Crystal and mol-ecular structure of aflatrem.

The crystal structure of the title compound, C32H39NO4, confirms the absolute configuration of the seven chiral centres in the mol-ecule. The molecule has a 1,1-dimethylprop-2-enyl substituent on the indole nucleus and this nucleus shares one edge with the five-membered ring which is, in turn, connected to a sequence of three edge-shared fused rings. The skeleton is completed by the 7,7-trimethyl-6,8-dioxabi-cyclo-[3.2.1]oct-3-en-2-one group connected to the terminal cyclohexene ring. The two cyclohexane rings adopt chair and half-chair conformations, while in the dioxabi-cyclo-[3.2.1]oct-3-en-2-one unit, the six-membered ring has a half-chair conformation. The indole system of the mol-ecule exhibits a tilt of 2.02 (1)° between its two rings. In the crystal, O-H⋯O hydrogen bonds connect mol-ecules into chains along [010]. Weak N-H⋯π inter-actions connect these chains, forming sheets parallel to (10-1).

Related literature

For background to indole diterpenoids from endophytes, see: Strobel & Daisy (2003 ▸); Munday-Finch et al. (1996 ▸); Gallagher et al. (1980a ▸,b ▸); Lenta et al. (2007 ▸); Phongpaichit et al. (2007 ▸). For studies of Aspergillus sp, see: Nicholson et al. (2009 ▸); Duran et al. (2006 ▸). For the pharmacological basis of the behavioural effects of this mol­ecule, see: Tinao-Wooldridge et al. (1995 ▸). For the isolation of fungal endophytes from the stem of Symphonia globulifera, see: Petrini et al. (1992 ▸); Amin et al. (2014 ▸). For geometric details of indole compounds, see: Krishna et al. (1999 ▸). For circular dichroism experiments on the title compound, see: Sun et al. (2014 ▸). For information on the Cambridge Structural Database (CSD), see: Groom & Allen (2014 ▸).

Experimental

Crystal data

C32H39NO4

M = 501.64

Monoclinic,

a = 12.8022 (5) Å

b = 6.4019 (2) Å

c = 15.9557 (6) Å

β = 98.821 (4)°

V = 1292.24 (9) Å3

Z = 2

Cu Kα radiation

μ = 0.66 mm−1

T = 100 K

0.18 × 0.14 × 0.02 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector

Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013 ▸) T min = 0.899, T max = 1.000

19981 measured reflections

4585 independent reflections

4078 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.150

S = 1.06

4585 reflections

341 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack x determined using 1671 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons & Flack, 2004 ▸)

Absolute structure parameter: 0.09 (14)

Data collection: CrysAlis PRO (Agilent, 2013 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: DIAMOND (Brandenburg, 1999 ▸); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019040/lh5789sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019040/lh5789Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015019040/lh5789fig1.tif

The mol­ecular structure of aflatrem with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b x y z x y z x y z x y z . DOI: 10.1107/S2056989015019040/lh5789fig2.tif

Crystal packing of aflatrem showing O—H⋯O hydrogen-bonded (dashed lines) zigzag chains along the b axis in the (010) plane. Weak N—H⋯π inter­actions are also shown as dashed lines. Symmetry codes: (i) − x + 2, y − , −z + 2; (ii) −x + 1, y − , −z + 1; (iii) −x + 1, y + , −z + 1; (iv) −x + 2, y + , −z + 2.

Click here for additional data file.

b x y z x y z x y z x y z . DOI: 10.1107/S2056989015019040/lh5789fig3.tif

Crystal packing of aflatrem showing O—H⋯O hydrogen-bonded (dashed lines) zigzag chains along the b axis in the (001) plane. Weak N—H⋯π inter­actions are also shown as dashed lines. Symmetry codes: (i) −x + 2, y − , −z + 2; (ii) −x + 1, y − , −z + 1; (iii) −x + 1, y + , −z + 1 and (iv) −x + 2, y + , −z + 2.

CCDC reference: 1430332

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

C32H39NO4	F(000) = 540
Mr = 501.64	Dx = 1.289 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.5418 Å
a = 12.8022 (5) Å	Cell parameters from 6775 reflections
b = 6.4019 (2) Å	θ = 4.8–66.4°
c = 15.9557 (6) Å	µ = 0.66 mm−1
β = 98.821 (4)°	T = 100 K
V = 1292.24 (9) Å3	Plate, colourless
Z = 2	0.18 × 0.14 × 0.02 mm

Agilent SuperNova Dual Source diffractometer with an Atlas detector	4585 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	4078 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.050
Detector resolution: 5.3114 pixels mm-1	θmax = 66.9°, θmin = 2.8°
ω scans	h = −15→15
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2013)	k = −7→7
Tmin = 0.899, Tmax = 1.000	l = −18→18
19981 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.056	w = 1/[σ2(Fo2) + (0.0948P)2 + 0.4383P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.150	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.35 e Å−3
4585 reflections	Δρmin = −0.23 e Å−3
341 parameters	Absolute structure: Flack x determined using 1671 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
1 restraint	Absolute structure parameter: 0.09 (14)
Primary atom site location: structure-invariant direct methods

Experimental. Numerical absorption correction based on gaussian integration over a multifaceted crystal model

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.

	x	y	z	Uiso*/Ueq
O1	0.77480 (17)	0.1640 (3)	1.04104 (13)	0.0330 (5)
O2	0.64687 (16)	0.3772 (3)	0.97693 (13)	0.0307 (5)
O3	0.88440 (18)	0.5994 (4)	1.15707 (14)	0.0414 (6)
O4	0.91050 (17)	0.2056 (3)	0.85758 (13)	0.0316 (5)
H4	0.9698	0.2203	0.8449	0.047*
N1	0.61755 (19)	0.3716 (4)	0.58123 (15)	0.0267 (5)
H1	0.5782	0.2885	0.6050	0.032*
C1	0.7110 (2)	0.4610 (4)	0.61906 (19)	0.0260 (6)
C2	0.7906 (2)	0.4099 (4)	0.69719 (18)	0.0252 (6)
C3	0.7579 (2)	0.4000 (5)	0.78767 (18)	0.0264 (6)
C4	0.6942 (2)	0.1981 (4)	0.80235 (19)	0.0279 (6)
H4A	0.6195	0.2288	0.7870	0.033*
H4B	0.7117	0.0912	0.7637	0.033*
C5	0.7119 (2)	0.1065 (5)	0.89279 (19)	0.0301 (6)
H5A	0.6482	0.0338	0.9021	0.036*
H5B	0.7684	0.0044	0.8968	0.036*
C6	0.7394 (2)	0.2648 (5)	0.96202 (19)	0.0293 (7)
C7	0.7658 (3)	0.3273 (5)	1.10039 (19)	0.0327 (7)
H7	0.7714	0.2729	1.1583	0.039*
C8	0.8486 (2)	0.4967 (5)	1.0940 (2)	0.0338 (7)
C9	0.8771 (2)	0.5268 (5)	1.0107 (2)	0.0328 (7)
H9	0.9297	0.6218	1.0028	0.039*
C10	0.8270 (2)	0.4165 (5)	0.94420 (19)	0.0287 (6)
C11	0.8592 (2)	0.4071 (5)	0.85721 (18)	0.0270 (6)
C12	0.9380 (2)	0.5804 (5)	0.8432 (2)	0.0316 (7)
H12A	0.9080	0.7144	0.8551	0.038*
H12B	1.0022	0.5614	0.8834	0.038*
C13	0.9661 (2)	0.5851 (5)	0.75408 (19)	0.0326 (7)
H13A	1.0117	0.7032	0.7477	0.039*
H13B	1.0029	0.4580	0.7430	0.039*
C14	0.8634 (2)	0.6041 (5)	0.69266 (19)	0.0277 (6)
H14	0.8256	0.7216	0.7135	0.033*
C15	0.8636 (2)	0.6488 (5)	0.59791 (19)	0.0313 (7)
H15A	0.8759	0.7955	0.5876	0.038*
H15B	0.9157	0.5649	0.5751	0.038*
C16	0.7522 (2)	0.5841 (4)	0.56234 (19)	0.0276 (6)
C17	0.6812 (2)	0.5766 (4)	0.48313 (18)	0.0262 (6)
C18	0.6770 (2)	0.6725 (4)	0.40181 (18)	0.0267 (6)
C19	0.5951 (2)	0.6126 (5)	0.33970 (19)	0.0310 (7)
H19	0.5918	0.6687	0.2856	0.037*
C20	0.5165 (2)	0.4704 (5)	0.35503 (19)	0.0308 (7)
H20	0.4644	0.4318	0.3105	0.037*
C21	0.5147 (2)	0.3863 (5)	0.43453 (19)	0.0279 (6)
H21	0.4605	0.2986	0.4455	0.033*
C22	0.5987 (2)	0.4402 (4)	0.49762 (18)	0.0262 (6)
C23	0.8453 (3)	0.2072 (5)	0.6718 (2)	0.0308 (7)
H23A	0.7937	0.0983	0.6598	0.046*
H23B	0.8987	0.1648	0.7176	0.046*
H23C	0.8774	0.2338	0.6223	0.046*
C24	0.6862 (2)	0.5888 (4)	0.80049 (19)	0.0281 (6)
H24A	0.7270	0.7150	0.8035	0.042*
H24B	0.6576	0.5712	0.8523	0.042*
H24C	0.6294	0.5971	0.7537	0.042*
C25	0.6530 (2)	0.4108 (6)	1.06813 (19)	0.0336 (7)
C26	0.6353 (3)	0.6379 (5)	1.0847 (2)	0.0384 (8)
H26A	0.6817	0.7211	1.0565	0.058*
H26B	0.6497	0.6639	1.1447	0.058*
H26C	0.5633	0.6738	1.0637	0.058*
C27	0.5722 (3)	0.2731 (6)	1.1015 (2)	0.0376 (8)
H27A	0.5028	0.3075	1.0731	0.056*
H27B	0.5757	0.2954	1.1614	0.056*
H27C	0.5872	0.1292	1.0912	0.056*
C28	0.7593 (2)	0.8372 (4)	0.38782 (18)	0.0295 (7)
C29	0.7411 (3)	0.9297 (5)	0.2981 (2)	0.0381 (8)
H29A	0.7483	0.8217	0.2576	0.057*
H29B	0.7924	1.0372	0.2940	0.057*
H29C	0.6714	0.9881	0.2866	0.057*
C30	0.7512 (3)	1.0194 (5)	0.4492 (2)	0.0351 (7)
H30A	0.6870	1.0954	0.4313	0.053*
H30B	0.8106	1.1109	0.4494	0.053*
H30C	0.7508	0.9657	0.5054	0.053*
C31	0.8695 (3)	0.7438 (5)	0.4004 (2)	0.0340 (7)
H31	0.9255	0.8328	0.4195	0.041*
C32	0.8925 (3)	0.5482 (6)	0.3866 (2)	0.0426 (8)
H32A	0.8388	0.4540	0.3675	0.051*
H32B	0.9625	0.5039	0.3960	0.051*

	U11	U22	U33	U12	U13	U23
O1	0.0397 (12)	0.0260 (10)	0.0297 (11)	0.0012 (9)	−0.0062 (9)	0.0028 (9)
O2	0.0311 (10)	0.0307 (11)	0.0269 (10)	−0.0007 (9)	−0.0065 (8)	−0.0031 (9)
O3	0.0390 (12)	0.0489 (14)	0.0317 (12)	−0.0085 (11)	−0.0090 (10)	−0.0092 (11)
O4	0.0329 (11)	0.0272 (11)	0.0327 (11)	0.0059 (9)	−0.0019 (9)	0.0019 (9)
N1	0.0308 (12)	0.0218 (12)	0.0254 (12)	−0.0015 (10)	−0.0027 (10)	0.0024 (10)
C1	0.0273 (14)	0.0188 (13)	0.0298 (15)	0.0013 (11)	−0.0018 (12)	−0.0022 (11)
C2	0.0296 (14)	0.0163 (12)	0.0270 (14)	0.0012 (12)	−0.0037 (11)	−0.0015 (11)
C3	0.0304 (14)	0.0177 (13)	0.0276 (15)	0.0005 (12)	−0.0062 (12)	−0.0004 (11)
C4	0.0310 (15)	0.0198 (14)	0.0303 (14)	−0.0030 (12)	−0.0031 (12)	−0.0014 (11)
C5	0.0368 (16)	0.0186 (13)	0.0330 (16)	−0.0041 (12)	−0.0006 (13)	−0.0036 (12)
C6	0.0351 (16)	0.0229 (15)	0.0268 (15)	0.0005 (12)	−0.0055 (12)	−0.0014 (11)
C7	0.0348 (16)	0.0349 (16)	0.0250 (15)	−0.0017 (13)	−0.0065 (12)	0.0008 (13)
C8	0.0299 (15)	0.0364 (17)	0.0325 (16)	0.0013 (13)	−0.0034 (13)	−0.0014 (13)
C9	0.0330 (15)	0.0330 (16)	0.0296 (15)	−0.0062 (13)	−0.0044 (12)	−0.0008 (13)
C10	0.0307 (14)	0.0212 (14)	0.0314 (15)	0.0026 (12)	−0.0038 (12)	0.0015 (12)
C11	0.0281 (14)	0.0216 (13)	0.0286 (15)	0.0006 (12)	−0.0044 (12)	−0.0014 (12)
C12	0.0316 (15)	0.0278 (15)	0.0325 (16)	−0.0030 (13)	−0.0047 (12)	−0.0014 (13)
C13	0.0306 (15)	0.0311 (15)	0.0330 (16)	−0.0027 (13)	−0.0055 (13)	−0.0035 (13)
C14	0.0285 (14)	0.0231 (14)	0.0290 (15)	−0.0015 (12)	−0.0037 (12)	0.0008 (12)
C15	0.0386 (17)	0.0234 (14)	0.0283 (15)	−0.0022 (12)	−0.0056 (13)	0.0026 (12)
C16	0.0322 (14)	0.0193 (13)	0.0292 (15)	0.0002 (12)	−0.0021 (12)	−0.0022 (12)
C17	0.0307 (14)	0.0206 (13)	0.0260 (14)	0.0018 (12)	−0.0001 (12)	−0.0008 (11)
C18	0.0329 (15)	0.0207 (13)	0.0247 (14)	−0.0001 (12)	−0.0007 (11)	0.0007 (11)
C19	0.0353 (15)	0.0265 (15)	0.0287 (15)	0.0036 (13)	−0.0034 (13)	0.0026 (12)
C20	0.0329 (15)	0.0247 (14)	0.0300 (15)	0.0019 (12)	−0.0099 (13)	−0.0009 (12)
C21	0.0293 (14)	0.0200 (13)	0.0318 (15)	−0.0002 (12)	−0.0032 (12)	0.0019 (12)
C22	0.0327 (15)	0.0190 (14)	0.0254 (14)	0.0028 (11)	−0.0006 (12)	−0.0004 (11)
C23	0.0365 (16)	0.0212 (15)	0.0326 (15)	0.0024 (12)	−0.0016 (13)	−0.0028 (12)
C24	0.0362 (16)	0.0183 (13)	0.0280 (14)	0.0027 (12)	−0.0013 (12)	−0.0020 (11)
C25	0.0339 (16)	0.0382 (17)	0.0255 (15)	−0.0009 (14)	−0.0059 (12)	−0.0034 (13)
C26	0.0408 (17)	0.0387 (18)	0.0317 (16)	0.0011 (14)	−0.0074 (13)	−0.0077 (14)
C27	0.0336 (17)	0.0419 (19)	0.0354 (17)	−0.0041 (14)	−0.0010 (14)	−0.0025 (14)
C28	0.0384 (16)	0.0222 (15)	0.0262 (15)	−0.0027 (12)	−0.0007 (12)	0.0031 (12)
C29	0.0478 (19)	0.0319 (17)	0.0310 (16)	−0.0070 (14)	−0.0054 (14)	0.0056 (13)
C30	0.0453 (18)	0.0211 (15)	0.0359 (17)	−0.0015 (13)	−0.0034 (14)	0.0009 (13)
C31	0.0332 (16)	0.0319 (16)	0.0349 (16)	−0.0061 (13)	−0.0013 (13)	0.0006 (13)
C32	0.0397 (18)	0.0356 (18)	0.052 (2)	0.0042 (15)	0.0068 (16)	0.0025 (15)

O1—C7	1.427 (4)	C15—C16	1.509 (4)
O1—C6	1.427 (4)	C15—H15A	0.9700
O2—C6	1.437 (4)	C15—H15B	0.9700
O2—C25	1.461 (4)	C16—C17	1.440 (4)
O3—C8	1.231 (4)	C17—C22	1.417 (4)
O4—C11	1.447 (4)	C17—C18	1.429 (4)
O4—H4	0.8200	C18—C19	1.382 (4)
N1—C1	1.379 (4)	C18—C28	1.532 (4)
N1—C22	1.390 (4)	C19—C20	1.406 (5)
N1—H1	0.8600	C19—H19	0.9300
C1—C16	1.366 (4)	C20—C21	1.381 (4)
C1—C2	1.520 (4)	C20—H20	0.9300
C2—C23	1.557 (4)	C21—C22	1.399 (4)
C2—C14	1.562 (4)	C21—H21	0.9300
C2—C3	1.565 (4)	C23—H23A	0.9600
C3—C24	1.550 (4)	C23—H23B	0.9600
C3—C4	1.565 (4)	C23—H23C	0.9600
C3—C11	1.573 (4)	C24—H24A	0.9600
C4—C5	1.542 (4)	C24—H24B	0.9600
C4—H4A	0.9700	C24—H24C	0.9600
C4—H4B	0.9700	C25—C26	1.501 (5)
C5—C6	1.500 (4)	C25—C27	1.517 (5)
C5—H5A	0.9700	C26—H26A	0.9600
C5—H5B	0.9700	C26—H26B	0.9600
C6—C10	1.543 (4)	C26—H26C	0.9600
C7—C8	1.531 (5)	C27—H27A	0.9600
C7—C25	1.552 (4)	C27—H27B	0.9600
C7—H7	0.9800	C27—H27C	0.9600
C8—C9	1.443 (5)	C28—C31	1.516 (4)
C9—C10	1.351 (4)	C28—C29	1.533 (4)
C9—H9	0.9300	C28—C30	1.537 (4)
C10—C11	1.508 (4)	C29—H29A	0.9600
C11—C12	1.538 (4)	C29—H29B	0.9600
C12—C13	1.521 (4)	C29—H29C	0.9600
C12—H12A	0.9700	C30—H30A	0.9600
C12—H12B	0.9700	C30—H30B	0.9600
C13—C14	1.520 (4)	C30—H30C	0.9600
C13—H13A	0.9700	C31—C32	1.313 (5)
C13—H13B	0.9700	C31—H31	0.9300
C14—C15	1.539 (4)	C32—H32A	0.9300
C14—H14	0.9800	C32—H32B	0.9300
C7—O1—C6	102.0 (2)	C14—C15—H15A	111.8
C6—O2—C25	108.6 (2)	C16—C15—H15B	111.8
C11—O4—H4	109.5	C14—C15—H15B	111.8
C1—N1—C22	107.5 (2)	H15A—C15—H15B	109.5
C1—N1—H1	126.3	C1—C16—C17	107.9 (3)
C22—N1—H1	126.3	C1—C16—C15	110.4 (3)
C16—C1—N1	110.3 (2)	C17—C16—C15	140.5 (3)
C16—C1—C2	112.9 (2)	C22—C17—C18	119.1 (3)
N1—C1—C2	134.2 (3)	C22—C17—C16	105.3 (2)
C1—C2—C23	103.7 (2)	C18—C17—C16	135.6 (3)
C1—C2—C14	96.9 (2)	C19—C18—C17	116.8 (3)
C23—C2—C14	110.8 (2)	C19—C18—C28	123.4 (3)
C1—C2—C3	121.6 (2)	C17—C18—C28	119.8 (2)
C23—C2—C3	113.7 (2)	C18—C19—C20	122.6 (3)
C14—C2—C3	108.7 (2)	C18—C19—H19	118.7
C24—C3—C2	109.7 (2)	C20—C19—H19	118.7
C24—C3—C4	106.9 (2)	C21—C20—C19	121.7 (3)
C2—C3—C4	113.0 (2)	C21—C20—H20	119.2
C24—C3—C11	109.0 (2)	C19—C20—H20	119.2
C2—C3—C11	109.9 (2)	C20—C21—C22	116.5 (3)
C4—C3—C11	108.1 (2)	C20—C21—H21	121.8
C5—C4—C3	116.7 (2)	C22—C21—H21	121.8
C5—C4—H4A	108.1	N1—C22—C21	127.9 (3)
C3—C4—H4A	108.1	N1—C22—C17	109.1 (2)
C5—C4—H4B	108.1	C21—C22—C17	123.0 (3)
C3—C4—H4B	108.1	C2—C23—H23A	109.5
H4A—C4—H4B	107.3	C2—C23—H23B	109.5
C6—C5—C4	114.6 (2)	H23A—C23—H23B	109.5
C6—C5—H5A	108.6	C2—C23—H23C	109.5
C4—C5—H5A	108.6	H23A—C23—H23C	109.5
C6—C5—H5B	108.6	H23B—C23—H23C	109.5
C4—C5—H5B	108.6	C3—C24—H24A	109.5
H5A—C5—H5B	107.6	C3—C24—H24B	109.5
O1—C6—O2	103.8 (2)	H24A—C24—H24B	109.5
O1—C6—C5	110.6 (2)	C3—C24—H24C	109.5
O2—C6—C5	110.7 (2)	H24A—C24—H24C	109.5
O1—C6—C10	107.8 (2)	H24B—C24—H24C	109.5
O2—C6—C10	110.9 (2)	O2—C25—C26	109.4 (3)
C5—C6—C10	112.6 (3)	O2—C25—C27	109.2 (3)
O1—C7—C8	110.3 (3)	C26—C25—C27	111.8 (3)
O1—C7—C25	101.4 (2)	O2—C25—C7	100.7 (2)
C8—C7—C25	110.6 (3)	C26—C25—C7	115.7 (3)
O1—C7—H7	111.4	C27—C25—C7	109.5 (3)
C8—C7—H7	111.4	C25—C26—H26A	109.5
C25—C7—H7	111.4	C25—C26—H26B	109.5
O3—C8—C9	124.6 (3)	H26A—C26—H26B	109.5
O3—C8—C7	119.9 (3)	C25—C26—H26C	109.5
C9—C8—C7	115.5 (3)	H26A—C26—H26C	109.5
C10—C9—C8	119.8 (3)	H26B—C26—H26C	109.5
C10—C9—H9	120.1	C25—C27—H27A	109.5
C8—C9—H9	120.1	C25—C27—H27B	109.5
C9—C10—C11	125.4 (3)	H27A—C27—H27B	109.5
C9—C10—C6	117.1 (3)	C25—C27—H27C	109.5
C11—C10—C6	116.9 (3)	H27A—C27—H27C	109.5
O4—C11—C10	102.7 (2)	H27B—C27—H27C	109.5
O4—C11—C12	109.6 (2)	C31—C28—C18	110.9 (2)
C10—C11—C12	112.5 (2)	C31—C28—C29	106.3 (3)
O4—C11—C3	107.6 (2)	C18—C28—C29	113.1 (3)
C10—C11—C3	109.8 (2)	C31—C28—C30	111.6 (3)
C12—C11—C3	114.0 (2)	C18—C28—C30	108.3 (2)
C13—C12—C11	113.9 (2)	C29—C28—C30	106.7 (3)
C13—C12—H12A	108.8	C28—C29—H29A	109.5
C11—C12—H12A	108.8	C28—C29—H29B	109.5
C13—C12—H12B	108.8	H29A—C29—H29B	109.5
C11—C12—H12B	108.8	C28—C29—H29C	109.5
H12A—C12—H12B	107.7	H29A—C29—H29C	109.5
C14—C13—C12	107.4 (2)	H29B—C29—H29C	109.5
C14—C13—H13A	110.2	C28—C30—H30A	109.5
C12—C13—H13A	110.2	C28—C30—H30B	109.5
C14—C13—H13B	110.2	H30A—C30—H30B	109.5
C12—C13—H13B	110.2	C28—C30—H30C	109.5
H13A—C13—H13B	108.5	H30A—C30—H30C	109.5
C13—C14—C15	121.1 (3)	H30B—C30—H30C	109.5
C13—C14—C2	111.7 (2)	C32—C31—C28	125.6 (3)
C15—C14—C2	106.5 (2)	C32—C31—H31	117.2
C13—C14—H14	105.4	C28—C31—H31	117.2
C15—C14—H14	105.4	C31—C32—H32A	120.0
C2—C14—H14	105.4	C31—C32—H32B	120.0
C16—C15—C14	100.1 (2)	H32A—C32—H32B	120.0
C16—C15—H15A	111.8
C22—N1—C1—C16	0.0 (3)	C4—C3—C11—C12	171.7 (2)
C22—N1—C1—C2	−159.8 (3)	O4—C11—C12—C13	70.5 (3)
C16—C1—C2—C23	−88.8 (3)	C10—C11—C12—C13	−175.9 (2)
N1—C1—C2—C23	70.7 (4)	C3—C11—C12—C13	−50.1 (3)
C16—C1—C2—C14	24.7 (3)	C11—C12—C13—C14	55.7 (3)
N1—C1—C2—C14	−175.9 (3)	C12—C13—C14—C15	170.0 (3)
C16—C1—C2—C3	141.7 (3)	C12—C13—C14—C2	−63.3 (3)
N1—C1—C2—C3	−58.8 (4)	C1—C2—C14—C13	−169.4 (2)
C1—C2—C3—C24	−44.3 (3)	C23—C2—C14—C13	−61.8 (3)
C23—C2—C3—C24	−169.4 (2)	C3—C2—C14—C13	63.8 (3)
C14—C2—C3—C24	66.6 (3)	C1—C2—C14—C15	−35.2 (3)
C1—C2—C3—C4	74.9 (3)	C23—C2—C14—C15	72.4 (3)
C23—C2—C3—C4	−50.1 (3)	C3—C2—C14—C15	−162.0 (2)
C14—C2—C3—C4	−174.1 (2)	C13—C14—C15—C16	162.6 (3)
C1—C2—C3—C11	−164.2 (2)	C2—C14—C15—C16	33.6 (3)
C23—C2—C3—C11	70.7 (3)	N1—C1—C16—C17	0.6 (3)
C14—C2—C3—C11	−53.2 (3)	C2—C1—C16—C17	165.0 (2)
C24—C3—C4—C5	−93.2 (3)	N1—C1—C16—C15	−169.2 (2)
C2—C3—C4—C5	145.9 (3)	C2—C1—C16—C15	−4.8 (3)
C11—C3—C4—C5	24.0 (3)	C14—C15—C16—C1	−18.0 (3)
C3—C4—C5—C6	30.1 (4)	C14—C15—C16—C17	177.3 (4)
C7—O1—C6—O2	−44.4 (3)	C1—C16—C17—C22	−0.9 (3)
C7—O1—C6—C5	−163.2 (3)	C15—C16—C17—C22	164.0 (4)
C7—O1—C6—C10	73.3 (3)	C1—C16—C17—C18	177.8 (3)
C25—O2—C6—O1	22.5 (3)	C15—C16—C17—C18	−17.3 (6)
C25—O2—C6—C5	141.2 (2)	C22—C17—C18—C19	−4.7 (4)
C25—O2—C6—C10	−93.0 (3)	C16—C17—C18—C19	176.7 (3)
C4—C5—C6—O1	−168.4 (2)	C22—C17—C18—C28	173.7 (3)
C4—C5—C6—O2	77.1 (3)	C16—C17—C18—C28	−4.8 (5)
C4—C5—C6—C10	−47.7 (3)	C17—C18—C19—C20	2.3 (4)
C6—O1—C7—C8	−69.4 (3)	C28—C18—C19—C20	−176.1 (3)
C6—O1—C7—C25	47.9 (3)	C18—C19—C20—C21	2.1 (5)
O1—C7—C8—O3	−149.9 (3)	C19—C20—C21—C22	−3.8 (4)
C25—C7—C8—O3	98.7 (3)	C1—N1—C22—C21	178.2 (3)
O1—C7—C8—C9	31.6 (4)	C1—N1—C22—C17	−0.6 (3)
C25—C7—C8—C9	−79.8 (3)	C20—C21—C22—N1	−177.4 (3)
O3—C8—C9—C10	−174.8 (3)	C20—C21—C22—C17	1.2 (4)
C7—C8—C9—C10	3.5 (4)	C18—C17—C22—N1	−178.0 (3)
C8—C9—C10—C11	−170.2 (3)	C16—C17—C22—N1	0.9 (3)
C8—C9—C10—C6	1.0 (4)	C18—C17—C22—C21	3.1 (4)
O1—C6—C10—C9	−40.5 (4)	C16—C17—C22—C21	−178.0 (3)
O2—C6—C10—C9	72.5 (3)	C6—O2—C25—C26	128.7 (3)
C5—C6—C10—C9	−162.8 (3)	C6—O2—C25—C27	−108.7 (3)
O1—C6—C10—C11	131.5 (3)	C6—O2—C25—C7	6.5 (3)
O2—C6—C10—C11	−115.5 (3)	O1—C7—C25—O2	−33.0 (3)
C5—C6—C10—C11	9.2 (4)	C8—C7—C25—O2	84.1 (3)
C9—C10—C11—O4	102.7 (3)	O1—C7—C25—C26	−150.7 (3)
C6—C10—C11—O4	−68.5 (3)	C8—C7—C25—C26	−33.7 (4)
C9—C10—C11—C12	−15.1 (4)	O1—C7—C25—C27	81.9 (3)
C6—C10—C11—C12	173.7 (2)	C8—C7—C25—C27	−161.0 (3)
C9—C10—C11—C3	−143.1 (3)	C19—C18—C28—C31	−118.9 (3)
C6—C10—C11—C3	45.7 (3)	C17—C18—C28—C31	62.7 (3)
C24—C3—C11—O4	165.8 (2)	C19—C18—C28—C29	0.4 (4)
C2—C3—C11—O4	−73.9 (3)	C17—C18—C28—C29	−178.0 (3)
C4—C3—C11—O4	49.9 (3)	C19—C18—C28—C30	118.4 (3)
C24—C3—C11—C10	54.8 (3)	C17—C18—C28—C30	−60.0 (3)
C2—C3—C11—C10	175.1 (2)	C18—C28—C31—C32	29.3 (4)
C4—C3—C11—C10	−61.1 (3)	C29—C28—C31—C32	−94.0 (4)
C24—C3—C11—C12	−72.4 (3)	C30—C28—C31—C32	150.1 (3)
C2—C3—C11—C12	47.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3i	0.82	2.03	2.757 (3)	148
N1—H1···Cgii	0.86	2.78	3.527 (1)	146

Table 1

Hydrogen-bond geometry (, )

Cg is the centroid of the C17C22 ring.

DHA	DH	HA	D A	DHA
O4H4O3i	0.82	2.03	2.757(3)	148
N1H1Cg ii	0.86	2.78	3.527(1)	146

Symmetry codes: (i) ; (ii) .