Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039402/wn2184sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039402/wn2184Isup2.hkl |
CCDC reference: 222445
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.047
- wR factor = 0.125
- Data-to-parameter ratio = 10.2
checkCIF/PLATON results
No syntax errors found
Alert level C WEIGH01_ALERT_1_C Extra text has been found in the _refine_ls_weighting_scheme field. This should be in the _refine_ls_weighting_details field. Weighting scheme given as calc w=1/[\s^2^(Fo^2^)+(0.0777P)^2^] where Weighting scheme identified as calc PLAT412_ALERT_2_C Short Intra XH3 .. XHn H9 .. H18B .. 1.87 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 27.99 From the CIF: _reflns_number_total 2967 Count of symmetry unique reflns 3021 Completeness (_total/calc) 98.21% 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 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C14 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C15 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C17 = . R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 10 ALERT level G = General alerts; check 10 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 0 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
For related literature, see: Hodges et al. (1963); Zeumer et al. (2000); Geetha Gopalakrishnan et al. (2000, 2001).
For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Harris et al. (1968); Henderson et al. (1968); Narayanan et al. (1967); Suresh et al. (2002).
The microwave-oxidized product was obtained through the procedure reported in the literature (Geetha Gopalakrishnan et al., 2000; 2001). Good diffraction quality crystals were obtained from ethyl acetate/hexane (1:1) by slow evaporation.
In the absence of significant anomalous scattering, 1980 Friedel pairs were merged. The enantiomer employed in the refined model was chosen to agree with the accepted configuration of limonoids (Henderson et al., 1968; Narayanan et al., 1967; Harris et al., 1968). Methine and methylene H atoms were constrained to an ideal geometry (C—H = 0.98 and 0.97 Å, respectively), with Uiso(H) = 1.2Ueq(parent atom). Methyl and hydroxyl H hydrogen atoms were placed in geometrically idealized positions (C—H = 0.96 Å and O—H = 0.98 Å) and were constrained to ride on their parent atom with Uiso(H) = 1.5Ueq(C,O).
Cedrelone (Zeumer et al., 2000), one of the major limonoids extracted from Toona ciliata, shows minimum antifeedant activity; however it was reported that its photo and microwave products show enhanced and reduced activity, respectively (Suresh et al., 2002).
The present study reports the crystal structure of a microwave-modified product which has an additional carbonyl group at C21 in the furan ring. This substitution has modified only the furan ring orientation with respect to ring D. The torsion angle, C16—C17—C20—C22, showing the relative orientation of the furan ring with respect to ring D, is 25.5 (4)°, compared to 168.3 (4)° in cedrelone itself.
Ring A is in a boat conformation (Cremer & Pople, 1975). The atoms C3 and C10 deviate by 0.561 (2) Å & 0.405 (2) Å from the plane involving the other atoms of the ring. Ring B takes up a half-chair conformation, the atoms C9 and C8 deviating from the least-squares plane of the other four atoms by 0.530 (2) Å and -0.183 (2) Å. Ring C adopts a twist conformation, with the atoms C11 and C13 deviating from the plane through atoms C8, C9, C12, C14 by -0.789 (3) Å and 0.697 (2) Å. Ring D is in an envelope conformation with C17 as the flap atom, lying 0.543 (4) Å from the plane of the remaining four atoms. Ring E is in a planar conformation, the maximum deviation (for atom C22) being 0.045 (4) Å. The ring fusions at the junctions A/B, B/C and C/D are quasi-trans, trans and trans, respectively, as seen from the endocyclic torsion angles.
The packing of the molecules in the crystal structure (Fig. 2) is achieved through a network of O—H···O and C—H···O hydrogen bonds (Table 1). An S(5) motif is generated through the O6—H6···O7 intramolecular hydrogen bond. Three chain motifs C(7),C(7) and C(12) are generated through hydrogen bonds O6—H6···O3 (-1/2 + x, 3/2 - y, -z), C28—H28C···O7 (1/2 + x,3/2 - y,-z) and C2—H2···O21(1/2 + x, 1/2 - y,-z). These in turn generate a ring motif R22[10] (Bernstein et al.,1995).
For related literature, see: Hodges et al. (1963); Zeumer et al. (2000); Geetha Gopalakrishnan et al. (2000, 2001).
For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Harris et al. (1968); Henderson et al. (1968); Narayanan et al. (1967); Suresh et al. (2002).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and PARST97 (Nardelli, 1995).
C26H30O6 | F(000) = 936 |
Mr = 438.50 | Dx = 1.311 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5100 reflections |
a = 12.6858 (9) Å | θ = 2.2–28.0° |
b = 13.1117 (9) Å | µ = 0.09 mm−1 |
c = 13.353 (1) Å | T = 293 K |
V = 2221.0 (3) Å3 | Needle, yellow |
Z = 4 | 0.26 × 0.21 × 0.17 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2967 independent reflections |
Radiation source: fine-focus sealed tube | 2364 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 28.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→16 |
Tmin = 0.974, Tmax = 0.985 | k = −7→16 |
14146 measured reflections | l = −17→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.08 | Calculated w = 1/[σ2(Fo2) + (0.0777P)2] where P = (Fo2 + 2Fc2)/3 |
2967 reflections | (Δ/σ)max < 0.001 |
290 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C26H30O6 | V = 2221.0 (3) Å3 |
Mr = 438.50 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.6858 (9) Å | µ = 0.09 mm−1 |
b = 13.1117 (9) Å | T = 293 K |
c = 13.353 (1) Å | 0.26 × 0.21 × 0.17 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2967 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2364 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.985 | Rint = 0.035 |
14146 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.24 e Å−3 |
2967 reflections | Δρmin = −0.19 e Å−3 |
290 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. |
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 | ||
O3 | 0.81936 (15) | 0.57248 (16) | −0.04775 (16) | 0.0540 (5) | |
O6 | 0.49433 (14) | 0.78724 (13) | 0.06943 (16) | 0.0462 (5) | |
H6 | 0.4363 | 0.8130 | 0.0794 | 0.069* | |
O7 | 0.34393 (15) | 0.73469 (14) | 0.19410 (15) | 0.0484 (5) | |
O15 | 0.29074 (16) | 0.48982 (17) | 0.35735 (13) | 0.0534 (5) | |
O21 | 0.0963 (2) | 0.2091 (2) | 0.1912 (3) | 0.1014 (11) | |
O23 | −0.04455 (19) | 0.2598 (2) | 0.1022 (2) | 0.0797 (8) | |
C1 | 0.5936 (2) | 0.4466 (2) | 0.0257 (2) | 0.0449 (6) | |
H1 | 0.5544 | 0.3875 | 0.0154 | 0.054* | |
C2 | 0.6681 (2) | 0.4702 (2) | −0.0389 (2) | 0.0474 (6) | |
H2 | 0.6833 | 0.4270 | −0.0922 | 0.057* | |
C3 | 0.7267 (2) | 0.5652 (2) | −0.02574 (19) | 0.0405 (6) | |
C4 | 0.6621 (2) | 0.65651 (19) | 0.00986 (18) | 0.0375 (5) | |
C5 | 0.57172 (18) | 0.62388 (19) | 0.07896 (17) | 0.0338 (5) | |
C6 | 0.49469 (19) | 0.68980 (18) | 0.10440 (18) | 0.0362 (5) | |
C7 | 0.40724 (19) | 0.66755 (18) | 0.17463 (17) | 0.0353 (5) | |
C8 | 0.40818 (19) | 0.56473 (19) | 0.22575 (17) | 0.0350 (5) | |
C9 | 0.45650 (19) | 0.48718 (18) | 0.15132 (18) | 0.0351 (5) | |
H9 | 0.4137 | 0.4952 | 0.0907 | 0.042* | |
C10 | 0.56963 (18) | 0.51229 (19) | 0.11602 (19) | 0.0360 (5) | |
C11 | 0.4311 (2) | 0.3790 (2) | 0.1872 (2) | 0.0432 (6) | |
H11A | 0.4449 | 0.3732 | 0.2584 | 0.052* | |
H11B | 0.4753 | 0.3301 | 0.1523 | 0.052* | |
C12 | 0.3141 (2) | 0.35638 (19) | 0.1657 (2) | 0.0434 (6) | |
H12A | 0.2907 | 0.3012 | 0.2088 | 0.052* | |
H12B | 0.3066 | 0.3341 | 0.0968 | 0.052* | |
C13 | 0.24314 (18) | 0.45085 (18) | 0.18341 (18) | 0.0353 (5) | |
C14 | 0.2988 (2) | 0.5246 (2) | 0.25409 (17) | 0.0372 (5) | |
C15 | 0.2220 (2) | 0.5690 (2) | 0.3221 (2) | 0.0521 (7) | |
H15 | 0.2306 | 0.6392 | 0.3459 | 0.062* | |
C16 | 0.1141 (2) | 0.5284 (2) | 0.2979 (2) | 0.0551 (8) | |
H16A | 0.0756 | 0.5751 | 0.2550 | 0.066* | |
H16B | 0.0736 | 0.5163 | 0.3584 | 0.066* | |
C17 | 0.1385 (2) | 0.4279 (2) | 0.2433 (2) | 0.0422 (6) | |
H17 | 0.1554 | 0.3768 | 0.2944 | 0.051* | |
C18 | 0.2138 (2) | 0.5065 (2) | 0.0863 (2) | 0.0434 (6) | |
H18A | 0.1788 | 0.4600 | 0.0419 | 0.065* | |
H18B | 0.2766 | 0.5318 | 0.0549 | 0.065* | |
H18C | 0.1677 | 0.5625 | 0.1015 | 0.065* | |
C19 | 0.6576 (2) | 0.4912 (2) | 0.1933 (2) | 0.0519 (7) | |
H19A | 0.6576 | 0.4201 | 0.2105 | 0.078* | |
H19B | 0.6453 | 0.5311 | 0.2524 | 0.078* | |
H19C | 0.7247 | 0.5092 | 0.1650 | 0.078* | |
C20 | 0.0501 (2) | 0.3867 (2) | 0.1819 (2) | 0.0471 (7) | |
C21 | 0.0405 (3) | 0.2773 (3) | 0.1616 (3) | 0.0637 (9) | |
C22 | −0.0315 (2) | 0.4304 (3) | 0.1377 (4) | 0.0765 (11) | |
H22 | −0.0468 | 0.4997 | 0.1407 | 0.092* | |
C23 | −0.0956 (3) | 0.3537 (3) | 0.0829 (4) | 0.0822 (12) | |
H23A | −0.1675 | 0.3527 | 0.1075 | 0.099* | |
H23B | −0.0965 | 0.3683 | 0.0117 | 0.099* | |
C28 | 0.6164 (2) | 0.6976 (2) | −0.0908 (2) | 0.0513 (7) | |
H28A | 0.5738 | 0.7566 | −0.0779 | 0.077* | |
H28B | 0.5740 | 0.6457 | −0.1216 | 0.077* | |
H28C | 0.6733 | 0.7157 | −0.1347 | 0.077* | |
C29 | 0.7320 (2) | 0.7357 (2) | 0.0607 (2) | 0.0494 (7) | |
H29A | 0.6896 | 0.7922 | 0.0823 | 0.074* | |
H29B | 0.7843 | 0.7593 | 0.0142 | 0.074* | |
H29C | 0.7661 | 0.7055 | 0.1176 | 0.074* | |
C30 | 0.4720 (2) | 0.5847 (2) | 0.3232 (2) | 0.0505 (7) | |
H30A | 0.5347 | 0.6223 | 0.3073 | 0.076* | |
H30B | 0.4909 | 0.5208 | 0.3533 | 0.076* | |
H30C | 0.4297 | 0.6234 | 0.3692 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0394 (10) | 0.0535 (11) | 0.0692 (13) | −0.0030 (9) | 0.0126 (9) | −0.0034 (10) |
O6 | 0.0425 (10) | 0.0331 (9) | 0.0629 (12) | 0.0020 (8) | 0.0026 (9) | 0.0069 (9) |
O7 | 0.0473 (10) | 0.0382 (10) | 0.0597 (12) | 0.0082 (9) | 0.0059 (9) | 0.0002 (9) |
O15 | 0.0693 (13) | 0.0627 (13) | 0.0282 (9) | −0.0034 (11) | 0.0059 (8) | 0.0048 (9) |
O21 | 0.0861 (18) | 0.0517 (15) | 0.166 (3) | 0.0126 (14) | −0.017 (2) | −0.0224 (19) |
O23 | 0.0543 (13) | 0.0725 (16) | 0.112 (2) | −0.0035 (12) | −0.0076 (14) | −0.0265 (16) |
C1 | 0.0428 (13) | 0.0369 (14) | 0.0550 (15) | −0.0009 (11) | 0.0022 (12) | −0.0066 (12) |
C2 | 0.0475 (15) | 0.0449 (15) | 0.0497 (15) | −0.0020 (13) | 0.0094 (12) | −0.0145 (13) |
C3 | 0.0402 (13) | 0.0446 (14) | 0.0368 (12) | −0.0032 (11) | 0.0019 (10) | −0.0023 (11) |
C4 | 0.0368 (12) | 0.0366 (13) | 0.0392 (12) | −0.0040 (11) | −0.0006 (10) | −0.0007 (10) |
C5 | 0.0329 (11) | 0.0343 (12) | 0.0343 (11) | −0.0034 (10) | −0.0049 (9) | −0.0014 (10) |
C6 | 0.0388 (12) | 0.0302 (12) | 0.0395 (13) | −0.0016 (10) | −0.0049 (10) | 0.0024 (10) |
C7 | 0.0384 (12) | 0.0325 (12) | 0.0351 (11) | 0.0004 (10) | −0.0059 (10) | −0.0065 (10) |
C8 | 0.0381 (12) | 0.0346 (13) | 0.0322 (11) | 0.0015 (11) | −0.0013 (9) | 0.0015 (10) |
C9 | 0.0368 (12) | 0.0308 (12) | 0.0378 (12) | 0.0030 (10) | −0.0012 (10) | 0.0026 (10) |
C10 | 0.0351 (12) | 0.0325 (12) | 0.0403 (12) | 0.0019 (10) | −0.0011 (10) | 0.0015 (10) |
C11 | 0.0458 (14) | 0.0344 (13) | 0.0496 (14) | 0.0072 (11) | 0.0062 (12) | 0.0065 (12) |
C12 | 0.0495 (14) | 0.0314 (13) | 0.0494 (14) | −0.0012 (11) | 0.0101 (12) | 0.0022 (11) |
C13 | 0.0407 (13) | 0.0325 (12) | 0.0326 (11) | 0.0016 (10) | 0.0062 (10) | 0.0010 (10) |
C14 | 0.0451 (13) | 0.0381 (13) | 0.0284 (11) | 0.0029 (11) | 0.0023 (10) | 0.0032 (10) |
C15 | 0.0622 (17) | 0.0466 (16) | 0.0474 (15) | −0.0040 (14) | 0.0177 (13) | −0.0122 (13) |
C16 | 0.0556 (17) | 0.0500 (16) | 0.0599 (18) | 0.0012 (14) | 0.0230 (14) | −0.0108 (14) |
C17 | 0.0443 (13) | 0.0378 (13) | 0.0446 (14) | 0.0016 (12) | 0.0112 (11) | 0.0029 (11) |
C18 | 0.0472 (15) | 0.0453 (15) | 0.0377 (13) | −0.0047 (12) | −0.0013 (10) | 0.0048 (12) |
C19 | 0.0441 (14) | 0.0576 (18) | 0.0539 (16) | 0.0107 (13) | −0.0051 (12) | 0.0109 (14) |
C20 | 0.0410 (13) | 0.0437 (15) | 0.0565 (16) | 0.0018 (12) | 0.0145 (13) | 0.0042 (14) |
C21 | 0.0500 (16) | 0.0528 (18) | 0.088 (2) | 0.0009 (15) | 0.0083 (17) | −0.0156 (18) |
C22 | 0.0462 (17) | 0.058 (2) | 0.125 (3) | −0.0034 (16) | −0.007 (2) | 0.011 (2) |
C23 | 0.0549 (19) | 0.081 (3) | 0.111 (3) | −0.005 (2) | −0.012 (2) | 0.001 (2) |
C28 | 0.0538 (16) | 0.0568 (18) | 0.0432 (15) | −0.0037 (14) | 0.0000 (12) | 0.0081 (13) |
C29 | 0.0430 (14) | 0.0467 (15) | 0.0585 (17) | −0.0114 (13) | 0.0012 (12) | −0.0101 (14) |
C30 | 0.0580 (16) | 0.0553 (16) | 0.0382 (14) | 0.0027 (14) | −0.0083 (12) | −0.0035 (13) |
O3—C3 | 1.216 (3) | C12—H12A | 0.9700 |
O6—C6 | 1.360 (3) | C12—H12B | 0.9700 |
O6—H6 | 0.8200 | C13—C14 | 1.525 (4) |
O7—C7 | 1.220 (3) | C13—C18 | 1.533 (3) |
O15—C15 | 1.436 (4) | C13—C17 | 1.578 (3) |
O15—C14 | 1.456 (3) | C14—C15 | 1.454 (4) |
O21—C21 | 1.206 (4) | C15—C16 | 1.503 (4) |
O23—C21 | 1.359 (4) | C15—H15 | 0.9800 |
O23—C23 | 1.416 (5) | C16—C17 | 1.538 (4) |
C1—C2 | 1.317 (4) | C16—H16A | 0.9700 |
C1—C10 | 1.514 (4) | C16—H16B | 0.9700 |
C1—H1 | 0.9300 | C17—C20 | 1.491 (4) |
C2—C3 | 1.461 (4) | C17—H17 | 0.9800 |
C2—H2 | 0.9300 | C18—H18A | 0.9600 |
C3—C4 | 1.527 (4) | C18—H18B | 0.9600 |
C4—C29 | 1.526 (3) | C18—H18C | 0.9600 |
C4—C5 | 1.532 (3) | C19—H19A | 0.9600 |
C4—C28 | 1.559 (4) | C19—H19B | 0.9600 |
C5—C6 | 1.348 (3) | C19—H19C | 0.9600 |
C5—C10 | 1.545 (3) | C20—C22 | 1.323 (4) |
C6—C7 | 1.482 (3) | C20—C21 | 1.465 (4) |
C7—O7 | 1.220 (3) | C22—C23 | 1.486 (5) |
C7—C8 | 1.511 (3) | C22—H22 | 0.9300 |
C8—C14 | 1.531 (4) | C23—H23A | 0.9700 |
C8—C9 | 1.548 (3) | C23—H23B | 0.9700 |
C8—C30 | 1.555 (3) | C28—H28A | 0.9600 |
C9—C11 | 1.531 (3) | C28—H28B | 0.9600 |
C9—C10 | 1.546 (3) | C28—H28C | 0.9600 |
C9—H9 | 0.9800 | C29—H29A | 0.9600 |
C10—C19 | 1.545 (4) | C29—H29B | 0.9600 |
C11—C12 | 1.540 (4) | C29—H29C | 0.9600 |
C11—H11A | 0.9700 | C30—H30A | 0.9600 |
C11—H11B | 0.9700 | C30—H30B | 0.9600 |
C12—C13 | 1.549 (3) | C30—H30C | 0.9600 |
C6—O6—H6 | 109.5 | C15—C14—C8 | 128.6 (2) |
C15—O15—C14 | 60.35 (17) | O15—C14—C8 | 113.9 (2) |
C21—O23—C23 | 108.8 (3) | C13—C14—C8 | 119.0 (2) |
C2—C1—C10 | 122.2 (2) | O15—C15—C14 | 60.51 (17) |
C2—C1—H1 | 118.9 | O15—C15—C16 | 111.5 (3) |
C10—C1—H1 | 118.9 | C14—C15—C16 | 109.5 (2) |
C1—C2—C3 | 119.1 (2) | O15—C15—H15 | 120.3 |
C1—C2—H2 | 120.4 | C14—C15—H15 | 120.3 |
C3—C2—H2 | 120.4 | C16—C15—H15 | 120.3 |
O3—C3—C2 | 122.0 (3) | C15—C16—C17 | 102.8 (2) |
O3—C3—C4 | 122.2 (2) | C15—C16—H16A | 111.2 |
C2—C3—C4 | 115.7 (2) | C17—C16—H16A | 111.2 |
C29—C4—C3 | 111.1 (2) | C15—C16—H16B | 111.2 |
C29—C4—C5 | 110.9 (2) | C17—C16—H16B | 111.2 |
C3—C4—C5 | 111.7 (2) | H16A—C16—H16B | 109.1 |
C29—C4—C28 | 111.4 (2) | C20—C17—C16 | 114.9 (2) |
C3—C4—C28 | 101.7 (2) | C20—C17—C13 | 115.0 (2) |
C5—C4—C28 | 109.7 (2) | C16—C17—C13 | 104.3 (2) |
C6—C5—C4 | 121.0 (2) | C20—C17—H17 | 107.4 |
C6—C5—C10 | 120.9 (2) | C16—C17—H17 | 107.4 |
C4—C5—C10 | 118.1 (2) | C13—C17—H17 | 107.4 |
C5—C6—O6 | 121.2 (2) | C13—C18—H18A | 109.5 |
C5—C6—C7 | 125.2 (2) | C13—C18—H18B | 109.5 |
O6—C6—C7 | 113.6 (2) | H18A—C18—H18B | 109.5 |
O7—C7—C6 | 119.1 (2) | C13—C18—H18C | 109.5 |
O7—C7—C8 | 123.6 (2) | H18A—C18—H18C | 109.5 |
C6—C7—C8 | 117.1 (2) | H18B—C18—H18C | 109.5 |
C7—C8—C14 | 114.3 (2) | C10—C19—H19A | 109.5 |
C7—C8—C9 | 107.40 (19) | C10—C19—H19B | 109.5 |
C14—C8—C9 | 106.9 (2) | H19A—C19—H19B | 109.5 |
C7—C8—C30 | 103.4 (2) | C10—C19—H19C | 109.5 |
C14—C8—C30 | 108.8 (2) | H19A—C19—H19C | 109.5 |
C9—C8—C30 | 116.2 (2) | H19B—C19—H19C | 109.5 |
C11—C9—C10 | 119.2 (2) | C22—C20—C21 | 106.1 (3) |
C11—C9—C8 | 108.9 (2) | C22—C20—C17 | 132.6 (3) |
C10—C9—C8 | 115.0 (2) | C21—C20—C17 | 121.3 (3) |
C11—C9—H9 | 103.9 | O21—C21—O23 | 122.1 (3) |
C10—C9—H9 | 103.9 | O21—C21—C20 | 128.1 (3) |
C8—C9—H9 | 103.9 | O23—C21—C20 | 109.8 (3) |
C1—C10—C5 | 106.3 (2) | C20—C22—C23 | 110.7 (3) |
C1—C10—C19 | 106.6 (2) | C20—C22—H22 | 124.6 |
C5—C10—C19 | 111.8 (2) | C23—C22—H22 | 124.6 |
C1—C10—C9 | 107.9 (2) | O23—C23—C22 | 104.4 (3) |
C5—C10—C9 | 108.38 (19) | O23—C23—H23A | 110.9 |
C19—C10—C9 | 115.4 (2) | C22—C23—H23A | 110.9 |
C9—C11—C12 | 108.8 (2) | O23—C23—H23B | 110.9 |
C9—C11—H11A | 109.9 | C22—C23—H23B | 110.9 |
C12—C11—H11A | 109.9 | H23A—C23—H23B | 108.9 |
C9—C11—H11B | 109.9 | C4—C28—H28A | 109.5 |
C12—C11—H11B | 109.9 | C4—C28—H28B | 109.5 |
H11A—C11—H11B | 108.3 | H28A—C28—H28B | 109.5 |
C11—C12—C13 | 112.2 (2) | C4—C28—H28C | 109.5 |
C11—C12—H12A | 109.2 | H28A—C28—H28C | 109.5 |
C13—C12—H12A | 109.2 | H28B—C28—H28C | 109.5 |
C11—C12—H12B | 109.2 | C4—C29—H29A | 109.5 |
C13—C12—H12B | 109.2 | C4—C29—H29B | 109.5 |
H12A—C12—H12B | 107.9 | H29A—C29—H29B | 109.5 |
C14—C13—C18 | 109.5 (2) | C4—C29—H29C | 109.5 |
C14—C13—C12 | 109.4 (2) | H29A—C29—H29C | 109.5 |
C18—C13—C12 | 113.1 (2) | H29B—C29—H29C | 109.5 |
C14—C13—C17 | 101.3 (2) | C8—C30—H30A | 109.5 |
C18—C13—C17 | 108.3 (2) | C8—C30—H30B | 109.5 |
C12—C13—C17 | 114.4 (2) | H30A—C30—H30B | 109.5 |
C15—C14—O15 | 59.14 (17) | C8—C30—H30C | 109.5 |
C15—C14—C13 | 109.3 (2) | H30A—C30—H30C | 109.5 |
O15—C14—C13 | 110.8 (2) | H30B—C30—H30C | 109.5 |
C10—C1—C2—C3 | −2.8 (4) | C11—C12—C13—C14 | −22.2 (3) |
C1—C2—C3—O3 | 145.9 (3) | C11—C12—C13—C18 | 100.2 (3) |
C1—C2—C3—C4 | −38.6 (4) | C11—C12—C13—C17 | −135.1 (2) |
O3—C3—C4—C29 | −27.5 (3) | C15—O15—C14—C13 | −100.6 (2) |
C2—C3—C4—C29 | 157.0 (2) | C15—O15—C14—C8 | 122.0 (3) |
O3—C3—C4—C5 | −151.9 (2) | C18—C13—C14—C15 | 94.1 (2) |
C2—C3—C4—C5 | 32.5 (3) | C12—C13—C14—C15 | −141.4 (2) |
O3—C3—C4—C28 | 91.1 (3) | C17—C13—C14—C15 | −20.2 (3) |
C2—C3—C4—C28 | −84.4 (3) | C18—C13—C14—O15 | 157.5 (2) |
C29—C4—C5—C6 | 67.1 (3) | C12—C13—C14—O15 | −78.0 (3) |
C3—C4—C5—C6 | −168.3 (2) | C17—C13—C14—O15 | 43.2 (2) |
C28—C4—C5—C6 | −56.3 (3) | C18—C13—C14—C8 | −67.6 (3) |
C29—C4—C5—C10 | −114.7 (2) | C12—C13—C14—C8 | 56.9 (3) |
C3—C4—C5—C10 | 9.9 (3) | C17—C13—C14—C8 | 178.1 (2) |
C28—C4—C5—C10 | 121.8 (2) | C7—C8—C14—C15 | −61.7 (3) |
C4—C5—C6—O6 | 0.2 (4) | C9—C8—C14—C15 | 179.5 (3) |
C10—C5—C6—O6 | −177.9 (2) | C30—C8—C14—C15 | 53.2 (3) |
C4—C5—C6—C7 | −176.6 (2) | C7—C8—C14—O15 | −130.4 (2) |
C10—C5—C6—C7 | 5.2 (4) | C9—C8—C14—O15 | 110.9 (2) |
C5—C6—C7—O7 | 177.8 (2) | C30—C8—C14—O15 | −15.4 (3) |
O6—C6—C7—O7 | 0.7 (3) | C7—C8—C14—C13 | 96.0 (3) |
C5—C6—C7—C8 | 3.5 (3) | C9—C8—C14—C13 | −22.7 (3) |
O6—C6—C7—C8 | −173.6 (2) | C30—C8—C14—C13 | −149.0 (2) |
O7—C7—C8—C14 | 34.2 (3) | C14—O15—C15—C16 | 100.9 (2) |
C6—C7—C8—C14 | −151.8 (2) | C13—C14—C15—O15 | 103.3 (2) |
O7—C7—C8—C9 | 152.6 (2) | C8—C14—C15—O15 | −97.3 (3) |
C6—C7—C8—C9 | −33.3 (3) | O15—C14—C15—C16 | −104.3 (3) |
O7—C7—C8—C30 | −83.9 (3) | C13—C14—C15—C16 | −1.0 (3) |
C6—C7—C8—C30 | 90.1 (2) | C8—C14—C15—C16 | 158.4 (3) |
C7—C8—C9—C11 | −164.3 (2) | O15—C15—C16—C17 | −42.6 (3) |
C14—C8—C9—C11 | −41.2 (3) | C14—C15—C16—C17 | 22.5 (3) |
C30—C8—C9—C11 | 80.5 (3) | C15—C16—C17—C20 | −161.3 (2) |
C7—C8—C9—C10 | 58.9 (3) | C15—C16—C17—C13 | −34.5 (3) |
C14—C8—C9—C10 | −178.05 (19) | C14—C13—C17—C20 | 160.2 (2) |
C30—C8—C9—C10 | −56.3 (3) | C18—C13—C17—C20 | 45.0 (3) |
C2—C1—C10—C5 | 43.0 (3) | C12—C13—C17—C20 | −82.2 (3) |
C2—C1—C10—C19 | −76.4 (3) | C14—C13—C17—C16 | 33.5 (3) |
C2—C1—C10—C9 | 159.1 (3) | C18—C13—C17—C16 | −81.7 (3) |
C6—C5—C10—C1 | 133.6 (2) | C12—C13—C17—C16 | 151.1 (2) |
C4—C5—C10—C1 | −44.6 (3) | C16—C17—C20—C22 | 25.6 (5) |
C6—C5—C10—C19 | −110.5 (3) | C13—C17—C20—C22 | −95.5 (4) |
C4—C5—C10—C19 | 71.3 (3) | C16—C17—C20—C21 | −153.1 (3) |
C6—C5—C10—C9 | 17.7 (3) | C13—C17—C20—C21 | 85.8 (4) |
C4—C5—C10—C9 | −160.42 (19) | C23—O23—C21—O21 | 178.1 (4) |
C11—C9—C10—C1 | 62.3 (3) | C23—O23—C21—C20 | −1.4 (4) |
C8—C9—C10—C1 | −165.6 (2) | C22—C20—C21—O21 | −176.9 (4) |
C11—C9—C10—C5 | 177.0 (2) | C17—C20—C21—O21 | 2.1 (6) |
C8—C9—C10—C5 | −50.8 (3) | C22—C20—C21—O23 | 2.5 (4) |
C11—C9—C10—C19 | −56.8 (3) | C17—C20—C21—O23 | −178.4 (2) |
C8—C9—C10—C19 | 75.4 (3) | C21—C20—C22—C23 | −2.6 (4) |
C10—C9—C11—C12 | −150.8 (2) | C17—C20—C22—C23 | 178.5 (3) |
C8—C9—C11—C12 | 74.4 (3) | C21—O23—C23—C22 | −0.1 (4) |
C9—C11—C12—C13 | −37.8 (3) | C20—C22—C23—O23 | 1.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O7 | 0.82 | 2.18 | 2.624 (3) | 114 |
O6—H6···O3i | 0.82 | 2.15 | 2.897 (3) | 151 |
C2—H2···O21ii | 0.93 | 2.48 | 3.239 (4) | 139 |
C28—H28C···O7iii | 0.96 | 2.40 | 3.320 (4) | 162 |
Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x+1/2, −y+1/2, −z; (iii) x+1/2, −y+3/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C26H30O6 |
Mr | 438.50 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 12.6858 (9), 13.1117 (9), 13.353 (1) |
V (Å3) | 2221.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.26 × 0.21 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.974, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14146, 2967, 2364 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.125, 1.08 |
No. of reflections | 2967 |
No. of parameters | 290 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.19 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 and PARST97 (Nardelli, 1995).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O7 | 0.82 | 2.18 | 2.624 (3) | 113.7 |
O6—H6···O3i | 0.82 | 2.15 | 2.897 (3) | 150.8 |
C2—H2···O21ii | 0.93 | 2.48 | 3.239 (4) | 139.0 |
C28—H28C···O7iii | 0.96 | 2.40 | 3.320 (4) | 161.6 |
Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x+1/2, −y+1/2, −z; (iii) x+1/2, −y+3/2, −z. |
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Cedrelone (Zeumer et al., 2000), one of the major limonoids extracted from Toona ciliata, shows minimum antifeedant activity; however it was reported that its photo and microwave products show enhanced and reduced activity, respectively (Suresh et al., 2002).
The present study reports the crystal structure of a microwave-modified product which has an additional carbonyl group at C21 in the furan ring. This substitution has modified only the furan ring orientation with respect to ring D. The torsion angle, C16—C17—C20—C22, showing the relative orientation of the furan ring with respect to ring D, is 25.5 (4)°, compared to 168.3 (4)° in cedrelone itself.
Ring A is in a boat conformation (Cremer & Pople, 1975). The atoms C3 and C10 deviate by 0.561 (2) Å & 0.405 (2) Å from the plane involving the other atoms of the ring. Ring B takes up a half-chair conformation, the atoms C9 and C8 deviating from the least-squares plane of the other four atoms by 0.530 (2) Å and -0.183 (2) Å. Ring C adopts a twist conformation, with the atoms C11 and C13 deviating from the plane through atoms C8, C9, C12, C14 by -0.789 (3) Å and 0.697 (2) Å. Ring D is in an envelope conformation with C17 as the flap atom, lying 0.543 (4) Å from the plane of the remaining four atoms. Ring E is in a planar conformation, the maximum deviation (for atom C22) being 0.045 (4) Å. The ring fusions at the junctions A/B, B/C and C/D are quasi-trans, trans and trans, respectively, as seen from the endocyclic torsion angles.
The packing of the molecules in the crystal structure (Fig. 2) is achieved through a network of O—H···O and C—H···O hydrogen bonds (Table 1). An S(5) motif is generated through the O6—H6···O7 intramolecular hydrogen bond. Three chain motifs C(7),C(7) and C(12) are generated through hydrogen bonds O6—H6···O3 (-1/2 + x, 3/2 - y, -z), C28—H28C···O7 (1/2 + x,3/2 - y,-z) and C2—H2···O21(1/2 + x, 1/2 - y,-z). These in turn generate a ring motif R22[10] (Bernstein et al.,1995).