1.393 (4) | C16—C17 | 1.329 (4) |
C10—O4 | 1.368 (3) | C17—C18 | 1.499 (5) |
C12—O1 | 1.338 (3) | C18—O3 | 1.475 (3) |
C14—O3 | 1.356 (3) | C21—O2 | 1.247 (3) |
C14—O3—C18 | 118.4 (2) | C10—O4—C9 | 121.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.82 | 1.73 | 2.467 (3) | 149 |
C4—H4···O5i | 0.93 | 2.58 | 3.234 (4) | 128 |
C19—H19B···O5ii | 0.96 | 2.58 | 3.523 (4) | 168 |
C20—H20A···Cgiii | 0.96 | 2.601 | 3.534 (3) | 165 |
Symmetry codes: (i) x−1/2, −y−1/2, z+1/2; (ii) x, −y, z−1/2; (iii) x+1/2, y+1/2, z. |
In the course of our chemical studies of plants belonging to the family Guttiferae, we have investigated the lipophilic extract of the fruits of Kilmeyera pumila Pohl and this led to the isolation of two phenylcoumarins, (I) and (II) (see scheme). The title compound, (I), named mammeigin (or mammea A/AA cycle D, or 5-hydroxy-8,8-dimethyl-6-(3-methylbutanoyl)-4-phenyl-2H,8H-pyrano[2,3-f]chromen-2-one (9CI), has already been isolated from Guttiferae species (Lopez-Perez et al., 2005; Reutrakul et al., 2003; Gramacho et al., 1999; Dennis & Akshaya Kumar, 1998; Castellano et al., 1988; Crombie et al., 1987, 1967; Carpenter et al., 1971; Chakraborty & Chatterji, 1969; Finnegan & Mueller, 1964), and its structure has been established based on spectroscopic evidence and chemical correlation (Finnegan & Mueller, 1965). The structure of (II), a phenylcoumarin from Guttiferae species, was proposed for a new natural product named isomammeigin from IR and NMR data (de Abreu e Silva, 1987). Later, its structure was unambiguously determined by X-ray diffraction by Castellano et al. (1988).
Some phenylcoumarins described previously have shown cytotoxic (Reutrakul et al., 2003; Scio et al., 2003) and anti-HIV (Ishikawa, 2000; Spino et al., 1998) activities. Chemopreventive activity against cancer in vitro without cytotoxicity has also been reported for some of these derivatives (Itoigawa et al., 2001; Ito et al., 2003).
The crystal structure of (I), reported here, was part of a chemotaxonomic study of the Guttiferae family. X-ray analysis is important in this case, since from spectroscopic data alone, structures (I) and (II) are possible alternatives. In this way, we have identified (I) by spectroscopic methods (UV, EI—MS, and 1H and 13C NMR) and its structure was unambiguously confirmed by the X-ray data.
Fig. 1 is an ORTEP-3 (Farrugia, 1997) view of the title compound. The main geometrical parameters are given in Table 1. The intramolecular conformation was analyzed using Mogul (Bruno et al., 2004). This study showed that all bond lengths and angles are in agreement with the expected values. As expected, aromatic ring A is planar and shows nearly equal C—C distances and C—C—C angles. The molecular moiety, considering only the atoms of rings B, C and D, is also almost planar. All atoms in rings B, C and D, except for atom C18, which is an sp3 C atom, lie within ±0.152 (3) Å of the least-squares plane through the three-ring system. Ring D presents an envelope conformation, with atom C18, which deviates by 0.488 (4) Å from the least-squares plane through the three-ring system, at the flip point. The weighted average absolute torsion angle (Domenicano et al., 1975) in ring D is 24.2 (1)°. Rings B and C are also individually almost planar, including the first-neighbour atoms linked to them. The largest deviations from the individual least-squares planes are 0.059 (2) Å (C9) and 0.033 (2) Å (C12) for rings B and C, respectively. The least-squares planes of rings B and C form an angle of 5.5 (1)° and those of rings C and D form an angle of 1.9 (2)°. Phenyl ring A and the least-squares plane through ring B form an angle of 51.9 (1)°. This appreciable deviation from 90° can be viewed as a cooperative consequence of the non-classical intermolecular hydrogen-bond interactions [C4—H4···O5i and C20—H20A···Cgiii, where Cg is the centroid of ring A; symmetry code as in Table 2] (Figs. 2 and 3; Table 2).
Compound (I) exhibits a strong classical intramolecular hydrogen bond, O1—H1···O2 (Fig. 1, Table 2). An interesting structural feature is that the crystal packing of (I) is formed by an infinite three-dimensional network involving non-classical hydrogen bonds. The intermolecular hydrogen bond between phenyl ring A and the adjacent carboxyl atom O5 (C4—H4···O5) gives rise to a chain, in a zigzag molecular fashion, parallel to the [101] direction (Fig. 2). Networks parallel to the [101] direction are themselves hydrogen-bonded via two other non-classical associations, forming infinite chains along the [001] and [101] directions. The chain along [001] is stabilized by C19—H19B···O5 interactions, whereas that along [101] is stabilized by intermolecular bonds of the type H···π-aryl (Fig. 3). The result is an extended three-dimensional supramolecular assembly mediated by non-classical C—H··· bonding. Details of all hydrogen-bond contacts involved in these networks are given in Table 2.