5,8-Dihy­droxy-2,2-dimethyl-12-(3-methyl­but-2-en­yl)pyrano[3,2-b]xanthen-6-one (brasixanthone B)

The title compound (trivial name brasixanthone B), C₂₃H₂₂O₅, isolated from Calophyllum gracilentum, is characterized by a xanthone skeleton of three fused six-membered rings plus an additional fused pyrano ring and one 3-methyl­but-2-enyl side chain. The core xanthone moiety is almost planar, with a maximum deviation 0.057 (4) Å from the mean plane. In the mol­ecule, an intra­molecular O—H...O hydrogen bond forms an S(6) ring motif. The crystal structure features inter­molecular O—H...O and C—H...O inter­actions.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.063
• wR factor = 0.198
• Data-to-parameter ratio = 9.3

checkCIF/PLATON results

No syntax errors found



Alert level A
THETM01_ALERT_3_A  The value of sine(theta_max)/wavelength is less than 0.550
            Calculated sin(theta_max)/wavelength =    0.5384

Author Response: The dataset at higher diffraction angles (> 45\%) is weak and we are unable to recollect the data since the compound was isolated in a small amount (15 mg) and have been used up for the spectroscopic and crystallography analysis. We are convinced the structure is correct.

PLAT023_ALERT_3_A Resolution (too) Low [sin(theta)/Lambda < 0.6]..       0.54 Ang-1

Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given (or Incomplete) ........     Please Check
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.26 Note
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of        C21 Check
PLAT334_ALERT_2_C Small <C-C> Benzene Dist.   C4       -C16      .       1.37 Ang.
PLAT334_ALERT_2_C Small <C-C> Benzene Dist.   C8       -C13      .       1.35 Ang.
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00625 Ang.
PLAT411_ALERT_2_C Short Inter H...H Contact  H9A      ..H9A      .       2.03 Ang.
                                                 1-x,-y,2-z  =      3_657 Check
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........       H1O3 Check
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........       H1O5 Check
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -2.597 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          2 Check
PLAT965_ALERT_2_G The SHELXL WEIGHT Optimisation has not Converged     Please Check
PLAT967_ALERT_5_G Note: Two-Theta Cutoff Value in Embedded .res ..       45.0 Degree
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          0 Info

   2 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  10 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

# start Validation Reply Form
_vrf_PLAT023_I
;
PROBLEM: Resolution (too) Low [sin(theta)/Lambda < 0.6]..       0.54 Ang-1
RESPONSE: ...
;
# end Validation Reply Form 

---

Reference check results

The following references were not checked in detail as they were not recognized as references to journal articles

Bruker (2012). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. [software reference?]

Corner, E. J. H. (1952). Wayside Trees of Malaya: Volume 1 (Vol. 1). The Government Printing Office, Singapore.

The following references may be incorrectly formatted

Lim, C. K., Ham, Y. P., Lim, L. Q. & Jong, V. Y. M. (2019). Phytochemistry Letters, 30, 99--102.
[Unrecognized journal title.]

Wang, Z., Sun, F., Wang, J., Dong, J., Xie, S., Sun, M. & Sun, B. (2019). Historical Biology, 31(10), 1379--1393.
[Unrecognized journal title.]

Zamakshshari, N. H., Ee, G. C. L., Ismail, I. S., Ibrahim, Z. & Mah, S. H. (2019). Food and Chemical Toxicology, 133, 110800.
[Missing final page numbers?]

The following references do not appear to be cited in the IUCrData preprint (though cited elsewhere in the CIF)

Aminudin, N. I., Ahmad, F., Taher, M. & Zulkifli, R. M. (2015). Natural Product Communications, 10(9), 167--178.

Corner, E. J. H. (1952). Wayside Trees of Malaya: Volume 1 (Vol. 1). The Government Printing Office, Singapore.

Crane, S., Aurore, G., Joseph, H., Mouloungui, Z. & Bourgeois, P. (2005). Phytochemistry, 66(15), 1825--1831.

Cremer, D. & Pople, J. A. (1975). Journal of American Chemical Society , 97, 1354--1358.

Dweck, A. & Meadows, T. (2002). International Journal of Cosmetic Science, 24(6), 341-348.

Ee, G. C. L., Mah, S. H., Teh, S. S., Rahmani, M., Go, R. & Taufiq-Yap, Y. H. (2011). Molecules, 16(11), 9721--9727.

Ee, G. C. L., Sim, W. C., Kwong, H. C., Mohamed Tahir, M. I. & Silong, S. (2010). Acta Cryst. E66, 3362--3363.

Filho, V. C., Meyre-Silva, C. & Niero, R. (2009). Chemistry & Biodiversity, 6, 313--327.

Guilet, D., H\'elesbeux, J.-J., S\'eraphin, D., S\'evenet, T., Richomme, P. & Bruneton, J. (2001). Journal of Natural Products, 64(5), 563--568.

Gupta, S. & Gupta, P. (2020). Bioactive Natural products in Drug Discovery, 8, 215--242.

Ito, C., Itoigawa, M., Mishina, Y., Filho, V. C., Mukainaka, T., Tokuda, H., Nishino, H. & Furukawa, H. (2002). Journal of Natural Products, 65(3), 267--272.

Karunakaran, T., Firouz, N. S., Santham, R. & Jong, V. Y. M. (2022). Natural Product Research, 36(2), 654--659.

Li, W., Guo, Y., Zhang, C., Wu, R., Yang, A. Y., Gaspar, J. & Kong, A. N. T. (2016). Chemical Research in Toxicology, 29(12), 2071--2095.

Lim, C. K., Ham, Y. P., Lim, L. Q. & Jong, V. Y. M. (2019). Phytochemistry Letters, 30, 99--102.

Lim, C.-K., Hemaroopini, S., Say, Y.-H. & Jong, V. Y.-M. (2017). Natural Product Communications, 12(9), 1469--1471.

Mah, S. H., Ee, G. C. L., Teh, S. S., Rahmani, M., Lim, Y. M. & Go, R. (2012). Molecules, 17(7), 8303-8311.

Reyes-Chilpa, R., Estrada-Mu\~niz, E., Ram\'irez Apan, T., Amekraz, B., Aumelas, A., Jankowski, C. K. & V\'azquez-Torres, M. (2004). Life Sciences, 75(13), 1635--1647.

Thiagarajan, S., Yong, F.-L., Subramaniam, H., Jong, V. Y.-M., Lim, C.-K. & Say, Y.-H. (2017). Tropical Journal of Pharmaceutical Research, 163, 563--572.

Wang, Z., Sun, F., Wang, J., Dong, J., Xie, S., Sun, M. & Sun, B. (2019). Historical Biology, 31(10), 1379--1393.

Zamakshshari, N. H., Ee, G. C. L., Ismail, I. S., Ibrahim, Z. & Mah, S. H. (2019). Food and Chemical Toxicology, 133, 110800.

---

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2020).

5,8-Dihydroxy-2,2-dimethyl-12-(3-methylbut-2-enyl)pyrano[3,2-b]xanthen-6-one

Crystal data

C23H22O5	F(000) = 800
Mr = 378.40	Dx = 1.377 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.071 (3) Å	Cell parameters from 2238 reflections
b = 10.458 (3) Å	θ = 2.2–26.0°
c = 13.358 (3) Å	µ = 0.10 mm^−1
β = 90.576 (19)°	T = 296 K
V = 1825.9 (8) Å^3	Block, orange
Z = 4	0.31 × 0.31 × 0.31 mm

Data collection

Bruker APEX Duo CCD area detector diffractometer	1409 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.117
φ and ω scans	θmax = 22.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −14→14
Tmin = 0.773, Tmax = 0.944	k = −11→11
39924 measured reflections	l = −14→14
2381 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.063	H-atom parameters constrained
wR(F^2) = 0.198	w = 1/[σ^2(Fo^2) + (0.1114P)^2 + 0.0299P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2381 reflections	Δρmax = 0.27 e Å^−3
257 parameters	Δρmin = −0.24 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The O-bound H atoms were located in a difference map, but fixed during refinement, with distance set to 0.82 Å and U_iso(H) = 1.5U_eq(O). The remaining H atoms were place in calculated positions with d(C-H) = 0.93 Å for aromatic, 0.97 Å for CH₂ and 0.96 Å for CH₃ atoms. The U_iso(H) values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.6393 (2)	0.7811 (2)	0.86169 (18)	0.0705 (8)
O2	0.44525 (18)	0.4259 (2)	0.80181 (17)	0.0591 (7)
O3	0.70808 (19)	0.4135 (2)	1.04401 (18)	0.0706 (8)
H1O3	0.6883	0.3391	1.0424	0.106*
O4	0.60038 (19)	0.2194 (2)	1.00573 (19)	0.0700 (8)
O5	0.3386 (2)	−0.0672 (2)	0.8438 (2)	0.0850 (9)
H1O5	0.3681	−0.1001	0.8918	0.127*
C1	0.7421 (3)	0.8284 (4)	0.8784 (3)	0.0756 (12)
C2	0.7815 (3)	0.7784 (4)	0.9731 (3)	0.0755 (12)
H2A	0.8273	0.8272	1.0107	0.091*
C3	0.7539 (3)	0.6671 (4)	1.0056 (3)	0.0694 (11)
H3A	0.7841	0.6333	1.0632	0.083*
C4	0.6778 (3)	0.5970 (4)	0.9535 (3)	0.0554 (10)
C5	0.6545 (3)	0.4736 (4)	0.9740 (3)	0.0560 (10)
C6	0.5765 (3)	0.4110 (3)	0.9236 (3)	0.0496 (9)
C7	0.5540 (3)	0.2827 (4)	0.9415 (3)	0.0536 (10)
C8	0.4738 (3)	0.2279 (4)	0.8831 (3)	0.0515 (9)
C9	0.4461 (3)	0.1026 (4)	0.8922 (3)	0.0629 (11)
H9A	0.4805	0.0505	0.9378	0.076*
C10	0.3699 (3)	0.0538 (4)	0.8363 (3)	0.0624 (10)
C11	0.3208 (3)	0.1285 (4)	0.7681 (3)	0.0634 (11)
H11A	0.2690	0.0940	0.7282	0.076*
C12	0.3464 (3)	0.2513 (4)	0.7580 (3)	0.0604 (10)
H12A	0.3119	0.3026	0.7119	0.072*
C13	0.4232 (3)	0.3012 (4)	0.8152 (3)	0.0517 (9)
C14	0.5218 (3)	0.4796 (4)	0.8538 (3)	0.0515 (9)
C15	0.5407 (3)	0.6040 (4)	0.8320 (3)	0.0533 (10)
C16	0.6206 (3)	0.6586 (4)	0.8813 (3)	0.0573 (10)
C17	0.7282 (4)	0.9696 (4)	0.8798 (4)	0.0996 (15)
H17A	0.7940	1.0104	0.8830	0.149*
H17B	0.6891	0.9933	0.9373	0.149*
H17C	0.6928	0.9960	0.8200	0.149*
C18	0.8048 (4)	0.7856 (5)	0.7928 (4)	0.1052 (16)
H18A	0.8721	0.8217	0.7985	0.158*
H18B	0.7734	0.8133	0.7313	0.158*
H18C	0.8096	0.6940	0.7932	0.158*
C19	0.4787 (3)	0.6755 (4)	0.7582 (3)	0.0663 (11)
H19A	0.4081	0.6478	0.7629	0.080*
H19B	0.4811	0.7657	0.7751	0.080*
C20	0.5124 (3)	0.6594 (4)	0.6548 (3)	0.0754 (12)
H20A	0.5130	0.5761	0.6304	0.091*
C21	0.5412 (4)	0.7472 (6)	0.5937 (4)	0.0971 (16)
C22	0.5441 (5)	0.8841 (6)	0.6180 (5)	0.150 (3)
H22A	0.6108	0.9175	0.6039	0.225*
H22B	0.5297	0.8957	0.6878	0.225*
H22C	0.4938	0.9285	0.5784	0.225*
C23	0.5722 (4)	0.7131 (7)	0.4911 (4)	0.150 (3)
H23A	0.5340	0.7634	0.4437	0.225*
H23B	0.5589	0.6240	0.4796	0.225*
H23C	0.6439	0.7296	0.4834	0.225*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.074 (2)	0.0613 (19)	0.0765 (19)	−0.0085 (14)	0.0017 (15)	0.0073 (14)
O2	0.0612 (16)	0.0555 (17)	0.0604 (16)	−0.0020 (13)	−0.0084 (13)	0.0054 (13)
O3	0.0690 (19)	0.0756 (19)	0.0669 (18)	−0.0041 (14)	−0.0158 (15)	0.0045 (14)
O4	0.0730 (19)	0.0682 (18)	0.0683 (18)	0.0026 (14)	−0.0207 (15)	0.0108 (14)
O5	0.099 (2)	0.0598 (19)	0.095 (2)	−0.0146 (15)	−0.0337 (17)	0.0113 (15)
C1	0.070 (3)	0.074 (3)	0.083 (3)	−0.017 (2)	0.005 (3)	0.006 (3)
C2	0.067 (3)	0.079 (3)	0.081 (3)	−0.011 (2)	0.000 (2)	−0.008 (3)
C3	0.068 (3)	0.075 (3)	0.065 (3)	−0.004 (2)	−0.004 (2)	−0.002 (2)
C4	0.049 (2)	0.062 (3)	0.055 (2)	−0.005 (2)	0.0009 (19)	−0.001 (2)
C5	0.050 (2)	0.067 (3)	0.052 (2)	0.009 (2)	−0.002 (2)	0.004 (2)
C6	0.046 (2)	0.054 (2)	0.049 (2)	0.0064 (18)	0.0004 (18)	0.0034 (19)
C7	0.051 (2)	0.059 (3)	0.051 (2)	0.0056 (19)	−0.001 (2)	0.006 (2)
C8	0.053 (2)	0.053 (2)	0.048 (2)	0.0031 (19)	−0.0023 (19)	0.0026 (19)
C9	0.067 (3)	0.059 (3)	0.063 (3)	0.007 (2)	−0.013 (2)	0.002 (2)
C10	0.068 (3)	0.051 (3)	0.067 (3)	0.001 (2)	−0.011 (2)	0.003 (2)
C11	0.066 (3)	0.062 (3)	0.062 (3)	−0.001 (2)	−0.013 (2)	0.001 (2)
C12	0.061 (3)	0.064 (3)	0.055 (2)	0.006 (2)	−0.011 (2)	0.004 (2)
C13	0.055 (2)	0.052 (3)	0.048 (2)	−0.0012 (19)	0.0014 (19)	0.0014 (19)
C14	0.047 (2)	0.055 (3)	0.053 (2)	−0.0028 (18)	−0.0011 (19)	−0.0026 (19)
C15	0.054 (2)	0.053 (2)	0.052 (2)	0.0002 (19)	0.0054 (19)	0.0014 (19)
C16	0.061 (3)	0.056 (3)	0.055 (2)	−0.003 (2)	0.006 (2)	0.003 (2)
C17	0.105 (4)	0.076 (3)	0.118 (4)	−0.027 (3)	−0.002 (3)	0.008 (3)
C18	0.104 (4)	0.123 (4)	0.089 (3)	−0.019 (3)	0.030 (3)	−0.004 (3)
C19	0.070 (3)	0.059 (3)	0.070 (3)	−0.002 (2)	−0.004 (2)	0.015 (2)
C20	0.075 (3)	0.085 (3)	0.066 (3)	0.002 (2)	−0.008 (2)	0.008 (3)
C21	0.086 (3)	0.128 (5)	0.078 (4)	−0.023 (3)	−0.012 (3)	0.034 (3)
C22	0.181 (6)	0.117 (5)	0.151 (6)	−0.050 (4)	−0.026 (5)	0.068 (4)
C23	0.122 (5)	0.263 (8)	0.065 (4)	−0.019 (5)	0.005 (3)	0.032 (4)

Geometric parameters (Å, º)

O1—C16	1.330 (4)	C11—C12	1.335 (5)
O1—C1	1.446 (4)	C11—H11A	0.9300
O2—C14	1.336 (4)	C12—C13	1.360 (5)
O2—C13	1.348 (4)	C12—H12A	0.9300
O3—C5	1.321 (4)	C14—C15	1.357 (5)
O3—H1O3	0.8200	C15—C16	1.356 (5)
O4—C7	1.238 (4)	C15—C19	1.474 (5)
O5—C10	1.334 (4)	C17—H17A	0.9600
O5—H1O5	0.8199	C17—H17B	0.9600
C1—C2	1.458 (6)	C17—H17C	0.9600
C1—C18	1.483 (6)	C18—H18A	0.9600
C1—C17	1.488 (6)	C18—H18B	0.9600
C2—C3	1.295 (5)	C18—H18C	0.9600
C2—H2A	0.9300	C19—C20	1.464 (5)
C3—C4	1.414 (5)	C19—H19A	0.9700
C3—H3A	0.9300	C19—H19B	0.9700
C4—C5	1.354 (5)	C20—C21	1.287 (6)
C4—C16	1.374 (5)	C20—H20A	0.9300
C5—C6	1.382 (5)	C21—C22	1.468 (8)
C6—C14	1.371 (5)	C21—C23	1.477 (7)
C6—C7	1.395 (5)	C22—H22A	0.9600
C7—C8	1.421 (5)	C22—H22B	0.9600
C8—C13	1.355 (5)	C22—H22C	0.9600
C8—C9	1.365 (5)	C23—H23A	0.9600
C9—C10	1.340 (5)	C23—H23B	0.9600
C9—H9A	0.9300	C23—H23C	0.9600
C10—C11	1.357 (5)
C16—O1—C1	118.1 (3)	O2—C14—C15	115.4 (3)
C14—O2—C13	119.8 (3)	O2—C14—C6	121.1 (3)
C5—O3—H1O3	105.6	C15—C14—C6	123.5 (4)
C10—O5—H1O5	108.3	C16—C15—C14	116.2 (3)
O1—C1—C2	109.3 (3)	C16—C15—C19	121.8 (4)
O1—C1—C18	107.3 (4)	C14—C15—C19	122.0 (4)
C2—C1—C18	111.5 (4)	O1—C16—C15	116.9 (3)
O1—C1—C17	103.2 (4)	O1—C16—C4	119.4 (4)
C2—C1—C17	112.7 (4)	C15—C16—C4	123.6 (4)
C18—C1—C17	112.2 (4)	C1—C17—H17A	109.5
C3—C2—C1	121.1 (4)	C1—C17—H17B	109.5
C3—C2—H2A	119.5	H17A—C17—H17B	109.5
C1—C2—H2A	119.5	C1—C17—H17C	109.5
C2—C3—C4	119.9 (4)	H17A—C17—H17C	109.5
C2—C3—H3A	120.1	H17B—C17—H17C	109.5
C4—C3—H3A	120.1	C1—C18—H18A	109.5
C5—C4—C16	117.9 (4)	C1—C18—H18B	109.5
C5—C4—C3	123.6 (4)	H18A—C18—H18B	109.5
C16—C4—C3	118.5 (4)	C1—C18—H18C	109.5
O3—C5—C4	118.6 (4)	H18A—C18—H18C	109.5
O3—C5—C6	120.2 (4)	H18B—C18—H18C	109.5
C4—C5—C6	121.3 (3)	C20—C19—C15	113.8 (3)
C14—C6—C5	117.4 (4)	C20—C19—H19A	108.8
C14—C6—C7	120.7 (4)	C15—C19—H19A	108.8
C5—C6—C7	121.9 (3)	C20—C19—H19B	108.8
O4—C7—C6	122.0 (4)	C15—C19—H19B	108.8
O4—C7—C8	121.2 (3)	H19A—C19—H19B	107.7
C6—C7—C8	116.7 (3)	C21—C20—C19	127.5 (5)
C13—C8—C9	118.3 (3)	C21—C20—H20A	116.3
C13—C8—C7	119.4 (4)	C19—C20—H20A	116.3
C9—C8—C7	122.2 (3)	C20—C21—C22	124.2 (5)
C10—C9—C8	120.8 (4)	C20—C21—C23	120.0 (6)
C10—C9—H9A	119.6	C22—C21—C23	115.7 (5)
C8—C9—H9A	119.6	C21—C22—H22A	109.5
O5—C10—C9	123.1 (4)	C21—C22—H22B	109.5
O5—C10—C11	117.0 (4)	H22A—C22—H22B	109.5
C9—C10—C11	119.9 (4)	C21—C22—H22C	109.5
C12—C11—C10	120.3 (4)	H22A—C22—H22C	109.5
C12—C11—H11A	119.8	H22B—C22—H22C	109.5
C10—C11—H11A	119.8	C21—C23—H23A	109.5
C11—C12—C13	119.8 (4)	C21—C23—H23B	109.5
C11—C12—H12A	120.1	H23A—C23—H23B	109.5
C13—C12—H12A	120.1	C21—C23—H23C	109.5
O2—C13—C8	122.2 (3)	H23A—C23—H23C	109.5
O2—C13—C12	117.0 (3)	H23B—C23—H23C	109.5
C8—C13—C12	120.8 (4)
C16—O1—C1—C2	−43.1 (5)	C14—O2—C13—C12	−178.1 (3)
C16—O1—C1—C18	78.0 (4)	C9—C8—C13—O2	179.6 (3)
C16—O1—C1—C17	−163.3 (3)	C7—C8—C13—O2	−1.0 (5)
O1—C1—C2—C3	31.7 (6)	C9—C8—C13—C12	0.3 (5)
C18—C1—C2—C3	−86.9 (5)	C7—C8—C13—C12	179.7 (3)
C17—C1—C2—C3	145.9 (4)	C11—C12—C13—O2	−179.8 (3)
C1—C2—C3—C4	−5.5 (6)	C11—C12—C13—C8	−0.4 (5)
C2—C3—C4—C5	170.6 (4)	C13—O2—C14—C15	177.4 (3)
C2—C3—C4—C16	−12.8 (6)	C13—O2—C14—C6	−2.3 (5)
C16—C4—C5—O3	−179.3 (3)	C5—C6—C14—O2	180.0 (3)
C3—C4—C5—O3	−2.6 (5)	C7—C6—C14—O2	0.5 (5)
C16—C4—C5—C6	0.7 (5)	C5—C6—C14—C15	0.3 (5)
C3—C4—C5—C6	177.3 (3)	C7—C6—C14—C15	−179.1 (3)
O3—C5—C6—C14	178.2 (3)	O2—C14—C15—C16	−177.6 (3)
C4—C5—C6—C14	−1.7 (5)	C6—C14—C15—C16	2.1 (5)
O3—C5—C6—C7	−2.4 (5)	O2—C14—C15—C19	1.8 (5)
C4—C5—C6—C7	177.7 (3)	C6—C14—C15—C19	−178.5 (3)
C14—C6—C7—O4	−178.1 (3)	C1—O1—C16—C15	−155.5 (3)
C5—C6—C7—O4	2.4 (5)	C1—O1—C16—C4	28.4 (5)
C14—C6—C7—C8	1.0 (5)	C14—C15—C16—O1	−179.2 (3)
C5—C6—C7—C8	−178.4 (3)	C19—C15—C16—O1	1.4 (5)
O4—C7—C8—C13	178.4 (3)	C14—C15—C16—C4	−3.3 (5)
C6—C7—C8—C13	−0.8 (5)	C19—C15—C16—C4	177.3 (3)
O4—C7—C8—C9	−2.2 (5)	C5—C4—C16—O1	177.8 (3)
C6—C7—C8—C9	178.6 (3)	C3—C4—C16—O1	1.0 (5)
C13—C8—C9—C10	−0.8 (5)	C5—C4—C16—C15	2.0 (6)
C7—C8—C9—C10	179.8 (3)	C3—C4—C16—C15	−174.8 (3)
C8—C9—C10—O5	−178.6 (3)	C16—C15—C19—C20	94.2 (4)
C8—C9—C10—C11	1.4 (6)	C14—C15—C19—C20	−85.2 (5)
O5—C10—C11—C12	178.5 (4)	C15—C19—C20—C21	−121.4 (5)
C9—C10—C11—C12	−1.5 (6)	C19—C20—C21—C22	−0.8 (8)
C10—C11—C12—C13	1.0 (6)	C19—C20—C21—C23	−179.6 (4)
C14—O2—C13—C8	2.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O4	0.82	1.77	2.520 (3)	152
O5—H1O5···O4^i	0.82	1.89	2.679 (4)	160
C11—H11A···O3^ii	0.93	2.58	3.352 (5)	141
C12—H12A···O5^iii	0.93	2.50	3.352 (5)	152

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x−3/2, −y−1/2, z−3/2; (iii) −x+1/2, y+1/2, −z+3/2.