Crystal structure of (3S*,4S*,4aS*,5R*,6R*,6aS*,7R*,11aS*,11bR*)-5,6-bis(benzo-yloxy)-3,4a-dihy-droxy-4,7,11b-trimethyl-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodeca-hydro-phenanthro[3,2-b]furan-4-carb-oxy-lic acid methanol monosolvate.

The title compound, C34H36O9·CH3OH, is a diterpenoid isolated from the roots of Caesalpinia pulcherrima (L.) Swartz. The three trans-fused six-membered rings are in chair, chair and half-chair conformations. The mean plane of this fused-ring system makes dihedral angles of 67.95 (15) and 83.72 (14)° with the two phenyl rings of the benzo-yloxy groups. An intra-molecular C-H⋯O hydrogen bond is observed. In the crystal, mol-ecules are linked via O-H⋯O hydrogen bonds, forming an infinite chain along the b-axis direction.

Related literature

For background to Caesalpinia pulcherrima (L.) Swartz and its biological activities, see: Pawar et al. (2009 ▸); Udenigwe et al. (2007 ▸); Sudhakar et al. (2006 ▸); Gupta et al. (2000 ▸); Patil et al. (1997 ▸). For the biological applications of Pulcherrimin A, see: Yodsaoue et al. (2011 ▸); Patil et al. (1997 ▸). For the crystal structure of a related compound, see: Fun et al. (2010 ▸).

Experimental

Crystal data

C34H36O9·CH4O

M = 620.67

Orthorhombic,

a = 11.7943 (6) Å

b = 13.5934 (7) Å

c = 19.2988 (11) Å

V = 3094.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.45 × 0.30 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

18238 measured reflections

3916 independent reflections

2882 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.139

S = 1.03

3916 reflections

411 parameters

13 restraints

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2000 ▸); cell refinement: SAINT (Bruker, 2000 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016461/is5414sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016461/is5414Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016461/is5414Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015016461/is5414fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Only H atoms related to stereochemistry, of OH groups and involved in the hydrogen bonds are shown.

Click here for additional data file.

ab . DOI: 10.1107/S2056989015016461/is5414fig2.tif

A packing diagram of the title compound viewed perpendicular to the ab plane. Only H atoms involved in the O—H⋯O hydrogen bonds are shown.

CCDC reference: 1422031

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

C34H36O9·CH4O	F(000) = 1320
Mr = 620.67	Dx = 1.332 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2827 reflections
a = 11.7943 (6) Å	θ = 2.3–24.7°
b = 13.5934 (7) Å	µ = 0.10 mm−1
c = 19.2988 (11) Å	T = 293 K
V = 3094.1 (3) Å3	Prism, colorless
Z = 4	0.45 × 0.30 × 0.10 mm

Bruker SMART APEX CCD area-detector diffractometer	2882 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 27.5°, θmin = 1.8°
ω scan	h = −14→14
18238 measured reflections	k = −7→17
3916 independent reflections	l = −25→25

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0769P)2 + 0.1739P] where P = (Fo2 + 2Fc2)/3
3916 reflections	(Δ/σ)max = 0.001
411 parameters	Δρmax = 0.30 e Å−3
13 restraints	Δρmin = −0.18 e Å−3

	x	y	z	Uiso*/Ueq
O1	0.4694 (2)	1.25976 (18)	0.17389 (15)	0.0559 (7)
O2	0.0387 (3)	0.72827 (18)	0.27984 (16)	0.0644 (8)
O3	0.1186 (3)	0.7991 (2)	0.36988 (16)	0.0703 (9)
H3	0.1319	0.7403	0.3803	0.084*
O4	0.0845 (2)	0.72060 (18)	0.11387 (14)	0.0523 (7)
O5	0.18140 (19)	0.82310 (14)	0.18442 (11)	0.0379 (5)
O6	−0.0009 (2)	0.9189 (2)	0.01641 (15)	0.0697 (9)
O7	0.1773 (2)	0.90679 (17)	0.05536 (11)	0.0417 (5)
O8	−0.0053 (2)	1.03030 (16)	0.20910 (12)	0.0425 (6)
H8	0.0011	1.0840	0.2303	0.064*
O9	−0.0646 (3)	0.9195 (2)	0.41210 (14)	0.0669 (8)
H9	−0.0195	0.9114	0.4453	0.100*
O10	0.1596 (4)	0.6133 (3)	0.3973 (2)	0.1137 (15)
H10	0.1259	0.5658	0.3785	0.171*
C1	0.5090 (4)	1.2791 (3)	0.1087 (2)	0.0647 (12)
H1	0.5657	1.3245	0.0988	0.078*
C2	0.4571 (4)	1.2255 (3)	0.0619 (2)	0.0627 (11)
H2	0.4702	1.2262	0.0144	0.075*
C3	0.3767 (3)	1.1659 (3)	0.09769 (19)	0.0484 (9)
C4	0.3866 (3)	1.1895 (3)	0.1646 (2)	0.0462 (8)
C5	0.3261 (3)	1.1496 (3)	0.22463 (19)	0.0472 (9)
H5A	0.2985	1.2033	0.2531	0.057*
H5B	0.3778	1.1105	0.2524	0.057*
C6	0.2257 (3)	1.0853 (2)	0.20139 (16)	0.0365 (7)
H6	0.1631	1.1302	0.1904	0.044*
C7	0.2520 (3)	1.0271 (2)	0.13434 (16)	0.0388 (7)
H7	0.3137	0.9810	0.1443	0.047*
C8	0.2893 (3)	1.0936 (3)	0.07297 (18)	0.0500 (9)
H8A	0.3258	1.0512	0.0385	0.060*
C9	0.1936 (4)	1.1480 (3)	0.0365 (2)	0.0759 (14)
H9A	0.2241	1.1860	−0.0010	0.114*
H9B	0.1566	1.1910	0.0689	0.114*
H9C	0.1399	1.1013	0.0188	0.114*
C10	0.1479 (3)	0.9680 (2)	0.11460 (16)	0.0384 (7)
H10A	0.0879	1.0137	0.1006	0.046*
C11	0.1013 (3)	0.9004 (2)	0.17067 (16)	0.0359 (7)
H11	0.0305	0.8710	0.1540	0.043*
C12	0.0757 (3)	0.9609 (2)	0.23601 (17)	0.0357 (7)
C13	0.1838 (3)	1.0178 (2)	0.26167 (17)	0.0360 (7)
C14	−0.1111 (3)	0.8765 (3)	0.2674 (2)	0.0551 (10)
H14A	−0.1523	0.8416	0.3025	0.083*
H14B	−0.1047	0.8360	0.2268	0.083*
H14C	−0.1507	0.9360	0.2559	0.083*
C15	0.2801 (3)	0.9489 (3)	0.28529 (19)	0.0442 (8)
H15A	0.2532	0.9072	0.3220	0.066*
H15B	0.3428	0.9875	0.3017	0.066*
H15C	0.3042	0.9091	0.2469	0.066*
C16	0.1502 (3)	1.0825 (2)	0.32402 (16)	0.0427 (8)
H16A	0.2171	1.1157	0.3415	0.051*
H16B	0.0971	1.1325	0.3087	0.051*
C17	0.0964 (4)	1.0236 (3)	0.38239 (19)	0.0518 (9)
H17A	0.1506	0.9759	0.3998	0.062*
H17B	0.0763	1.0674	0.4201	0.062*
C18	−0.0080 (3)	0.9710 (3)	0.35714 (18)	0.0476 (9)
H18	−0.0606	1.0225	0.3419	0.057*
C19	0.0082 (3)	0.9019 (2)	0.29442 (17)	0.0408 (8)
C20	0.0577 (3)	0.8022 (3)	0.3134 (2)	0.0483 (9)
C21	0.1623 (3)	0.7356 (2)	0.15241 (18)	0.0398 (8)
C22	0.2491 (3)	0.6604 (2)	0.17071 (19)	0.0418 (8)
C23	0.2675 (3)	0.5849 (3)	0.1240 (2)	0.0512 (9)
H23	0.2303	0.5844	0.0815	0.061*
C24	0.3419 (4)	0.5101 (3)	0.1413 (3)	0.0645 (12)
H24	0.3564	0.4601	0.1096	0.077*
C25	0.3941 (3)	0.5091 (3)	0.2045 (3)	0.0631 (12)
H25	0.4421	0.4574	0.2161	0.076*
C26	0.3761 (3)	0.5835 (3)	0.2506 (2)	0.0614 (11)
H26	0.4118	0.5823	0.2936	0.074*
C27	0.3049 (3)	0.6606 (3)	0.2337 (2)	0.0522 (9)
H27	0.2946	0.7124	0.2645	0.063*
C28	0.0917 (3)	0.8830 (3)	0.01251 (19)	0.0468 (9)
C29	0.1236 (3)	0.8057 (3)	−0.03808 (17)	0.0450 (8)
C30	0.0424 (4)	0.7756 (3)	−0.0852 (2)	0.0634 (11)
H30	−0.0287	0.8053	−0.0856	0.076*
C31	0.0671 (5)	0.7011 (4)	−0.1319 (2)	0.0719 (13)
H31	0.0128	0.6809	−0.1637	0.086*
C32	0.1714 (5)	0.6575 (3)	−0.1309 (2)	0.0728 (13)
H32	0.1872	0.6067	−0.1618	0.087*
C33	0.2524 (4)	0.6874 (3)	−0.0856 (2)	0.0621 (11)
H33	0.3235	0.6579	−0.0860	0.075*
C34	0.2286 (4)	0.7623 (3)	−0.03847 (19)	0.0515 (9)
H34	0.2839	0.7828	−0.0073	0.062*
C35	0.2242 (6)	0.5792 (4)	0.4516 (3)	0.1029 (19)
H35A	0.2113	0.6195	0.4917	0.154*
H35B	0.3030	0.5818	0.4392	0.154*
H35C	0.2034	0.5125	0.4619	0.154*

	U11	U22	U33	U12	U13	U23
O1	0.0554 (16)	0.0453 (14)	0.0669 (17)	−0.0164 (13)	0.0011 (14)	0.0026 (13)
O2	0.084 (2)	0.0307 (12)	0.0785 (19)	−0.0077 (14)	0.0104 (17)	−0.0003 (14)
O3	0.090 (2)	0.0456 (15)	0.0753 (19)	0.0088 (17)	−0.0095 (19)	0.0116 (15)
O4	0.0555 (15)	0.0359 (12)	0.0656 (16)	−0.0013 (13)	−0.0091 (14)	−0.0074 (12)
O5	0.0385 (12)	0.0261 (10)	0.0492 (12)	0.0024 (10)	−0.0027 (11)	−0.0016 (10)
O6	0.0553 (17)	0.084 (2)	0.0696 (17)	0.0195 (17)	−0.0182 (15)	−0.0230 (17)
O7	0.0440 (13)	0.0402 (12)	0.0410 (12)	0.0004 (11)	−0.0022 (11)	−0.0055 (11)
O8	0.0436 (13)	0.0292 (10)	0.0548 (14)	0.0070 (11)	−0.0053 (12)	−0.0012 (11)
O9	0.081 (2)	0.0635 (17)	0.0566 (16)	−0.0089 (18)	0.0196 (15)	0.0086 (15)
O10	0.147 (4)	0.074 (2)	0.120 (3)	−0.002 (3)	−0.062 (3)	0.018 (2)
C1	0.068 (3)	0.054 (2)	0.072 (3)	−0.023 (2)	0.014 (2)	0.006 (2)
C2	0.075 (3)	0.056 (2)	0.057 (2)	−0.018 (2)	0.018 (2)	0.004 (2)
C3	0.054 (2)	0.0383 (18)	0.053 (2)	−0.0049 (17)	0.0055 (19)	0.0056 (17)
C4	0.046 (2)	0.0353 (16)	0.058 (2)	−0.0065 (16)	−0.0005 (18)	0.0031 (17)
C5	0.049 (2)	0.0464 (18)	0.0461 (18)	−0.0091 (18)	−0.0019 (18)	−0.0021 (16)
C6	0.0391 (18)	0.0305 (15)	0.0399 (16)	−0.0005 (14)	−0.0025 (14)	0.0011 (14)
C7	0.0417 (18)	0.0329 (16)	0.0417 (16)	0.0000 (16)	−0.0030 (15)	−0.0014 (14)
C8	0.060 (2)	0.048 (2)	0.0418 (18)	−0.0085 (19)	0.0044 (17)	−0.0004 (17)
C9	0.093 (3)	0.070 (3)	0.065 (3)	−0.022 (3)	−0.025 (3)	0.032 (2)
C10	0.0430 (19)	0.0321 (15)	0.0400 (16)	0.0040 (15)	−0.0039 (15)	−0.0040 (14)
C11	0.0362 (17)	0.0284 (14)	0.0431 (16)	0.0024 (14)	−0.0018 (15)	−0.0003 (14)
C12	0.0396 (18)	0.0239 (13)	0.0434 (17)	0.0046 (13)	−0.0014 (15)	0.0018 (14)
C13	0.0382 (17)	0.0290 (14)	0.0408 (16)	0.0014 (14)	−0.0027 (15)	0.0016 (14)
C14	0.044 (2)	0.055 (2)	0.067 (2)	−0.0051 (19)	0.009 (2)	0.000 (2)
C15	0.045 (2)	0.0386 (17)	0.0490 (18)	0.0030 (16)	−0.0116 (17)	0.0031 (15)
C16	0.053 (2)	0.0359 (16)	0.0389 (16)	−0.0019 (16)	−0.0009 (16)	−0.0022 (15)
C17	0.065 (2)	0.048 (2)	0.0420 (18)	−0.001 (2)	0.0019 (19)	−0.0015 (17)
C18	0.056 (2)	0.0403 (18)	0.0460 (19)	0.0056 (18)	0.0126 (18)	0.0049 (16)
C19	0.0431 (19)	0.0310 (15)	0.0484 (18)	−0.0010 (16)	0.0049 (16)	0.0001 (15)
C20	0.050 (2)	0.0416 (19)	0.053 (2)	−0.0004 (17)	0.0092 (19)	0.0083 (18)
C21	0.044 (2)	0.0291 (15)	0.0461 (18)	−0.0032 (15)	0.0049 (17)	−0.0020 (14)
C22	0.0390 (18)	0.0289 (15)	0.058 (2)	−0.0018 (15)	0.0099 (17)	−0.0001 (15)
C23	0.054 (2)	0.0381 (18)	0.062 (2)	0.0010 (18)	0.011 (2)	−0.0062 (18)
C24	0.058 (3)	0.044 (2)	0.092 (3)	0.010 (2)	0.017 (3)	−0.011 (2)
C25	0.043 (2)	0.0403 (19)	0.106 (4)	0.0108 (18)	0.009 (2)	0.007 (2)
C26	0.049 (2)	0.050 (2)	0.085 (3)	0.0040 (19)	−0.007 (2)	0.007 (2)
C27	0.050 (2)	0.0388 (18)	0.067 (2)	0.0048 (18)	0.001 (2)	−0.0040 (18)
C28	0.047 (2)	0.0454 (19)	0.0482 (19)	0.0047 (18)	−0.0029 (18)	−0.0011 (17)
C29	0.054 (2)	0.0417 (18)	0.0396 (17)	−0.0030 (17)	0.0006 (17)	−0.0022 (16)
C30	0.058 (3)	0.068 (3)	0.064 (2)	−0.005 (2)	−0.007 (2)	−0.010 (2)
C31	0.081 (3)	0.078 (3)	0.057 (2)	−0.009 (3)	−0.013 (2)	−0.022 (2)
C32	0.100 (4)	0.056 (2)	0.062 (3)	0.001 (3)	0.012 (3)	−0.021 (2)
C33	0.073 (3)	0.056 (2)	0.057 (2)	0.007 (2)	0.009 (2)	−0.005 (2)
C34	0.057 (2)	0.049 (2)	0.0490 (19)	−0.0029 (19)	−0.0032 (19)	−0.0026 (17)
C35	0.131 (5)	0.071 (3)	0.106 (4)	0.001 (3)	−0.021 (4)	0.009 (3)

O1—C1	1.367 (5)	C13—C16	1.542 (4)
O1—C4	1.377 (4)	C14—C19	1.540 (5)
O2—C20	1.216 (5)	C14—H14A	0.9600
O3—C20	1.306 (5)	C14—H14B	0.9600
O3—H3	0.8400	C14—H14C	0.9600
O4—C21	1.198 (4)	C15—H15A	0.9600
O5—C21	1.359 (4)	C15—H15B	0.9600
O5—C11	1.438 (4)	C15—H15C	0.9600
O6—C28	1.199 (4)	C16—C17	1.521 (5)
O7—C28	1.345 (4)	C16—H16A	0.9700
O7—C10	1.456 (4)	C16—H16B	0.9700
O8—C12	1.439 (4)	C17—C18	1.505 (6)
O8—H8	0.8400	C17—H17A	0.9700
O9—C18	1.435 (4)	C17—H17B	0.9700
O9—H9	0.8400	C18—C19	1.544 (5)
O10—C35	1.376 (6)	C18—H18	0.9800
O10—H10	0.8400	C19—C20	1.521 (5)
C1—C2	1.313 (6)	C21—C22	1.489 (5)
C1—H1	0.9300	C22—C27	1.382 (6)
C2—C3	1.425 (5)	C22—C23	1.384 (5)
C2—H2	0.9300	C23—C24	1.383 (6)
C3—C4	1.335 (5)	C23—H23	0.9300
C3—C8	1.502 (5)	C24—C25	1.368 (7)
C4—C5	1.465 (5)	C24—H24	0.9300
C5—C6	1.539 (5)	C25—C26	1.364 (6)
C5—H5A	0.9700	C25—H25	0.9300
C5—H5B	0.9700	C26—C27	1.383 (5)
C6—C7	1.548 (4)	C26—H26	0.9300
C6—C13	1.562 (4)	C27—H27	0.9300
C6—H6	0.9800	C28—C29	1.483 (5)
C7—C10	1.515 (5)	C29—C34	1.372 (5)
C7—C8	1.554 (5)	C29—C30	1.383 (5)
C7—H7	0.9800	C30—C31	1.386 (6)
C8—C9	1.521 (6)	C30—H30	0.9300
C8—H8A	0.9800	C31—C32	1.366 (7)
C9—H9A	0.9600	C31—H31	0.9300
C9—H9B	0.9600	C32—C33	1.357 (6)
C9—H9C	0.9600	C32—H32	0.9300
C10—C11	1.522 (5)	C33—C34	1.393 (5)
C10—H10A	0.9800	C33—H33	0.9300
C11—C12	1.536 (4)	C34—H34	0.9300
C11—H11	0.9800	C35—H35A	0.9600
C12—C13	1.571 (5)	C35—H35B	0.9600
C12—C19	1.596 (5)	C35—H35C	0.9600
C13—C15	1.541 (4)
C1—O1—C4	104.8 (3)	C13—C15—H15B	109.5
C20—O3—H3	109.5	H15A—C15—H15B	109.5
C21—O5—C11	116.5 (2)	C13—C15—H15C	109.5
C28—O7—C10	116.2 (3)	H15A—C15—H15C	109.5
C12—O8—H8	109.5	H15B—C15—H15C	109.5
C18—O9—H9	109.5	C17—C16—C13	112.6 (3)
C35—O10—H10	109.5	C17—C16—H16A	109.1
C2—C1—O1	111.5 (4)	C13—C16—H16A	109.1
C2—C1—H1	124.2	C17—C16—H16B	109.1
O1—C1—H1	124.2	C13—C16—H16B	109.1
C1—C2—C3	107.0 (4)	H16A—C16—H16B	107.8
C1—C2—H2	126.5	C18—C17—C16	110.6 (3)
C3—C2—H2	126.5	C18—C17—H17A	109.5
C4—C3—C2	105.9 (4)	C16—C17—H17A	109.5
C4—C3—C8	121.6 (3)	C18—C17—H17B	109.5
C2—C3—C8	132.4 (4)	C16—C17—H17B	109.5
C3—C4—O1	110.8 (3)	H17A—C17—H17B	108.1
C3—C4—C5	129.3 (3)	O9—C18—C17	111.9 (3)
O1—C4—C5	119.9 (3)	O9—C18—C19	109.9 (3)
C4—C5—C6	110.8 (3)	C17—C18—C19	116.2 (3)
C4—C5—H5A	109.5	O9—C18—H18	106.1
C6—C5—H5A	109.5	C17—C18—H18	106.1
C4—C5—H5B	109.5	C19—C18—H18	106.1
C6—C5—H5B	109.5	C20—C19—C14	103.4 (3)
H5A—C5—H5B	108.1	C20—C19—C18	113.7 (3)
C5—C6—C7	112.3 (3)	C14—C19—C18	106.8 (3)
C5—C6—C13	111.1 (3)	C20—C19—C12	115.3 (3)
C7—C6—C13	112.7 (2)	C14—C19—C12	109.2 (3)
C5—C6—H6	106.8	C18—C19—C12	108.0 (3)
C7—C6—H6	106.8	O2—C20—O3	121.3 (4)
C13—C6—H6	106.8	O2—C20—C19	122.5 (4)
C10—C7—C6	108.6 (3)	O3—C20—C19	116.1 (3)
C10—C7—C8	110.3 (3)	O4—C21—O5	123.9 (3)
C6—C7—C8	113.3 (3)	O4—C21—C22	123.8 (3)
C10—C7—H7	108.2	O5—C21—C22	112.2 (3)
C6—C7—H7	108.2	C27—C22—C23	120.0 (3)
C8—C7—H7	108.2	C27—C22—C21	122.3 (3)
C3—C8—C9	109.8 (3)	C23—C22—C21	117.5 (3)
C3—C8—C7	109.4 (3)	C24—C23—C22	119.2 (4)
C9—C8—C7	115.2 (3)	C24—C23—H23	120.4
C3—C8—H8A	107.4	C22—C23—H23	120.4
C9—C8—H8A	107.4	C25—C24—C23	120.6 (4)
C7—C8—H8A	107.4	C25—C24—H24	119.7
C8—C9—H9A	109.5	C23—C24—H24	119.7
C8—C9—H9B	109.5	C26—C25—C24	120.3 (4)
H9A—C9—H9B	109.5	C26—C25—H25	119.8
C8—C9—H9C	109.5	C24—C25—H25	119.8
H9A—C9—H9C	109.5	C25—C26—C27	120.2 (4)
H9B—C9—H9C	109.5	C25—C26—H26	119.9
O7—C10—C7	107.9 (3)	C27—C26—H26	119.9
O7—C10—C11	107.5 (2)	C22—C27—C26	119.7 (4)
C7—C10—C11	115.7 (3)	C22—C27—H27	120.1
O7—C10—H10A	108.5	C26—C27—H27	120.1
C7—C10—H10A	108.5	O6—C28—O7	123.2 (3)
C11—C10—H10A	108.5	O6—C28—C29	124.1 (4)
O5—C11—C10	109.5 (3)	O7—C28—C29	112.6 (3)
O5—C11—C12	111.7 (2)	C34—C29—C30	119.6 (3)
C10—C11—C12	109.4 (2)	C34—C29—C28	122.5 (3)
O5—C11—H11	108.7	C30—C29—C28	117.8 (4)
C10—C11—H11	108.7	C29—C30—C31	119.8 (4)
C12—C11—H11	108.7	C29—C30—H30	120.1
O8—C12—C11	100.7 (2)	C31—C30—H30	120.1
O8—C12—C13	109.3 (2)	C32—C31—C30	119.9 (4)
C11—C12—C13	111.3 (3)	C32—C31—H31	120.1
O8—C12—C19	104.7 (3)	C30—C31—H31	120.1
C11—C12—C19	114.1 (2)	C33—C32—C31	120.8 (4)
C13—C12—C19	115.4 (3)	C33—C32—H32	119.6
C15—C13—C16	107.8 (3)	C31—C32—H32	119.6
C15—C13—C6	110.1 (3)	C32—C33—C34	119.9 (4)
C16—C13—C6	109.1 (2)	C32—C33—H33	120.1
C15—C13—C12	113.1 (2)	C34—C33—H33	120.1
C16—C13—C12	108.5 (3)	C29—C34—C33	120.0 (4)
C6—C13—C12	108.1 (3)	C29—C34—H34	120.0
C19—C14—H14A	109.5	C33—C34—H34	120.0
C19—C14—H14B	109.5	O10—C35—H35A	109.5
H14A—C14—H14B	109.5	O10—C35—H35B	109.5
C19—C14—H14C	109.5	H35A—C35—H35B	109.5
H14A—C14—H14C	109.5	O10—C35—H35C	109.5
H14B—C14—H14C	109.5	H35A—C35—H35C	109.5
C13—C15—H15A	109.5	H35B—C35—H35C	109.5
C4—O1—C1—C2	−0.5 (5)	C11—C12—C13—C6	57.8 (3)
O1—C1—C2—C3	0.1 (5)	C19—C12—C13—C6	−170.1 (2)
C1—C2—C3—C4	0.4 (5)	C15—C13—C16—C17	−66.6 (4)
C1—C2—C3—C8	176.8 (4)	C6—C13—C16—C17	173.9 (3)
C2—C3—C4—O1	−0.8 (4)	C12—C13—C16—C17	56.3 (4)
C8—C3—C4—O1	−177.6 (3)	C13—C16—C17—C18	−58.8 (4)
C2—C3—C4—C5	−178.7 (4)	C16—C17—C18—O9	−176.5 (3)
C8—C3—C4—C5	4.4 (6)	C16—C17—C18—C19	56.3 (4)
C1—O1—C4—C3	0.8 (4)	O9—C18—C19—C20	−48.5 (4)
C1—O1—C4—C5	179.0 (4)	C17—C18—C19—C20	79.8 (4)
C3—C4—C5—C6	−11.2 (6)	O9—C18—C19—C14	64.9 (4)
O1—C4—C5—C6	171.0 (3)	C17—C18—C19—C14	−166.8 (3)
C4—C5—C6—C7	35.5 (4)	O9—C18—C19—C12	−177.7 (3)
C4—C5—C6—C13	162.8 (3)	C17—C18—C19—C12	−49.5 (4)
C5—C6—C7—C10	−178.8 (3)	O8—C12—C19—C20	159.2 (3)
C13—C6—C7—C10	54.8 (3)	C11—C12—C19—C20	50.1 (4)
C5—C6—C7—C8	−55.9 (4)	C13—C12—C19—C20	−80.7 (4)
C13—C6—C7—C8	177.8 (3)	O8—C12—C19—C14	43.3 (3)
C4—C3—C8—C9	105.7 (4)	C11—C12—C19—C14	−65.8 (3)
C2—C3—C8—C9	−70.2 (5)	C13—C12—C19—C14	163.4 (3)
C4—C3—C8—C7	−21.6 (5)	O8—C12—C19—C18	−72.5 (3)
C2—C3—C8—C7	162.5 (4)	C11—C12—C19—C18	178.4 (3)
C10—C7—C8—C3	168.7 (3)	C13—C12—C19—C18	47.6 (4)
C6—C7—C8—C3	46.7 (4)	C14—C19—C20—O2	36.5 (5)
C10—C7—C8—C9	44.4 (4)	C18—C19—C20—O2	151.9 (4)
C6—C7—C8—C9	−77.5 (4)	C12—C19—C20—O2	−82.6 (4)
C28—O7—C10—C7	−152.1 (3)	C14—C19—C20—O3	−140.7 (3)
C28—O7—C10—C11	82.5 (3)	C18—C19—C20—O3	−25.3 (5)
C6—C7—C10—O7	−174.8 (2)	C12—C19—C20—O3	100.1 (4)
C8—C7—C10—O7	60.5 (3)	C11—O5—C21—O4	0.7 (5)
C6—C7—C10—C11	−54.4 (4)	C11—O5—C21—C22	−179.3 (3)
C8—C7—C10—C11	−179.2 (3)	O4—C21—C22—C27	−150.8 (4)
C21—O5—C11—C10	−97.8 (3)	O5—C21—C22—C27	29.2 (5)
C21—O5—C11—C12	140.8 (3)	O4—C21—C22—C23	24.9 (5)
O7—C10—C11—O5	53.9 (3)	O5—C21—C22—C23	−155.1 (3)
C7—C10—C11—O5	−66.7 (3)	C27—C22—C23—C24	0.1 (6)
O7—C10—C11—C12	176.6 (2)	C21—C22—C23—C24	−175.7 (3)
C7—C10—C11—C12	56.0 (4)	C22—C23—C24—C25	1.9 (6)
O5—C11—C12—O8	−179.3 (2)	C23—C24—C25—C26	−2.0 (7)
C10—C11—C12—O8	59.3 (3)	C24—C25—C26—C27	−0.1 (6)
O5—C11—C12—C13	65.0 (3)	C23—C22—C27—C26	−2.1 (6)
C10—C11—C12—C13	−56.4 (3)	C21—C22—C27—C26	173.4 (3)
O5—C11—C12—C19	−67.7 (3)	C25—C26—C27—C22	2.1 (6)
C10—C11—C12—C19	170.8 (3)	C10—O7—C28—O6	9.3 (5)
C5—C6—C13—C15	−60.4 (3)	C10—O7—C28—C29	−168.8 (3)
C7—C6—C13—C15	66.6 (3)	O6—C28—C29—C34	−176.1 (4)
C5—C6—C13—C16	57.7 (4)	O7—C28—C29—C34	1.9 (5)
C7—C6—C13—C16	−175.3 (3)	O6—C28—C29—C30	2.3 (6)
C5—C6—C13—C12	175.5 (3)	O7—C28—C29—C30	−179.6 (3)
C7—C6—C13—C12	−57.4 (3)	C34—C29—C30—C31	0.7 (6)
O8—C12—C13—C15	−174.7 (3)	C28—C29—C30—C31	−177.7 (4)
C11—C12—C13—C15	−64.4 (4)	C29—C30—C31—C32	0.3 (7)
C19—C12—C13—C15	67.7 (4)	C30—C31—C32—C33	−1.2 (8)
O8—C12—C13—C16	65.8 (3)	C31—C32—C33—C34	1.1 (7)
C11—C12—C13—C16	176.0 (2)	C30—C29—C34—C33	−0.8 (6)
C19—C12—C13—C16	−51.9 (3)	C28—C29—C34—C33	177.6 (3)
O8—C12—C13—C6	−52.5 (3)	C32—C33—C34—C29	−0.1 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O10	0.84	1.79	2.626 (5)	177
O8—H8···O2i	0.84	2.03	2.728 (3)	141
O10—H10···O8ii	0.84	2.26	2.967 (4)	142
C15—H15A···O3	0.96	2.35	3.231 (5)	152

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O3H3O10	0.84	1.79	2.626(5)	177
O8H8O2i	0.84	2.03	2.728(3)	141
O10H10O8ii	0.84	2.26	2.967(4)	142
C15H15AO3	0.96	2.35	3.231(5)	152

Symmetry codes: (i) ; (ii) .