Redetermined structure of gossypol (P3 polymorph).

An improved crystal structure of the title compound, C30H30O8 (systematic name: 1,1',6,6',7,7'-hexa-hydroxy-5,5'-diisopropyl-3,3'-dimeth-yl[2,2'-bi-naphthalene]-8,8'-dicarbaldehyde), was determined based on modern CCD data. Compared to the previous structure [Talipov et al. (1985). Khim. Prirod. Soedin. (Chem. Nat. Prod.), 6, 20-24], geometrical precision has been improved (typical C-C bond-distance s.u. = 0.002 Å in the present structure compared to 0.005 Å in the previous structure) and the locations of several H atoms have been corrected. The gossypol mol-ecules are in the aldehyde tautomeric form and the dihedral angle between the naphthyl fragments is 80.42 (4)°. Four intra-molecular O-H⋯O hydrogen bonds are formed. In the crystal, inversion dimers with graph-set motif R 2 (2)(20) are formed by pairs of O-H⋯O hydrogen bonds; another pair of O-H⋯O hydrogen bonds with the same graph-set motif links the dimers into [001] chains. The packing of such chains in the crystal leads to the formation of channels (diameter = 5-8 Å) propagating in the [101] direction. The channels presumably contain highly disordered solvent mol-ecules; their contribution to the scattering was removed with the SQUEEZE [Spek (2015). Acta Cryst. C71, 9-18] routine in PLATON and the stated mol-ecular mass, density etc., do not take them into account.

Related literature

For the previous structure determination of gossypol P3 polymorph, see: Talipov et al., (1985 ▸). For details of the extraction and synthesis of gossypol and its derivatives, see: Adams et al. (1960 ▸). For its synthesis and biological activities, see: Baram & Ismailov (1993 ▸); Polsky et al. (1989 ▸); Radloff et al. (1985 ▸). For information on crystalline inclusion compounds, see: Ibragimov & Talipov (1999 ▸, 2004 ▸); Ibragimov et al. (1997 ▸); Gdaniec et al. (1996 ▸); Talipov et al. (1988 ▸). For the use of SQUEEZE, see: Spek (2015 ▸).

Experimental

Crystal data

C30H30O8

M = 518.54

Monoclinic,

a = 21.2196 (4) Å

b = 19.0886 (2) Å

c = 15.2564 (2) Å

β = 113.262 (2)°

V = 5677.29 (16) Å3

Z = 8

Cu Kα radiation

μ = 0.73 mm−1

T = 293 K

0.30 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▸) T min = 0.730, T max = 1.000

13408 measured reflections

5810 independent reflections

4382 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.161

S = 1.11

5810 reflections

374 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S205698901500941X/hb7412sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500941X/hb7412Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901500941X/hb7412Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901500941X/hb7412fig1.tif

The mol­ecular structure of title compound, with displacement ellipsoids shown at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S205698901500941X/hb7412fig2.tif

A packing diagram for title compound.

CCDC reference: 1401388

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

C30H30O8	Dx = 1.213 Mg m−3
Mr = 518.54	Melting point: 455 K
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 21.2196 (4) Å	Cell parameters from 6170 reflections
b = 19.0886 (2) Å	θ = 3.9–75.6°
c = 15.2564 (2) Å	µ = 0.73 mm−1
β = 113.262 (2)°	T = 293 K
V = 5677.29 (16) Å3	Prism, light brown
Z = 8	0.30 × 0.30 × 0.30 mm
F(000) = 2192

Oxford Diffraction Xcalibur Ruby diffractometer	5810 independent reflections
Radiation source: fine-focus sealed tube	4382 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 10.2576 pixels mm-1	θmax = 75.8°, θmin = 3.9°
ω scans	h = −26→25
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −23→20
Tmin = 0.730, Tmax = 1.000	l = −17→19
13408 measured reflections

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.047	w = 1/[σ2(Fo2) + (0.0994P)2 + 0.2158P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.161	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.44 e Å−3
5810 reflections	Δρmin = −0.30 e Å−3
374 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.00026 (5)
Primary atom site location: structure-invariant direct methods

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.40 (release 27-04-2009 CrysAlis171 .NET) (compiled Apr 27 2009,10:20:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
C1	0.04702 (8)	0.15341 (8)	0.55658 (11)	0.0429 (3)
C2	0.10359 (8)	0.18397 (8)	0.54801 (11)	0.0447 (3)
C3	0.16553 (8)	0.14655 (9)	0.57686 (13)	0.0547 (4)
C4	0.16876 (9)	0.08045 (9)	0.61308 (14)	0.0564 (4)
H4	0.2100	0.0562	0.6322	0.068*
C5	0.11810 (9)	−0.02370 (8)	0.65817 (12)	0.0518 (4)
C6	0.06006 (9)	−0.05514 (8)	0.65630 (12)	0.0512 (4)
C7	−0.00297 (9)	−0.01904 (8)	0.62878 (11)	0.0480 (4)
C8	−0.00888 (8)	0.05136 (8)	0.60352 (11)	0.0465 (3)
C9	0.04970 (8)	0.08525 (8)	0.59537 (11)	0.0433 (3)
C10	0.11255 (8)	0.04756 (8)	0.62278 (12)	0.0472 (4)
C11	0.09182 (8)	0.26474 (7)	0.41457 (11)	0.0428 (3)
C12	0.09891 (8)	0.25641 (7)	0.50805 (11)	0.0427 (3)
C13	0.10483 (9)	0.31582 (8)	0.56537 (11)	0.0477 (4)
C14	0.10549 (9)	0.38096 (8)	0.52707 (11)	0.0466 (4)
H14	0.1090	0.4202	0.5649	0.056*
C15	0.10583 (9)	0.46057 (7)	0.39810 (11)	0.0479 (4)
C16	0.10033 (11)	0.46668 (8)	0.30665 (13)	0.0605 (5)
C17	0.08923 (10)	0.40867 (9)	0.24522 (12)	0.0559 (4)
C18	0.08645 (8)	0.34087 (7)	0.27596 (11)	0.0434 (3)
C19	0.09259 (7)	0.33132 (7)	0.37324 (10)	0.0393 (3)
C20	0.10103 (7)	0.39099 (7)	0.43325 (10)	0.0407 (3)
C21	0.22811 (10)	0.17856 (12)	0.5684 (2)	0.0817 (7)
H21A	0.2176	0.1905	0.5030	0.123*
H21B	0.2652	0.1455	0.5899	0.123*
H21C	0.2413	0.2201	0.6070	0.123*
C22	−0.07150 (10)	0.08521 (11)	0.59498 (18)	0.0725 (6)
H22	−0.0747	0.1336	0.5872	0.087*
C23	0.18663 (11)	−0.06196 (10)	0.69912 (17)	0.0703 (6)
H23	0.2214	−0.0300	0.6947	0.084*
C24	0.18936 (15)	−0.12839 (16)	0.6460 (2)	0.1056 (9)
H24A	0.1578	−0.1621	0.6520	0.158*
H24B	0.2350	−0.1473	0.6725	0.158*
H24C	0.1771	−0.1178	0.5798	0.158*
C25	0.20640 (17)	−0.0777 (2)	0.8058 (2)	0.1318 (14)
H25A	0.2067	−0.0348	0.8390	0.198*
H25B	0.2512	−0.0986	0.8320	0.198*
H25C	0.1736	−0.1094	0.8128	0.198*
C26	0.11096 (13)	0.30777 (10)	0.66665 (13)	0.0706 (6)
H26A	0.0693	0.2881	0.6666	0.106*
H26B	0.1188	0.3528	0.6971	0.106*
H26C	0.1487	0.2772	0.7007	0.106*
C27	0.07713 (11)	0.28657 (9)	0.20641 (13)	0.0591 (4)
H27	0.0776	0.2404	0.2260	0.071*
C28	0.11809 (12)	0.52550 (8)	0.46049 (13)	0.0629 (5)
H28	0.1217	0.5097	0.5234	0.075*
C29	0.05884 (17)	0.57648 (13)	0.4239 (2)	0.1027 (9)
H29A	0.0533	0.5928	0.3618	0.154*
H29B	0.0680	0.6156	0.4668	0.154*
H29C	0.0176	0.5534	0.4199	0.154*
C30	0.18621 (17)	0.56118 (16)	0.4751 (2)	0.1138 (11)
H30A	0.2213	0.5263	0.4878	0.171*
H30B	0.1987	0.5929	0.5281	0.171*
H30C	0.1813	0.5867	0.4185	0.171*
O1	−0.01395 (6)	0.18820 (6)	0.52761 (9)	0.0547 (3)
O2	−0.12161 (8)	0.05299 (9)	0.59743 (15)	0.0931 (6)
O3	−0.05495 (7)	−0.05604 (7)	0.63411 (10)	0.0615 (3)
O4	0.06055 (9)	−0.12336 (6)	0.68412 (11)	0.0692 (4)
O5	0.08350 (7)	0.20689 (6)	0.35806 (9)	0.0590 (3)
O6	0.06858 (8)	0.29704 (7)	0.12265 (9)	0.0644 (4)
O7	0.08315 (11)	0.42438 (8)	0.15667 (10)	0.0847 (5)
O8	0.10566 (13)	0.53046 (7)	0.26920 (13)	0.1047 (8)
H1	−0.0135 (11)	0.2226 (13)	0.4879 (17)	0.077 (7)*
H3	−0.0864 (15)	−0.0220 (15)	0.6236 (19)	0.095 (9)*
H5	0.0875 (12)	0.1717 (13)	0.3922 (16)	0.075 (7)*
H7	0.0769 (15)	0.3820 (18)	0.126 (2)	0.111 (10)*
H4A	0.0132 (19)	−0.1253 (18)	0.680 (3)	0.147 (13)*
H8	0.094 (2)	0.523 (2)	0.209 (3)	0.150 (14)*

	U11	U22	U33	U12	U13	U23
C1	0.0461 (8)	0.0365 (7)	0.0473 (7)	0.0015 (6)	0.0197 (6)	0.0053 (6)
C2	0.0508 (8)	0.0338 (7)	0.0500 (8)	−0.0038 (6)	0.0206 (7)	0.0057 (6)
C3	0.0477 (9)	0.0472 (8)	0.0699 (10)	−0.0027 (7)	0.0240 (8)	0.0120 (8)
C4	0.0468 (9)	0.0466 (9)	0.0758 (11)	0.0064 (7)	0.0242 (8)	0.0159 (8)
C5	0.0574 (9)	0.0379 (8)	0.0594 (9)	0.0047 (7)	0.0224 (8)	0.0097 (7)
C6	0.0695 (10)	0.0341 (7)	0.0532 (9)	−0.0007 (7)	0.0275 (8)	0.0091 (6)
C7	0.0574 (9)	0.0423 (8)	0.0479 (8)	−0.0098 (7)	0.0246 (7)	0.0035 (6)
C8	0.0485 (8)	0.0411 (7)	0.0512 (8)	−0.0023 (6)	0.0213 (7)	0.0078 (6)
C9	0.0474 (8)	0.0357 (7)	0.0476 (7)	−0.0029 (6)	0.0198 (6)	0.0047 (6)
C10	0.0502 (8)	0.0361 (7)	0.0543 (8)	0.0005 (6)	0.0197 (7)	0.0085 (6)
C11	0.0479 (8)	0.0323 (7)	0.0509 (8)	−0.0046 (6)	0.0224 (6)	−0.0012 (6)
C12	0.0448 (8)	0.0337 (7)	0.0506 (8)	−0.0049 (6)	0.0199 (6)	0.0045 (6)
C13	0.0583 (9)	0.0410 (8)	0.0445 (8)	−0.0044 (7)	0.0209 (7)	0.0028 (6)
C14	0.0616 (9)	0.0335 (7)	0.0466 (8)	−0.0037 (6)	0.0233 (7)	−0.0017 (6)
C15	0.0642 (10)	0.0327 (7)	0.0498 (8)	−0.0031 (6)	0.0256 (7)	0.0002 (6)
C16	0.0982 (14)	0.0334 (7)	0.0564 (9)	−0.0045 (8)	0.0377 (10)	0.0046 (7)
C17	0.0837 (12)	0.0442 (8)	0.0472 (8)	−0.0039 (8)	0.0336 (8)	0.0027 (7)
C18	0.0487 (8)	0.0366 (7)	0.0474 (8)	−0.0038 (6)	0.0217 (6)	−0.0010 (6)
C19	0.0396 (7)	0.0347 (7)	0.0449 (7)	−0.0022 (5)	0.0179 (6)	0.0016 (6)
C20	0.0445 (7)	0.0328 (6)	0.0453 (7)	−0.0029 (5)	0.0184 (6)	0.0018 (6)
C21	0.0505 (10)	0.0701 (13)	0.1269 (19)	−0.0021 (9)	0.0375 (11)	0.0316 (13)
C22	0.0609 (11)	0.0571 (10)	0.1109 (17)	0.0042 (9)	0.0459 (11)	0.0266 (11)
C23	0.0620 (11)	0.0503 (10)	0.0965 (15)	0.0120 (8)	0.0291 (10)	0.0236 (10)
C24	0.0982 (19)	0.0973 (19)	0.123 (2)	0.0388 (16)	0.0454 (17)	0.0012 (17)
C25	0.097 (2)	0.178 (3)	0.0897 (19)	0.064 (2)	0.0040 (15)	0.005 (2)
C26	0.1167 (17)	0.0480 (9)	0.0512 (9)	−0.0095 (10)	0.0375 (10)	0.0026 (8)
C27	0.0861 (13)	0.0436 (8)	0.0529 (9)	−0.0074 (8)	0.0332 (9)	−0.0031 (7)
C28	0.1036 (15)	0.0339 (7)	0.0555 (9)	−0.0079 (8)	0.0361 (10)	−0.0011 (7)
C29	0.146 (3)	0.0668 (14)	0.0910 (17)	0.0310 (15)	0.0415 (17)	−0.0126 (12)
C30	0.132 (3)	0.0823 (17)	0.120 (2)	−0.0452 (17)	0.0423 (19)	−0.0307 (16)
O1	0.0512 (6)	0.0445 (6)	0.0724 (8)	0.0076 (5)	0.0288 (6)	0.0194 (5)
O2	0.0632 (9)	0.0838 (11)	0.1484 (16)	0.0039 (7)	0.0589 (10)	0.0385 (10)
O3	0.0680 (8)	0.0479 (7)	0.0764 (8)	−0.0133 (6)	0.0369 (7)	0.0076 (6)
O4	0.0928 (10)	0.0367 (6)	0.0868 (10)	0.0017 (6)	0.0449 (8)	0.0167 (6)
O5	0.0923 (9)	0.0322 (5)	0.0590 (7)	−0.0084 (6)	0.0367 (6)	−0.0027 (5)
O6	0.0897 (9)	0.0578 (7)	0.0516 (7)	−0.0050 (6)	0.0343 (6)	−0.0086 (5)
O7	0.1637 (17)	0.0497 (7)	0.0551 (8)	−0.0093 (9)	0.0587 (9)	0.0028 (6)
O8	0.222 (2)	0.0387 (7)	0.0723 (10)	−0.0190 (10)	0.0786 (13)	0.0043 (6)

C1—C2	1.387 (2)	C19—C20	1.428 (2)
C1—C9	1.421 (2)	C21—H21A	0.9600
C1—O1	1.3633 (18)	C21—H21B	0.9600
C2—C3	1.405 (2)	C21—H21C	0.9600
C2—C12	1.4985 (19)	C22—H22	0.9300
C3—C4	1.368 (2)	C22—O2	1.242 (2)
C3—C21	1.513 (2)	C23—H23	0.9800
C4—H4	0.9300	C23—C24	1.519 (4)
C4—C10	1.406 (2)	C23—C25	1.541 (4)
C5—C6	1.360 (2)	C24—H24A	0.9600
C5—C10	1.451 (2)	C24—H24B	0.9600
C5—C23	1.523 (2)	C24—H24C	0.9600
C6—C7	1.413 (2)	C25—H25A	0.9600
C6—O4	1.3685 (18)	C25—H25B	0.9600
C7—C8	1.390 (2)	C25—H25C	0.9600
C7—O3	1.3392 (19)	C26—H26A	0.9600
C8—C9	1.450 (2)	C26—H26B	0.9600
C8—C22	1.436 (2)	C26—H26C	0.9600
C9—C10	1.425 (2)	C27—H27	0.9300
C11—C12	1.383 (2)	C27—O6	1.234 (2)
C11—C19	1.4218 (19)	C28—H28	0.9800
C11—O5	1.3688 (18)	C28—C29	1.512 (3)
C12—C13	1.407 (2)	C28—C30	1.533 (4)
C13—C14	1.376 (2)	C29—H29A	0.9600
C13—C26	1.507 (2)	C29—H29B	0.9600
C14—H14	0.9300	C29—H29C	0.9600
C14—C20	1.410 (2)	C30—H30A	0.9600
C15—C16	1.358 (2)	C30—H30B	0.9600
C15—C20	1.4509 (19)	C30—H30C	0.9600
C15—C28	1.521 (2)	O1—H1	0.90 (2)
C16—C17	1.409 (2)	O3—H3	0.90 (3)
C16—O8	1.368 (2)	O4—H4A	0.98 (4)
C17—C18	1.386 (2)	O5—H5	0.83 (2)
C17—O7	1.339 (2)	O7—H7	0.92 (3)
C18—C19	1.449 (2)	O8—H8	0.87 (4)
C18—C27	1.440 (2)
C2—C1—C9	122.05 (14)	C3—C21—H21A	109.5
O1—C1—C2	120.70 (13)	C3—C21—H21B	109.5
O1—C1—C9	117.25 (13)	C3—C21—H21C	109.5
C1—C2—C3	119.61 (14)	H21A—C21—H21B	109.5
C1—C2—C12	120.39 (14)	H21A—C21—H21C	109.5
C3—C2—C12	120.00 (13)	H21B—C21—H21C	109.5
C2—C3—C21	120.78 (15)	C8—C22—H22	118.4
C4—C3—C2	119.13 (15)	O2—C22—C8	123.15 (18)
C4—C3—C21	120.08 (16)	O2—C22—H22	118.4
C3—C4—H4	118.5	C5—C23—H23	107.2
C3—C4—C10	123.02 (15)	C5—C23—C25	110.12 (19)
C10—C4—H4	118.5	C24—C23—C5	114.39 (19)
C6—C5—C10	117.78 (15)	C24—C23—H23	107.2
C6—C5—C23	120.46 (15)	C24—C23—C25	110.5 (2)
C10—C5—C23	121.73 (16)	C25—C23—H23	107.2
C5—C6—C7	122.28 (14)	C23—C24—H24A	109.5
C5—C6—O4	121.16 (16)	C23—C24—H24B	109.5
O4—C6—C7	116.53 (15)	C23—C24—H24C	109.5
C8—C7—C6	121.68 (14)	H24A—C24—H24B	109.5
O3—C7—C6	115.50 (14)	H24A—C24—H24C	109.5
O3—C7—C8	122.71 (16)	H24B—C24—H24C	109.5
C7—C8—C9	117.94 (14)	C23—C25—H25A	109.5
C7—C8—C22	116.05 (14)	C23—C25—H25B	109.5
C22—C8—C9	125.83 (14)	C23—C25—H25C	109.5
C1—C9—C8	123.34 (14)	H25A—C25—H25B	109.5
C1—C9—C10	117.61 (13)	H25A—C25—H25C	109.5
C10—C9—C8	118.97 (13)	H25B—C25—H25C	109.5
C4—C10—C5	120.68 (15)	C13—C26—H26A	109.5
C4—C10—C9	118.55 (13)	C13—C26—H26B	109.5
C9—C10—C5	120.76 (14)	C13—C26—H26C	109.5
C12—C11—C19	122.99 (13)	H26A—C26—H26B	109.5
O5—C11—C12	119.42 (13)	H26A—C26—H26C	109.5
O5—C11—C19	117.59 (13)	H26B—C26—H26C	109.5
C11—C12—C2	119.23 (13)	C18—C27—H27	117.7
C11—C12—C13	119.66 (13)	O6—C27—C18	124.58 (16)
C13—C12—C2	121.04 (14)	O6—C27—H27	117.7
C12—C13—C26	120.37 (14)	C15—C28—H28	106.9
C14—C13—C12	118.54 (14)	C15—C28—C30	111.80 (19)
C14—C13—C26	121.09 (15)	C29—C28—C15	112.44 (18)
C13—C14—H14	118.5	C29—C28—H28	106.9
C13—C14—C20	123.09 (14)	C29—C28—C30	111.5 (2)
C20—C14—H14	118.5	C30—C28—H28	106.9
C16—C15—C20	117.91 (14)	C28—C29—H29A	109.5
C16—C15—C28	119.79 (14)	C28—C29—H29B	109.5
C20—C15—C28	122.29 (14)	C28—C29—H29C	109.5
C15—C16—C17	122.66 (14)	H29A—C29—H29B	109.5
C15—C16—O8	121.16 (15)	H29A—C29—H29C	109.5
O8—C16—C17	116.18 (15)	H29B—C29—H29C	109.5
C18—C17—C16	121.81 (14)	C28—C30—H30A	109.5
O7—C17—C16	114.77 (15)	C28—C30—H30B	109.5
O7—C17—C18	123.41 (15)	C28—C30—H30C	109.5
C17—C18—C19	117.74 (13)	H30A—C30—H30B	109.5
C17—C18—C27	115.76 (14)	H30A—C30—H30C	109.5
C27—C18—C19	126.49 (14)	H30B—C30—H30C	109.5
C11—C19—C18	123.67 (13)	C1—O1—H1	108.3 (15)
C11—C19—C20	116.70 (13)	C7—O3—H3	100.3 (18)
C20—C19—C18	119.62 (12)	C6—O4—H4A	98 (2)
C14—C20—C15	120.88 (13)	C11—O5—H5	107.5 (16)
C14—C20—C19	118.94 (12)	C17—O7—H7	104.4 (19)
C19—C20—C15	120.17 (13)	C16—O8—H8	105 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O6i	0.90 (2)	2.16 (2)	2.9692 (17)	150 (2)
O3—H3···O2	0.90 (3)	1.59 (3)	2.454 (2)	160 (3)
O5—H5···O3ii	0.83 (2)	2.30 (2)	2.9546 (17)	136 (2)
O4—H4A···O3	0.98 (4)	1.88 (4)	2.601 (2)	128 (3)
O4—H4A···O5ii	0.98 (4)	2.46 (4)	3.278 (2)	141 (3)
O7—H7···O6	0.92 (3)	1.63 (3)	2.479 (2)	152 (3)
O8—H8···O7	0.87 (4)	2.02 (4)	2.575 (2)	120 (3)
C22—H22···O1	0.93	2.12	2.721 (2)	121
C26—H26B···O8iii	0.96	2.55	3.483 (2)	165
C27—H27···O4iv	0.93	2.31	3.138 (2)	148
C27—H27···O5	0.93	2.07	2.727 (2)	127

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1O6i	0.90(2)	2.16(2)	2.9692(17)	150(2)
O3H3O2	0.90(3)	1.59(3)	2.454(2)	160(3)
O5H5O3ii	0.83(2)	2.30(2)	2.9546(17)	136(2)
O4H4AO3	0.98(4)	1.88(4)	2.601(2)	128(3)
O4H4AO5ii	0.98(4)	2.46(4)	3.278(2)	141(3)
O7H7O6	0.92(3)	1.63(3)	2.479(2)	152(3)
O8H8O7	0.87(4)	2.02(4)	2.575(2)	120(3)
C22H22O1	0.93	2.12	2.721(2)	121
C26H26BO8iii	0.96	2.55	3.483(2)	165
C27H27O4iv	0.93	2.31	3.138(2)	148
C27H27O5	0.93	2.07	2.727(2)	127

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .