Redetermined structure of gossypol (P3 polymorph)

Honkeldieva, M.; Kunafiev, R.; Hamidov, H.I.

doi:10.1107/S205698901500941X

organic compounds

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ISSN: 2056-9890

Volume 71| Part 7| July 2015| Pages o442-o443

doi:10.1107/S205698901500941X

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Redetermined structure of gossypol (P3 polymorph)

Muhabbat Honkeldieva,^a ^* Rishad Kunafiev ^a and Hayrullo I. Hamidov ^a

^aInstitute of Biorganic Chemistry, Mirzo-Ulughbek Str. 83, Tashkent 100125, Uzbekistan
^*Correspondence e-mail: muhabbat.n75@mail.ru

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 20 April 2015; accepted 18 May 2015; online 3 June 2015)

An improved crystal structure of the title compound, C₃₀H₃₀O₈ (systematic name: 1,1′,6,6′,7,7′-hexahydroxy-5,5′-diisopropyl-3,3′-dimethyl[2,2′-binaphthalene]-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 molecules are in the aldehyde tautomeric form and the dihedral angle between the naphthyl fragments is 80.42 (4)°. Four intramolecular O—H⋯O hydrogen bonds are formed. In the crystal, inversion dimers with graph-set motif R₂²(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 molecules; their contribution to the scattering was removed with the SQUEEZE [Spek (2015). Acta Cryst. C71, 9–18] routine in PLATON and the stated molecular mass, density etc., do not take them into account.

Keywords: crystal structure; redetermination; gossypol; polymorph; hydrogen bonding.

CCDC reference: 1401388

1. 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 ).

2. Experimental

2.1. Crystal data

C₃₀H₃₀O₈
M_r = 518.54
Monoclinic, C 2/c
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

2.2. Data collection

Oxford Diffraction Xcalibur Ruby diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.730, T_max = 1.000
13408 measured reflections
5810 independent reflections
4382 reflections with I > 2σ(I)
R_int = 0.021

2.3. Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.161
S = 1.11
5810 reflections
374 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O4^iv	0.93	2.31	3.138 (2)	148
C27—H27⋯O5	0.93	2.07	2.727 (2)	127
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z+1; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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.

Supporting information

CCDC reference: 1401388

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

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

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

checkCIF report

Experimental top

Synthesis and crystallization top

Preparative details of the material

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Comment

Gossypol, a phenolic pigment extracted from cotton seeds [Adams et al., 1960], demonstrates a wide range of biological activity [Baram et al., 1993; Polsky et al., 1989: Radloff et al.,1985] and versatile host properties [Ibragimov, Talipov. 1999; 2004; Gdaniec et al., 1996]. Unique ability as a host compound to form crystalline inclusion compounds with many organic solvents makes gossypol an interesting object of solid supramolecular chemistry. Gossypol has also been found to form pseudopolymorphic structures with same guest molecule, e.g., clathrates formed with dichloromethane [Ibragimov et al., 1997] and diethyl ether [Talipov et al., 1988]. Unsolvated polymorphs of the compound are also known [Gdaniec et al., 1996]. In the crystal of the title compound, gossypol (1,1',6,6',7,7'-hexahydroxy -5,5'diisopropyl - 3,3'dimethyl[2,2' - binaphthalene] - 8,8'- dicarboxaldehyde), C₃₀H₃₀O₈, is one independent molecule in the asymmetric part of the unit cell. The crystals of the title compound were obtained after decomposition of gossypol clathrate with dichloromethane, where the single crystals are not destroyed and their cell volumes are only reduced by ~4%. In the title compound gossypol molecules are in the aldehyde tautomeric form (Fig. 1). H-bonds O4—H···O3 (O8—H···O7) and O3—H···O2 (O7—H···O6) form five- and six-membered rings. Naphthyl fragments C(1)—C(10) (C7 0.07A) and C(11)—C(20) (C12 0.04 A) are planar and dihedral angle between their planes are equal to 80.42 (4)°. One of the most commonly found associations is a centrosymmetric dimer that is linked by two pairs O5–H···O3 and O4–H···O5 hydrogen bonds and hydrophobic stacking interactions between two of the naphthalene rings [Gdaniec et al., 1996]. In the title crystal centrosymmetric dimers are formed as above, these assemble into extended serpentine chains by other pair of hydrogen bonds O1—H···O6 directed along the c axis through a twofold rotation axis with direction [0 1 0]. The packing of such chains in the crystal leads to the formation of broadly rough channels (Fig. 2) (where diameter varied 5-7 A), parallel to the ac diagonal.

Related literature top

For the previous structure determination of gossypol P3 polymorph, see: Talipov et al., (1985). For details of 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).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of title compound, with displacement ellipsoids shown at the 50% probability level.
	Fig. 2. A packing diagram for title compound.

1,1',6,6',7,7'-Hexahydroxy-5,5'-diisopropyl-3,3'-dimethyl[2,2'-binaphthalene]-8,8'-dicarbaldehyde top

Crystal data top

C₃₀H₃₀O₈	D_x = 1.213 Mg m⁻³
M_r = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0994P)² + 0.2158P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.161	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.44 e Å⁻³
5810 reflections	Δρ_min = −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

Crystal data top

C₃₀H₃₀O₈	V = 5677.29 (16) Å³
M_r = 518.54	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 21.2196 (4) Å	µ = 0.73 mm⁻¹
b = 19.0886 (2) Å	T = 293 K
c = 15.2564 (2) Å	0.30 × 0.30 × 0.30 mm
β = 113.262 (2)°

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	5810 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	4382 reflections with I > 2σ(I)
T_min = 0.730, T_max = 1.000	R_int = 0.021
13408 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.44 e Å⁻³
5810 reflections	Δρ_min = −0.30 e Å⁻³
374 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O4^iv	0.93	2.31	3.138 (2)	148
C27—H27···O5	0.93	2.07	2.727 (2)	127

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

Hydrogen-bond geometry (Å, º) top

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···O4^iv	0.93	2.31	3.138 (2)	148
C27—H27···O5	0.93	2.07	2.727 (2)	127

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

Acknowledgements

We thank the Academy of Sciencesof the Republic of Uzbekistan for supporting this study (F7-T048).

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Volume 71| Part 7| July 2015| Pages o442-o443

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