Crystal structure and computational study of 3,4-dihy-droxy-3-hy-droxy-methyl-9-methyl-6-methyl-idene-3a,4,5,6,6a,9,9a,9b-octa-hydro-azuleno[4,5-b]furan-2,8(3H,7H)-dione.

In the mol-ecule of title compound, C15H20O6, also known as cynarinin A, the cyclo-pentane ring having twist conformation and a γ-lactone ring assuming an envelope conformation are trans- and cis-fused, respectively, to a cyclo-heptane ring adopting a twist-chair conformation. In the crystal, O-H⋯O hydrogen bonds link neighbouring mol-ecules, forming a three-dimensional network. Theoretical calculations of the mol-ecular 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)

Computer programs: CrysAlis PRO (Agilent, 2013 ▸), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

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

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015019623/rz5172Isup3.cml

CCDC reference: 1048445

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

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 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

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.

	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*

	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)

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)

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)