The title structure, 15,18-dimethyl-5-dioxo-14-oxapentacyclo[11.4.1.0
2,15.0
4,13.0
6,11]octadeca-3,6,8,10-tetraene-18-carbaldehyde, C
20H
18O
4, is a novel naphthoquinone, isolated from
Stereospermum personatum. In the bicyclic system, all three six-membered rings adopt a boat conformation. Two intermolecular C=O
H—C interactions link the molecules into a chain.
Supporting information
CCDC reference: 264098
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.003 Å
- R factor = 0.039
- wR factor = 0.105
- Data-to-parameter ratio = 8.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98
PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 3.09 Ratio
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 27.96
From the CIF: _reflns_number_total 1954
Count of symmetry unique reflns 2005
Completeness (_total/calc) 97.46%
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
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 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
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
15,18-dimethyl-5-dioxo-14-
oxapentacyclo[11.4.1.0
2,15.0
4,13.0
6,11]octadeca-3,6,8,10-tetraene-
18-carbaldehyde
top
Crystal data top
C20H18O4 | F(000) = 680 |
Mr = 322.34 | Dx = 1.338 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 6143 reflections |
a = 13.3078 (19) Å | θ = 2.7–27.9° |
b = 7.9299 (11) Å | µ = 0.09 mm−1 |
c = 15.168 (2) Å | T = 273 K |
V = 1600.7 (4) Å3 | Needle, pale yellow |
Z = 4 | 0.25 × 0.13 × 0.10 mm |
Data collection top
CCD Area Detector diffractometer | 1879 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 28.0°, θmin = 3.0° |
ω scans | h = −17→13 |
9248 measured reflections | k = −10→10 |
1954 independent reflections | l = −19→19 |
Refinement top
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0762P)2 + 0.1221P] where P = (Fo2 + 2Fc2)/3 |
1954 reflections | (Δ/σ)max < 0.001 |
219 parameters | Δρmax = 0.20 e Å−3 |
1 restraint | Δρmin = −0.24 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.87648 (14) | 0.0283 (2) | 0.75882 (12) | 0.0437 (4) | |
C2 | 0.93689 (14) | 0.0353 (3) | 0.67646 (12) | 0.0425 (4) | |
C3 | 1.00326 (16) | −0.0978 (3) | 0.66023 (15) | 0.0558 (5) | |
H3 | 1.0074 | −0.1876 | 0.6995 | 0.067* | |
C4 | 1.06305 (17) | −0.0951 (4) | 0.58516 (18) | 0.0675 (7) | |
H4 | 1.1075 | −0.1833 | 0.5744 | 0.081* | |
C5 | 1.05701 (18) | 0.0371 (4) | 0.52658 (16) | 0.0708 (8) | |
H5 | 1.0976 | 0.0376 | 0.4767 | 0.085* | |
C6 | 0.9914 (2) | 0.1687 (3) | 0.54110 (16) | 0.0639 (6) | |
H6 | 0.9877 | 0.2569 | 0.5008 | 0.077* | |
C7 | 0.93012 (16) | 0.1701 (3) | 0.61678 (13) | 0.0493 (4) | |
C8 | 0.8620 (2) | 0.3162 (3) | 0.63272 (16) | 0.0620 (6) | |
C9 | 0.80118 (17) | 0.3133 (3) | 0.71384 (13) | 0.0470 (4) | |
C10 | 0.79883 (13) | 0.1672 (2) | 0.77739 (10) | 0.0361 (3) | |
C11 | 0.68926 (14) | 0.0927 (2) | 0.77901 (12) | 0.0398 (4) | |
C12 | 0.62095 (14) | 0.2372 (2) | 0.81775 (14) | 0.0446 (4) | |
H12 | 0.5602 | 0.2505 | 0.7819 | 0.053* | |
C13 | 0.68179 (15) | 0.4045 (2) | 0.81941 (15) | 0.0452 (4) | |
H13 | 0.6386 | 0.5003 | 0.8345 | 0.054* | |
C14 | 0.73881 (18) | 0.4377 (2) | 0.73770 (15) | 0.0515 (5) | |
H14 | 0.7320 | 0.5368 | 0.7055 | 0.062* | |
C15 | 0.6543 (2) | 0.0400 (3) | 0.68666 (16) | 0.0594 (6) | |
H15A | 0.7004 | −0.0412 | 0.6628 | 0.089* | |
H15B | 0.6521 | 0.1372 | 0.6490 | 0.089* | |
H15C | 0.5885 | −0.0091 | 0.6904 | 0.089* | |
C16 | 0.68555 (15) | −0.0594 (2) | 0.84040 (16) | 0.0481 (4) | |
H16 | 0.7182 | −0.0518 | 0.8945 | 0.058* | |
C17 | 0.59298 (16) | 0.2195 (3) | 0.91621 (16) | 0.0532 (5) | |
H17A | 0.5331 | 0.2842 | 0.9298 | 0.064* | |
H17B | 0.5812 | 0.1024 | 0.9314 | 0.064* | |
C18 | 0.68435 (15) | 0.2893 (3) | 0.96651 (13) | 0.0490 (4) | |
H18A | 0.6637 | 0.3766 | 1.0075 | 0.059* | |
H18B | 0.7175 | 0.2001 | 0.9993 | 0.059* | |
C19 | 0.75483 (14) | 0.3617 (2) | 0.89646 (13) | 0.0417 (4) | |
C20 | 0.82098 (19) | 0.5065 (3) | 0.92709 (18) | 0.0591 (5) | |
H20A | 0.8645 | 0.4681 | 0.9734 | 0.089* | |
H20B | 0.7795 | 0.5966 | 0.9487 | 0.089* | |
H20C | 0.8607 | 0.5464 | 0.8785 | 0.089* | |
O1 | 0.88646 (16) | −0.0859 (2) | 0.81077 (12) | 0.0710 (6) | |
O2 | 0.8574 (3) | 0.4315 (3) | 0.58089 (18) | 0.1188 (12) | |
O3 | 0.64282 (18) | −0.1887 (2) | 0.82283 (18) | 0.0806 (6) | |
O4 | 0.82152 (9) | 0.22651 (15) | 0.86547 (8) | 0.0384 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0510 (9) | 0.0439 (9) | 0.0361 (8) | 0.0132 (7) | 0.0001 (7) | 0.0008 (7) |
C2 | 0.0410 (8) | 0.0526 (9) | 0.0339 (8) | 0.0018 (7) | −0.0045 (6) | −0.0074 (7) |
C3 | 0.0491 (10) | 0.0732 (13) | 0.0451 (10) | 0.0127 (10) | −0.0040 (8) | −0.0116 (10) |
C4 | 0.0489 (11) | 0.099 (2) | 0.0551 (12) | 0.0112 (11) | 0.0020 (10) | −0.0245 (14) |
C5 | 0.0532 (12) | 0.112 (2) | 0.0471 (12) | −0.0166 (13) | 0.0117 (9) | −0.0255 (13) |
C6 | 0.0703 (14) | 0.0821 (15) | 0.0394 (9) | −0.0220 (12) | 0.0067 (10) | −0.0054 (11) |
C7 | 0.0530 (10) | 0.0590 (11) | 0.0360 (8) | −0.0096 (8) | 0.0001 (8) | −0.0042 (8) |
C8 | 0.0854 (16) | 0.0563 (13) | 0.0442 (10) | 0.0034 (12) | 0.0090 (11) | 0.0130 (10) |
C9 | 0.0638 (11) | 0.0384 (9) | 0.0387 (8) | 0.0047 (8) | −0.0018 (8) | 0.0091 (7) |
C10 | 0.0467 (8) | 0.0319 (7) | 0.0297 (7) | 0.0068 (6) | −0.0018 (6) | 0.0027 (6) |
C11 | 0.0468 (8) | 0.0326 (7) | 0.0400 (8) | 0.0051 (6) | −0.0085 (7) | −0.0024 (6) |
C12 | 0.0414 (8) | 0.0404 (8) | 0.0520 (10) | 0.0096 (7) | −0.0088 (8) | −0.0041 (8) |
C13 | 0.0536 (10) | 0.0315 (8) | 0.0505 (9) | 0.0114 (7) | −0.0067 (8) | −0.0017 (7) |
C14 | 0.0717 (12) | 0.0353 (8) | 0.0477 (10) | 0.0095 (8) | −0.0091 (9) | 0.0086 (7) |
C15 | 0.0729 (14) | 0.0558 (12) | 0.0494 (11) | 0.0061 (10) | −0.0193 (10) | −0.0122 (10) |
C16 | 0.0523 (9) | 0.0352 (8) | 0.0568 (11) | 0.0031 (7) | −0.0025 (8) | 0.0027 (8) |
C17 | 0.0453 (9) | 0.0534 (10) | 0.0609 (13) | 0.0062 (8) | 0.0087 (9) | −0.0049 (9) |
C18 | 0.0532 (10) | 0.0514 (10) | 0.0422 (9) | 0.0078 (8) | 0.0048 (7) | −0.0067 (8) |
C19 | 0.0500 (9) | 0.0342 (7) | 0.0408 (8) | 0.0045 (7) | −0.0041 (7) | −0.0053 (7) |
C20 | 0.0698 (13) | 0.0456 (10) | 0.0618 (12) | −0.0063 (9) | −0.0108 (11) | −0.0112 (10) |
O1 | 0.0960 (13) | 0.0626 (9) | 0.0543 (9) | 0.0444 (9) | 0.0204 (9) | 0.0193 (8) |
O2 | 0.184 (3) | 0.0931 (17) | 0.0792 (16) | 0.0420 (19) | 0.0494 (18) | 0.0518 (14) |
O3 | 0.1012 (14) | 0.0407 (8) | 0.0999 (15) | −0.0144 (9) | −0.0171 (13) | 0.0032 (9) |
O4 | 0.0420 (6) | 0.0392 (6) | 0.0339 (5) | 0.0057 (4) | −0.0052 (5) | −0.0007 (5) |
Geometric parameters (Å, º) top
C1—O1 | 1.207 (2) | C12—C17 | 1.545 (3) |
C1—C2 | 1.487 (3) | C12—C13 | 1.554 (3) |
C1—C10 | 1.536 (2) | C12—H12 | 0.9800 |
C2—C3 | 1.398 (3) | C13—C14 | 1.477 (3) |
C2—C7 | 1.404 (3) | C13—C19 | 1.557 (3) |
C3—C4 | 1.389 (3) | C13—H13 | 0.9800 |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.377 (4) | C15—H15A | 0.9600 |
C4—H4 | 0.9300 | C15—H15B | 0.9600 |
C5—C6 | 1.378 (4) | C15—H15C | 0.9600 |
C5—H5 | 0.9300 | C16—O3 | 1.202 (3) |
C6—C7 | 1.408 (3) | C16—H16 | 0.9300 |
C6—H6 | 0.9300 | C17—C18 | 1.538 (3) |
C7—C8 | 1.490 (3) | C17—H17A | 0.9700 |
C8—O2 | 1.208 (3) | C17—H17B | 0.9700 |
C8—C9 | 1.473 (3) | C18—C19 | 1.529 (3) |
C9—C14 | 1.339 (3) | C18—H18A | 0.9700 |
C9—C10 | 1.507 (2) | C18—H18B | 0.9700 |
C10—O4 | 1.448 (2) | C19—O4 | 1.469 (2) |
C10—C11 | 1.573 (3) | C19—C20 | 1.520 (3) |
C11—C16 | 1.525 (3) | C20—H20A | 0.9600 |
C11—C15 | 1.534 (3) | C20—H20B | 0.9600 |
C11—C12 | 1.576 (3) | C20—H20C | 0.9600 |
| | | |
O1—C1—C2 | 121.12 (17) | C11—C12—H12 | 110.3 |
O1—C1—C10 | 119.45 (17) | C14—C13—C12 | 113.98 (17) |
C2—C1—C10 | 119.42 (16) | C14—C13—C19 | 110.35 (16) |
C3—C2—C7 | 120.13 (19) | C12—C13—C19 | 98.71 (14) |
C3—C2—C1 | 117.49 (19) | C14—C13—H13 | 111.1 |
C7—C2—C1 | 122.37 (17) | C12—C13—H13 | 111.1 |
C4—C3—C2 | 119.7 (2) | C19—C13—H13 | 111.1 |
C4—C3—H3 | 120.2 | C9—C14—C13 | 114.44 (17) |
C2—C3—H3 | 120.2 | C9—C14—H14 | 122.8 |
C5—C4—C3 | 120.5 (2) | C13—C14—H14 | 122.8 |
C5—C4—H4 | 119.8 | C11—C15—H15A | 109.5 |
C3—C4—H4 | 119.8 | C11—C15—H15B | 109.5 |
C4—C5—C6 | 120.7 (2) | H15A—C15—H15B | 109.5 |
C4—C5—H5 | 119.6 | C11—C15—H15C | 109.5 |
C6—C5—H5 | 119.6 | H15A—C15—H15C | 109.5 |
C5—C6—C7 | 120.2 (3) | H15B—C15—H15C | 109.5 |
C5—C6—H6 | 119.9 | O3—C16—C11 | 123.7 (2) |
C7—C6—H6 | 119.9 | O3—C16—H16 | 118.2 |
C2—C7—C6 | 118.8 (2) | C11—C16—H16 | 118.2 |
C2—C7—C8 | 121.76 (18) | C18—C17—C12 | 104.85 (16) |
C6—C7—C8 | 119.4 (2) | C18—C17—H17A | 110.8 |
O2—C8—C9 | 121.8 (2) | C12—C17—H17A | 110.8 |
O2—C8—C7 | 120.9 (2) | C18—C17—H17B | 110.8 |
C9—C8—C7 | 117.24 (18) | C12—C17—H17B | 110.8 |
C14—C9—C8 | 123.70 (19) | H17A—C17—H17B | 108.9 |
C14—C9—C10 | 112.38 (18) | C19—C18—C17 | 105.97 (17) |
C8—C9—C10 | 123.88 (18) | C19—C18—H18A | 110.5 |
O4—C10—C9 | 109.62 (14) | C17—C18—H18A | 110.5 |
O4—C10—C1 | 105.18 (13) | C19—C18—H18B | 110.5 |
C9—C10—C1 | 114.82 (16) | C17—C18—H18B | 110.5 |
O4—C10—C11 | 107.50 (13) | H18A—C18—H18B | 108.7 |
C9—C10—C11 | 108.51 (15) | O4—C19—C20 | 107.43 (16) |
C1—C10—C11 | 110.94 (14) | O4—C19—C18 | 108.60 (14) |
C16—C11—C15 | 109.38 (16) | C20—C19—C18 | 115.24 (18) |
C16—C11—C10 | 109.65 (14) | O4—C19—C13 | 107.21 (14) |
C15—C11—C10 | 111.66 (17) | C20—C19—C13 | 115.23 (17) |
C16—C11—C12 | 109.20 (16) | C18—C19—C13 | 102.73 (16) |
C15—C11—C12 | 111.33 (16) | C19—C20—H20A | 109.5 |
C10—C11—C12 | 105.53 (14) | C19—C20—H20B | 109.5 |
C17—C12—C13 | 100.79 (17) | H20A—C20—H20B | 109.5 |
C17—C12—C11 | 115.67 (16) | C19—C20—H20C | 109.5 |
C13—C12—C11 | 109.02 (15) | H20A—C20—H20C | 109.5 |
C17—C12—H12 | 110.3 | H20B—C20—H20C | 109.5 |
C13—C12—H12 | 110.3 | C10—O4—C19 | 113.98 (12) |
| | | |
O1—C1—C2—C3 | 1.9 (3) | C1—C10—C11—C15 | −70.41 (19) |
C10—C1—C2—C3 | −177.07 (17) | O4—C10—C11—C12 | 53.98 (17) |
O1—C1—C2—C7 | −177.1 (2) | C9—C10—C11—C12 | −64.49 (18) |
C10—C1—C2—C7 | 3.9 (3) | C1—C10—C11—C12 | 168.48 (15) |
C7—C2—C3—C4 | 0.5 (3) | C16—C11—C12—C17 | 17.4 (2) |
C1—C2—C3—C4 | −178.54 (19) | C15—C11—C12—C17 | 138.31 (18) |
C2—C3—C4—C5 | −0.3 (3) | C10—C11—C12—C17 | −100.37 (18) |
C3—C4—C5—C6 | −0.2 (4) | C16—C11—C12—C13 | 130.10 (17) |
C4—C5—C6—C7 | 0.5 (4) | C15—C11—C12—C13 | −109.02 (19) |
C3—C2—C7—C6 | −0.3 (3) | C10—C11—C12—C13 | 12.3 (2) |
C1—C2—C7—C6 | 178.76 (19) | C17—C12—C13—C14 | 167.05 (16) |
C3—C2—C7—C8 | −178.6 (2) | C11—C12—C13—C14 | 44.9 (2) |
C1—C2—C7—C8 | 0.4 (3) | C17—C12—C13—C19 | 50.10 (16) |
C5—C6—C7—C2 | −0.3 (3) | C11—C12—C13—C19 | −72.05 (19) |
C5—C6—C7—C8 | 178.1 (2) | C8—C9—C14—C13 | 177.3 (2) |
C2—C7—C8—O2 | 179.7 (3) | C10—C9—C14—C13 | −0.4 (3) |
C6—C7—C8—O2 | 1.4 (4) | C12—C13—C14—C9 | −54.9 (2) |
C2—C7—C8—C9 | −0.3 (3) | C19—C13—C14—C9 | 55.1 (2) |
C6—C7—C8—C9 | −178.6 (2) | C15—C11—C16—O3 | −13.7 (3) |
O2—C8—C9—C14 | −1.8 (5) | C10—C11—C16—O3 | −136.5 (2) |
C7—C8—C9—C14 | 178.2 (2) | C12—C11—C16—O3 | 108.3 (3) |
O2—C8—C9—C10 | 175.6 (3) | C13—C12—C17—C18 | −35.32 (18) |
C7—C8—C9—C10 | −4.4 (3) | C11—C12—C17—C18 | 82.0 (2) |
C14—C9—C10—O4 | −56.0 (2) | C12—C17—C18—C19 | 6.2 (2) |
C8—C9—C10—O4 | 126.4 (2) | C17—C18—C19—O4 | −88.02 (18) |
C14—C9—C10—C1 | −174.09 (18) | C17—C18—C19—C20 | 151.45 (18) |
C8—C9—C10—C1 | 8.2 (3) | C17—C18—C19—C13 | 25.31 (19) |
C14—C9—C10—C11 | 61.2 (2) | C14—C13—C19—O4 | −51.98 (19) |
C8—C9—C10—C11 | −116.5 (2) | C12—C13—C19—O4 | 67.71 (17) |
O1—C1—C10—O4 | 52.6 (2) | C14—C13—C19—C20 | 67.5 (2) |
C2—C1—C10—O4 | −128.35 (16) | C12—C13—C19—C20 | −172.78 (18) |
O1—C1—C10—C9 | 173.2 (2) | C14—C13—C19—C18 | −166.33 (15) |
C2—C1—C10—C9 | −7.8 (2) | C12—C13—C19—C18 | −46.64 (17) |
O1—C1—C10—C11 | −63.3 (3) | C9—C10—O4—C19 | 56.08 (19) |
C2—C1—C10—C11 | 115.71 (18) | C1—C10—O4—C19 | −179.97 (14) |
O4—C10—C11—C16 | −63.52 (17) | C11—C10—O4—C19 | −61.68 (16) |
C9—C10—C11—C16 | 178.00 (16) | C20—C19—O4—C10 | −127.16 (17) |
C1—C10—C11—C16 | 50.98 (19) | C18—C19—O4—C10 | 107.58 (16) |
O4—C10—C11—C15 | 175.09 (15) | C13—C19—O4—C10 | −2.77 (19) |
C9—C10—C11—C15 | 56.61 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 | 2.55 | 3.381 (3) | 148 |
C13—H13···O3ii | 0.98 | 2.47 | 3.268 (3) | 138 |
Symmetry codes: (i) −x+2, −y, z−1/2; (ii) x, y+1, z. |