The cyclopentane ring displays a twist conformation and the γ-lactone ring has an envelope conformation while the cycloheptane ring adopts a twist-chair conformation. O—H⋯O hydrogen bonds link the molecules, forming a three-dimensional network. A comparison between the structural parameters obtained by X-ray structure analysis and theoretical calculations give a satisfactory agreement.
Keywords: crystal structure, cynarinin A, Centaurea polypodiifolia, theoretical investigation, CNDO, PM3, HOMO, LUMO
Abstract
In the molecule of title compound, C15H20O6, also known as cynarinin A, the cyclopentane ring having twist conformation and a γ-lactone ring assuming an envelope conformation are trans- and cis-fused, respectively, to a cycloheptane ring adopting a twist-chair conformation. In the crystal, O—H⋯O hydrogen bonds link neighbouring molecules, forming a three-dimensional network. Theoretical calculations of the molecular structure using the CNDO approximation and MOPAC PM3 geometry optimization are in satisfactory agreement with the results of the X-ray structure analysis.
Chemical context
The genus Centaurea belongs to the asteraceae family and consists of more than seven hundred species throughout the world. One hundred and ninety species are found in Turkey, one hundred of which are endemic (Davis et al., 1988 ▸). Centaurea species contain acetylenic compounds (Christensen & Lam, 1990 ▸), flavonoids (Gulcemal et al., 2010 ▸; Kubacey et al., 2012 ▸; Khalfallah et al., 2012 ▸; Forgo et al., 2012 ▸) and sesquiterpene lactones (Bruno et al., 1996 ▸; Koukoulitsa et al., 2002 ▸; Janackovic et al., 2004 ▸; Bensouici et al., 2012 ▸), and display anticancer (Chicca et al., 2011 ▸; Csapi et al., 2010 ▸), antimicrobial, and anti-oxidant activities (Uysal et al., 2013 ▸; Politeo et al., 2012 ▸; Djeddi et al., 2011 ▸). Sesquiterpene lactones (SLs) are a class of plant secondary metabolites of lipophilic character. SLs exhibit diverse biological activities such as anti-inflammatory, anti-ulcer, antibacterial, antiviral, antifungal, and cytotoxic activity, and have an influence on the central nervous system and cardiovascular system (Yeşilada et al., 1995 ▸). As a contribution to this research field, the X-ray crystal structure of the title compound, also known as cynarinin A (Kamanzi et al., 1983 ▸), is reported herein.
Structural commentary
The title compound contains a cyclopentane ring and a γ-lactone ring trans- and cis-fused, respectively, to a cycloheptane ring (Fig. 1 ▸). The relative configurations at the asymmetric centres are C1(S), C4(R), C5(R), C6(R), C7(R), C8(R) and C10(S). The cyclopentane ring (C4/C5/C10–C12) is in a twist conformation about the C4—C5 bond with puckering parameters Q = 0.340 (3) Å and φ = 21.3 (4)°. The γ-lactone ring (O1/C6–C9) has an envelope conformation, with C7 at the flap [puckering parameters: Q = 0.271 (2) Å, φ = 259.0 (5)°]. The cycloheptane ring has a twist-chair conformation [puckering parameters: Q2 = 0.534 (2) Å, φ2 = 34.5 (3)°; Q3 = 0.650 (2) Å, φ3 = 191.5 (2)° and Q T = 0.841 (2) Å]. The pseudo-diad axis bisects the C1—C2 bond and passes through atom C5. All bond lengths and angles are unexceptional and comparable with those reported for a similar compound (Swamy et al., 2005 ▸).
Figure 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
Supramolecular features
In the crystal, neighbouring molecules are connected by O—H⋯O hydrogen bonds (Table 1 ▸; Fig. 2 ▸), forming a three dimensional network.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O3—H3O⋯O2i | 0.78 (5) | 2.06 (4) | 2.818 (3) | 168 (4) |
| O4—H4O⋯O3ii | 0.95 (5) | 2.14 (5) | 2.956 (3) | 144 (4) |
| O4—H4O⋯O5ii | 0.95 (5) | 2.45 (5) | 3.156 (3) | 132 (4) |
| O5—H5O⋯O6 | 0.90 (4) | 2.45 (4) | 2.877 (3) | 109 (3) |
| O5—H5O⋯O2iii | 0.90 (4) | 2.22 (4) | 3.096 (2) | 164 (4) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Figure 2.
The crystal packing of the title compound, viewed down the b axis, showing the three-dimensional hydrogen-bonding network (dashed lines).
Theoretical calculations
According to the results of a quantum mechanical calculation using the CNDO approximation (Pople et al., 1970 ▸), the charges at atoms O1, O2, O3, O4, O5 and O6 are −0.270, −0.241, −0.261, −0.255, −0.243 and −0.268 e−, respectively. The total energy and dipole moment of the title molecule are −6339.85 eV and 3.211 Debye. The HOMO and LUMO energy levels are −12.5301 and 3.7741 eV, respectively. In addition, a geometrical optimization calculation of the title compound was performed using MOPAC PM3 (Stewart, 1985 ▸). The spatial disposition of the atoms of the title molecule calculated with PM3 is shown in Fig. 3 ▸. The net charges at atoms O1, O2, O3, O4, O5 and O6 are −0.225, −0.304, −0.340, −0.318, −0.287 and −0.307e−, respectively. The total energy and dipole moment of the title molecule are −3848.31 eV and 3.305 Debye. The HOMO and LUMO energy levels are −10.3738 and 0.5350 eV, respectively. In the calculations, the molecule was assumed to be isolated and in an absolute vacuum therefore resulting in calculated bond lengths, bond angles and torsion angles that are greater than those observed experimentally. The PM3 method gives the lowest values for the HOMO and LUMO energy levels and the dipole moment.
Figure 3.
Spatial view of the molecule of the title compound calculated using the PM3 method.
Synthesis and crystallization
Centaurea polypodiifolia Boiss. (1.0 kg) was extracted with methanol (3 × 5L), filtered, and the solvent removed in vacuo to obtain the crude material which was dissolved in water (333 K) and extracted with ethyl acetate. The organic phase was separated by separator funnel and the solvent was removed by reduced pressure to yield the extract (10 g). The extract was subjected to silica gel (60, GF254) column chromatography (2.5 cm × 60 cm). A hexane/ethyl acetate mixture (6:4 v/v) was used as eluent. 24 fractions of 250 mL were collected. After checking by thin layer chromatography, 6–8 fractions were combined and crystallized in methanol to give suitable crystals of the title compound on slow evaporation of the solvent (yield: 10 mg). 13C NMR (150 MHz, DMSO-d 6) δ 219.04 (C3), 178.88 (C12), 145.62 (C10), 113.64 (C14), 81.65 (C6), 78.36 (C11), 69.19 (C8), 63.68 (C13), 55.76 (C7), 51.31 (C5), 48.58 (C9), 46.91 (C4), 43.23 (C2), 39.66 (C1), 14.83 (C15). 1H NMR (600 MHz, DMSO-d 6) δ 5.41 (s, 1H, 11-OH), 5.20 (t, 1H, J = 4.62 Hz 13-OH), 4.94 (s, 1H, H14a), 4.78 (d, 1H, J = 6.09 Hz, 8-OH), 4.63 (s, 1H, H14b), 4.04–3.93 (m, 3H, H6, H8 and H13a), 3.51 (dd, 1H, J = 9.78, 4.79 Hz, H13b), 3.07 (dt, 1H, J = 12.47, 4.06 Hz, H1), 2.67 (dd,1H, J = 12.28, 5.50 Hz, H9a), 2.51 (dd, 1H, J = 18.66, 8.97 Hz, H2a), 2.45 (t, 1H, J = 10.11 Hz, H7), 2.33 (dd, 1H, J = 18.66, 4.26 Hz, H2b), 2.21–2.14 (m, 2H, H4 and H5), 2.13–2.07 (m, 1H, H9b), 1.05 (d, 3H, J = 6.38 Hz, H15).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms bound to oxygen atoms were found in a difference Fourier map and allowed to ride on their parent atoms, with O—H = 0.82 Å and with U iso = 1.5 U eq(O). H atoms bound to carbon atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H = 0.93–0.98 Å, and with U iso = 1.2 U eq(C). One outlier (1 0 1) was omitted in the last cycles of refinement.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C15H20O6 |
| M r | 296.31 |
| Crystal system, space group | Orthorhombic, P212121 |
| Temperature (K) | 293 |
| a, b, c (Å) | 8.1980 (1), 10.0290 (2), 16.7720 (3) |
| V (Å3) | 1378.96 (4) |
| Z | 4 |
| Radiation type | Cu Kα |
| μ (mm−1) | 0.92 |
| Crystal size (mm) | 0.65 × 0.47 × 0.30 |
| Data collection | |
| Diffractometer | Agilent Xcalibur Ruby Gemini |
| Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2013 ▸) |
| T min, T max | 0.773, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 12778, 2623, 2502 |
| R int | 0.040 |
| (sin θ/λ)max (Å−1) | 0.613 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.035, 0.096, 1.05 |
| No. of reflections | 2623 |
| No. of parameters | 200 |
| Δρmax, Δρmin (e Å−3) | 0.27, −0.17 |
| Absolute structure | Flack (1983 ▸), 1073 Friedel pairs |
| Absolute structure parameter | −0.09 (9) |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019623/rz5172sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019623/rz5172Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015019623/rz5172Isup3.cml
CCDC reference: 1048445
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
This work was supported by the Scientific Research Project Fund of Cumhuriyet University under Project number F-436.
supplementary crystallographic information
Crystal data
| C15H20O6 | F(000) = 632 |
| Mr = 296.31 | Dx = 1.427 Mg m−3 |
| Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54184 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 7099 reflections |
| a = 8.1980 (1) Å | θ = 4.4–70.5° |
| b = 10.0290 (2) Å | µ = 0.92 mm−1 |
| c = 16.7720 (3) Å | T = 293 K |
| V = 1378.96 (4) Å3 | Prism, colourless |
| Z = 4 | 0.65 × 0.47 × 0.30 mm |
Data collection
| Agilent Xcalibur Ruby Gemini diffractometer | 2623 independent reflections |
| Radiation source: Enhance (Cu) X-ray Source | 2502 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.040 |
| Detector resolution: 10.2673 pixels mm-1 | θmax = 70.9°, θmin = 5.1° |
| ω scans | h = −10→7 |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = −12→12 |
| Tmin = 0.773, Tmax = 1.000 | l = −20→20 |
| 12778 measured reflections |
Refinement
| Refinement on F2 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.2045P] where P = (Fo2 + 2Fc2)/3 |
| Least-squares matrix: full | (Δ/σ)max < 0.001 |
| R[F2 > 2σ(F2)] = 0.035 | Δρmax = 0.27 e Å−3 |
| wR(F2) = 0.096 | Δρmin = −0.17 e Å−3 |
| S = 1.05 | Extinction correction: SHELXL97 (Sheldrick, 2008), FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
| 2623 reflections | Extinction coefficient: 0.0184 (14) |
| 200 parameters | Absolute structure: Flack (1983), 1073 Friedel pairs |
| 0 restraints | Absolute structure parameter: −0.09 (9) |
| Hydrogen site location: mixed |
Special details
| Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
| Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.2767 (2) | 0.42340 (18) | 0.94867 (10) | 0.0363 (5) | |
| O2 | 0.5458 (2) | 0.3191 (2) | 1.23883 (10) | 0.0417 (6) | |
| O3 | 0.6704 (3) | 0.7021 (2) | 0.83279 (12) | 0.0430 (6) | |
| O4 | 0.4798 (3) | 0.3608 (2) | 0.79632 (13) | 0.0583 (8) | |
| O5 | 0.2968 (2) | 0.68723 (17) | 0.81640 (11) | 0.0385 (5) | |
| O6 | 0.0874 (2) | 0.4674 (2) | 0.85721 (12) | 0.0526 (7) | |
| C1 | 0.6584 (3) | 0.5976 (2) | 0.89063 (13) | 0.0298 (7) | |
| C2 | 0.7676 (3) | 0.6329 (3) | 0.96189 (15) | 0.0371 (7) | |
| C3 | 0.7539 (3) | 0.5438 (2) | 1.03466 (14) | 0.0324 (7) | |
| C4 | 0.6038 (3) | 0.5670 (2) | 1.08525 (13) | 0.0294 (7) | |
| C5 | 0.4523 (3) | 0.4859 (2) | 1.05600 (13) | 0.0259 (6) | |
| C6 | 0.4448 (3) | 0.4643 (2) | 0.96656 (13) | 0.0266 (6) | |
| C7 | 0.4782 (3) | 0.5846 (2) | 0.91215 (13) | 0.0255 (6) | |
| C8 | 0.3588 (3) | 0.5632 (2) | 0.84275 (13) | 0.0284 (6) | |
| C9 | 0.2237 (3) | 0.4813 (2) | 0.88134 (14) | 0.0331 (7) | |
| C10 | 0.4595 (3) | 0.3538 (2) | 1.10233 (13) | 0.0280 (6) | |
| C11 | 0.5437 (3) | 0.3898 (2) | 1.17991 (13) | 0.0301 (7) | |
| C12 | 0.6183 (3) | 0.5262 (3) | 1.17351 (14) | 0.0347 (7) | |
| C13 | 0.8685 (3) | 0.4549 (3) | 1.05183 (18) | 0.0476 (9) | |
| C14 | 0.4213 (4) | 0.4848 (3) | 0.77071 (15) | 0.0384 (8) | |
| C15 | 0.3005 (3) | 0.2790 (3) | 1.11343 (15) | 0.0389 (8) | |
| H1 | 0.69630 | 0.51390 | 0.86680 | 0.0360* | |
| H2A | 0.88010 | 0.63170 | 0.94400 | 0.0450* | |
| H2B | 0.74270 | 0.72350 | 0.97810 | 0.0450* | |
| H3O | 0.755 (6) | 0.703 (4) | 0.812 (2) | 0.0650* | |
| H4 | 0.57660 | 0.66200 | 1.08300 | 0.0350* | |
| H4O | 0.480 (6) | 0.298 (5) | 0.754 (3) | 0.0880* | |
| H5 | 0.35370 | 0.53380 | 1.07230 | 0.0310* | |
| H5O | 0.200 (5) | 0.668 (4) | 0.794 (2) | 0.0580* | |
| H6 | 0.51910 | 0.39170 | 0.95210 | 0.0320* | |
| H7 | 0.44530 | 0.66550 | 0.94070 | 0.0310* | |
| H10 | 0.53330 | 0.29460 | 1.07310 | 0.0340* | |
| H12A | 0.73190 | 0.52400 | 1.18980 | 0.0420* | |
| H12B | 0.56050 | 0.58900 | 1.20720 | 0.0420* | |
| H13A | 0.85900 | 0.40230 | 1.09730 | 0.0570* | |
| H13B | 0.95820 | 0.44510 | 1.01840 | 0.0570* | |
| H14A | 0.33360 | 0.47210 | 0.73260 | 0.0460* | |
| H14B | 0.50810 | 0.53410 | 0.74470 | 0.0460* | |
| H15A | 0.25390 | 0.25940 | 1.06220 | 0.0580* | |
| H15B | 0.32090 | 0.19720 | 1.14150 | 0.0580* | |
| H15C | 0.22600 | 0.33280 | 1.14360 | 0.0580* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0354 (9) | 0.0441 (9) | 0.0295 (8) | −0.0134 (7) | −0.0076 (7) | 0.0066 (8) |
| O2 | 0.0504 (11) | 0.0463 (10) | 0.0285 (9) | −0.0056 (9) | −0.0076 (8) | 0.0089 (8) |
| O3 | 0.0399 (10) | 0.0489 (11) | 0.0403 (10) | −0.0025 (9) | 0.0115 (8) | 0.0163 (9) |
| O4 | 0.0839 (17) | 0.0463 (12) | 0.0448 (11) | 0.0247 (12) | −0.0133 (11) | −0.0176 (9) |
| O5 | 0.0447 (10) | 0.0302 (8) | 0.0407 (9) | 0.0053 (8) | −0.0094 (8) | 0.0039 (8) |
| O6 | 0.0391 (11) | 0.0711 (15) | 0.0477 (11) | −0.0126 (10) | −0.0136 (9) | 0.0099 (10) |
| C1 | 0.0314 (12) | 0.0314 (12) | 0.0266 (10) | −0.0001 (10) | 0.0055 (9) | 0.0032 (10) |
| C2 | 0.0306 (12) | 0.0426 (13) | 0.0380 (13) | −0.0097 (11) | 0.0022 (10) | 0.0041 (11) |
| C3 | 0.0280 (12) | 0.0377 (12) | 0.0316 (12) | −0.0081 (10) | −0.0029 (9) | 0.0002 (10) |
| C4 | 0.0336 (12) | 0.0265 (11) | 0.0280 (11) | −0.0041 (9) | −0.0003 (10) | −0.0019 (9) |
| C5 | 0.0263 (10) | 0.0268 (10) | 0.0245 (10) | −0.0014 (8) | 0.0010 (9) | −0.0005 (8) |
| C6 | 0.0271 (11) | 0.0273 (11) | 0.0254 (11) | −0.0027 (9) | −0.0011 (8) | 0.0001 (8) |
| C7 | 0.0294 (11) | 0.0239 (10) | 0.0232 (10) | 0.0018 (9) | 0.0020 (9) | −0.0017 (8) |
| C8 | 0.0341 (12) | 0.0255 (11) | 0.0256 (10) | 0.0043 (9) | −0.0024 (9) | −0.0004 (9) |
| C9 | 0.0339 (13) | 0.0363 (12) | 0.0290 (11) | −0.0009 (10) | −0.0050 (10) | −0.0016 (10) |
| C10 | 0.0322 (11) | 0.0280 (11) | 0.0239 (10) | −0.0019 (9) | 0.0002 (9) | −0.0003 (8) |
| C11 | 0.0285 (11) | 0.0360 (12) | 0.0257 (11) | 0.0012 (10) | −0.0001 (10) | −0.0007 (9) |
| C12 | 0.0390 (13) | 0.0385 (13) | 0.0266 (11) | −0.0052 (11) | −0.0022 (10) | −0.0040 (10) |
| C13 | 0.0364 (14) | 0.0650 (19) | 0.0413 (14) | 0.0038 (13) | −0.0002 (12) | 0.0033 (14) |
| C14 | 0.0478 (15) | 0.0404 (14) | 0.0269 (11) | 0.0048 (12) | −0.0004 (11) | −0.0054 (10) |
| C15 | 0.0414 (14) | 0.0425 (14) | 0.0328 (12) | −0.0135 (12) | −0.0028 (11) | 0.0052 (11) |
Geometric parameters (Å, º)
| O1—C6 | 1.469 (3) | C8—C9 | 1.523 (3) |
| O1—C9 | 1.342 (3) | C10—C11 | 1.517 (3) |
| O2—C11 | 1.216 (3) | C10—C15 | 1.515 (4) |
| O3—C1 | 1.432 (3) | C11—C12 | 1.502 (4) |
| O4—C14 | 1.400 (4) | C1—H1 | 0.9800 |
| O5—C8 | 1.415 (3) | C2—H2A | 0.9700 |
| O6—C9 | 1.197 (3) | C2—H2B | 0.9700 |
| O3—H3O | 0.78 (5) | C4—H4 | 0.9800 |
| O4—H4O | 0.95 (5) | C5—H5 | 0.9800 |
| O5—H5O | 0.90 (4) | C6—H6 | 0.9800 |
| C1—C2 | 1.535 (3) | C7—H7 | 0.9800 |
| C1—C7 | 1.526 (3) | C10—H10 | 0.9800 |
| C2—C3 | 1.517 (4) | C12—H12A | 0.9700 |
| C3—C4 | 1.513 (3) | C12—H12B | 0.9700 |
| C3—C13 | 1.327 (4) | C13—H13A | 0.9300 |
| C4—C5 | 1.564 (3) | C13—H13B | 0.9300 |
| C4—C12 | 1.540 (3) | C14—H14A | 0.9700 |
| C5—C6 | 1.517 (3) | C14—H14B | 0.9700 |
| C5—C10 | 1.537 (3) | C15—H15A | 0.9600 |
| C6—C7 | 1.537 (3) | C15—H15B | 0.9600 |
| C7—C8 | 1.536 (3) | C15—H15C | 0.9600 |
| C8—C14 | 1.530 (3) | ||
| C6—O1—C9 | 110.78 (17) | C2—C1—H1 | 109.00 |
| C1—O3—H3O | 112 (3) | C7—C1—H1 | 109.00 |
| C14—O4—H4O | 111 (3) | C1—C2—H2A | 108.00 |
| C8—O5—H5O | 105 (3) | C1—C2—H2B | 108.00 |
| O3—C1—C7 | 106.82 (19) | C3—C2—H2A | 108.00 |
| O3—C1—C2 | 108.59 (19) | C3—C2—H2B | 108.00 |
| C2—C1—C7 | 113.59 (19) | H2A—C2—H2B | 107.00 |
| C1—C2—C3 | 116.6 (2) | C3—C4—H4 | 108.00 |
| C2—C3—C4 | 114.90 (19) | C5—C4—H4 | 108.00 |
| C4—C3—C13 | 123.9 (2) | C12—C4—H4 | 108.00 |
| C2—C3—C13 | 121.2 (2) | C4—C5—H5 | 108.00 |
| C5—C4—C12 | 102.98 (18) | C6—C5—H5 | 108.00 |
| C3—C4—C5 | 112.96 (18) | C10—C5—H5 | 108.00 |
| C3—C4—C12 | 115.8 (2) | O1—C6—H6 | 109.00 |
| C4—C5—C6 | 114.63 (19) | C5—C6—H6 | 109.00 |
| C4—C5—C10 | 105.03 (18) | C7—C6—H6 | 109.00 |
| C6—C5—C10 | 112.24 (17) | C1—C7—H7 | 108.00 |
| O1—C6—C5 | 106.26 (18) | C6—C7—H7 | 108.00 |
| O1—C6—C7 | 105.37 (18) | C8—C7—H7 | 108.00 |
| C5—C6—C7 | 117.89 (17) | C5—C10—H10 | 107.00 |
| C1—C7—C8 | 116.72 (19) | C11—C10—H10 | 107.00 |
| C1—C7—C6 | 112.32 (18) | C15—C10—H10 | 107.00 |
| C6—C7—C8 | 103.10 (17) | C4—C12—H12A | 111.00 |
| O5—C8—C7 | 110.05 (17) | C4—C12—H12B | 110.00 |
| O5—C8—C9 | 110.22 (19) | C11—C12—H12A | 110.00 |
| C9—C8—C14 | 107.58 (19) | C11—C12—H12B | 111.00 |
| C7—C8—C14 | 117.2 (2) | H12A—C12—H12B | 109.00 |
| O5—C8—C14 | 109.00 (19) | C3—C13—H13A | 120.00 |
| C7—C8—C9 | 102.52 (18) | C3—C13—H13B | 120.00 |
| O1—C9—O6 | 122.5 (2) | H13A—C13—H13B | 120.00 |
| O1—C9—C8 | 110.8 (2) | O4—C14—H14A | 110.00 |
| O6—C9—C8 | 126.7 (2) | O4—C14—H14B | 110.00 |
| C5—C10—C11 | 104.24 (17) | C8—C14—H14A | 110.00 |
| C5—C10—C15 | 117.1 (2) | C8—C14—H14B | 110.00 |
| C11—C10—C15 | 113.83 (19) | H14A—C14—H14B | 108.00 |
| O2—C11—C12 | 125.7 (2) | C10—C15—H15A | 109.00 |
| O2—C11—C10 | 124.4 (2) | C10—C15—H15B | 109.00 |
| C10—C11—C12 | 109.92 (18) | C10—C15—H15C | 110.00 |
| C4—C12—C11 | 106.21 (19) | H15A—C15—H15B | 109.00 |
| O4—C14—C8 | 109.2 (2) | H15A—C15—H15C | 109.00 |
| O3—C1—H1 | 109.00 | H15B—C15—H15C | 109.00 |
| C6—O1—C9—O6 | −176.4 (2) | C6—C5—C10—C15 | −79.1 (3) |
| C6—O1—C9—C8 | 3.7 (2) | C4—C5—C6—O1 | −163.79 (17) |
| C9—O1—C6—C5 | 139.66 (18) | O1—C6—C7—C1 | −151.38 (17) |
| C9—O1—C6—C7 | 13.8 (2) | C5—C6—C7—C8 | −143.2 (2) |
| O3—C1—C2—C3 | 171.8 (2) | O1—C6—C7—C8 | −24.9 (2) |
| O3—C1—C7—C8 | 54.4 (2) | C5—C6—C7—C1 | 90.3 (2) |
| C7—C1—C2—C3 | 53.2 (3) | C1—C7—C8—C14 | 32.2 (3) |
| O3—C1—C7—C6 | 173.17 (17) | C6—C7—C8—O5 | 143.33 (18) |
| C2—C1—C7—C6 | −67.1 (2) | C6—C7—C8—C9 | 26.1 (2) |
| C2—C1—C7—C8 | 174.11 (19) | C6—C7—C8—C14 | −91.4 (2) |
| C1—C2—C3—C13 | 104.8 (3) | C1—C7—C8—C9 | 149.70 (18) |
| C1—C2—C3—C4 | −76.4 (3) | C1—C7—C8—O5 | −93.1 (2) |
| C2—C3—C4—C5 | 86.5 (2) | O5—C8—C9—O6 | 43.5 (3) |
| C2—C3—C4—C12 | −155.1 (2) | O5—C8—C9—O1 | −136.56 (19) |
| C13—C3—C4—C5 | −94.8 (3) | C14—C8—C9—O1 | 104.7 (2) |
| C13—C3—C4—C12 | 23.7 (3) | C14—C8—C9—O6 | −75.2 (3) |
| C12—C4—C5—C10 | −34.5 (2) | O5—C8—C14—O4 | −178.8 (2) |
| C12—C4—C5—C6 | −158.11 (19) | C7—C8—C14—O4 | 55.4 (3) |
| C5—C4—C12—C11 | 26.5 (2) | C9—C8—C14—O4 | −59.3 (3) |
| C3—C4—C5—C10 | 91.2 (2) | C7—C8—C9—O1 | −19.4 (2) |
| C3—C4—C5—C6 | −32.5 (2) | C7—C8—C9—O6 | 160.6 (2) |
| C3—C4—C12—C11 | −97.3 (2) | C5—C10—C11—O2 | 165.6 (2) |
| C10—C5—C6—C7 | −165.7 (2) | C5—C10—C11—C12 | −12.6 (3) |
| C4—C5—C10—C15 | 155.79 (19) | C15—C10—C11—O2 | 36.8 (3) |
| C6—C5—C10—C11 | 154.2 (2) | C15—C10—C11—C12 | −141.4 (2) |
| C4—C5—C10—C11 | 29.1 (2) | O2—C11—C12—C4 | 172.8 (2) |
| C4—C5—C6—C7 | −46.0 (3) | C10—C11—C12—C4 | −9.1 (3) |
| C10—C5—C6—O1 | 76.5 (2) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3O···O2i | 0.78 (5) | 2.06 (4) | 2.818 (3) | 168 (4) |
| O4—H4O···O3ii | 0.95 (5) | 2.14 (5) | 2.956 (3) | 144 (4) |
| O4—H4O···O5ii | 0.95 (5) | 2.45 (5) | 3.156 (3) | 132 (4) |
| O5—H5O···O6 | 0.90 (4) | 2.45 (4) | 2.877 (3) | 109 (3) |
| O5—H5O···O2iii | 0.90 (4) | 2.22 (4) | 3.096 (2) | 164 (4) |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1/2, −y+1, z−1/2.
References
- Agilent (2013). CrysAlis PRO. Agilent Technologies, Yarnton, England.
- Bensouici, C., Kabouche, A., Kabouche, Z., Touzani, R. & Bruneau, C. (2012). Chem. Nat. Compd, 48, 510–511.
- Bruno, M., Paternostro, M. P., Gedris, T. E. & Herz, W. (1996). Phytochemistry, 41, 335–336.
- Chicca, A., Tebano, M., Adinolfi, B., Ertugrul, K., Flamini, G. & Nieri, P. (2011). Eur. J. Med. Chem. 46, 3066–3070. [DOI] [PubMed]
- Christensen, L. P. & Lam, J. (1990). Phytochemistry, 29, 2753–2785.
- Csapi, B., Hajdú, Z., Zupkó, I., Berényi, A., Ágnes, , Forgo, P., Szabó, P. & Hohmann, J. (2010). Phytother. Res. 24, 1664–1669. [DOI] [PubMed]
- Davis, P. H., Mill, R. R. & Tan, K. (1988). In Flora of Turkey and the East Aegean Islands. Edinburgh: University Press.
- Djeddi, S., Sokovic, M. & Skaltsa, H. (2011). J Essential Oil Bearing Plants, 14, 658–666.
- Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
- Flack, H. D. (1983). Acta Cryst. A39, 876–881.
- Forgo, P., Zupkó, I., Molnár, J., Vasas, A., Dombi, G. & Hohmann, J. (2012). Fitoterapia, 83, 921–925. [DOI] [PubMed]
- Gülcemal, D., Alankuş-Çalışkan, Ö., Karaalp, C., Örs, A. U., Ballar, P. & Bedir, E. (2010). Carbohydr. Res. 345, 2529–2533. [DOI] [PubMed]
- Janaćković, P., Tešević, V., Milosavljević, S., Vajs, V. & Marin, P. D. (2004). Biochem. Syst. Ecol. 32, 355–357.
- Kamanzi, K., Raynaud, J. & Voirin, B. (1983). Plant. Med. Phytother. 17, 57–60.
- Khalfallah, A., Berrehal, D., Kabouche, A., Touzani, R. & Kabouche, Z. (2012). Chem. Nat. Compd, 48, 482–483.
- Koukoulitsa, E., Skaltsa, H., Karioti, A., Demetzos, C. & Dimas, K. (2002). Planta Med. 68, 649–652. [DOI] [PubMed]
- Kubacey, T. M., Haggag, E. G., El-Toumy, S. A., Ahmed, A. A., El-Ashmawy, I. M. & Youns, M. M. (2012). J. Pharm. Res. 5, 3352–3361.
- Politeo, O., Skocibusic, M., Carev, I., Burcul, F., Jerkovic, I., Sarolic, M. & Milos, M. (2012). Nat. Prod. Commun. 7, 1087–1090. [PubMed]
- Pople, J. A. & Beveridge, D. L. (1970). In Approximate Molecular Orbital Theory. New York: McGraw–Hill.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Spek, A. L. (2009). Acta Cryst. D65, 148–155. [DOI] [PMC free article] [PubMed]
- Stewart, J. J. P. (1985). MOPAC. QCPE Program 445. Quantum Chemistry Program Exchange, Indiana University, Bloomington, IN 47405, USA.
- Swamy, G. Y. S. K., Ravikumar, K., Das, B. & Mahender, G. (2005). Acta Cryst. E61, o121–o123.
- Uysal, I., Celik, S., Saglam, H. & Guven, K. (2013). Asian J. Chem. 25, 666–670.
- Yeşilada, E., Honda, G., Sezik, E., Tabata, M., Fujita, T., Tanaka, T., Takeda, Y. & Takaishi, Y. (1995). J. Ethnopharmacol. 46, 133–152. [DOI] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019623/rz5172sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019623/rz5172Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015019623/rz5172Isup3.cml
CCDC reference: 1048445
Additional supporting information: crystallographic information; 3D view; checkCIF report