(4R)-3-Hy­droxy-7-isopropyl-4-methyl-5,6-di­hydro­benzo­furan-2(4H)-one

Heinemann, F.W.; Herrera, A.; Agrifoglio, G.; Dorta, R.; Pastrán, J.

doi:10.1107/S1600536814014524

organic compounds

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ISSN: 2056-9890

Volume 70| Part 7| July 2014| Page o824

https://doi.org/10.1107/S1600536814014524

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(4R)-3-Hydroxy-7-isopropyl-4-methyl-5,6-dihydrobenzofuran-2(4H)-one

Frank W. Heinemann,^a Alberto Herrera,^a Giuseppe Agrifoglio,^b Romano Dorta ^a and Jesús Pastrán ^b ^*

^aInstitut für Anorganische Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Germany, and ^bDepartamento de Química, Universidad Simón Bolívar, Apartado 89000, Caracas 1020-A, Venezuela
^*Correspondence e-mail: frank.heinemann@fau.de, jpastran@usb.ve

(Received 25 April 2014; accepted 19 June 2014; online 25 June 2014)

In the title compound, alternatively called α-hydroxy-γ-alkylidenebutenolide, C₁₂H₁₆O₃, two independent molecules (A and B) crystallize in the asymmetric unit in each of which the 5,6-dihydrobenzo ring has an envelope conformation. The torsion angle along the butadiene chain in the γ-alkylidenebutenolide core is −177.9 (2)° for molecule A and 179.9 (2)° for molecule B. In the crystal, O—H⋯O hydrogen bonds between hydroxyl and carbonyl groups of adjacent independent molecules form dimers with R²₂(10) loops.

Keywords: crystal structure.

CCDC reference: 1009320

Related literature

For background to butenolides and their pharmacological activity, see: Rao (1964 ); Ma et al. (1999 ). For the synthesis of γ-alkylidenebutenolides, see: Park et al. (2012 ); Almeida et al. (2010 ); Xu et al. (2007 ); Langer et al. (2000 , 2001 ). For related structures, see: Schneider & Viljoen (1997 ); Langer & Saleh (2000 ). For standard bond lengths, see: Allen et al. (1987 ) and for puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₂H₁₆O₃
M_r = 208.25
Monoclinic, P 2₁
a = 9.0437 (3) Å
b = 13.2792 (6) Å
c = 9.8199 (5) Å
β = 104.694 (3)°
V = 1140.73 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.55 × 0.20 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.682, T_max = 0.746
37926 measured reflections
2821 independent reflections
2564 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.103
S = 1.09
2821 reflections
283 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5ⁱ	0.87 (3)	1.81 (3)	2.627 (2)	157 (3)
O6—H6⋯O2ⁱⁱ	0.84 (3)	1.93 (3)	2.727 (2)	156 (3)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+2]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+2]$ .

Data collection: COLLECT (Bruker–Nonius, 2002 ); cell refinement: EVALCCD (Duisenberg et al., 2003 ); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1009320

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014524/jj2187sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014524/jj2187Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814014524/jj2187Isup3.cml

checkCIF report

Introduction top

Butenolides are an important class of organic compounds present in natural products that have been studied for over 50 years (Rao, 1964). Most of them exhibit interesting pharmacological activities, such as antibacterial, anticancer, antibiotic and phospholipase A2 inhibition activity (Ma et al, 1999). During the last decades γ-alkylidenebutenolides have been considered as attractive synthetic targets due to their structural diversity and biological properties. As a result, several synthetic procedures have been developed for the preparation of these substances (Langer, et al., 2000; Langer, et al., 2001; Xu, et al., 2007; Almeida, et al., 2010; Park, et al., 2012). Also, α-Hydroxy-γ-alkylidenebutenolides are particularly suitable building blocks for analogues of pharmacologically relevant natural products (Langer & Saleh, 2000). Herein, we report the crystal structure of a bicyclic α-hydroxy-γ-alkylidenebutenolide based on l-Menthone, an inexpensive and accessible reagent from the chiral pool, which is also an important structural motif found in natural products. To the best of our knowledge, there is only one report on the preparation of a similar γ-alkylidenebutenolide, but no structural data were presented (Schneider & Viljoen, 1997).

Experimental top

Synthesis and crystallization top

Sodium hydride (60% dispersion in mineral oil, 2.44 g, 0.061 mmol) was stirred for 15 minutes in 200 mL of freshly distilled THF. Then a mixture of l-Menthone (7.71 g, 0.050 mmol) and di-ethyl oxalate (3.36 g, 0.023 mmol) in 100 mL of THF was added drop by drop. The resulting mixture was heated to reflux for 2 days. After this time, the solvent was removed by rotary evaporation. The crude reaction product was added to an ice-hydrochloric acid (1M) mixture and extracted with chloroform (3 x 50 mL). The organic layer was dried with MgSO₄, filtered and the solvent was removed under vacuum to afford orange oil, which was purified by Kugelrohr distillation (413 °K, 5 x 10^-2 mbar, bulbs cooled with dry ice), to obtain the desired product as a yellow oil that solidifies (1.95 g, 41%). Suitable crystals for X-ray diffraction analysis were obtained by slow diffusion of hexane into a saturated solution of the compound in dichloromethane cooled at 263 °K for 3 days. Elemental analysis calculated for C₁₂H₁₆O₃×1/3H₂O: C, 67.27 %, H 7.84 %. Found: C, 67.38 %, H 7.70 %.

Refinement top

The positions of the two oxygen bound hydrogen atoms H3 and H6 were taken from a difference fourier synthesis and their positional parameters were refined. All other H atoms were included in calculated positions (C–H = 0.93 Å for aromatic H, C–H = 0.96 Å for methyl H, C–H = 0.98 Å for methylene H, and C–H = 1.00 Å for tertiary H), and refined using a riding model with U_iso(H) = 1.2 Ueq or U_iso (H) = 1.5 Ueq (for methyl groups) of the carrier atom.

Results and discussion top

In the title compound,C₁₂H₁₆O₃, two independent molecules (A and B) crystallize in the asymmetric unit (Fig. 1). The 5,6-dihydrobenzo ring has an envelope conformation (puckering parameters Q, θ, and φ = 0.458 (2)Å, 126.4 (2)° and 295.8 (3)°, respectively; (Cremer & Pople, 1975)). The torsion angles along the butadiene chain in the γ-alkylidenebutenolide core are -177.9 (2)° for molecule A and 179.9 (2)° for molecule B. Bond lengths are in normal ranges (Allen et al., 1987). In the crystal O–H···O hydrogen bonds between hydroxyl and carbonyl groups of adjacent independent molecules form inversion dimers (Fig. 2).

Related literature top

For background to butenolides and their pharmacological activity, see: Rao (1964); Ma et al. (1999). For the synthesis of γ-alkylidenebutenolides, see: Park et al. (2012); Almeida et al. (2010); Xu et al. (2007); Langer et al. (2000, 2001). For related structures, see: Schneider & Viljoen (1997); Langer & Saleh (2000). For standard bond lengths, see: Allen et al. (1987) and for puckering parameters, see: Cremer & Pople (1975).

Structure description top

For background to butenolides and their pharmacological activity, see: Rao (1964); Ma et al. (1999). For the synthesis of γ-alkylidenebutenolides, see: Park et al. (2012); Almeida et al. (2010); Xu et al. (2007); Langer et al. (2000, 2001). For related structures, see: Schneider & Viljoen (1997); Langer & Saleh (2000). For standard bond lengths, see: Allen et al. (1987) and for puckering parameters, see: Cremer & Pople (1975).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: COLLECT (Bruker–Nonius, 2002); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of independent molecules A and B of the title compound, C₁₂H₁₆O₃, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Inversion dimer formed in the molecular packing of the title compound. Dashed lines indicate intermolecular O–H···O hydrogen bonds between hydroxyl and the carbonyl groups of neighboring molecules.

(4R)-3-Hydroxy-7-isopropyl-4-methyl-5,6-dihydrobenzofuran-2(4H)-one top

Crystal data top

C₁₂H₁₆O₃	F(000) = 448
M_r = 208.25	D_x = 1.213 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 96 reflections
a = 9.0437 (3) Å	θ = 6.0–20.0°
b = 13.2792 (6) Å	µ = 0.09 mm⁻¹
c = 9.8199 (5) Å	T = 150 K
β = 104.694 (3)°	Block, colorless
V = 1140.73 (9) Å³	0.55 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	2821 independent reflections
Radiation source: fine-focus sealed tube	2564 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 9 pixels mm^-1	θ_max = 27.9°, θ_min = 3.1°
φ– and ω–rotations with 2.00 ° and 60 sec per frame scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2002)	k = −17→17
T_min = 0.682, T_max = 0.746	l = −12→12
37926 measured reflections

Refinement top

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.064P)² + 0.1458P] where P = (F_o² + 2F_c²)/3
2821 reflections	(Δ/σ)_max < 0.001
283 parameters	Δρ_max = 0.26 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₂H₁₆O₃	V = 1140.73 (9) Å³
M_r = 208.25	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 9.0437 (3) Å	µ = 0.09 mm⁻¹
b = 13.2792 (6) Å	T = 150 K
c = 9.8199 (5) Å	0.55 × 0.20 × 0.20 mm
β = 104.694 (3)°

Data collection top

Bruker–Nonius KappaCCD diffractometer	2821 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2564 reflections with I > 2σ(I)
T_min = 0.682, T_max = 0.746	R_int = 0.042
37926 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.26 e Å⁻³
2821 reflections	Δρ_min = −0.22 e Å⁻³
283 parameters

Special details top

Experimental. ¹H NMR (400 MHz, CDCl₃) (δ, p.p.m..): 1.01–1.04 (t, 6H), 1.29–1.31 (d, 3H), 1.43–1.51 (m, 1H), 1.81–1.88 (m, 1H), 2.14–2.21 (m, 1H), 2.26–2.33 (m, 1H), 2.74–2.83 (m, 1H), 3.04–3.11 (m, 1H). ¹³C{1H} NMR (101 MHz, CDCl₃) (δ, p.p.m..): 17.65, 20.23, 20.40, 21.95, 27.89, 28.25, 31.22, 128.25, 128.75, 135.33, 140.89, 167.80. [α]_D²⁰ = +4.32 (c 0.018, CH₃OH)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.61403 (15)	0.10519 (12)	1.04435 (15)	0.0267 (3)
O2	0.81828 (17)	0.02807 (13)	1.18582 (17)	0.0340 (4)
O3	0.98766 (16)	0.21407 (13)	1.14537 (16)	0.0311 (3)
H3	1.033 (3)	0.165 (3)	1.197 (3)	0.047*
O4	0.59682 (16)	0.52380 (12)	0.55678 (16)	0.0293 (3)
O5	0.80720 (19)	0.59606 (14)	0.6939 (2)	0.0474 (5)
O6	0.95840 (16)	0.40045 (12)	0.67379 (16)	0.0293 (3)
H6	1.005 (3)	0.450 (3)	0.719 (3)	0.044*
C1	0.7648 (2)	0.10095 (17)	1.1155 (2)	0.0247 (4)
C2	0.8387 (2)	0.19425 (16)	1.08940 (19)	0.0230 (4)
C3	0.7337 (2)	0.25226 (16)	1.00204 (18)	0.0231 (4)
C4	0.7400 (2)	0.35151 (18)	0.9315 (2)	0.0299 (5)
H4A	0.7655	0.3382	0.8399	0.036*
C5	0.5796 (3)	0.39841 (18)	0.8990 (2)	0.0339 (5)
H5A	0.5559	0.4175	0.9886	0.041*
H5B	0.5791	0.4606	0.8433	0.041*
C6	0.4551 (2)	0.32752 (19)	0.8177 (2)	0.0329 (5)
H6B	0.3540	0.3592	0.8089	0.039*
H6C	0.4685	0.3179	0.7215	0.039*
C7	0.4576 (2)	0.22601 (17)	0.8872 (2)	0.0256 (4)
C8	0.5915 (2)	0.19749 (16)	0.97278 (19)	0.0234 (4)
C9	0.8623 (3)	0.4221 (2)	1.0174 (3)	0.0431 (6)
H9A	0.9632	0.3910	1.0303	0.065*
H9B	0.8424	0.4342	1.1096	0.065*
H9C	0.8596	0.4862	0.9674	0.065*
C10	0.3163 (2)	0.16088 (18)	0.8569 (2)	0.0316 (5)
H10A	0.3435	0.0952	0.9068	0.038*
C11	0.2613 (3)	0.1398 (3)	0.6991 (3)	0.0610 (9)
H11A	0.3450	0.1104	0.6655	0.091*
H11B	0.2284	0.2029	0.6488	0.091*
H11C	0.1752	0.0926	0.6817	0.091*
C12	0.1891 (3)	0.2093 (3)	0.9104 (3)	0.0492 (7)
H12A	0.2233	0.2179	1.0127	0.074*
H12B	0.0984	0.1661	0.8872	0.074*
H12C	0.1639	0.2753	0.8656	0.074*
C13	0.7478 (2)	0.52326 (17)	0.6280 (2)	0.0289 (4)
C14	0.8127 (2)	0.42486 (16)	0.60962 (19)	0.0233 (4)
C15	0.7014 (2)	0.36769 (15)	0.52805 (19)	0.0227 (4)
C16	0.6920 (2)	0.26074 (17)	0.4779 (2)	0.0297 (4)
H16A	0.6593	0.2184	0.5492	0.036*
C17	0.5661 (3)	0.2546 (2)	0.3396 (2)	0.0382 (5)
H17A	0.6003	0.2913	0.2653	0.046*
H17B	0.5507	0.1832	0.3104	0.046*
C18	0.4140 (3)	0.2984 (2)	0.3514 (3)	0.0362 (5)
H18A	0.3426	0.3000	0.2566	0.043*
H18B	0.3697	0.2533	0.4110	0.043*
C19	0.4274 (2)	0.40341 (17)	0.4132 (2)	0.0264 (4)
C20	0.5657 (2)	0.42904 (16)	0.49253 (19)	0.0241 (4)
C21	0.8449 (3)	0.2199 (2)	0.4629 (3)	0.0409 (6)
H21A	0.9211	0.2249	0.5535	0.061*
H21B	0.8789	0.2594	0.3921	0.061*
H21C	0.8329	0.1492	0.4334	0.061*
C22	0.2912 (2)	0.47316 (19)	0.3872 (3)	0.0343 (5)
H22A	0.3169	0.5299	0.4561	0.041*
C23	0.1499 (3)	0.4196 (2)	0.4103 (3)	0.0407 (6)
H23A	0.1726	0.3927	0.5063	0.061*
H23B	0.1214	0.3643	0.3427	0.061*
H23C	0.0650	0.4675	0.3968	0.061*
C24	0.2587 (3)	0.5178 (3)	0.2387 (3)	0.0612 (9)
H24A	0.3492	0.5541	0.2275	0.092*
H24B	0.1721	0.5644	0.2246	0.092*
H24C	0.2340	0.4634	0.1691	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0214 (7)	0.0257 (8)	0.0292 (7)	0.0018 (6)	−0.0005 (6)	0.0038 (6)
O2	0.0256 (7)	0.0287 (8)	0.0423 (9)	0.0028 (7)	−0.0013 (6)	0.0112 (7)
O3	0.0190 (7)	0.0347 (9)	0.0368 (8)	0.0006 (6)	0.0016 (6)	0.0113 (7)
O4	0.0244 (7)	0.0211 (7)	0.0349 (8)	−0.0017 (6)	−0.0065 (6)	−0.0013 (6)
O5	0.0308 (9)	0.0260 (9)	0.0684 (12)	0.0010 (7)	−0.0191 (8)	−0.0123 (9)
O6	0.0213 (7)	0.0269 (8)	0.0351 (8)	0.0001 (6)	−0.0016 (6)	−0.0064 (6)
C1	0.0210 (9)	0.0280 (10)	0.0237 (9)	0.0032 (8)	0.0029 (7)	0.0000 (8)
C2	0.0213 (9)	0.0276 (11)	0.0206 (8)	0.0032 (8)	0.0061 (7)	0.0020 (8)
C3	0.0243 (9)	0.0277 (10)	0.0175 (8)	0.0028 (8)	0.0058 (7)	−0.0003 (8)
C4	0.0270 (10)	0.0324 (11)	0.0292 (10)	0.0047 (9)	0.0050 (8)	0.0098 (9)
C5	0.0321 (11)	0.0286 (11)	0.0384 (11)	0.0061 (9)	0.0040 (9)	0.0106 (9)
C6	0.0275 (10)	0.0381 (13)	0.0307 (11)	0.0103 (9)	0.0030 (9)	0.0112 (9)
C7	0.0227 (9)	0.0322 (11)	0.0208 (8)	0.0051 (8)	0.0033 (7)	−0.0011 (8)
C8	0.0254 (9)	0.0241 (10)	0.0200 (8)	0.0036 (8)	0.0048 (7)	0.0009 (8)
C9	0.0368 (12)	0.0304 (12)	0.0555 (15)	−0.0035 (10)	−0.0005 (11)	0.0128 (11)
C10	0.0215 (9)	0.0337 (12)	0.0350 (11)	0.0053 (9)	−0.0013 (8)	0.0019 (9)
C11	0.0360 (13)	0.093 (3)	0.0480 (16)	−0.0079 (15)	−0.0006 (11)	−0.0274 (17)
C12	0.0327 (12)	0.0598 (18)	0.0610 (16)	0.0009 (12)	0.0231 (12)	−0.0029 (15)
C13	0.0255 (9)	0.0239 (10)	0.0310 (10)	−0.0035 (8)	−0.0046 (8)	0.0009 (8)
C14	0.0244 (9)	0.0244 (10)	0.0193 (8)	−0.0024 (8)	0.0025 (7)	0.0026 (7)
C15	0.0245 (9)	0.0244 (10)	0.0196 (8)	−0.0048 (7)	0.0066 (7)	−0.0006 (7)
C16	0.0314 (10)	0.0267 (10)	0.0332 (10)	−0.0078 (9)	0.0121 (8)	−0.0069 (9)
C17	0.0335 (11)	0.0433 (13)	0.0375 (11)	−0.0107 (11)	0.0085 (9)	−0.0199 (11)
C18	0.0307 (11)	0.0395 (13)	0.0363 (12)	−0.0151 (10)	0.0046 (9)	−0.0096 (10)
C19	0.0257 (10)	0.0293 (11)	0.0224 (9)	−0.0088 (9)	0.0030 (8)	0.0026 (8)
C20	0.0269 (9)	0.0228 (10)	0.0210 (9)	−0.0060 (8)	0.0032 (7)	0.0034 (8)
C21	0.0327 (11)	0.0388 (13)	0.0531 (14)	−0.0034 (10)	0.0140 (10)	−0.0181 (11)
C22	0.0248 (10)	0.0339 (13)	0.0382 (12)	−0.0064 (9)	−0.0031 (9)	0.0060 (10)
C23	0.0274 (11)	0.0453 (15)	0.0488 (14)	−0.0038 (10)	0.0087 (10)	0.0080 (12)
C24	0.0353 (13)	0.075 (2)	0.0624 (18)	−0.0123 (14)	−0.0078 (12)	0.0402 (17)

Geometric parameters (Å, º) top

O1—C1	1.367 (2)	C11—H11B	0.9800
O1—C8	1.402 (3)	C11—H11C	0.9800
O2—C1	1.216 (3)	C12—H12A	0.9800
O3—C2	1.346 (2)	C12—H12B	0.9800
O3—H3	0.87 (3)	C12—H12C	0.9800
O4—C13	1.367 (2)	C13—C14	1.462 (3)
O4—C20	1.404 (3)	C14—C15	1.350 (3)
O5—C13	1.210 (3)	C15—C20	1.440 (3)
O6—C14	1.348 (2)	C15—C16	1.499 (3)
O6—H6	0.84 (3)	C16—C21	1.527 (3)
C1—C2	1.461 (3)	C16—C17	1.538 (3)
C2—C3	1.348 (3)	C16—H16A	1.0000
C3—C8	1.442 (3)	C17—C18	1.524 (3)
C3—C4	1.497 (3)	C17—H17A	0.9900
C4—C9	1.529 (3)	C17—H17B	0.9900
C4—C5	1.536 (3)	C18—C19	1.514 (3)
C4—H4A	1.0000	C18—H18A	0.9900
C5—C6	1.528 (3)	C18—H18B	0.9900
C5—H5A	0.9900	C19—C20	1.339 (3)
C5—H5B	0.9900	C19—C22	1.510 (3)
C6—C7	1.509 (3)	C21—H21A	0.9800
C6—H6B	0.9900	C21—H21B	0.9800
C6—H6C	0.9900	C21—H21C	0.9800
C7—C8	1.341 (3)	C22—C23	1.530 (3)
C7—C10	1.509 (3)	C22—C24	1.531 (4)
C9—H9A	0.9800	C22—H22A	1.0000
C9—H9B	0.9800	C23—H23A	0.9800
C9—H9C	0.9800	C23—H23B	0.9800
C10—C12	1.523 (3)	C23—H23C	0.9800
C10—C11	1.529 (4)	C24—H24A	0.9800
C10—H10A	1.0000	C24—H24B	0.9800
C11—H11A	0.9800	C24—H24C	0.9800

C1—O1—C8	106.96 (16)	H12A—C12—H12C	109.5
C2—O3—H3	112 (2)	H12B—C12—H12C	109.5
C13—O4—C20	106.58 (16)	O5—C13—O4	121.3 (2)
C14—O6—H6	111 (2)	O5—C13—C14	129.96 (19)
O2—C1—O1	121.6 (2)	O4—C13—C14	108.76 (18)
O2—C1—C2	129.88 (19)	O6—C14—C15	129.5 (2)
O1—C1—C2	108.47 (17)	O6—C14—C13	122.17 (18)
O3—C2—C3	128.2 (2)	C15—C14—C13	108.26 (18)
O3—C2—C1	123.31 (18)	C14—C15—C20	106.68 (18)
C3—C2—C1	108.47 (18)	C14—C15—C16	134.4 (2)
C2—C3—C8	106.69 (19)	C20—C15—C16	118.89 (17)
C2—C3—C4	134.0 (2)	C15—C16—C21	113.05 (18)
C8—C3—C4	119.27 (17)	C15—C16—C17	107.96 (19)
C3—C4—C9	113.05 (18)	C21—C16—C17	112.45 (19)
C3—C4—C5	107.98 (17)	C15—C16—H16A	107.7
C9—C4—C5	112.3 (2)	C21—C16—H16A	107.7
C3—C4—H4A	107.8	C17—C16—H16A	107.7
C9—C4—H4A	107.8	C18—C17—C16	113.12 (19)
C5—C4—H4A	107.8	C18—C17—H17A	109.0
C6—C5—C4	113.0 (2)	C16—C17—H17A	109.0
C6—C5—H5A	109.0	C18—C17—H17B	109.0
C4—C5—H5A	109.0	C16—C17—H17B	109.0
C6—C5—H5B	109.0	H17A—C17—H17B	107.8
C4—C5—H5B	109.0	C19—C18—C17	113.62 (18)
H5A—C5—H5B	107.8	C19—C18—H18A	108.8
C7—C6—C5	112.91 (17)	C17—C18—H18A	108.8
C7—C6—H6B	109.0	C19—C18—H18B	108.8
C5—C6—H6B	109.0	C17—C18—H18B	108.8
C7—C6—H6C	109.0	H18A—C18—H18B	107.7
C5—C6—H6C	109.0	C20—C19—C22	123.0 (2)
H6B—C6—H6C	107.8	C20—C19—C18	115.8 (2)
C8—C7—C10	123.1 (2)	C22—C19—C18	121.25 (18)
C8—C7—C6	116.31 (19)	C19—C20—O4	122.70 (19)
C10—C7—C6	120.55 (17)	C19—C20—C15	127.6 (2)
C7—C8—O1	123.65 (19)	O4—C20—C15	109.70 (16)
C7—C8—C3	126.9 (2)	C16—C21—H21A	109.5
O1—C8—C3	109.41 (16)	C16—C21—H21B	109.5
C4—C9—H9A	109.5	H21A—C21—H21B	109.5
C4—C9—H9B	109.5	C16—C21—H21C	109.5
H9A—C9—H9B	109.5	H21A—C21—H21C	109.5
C4—C9—H9C	109.5	H21B—C21—H21C	109.5
H9A—C9—H9C	109.5	C19—C22—C23	111.5 (2)
H9B—C9—H9C	109.5	C19—C22—C24	110.5 (2)
C7—C10—C12	111.4 (2)	C23—C22—C24	110.81 (19)
C7—C10—C11	110.3 (2)	C19—C22—H22A	108.0
C12—C10—C11	110.3 (2)	C23—C22—H22A	108.0
C7—C10—H10A	108.2	C24—C22—H22A	108.0
C12—C10—H10A	108.2	C22—C23—H23A	109.5
C11—C10—H10A	108.2	C22—C23—H23B	109.5
C10—C11—H11A	109.5	H23A—C23—H23B	109.5
C10—C11—H11B	109.5	C22—C23—H23C	109.5
H11A—C11—H11B	109.5	H23A—C23—H23C	109.5
C10—C11—H11C	109.5	H23B—C23—H23C	109.5
H11A—C11—H11C	109.5	C22—C24—H24A	109.5
H11B—C11—H11C	109.5	C22—C24—H24B	109.5
C10—C12—H12A	109.5	H24A—C24—H24B	109.5
C10—C12—H12B	109.5	C22—C24—H24C	109.5
H12A—C12—H12B	109.5	H24A—C24—H24C	109.5
C10—C12—H12C	109.5	H24B—C24—H24C	109.5

C8—O1—C1—O2	−178.89 (19)	C20—O4—C13—O5	179.9 (2)
C8—O1—C1—C2	0.9 (2)	C20—O4—C13—C14	−0.9 (2)
O2—C1—C2—O3	−0.7 (3)	O5—C13—C14—O6	2.5 (4)
O1—C1—C2—O3	179.55 (17)	O4—C13—C14—O6	−176.68 (17)
O2—C1—C2—C3	178.7 (2)	O5—C13—C14—C15	179.3 (2)
O1—C1—C2—C3	−1.0 (2)	O4—C13—C14—C15	0.2 (2)
O3—C2—C3—C8	−179.90 (19)	O6—C14—C15—C20	177.15 (18)
C1—C2—C3—C8	0.7 (2)	C13—C14—C15—C20	0.6 (2)
O3—C2—C3—C4	3.4 (4)	O6—C14—C15—C16	0.2 (4)
C1—C2—C3—C4	−176.0 (2)	C13—C14—C15—C16	−176.3 (2)
C2—C3—C4—C9	−31.2 (3)	C14—C15—C16—C21	−29.2 (3)
C8—C3—C4—C9	152.4 (2)	C20—C15—C16—C21	154.17 (19)
C2—C3—C4—C5	−156.0 (2)	C14—C15—C16—C17	−154.2 (2)
C8—C3—C4—C5	27.6 (2)	C20—C15—C16—C17	29.1 (2)
C3—C4—C5—C6	−52.7 (2)	C15—C16—C17—C18	−52.6 (3)
C9—C4—C5—C6	−177.98 (19)	C21—C16—C17—C18	−178.0 (2)
C4—C5—C6—C7	52.7 (3)	C16—C17—C18—C19	51.4 (3)
C5—C6—C7—C8	−24.0 (3)	C17—C18—C19—C20	−22.8 (3)
C5—C6—C7—C10	157.55 (19)	C17—C18—C19—C22	157.9 (2)
C10—C7—C8—O1	−0.9 (3)	C22—C19—C20—O4	−1.0 (3)
C6—C7—C8—O1	−179.27 (17)	C18—C19—C20—O4	179.77 (18)
C10—C7—C8—C3	176.57 (19)	C22—C19—C20—C15	177.74 (19)
C6—C7—C8—C3	−1.8 (3)	C18—C19—C20—C15	−1.5 (3)
C1—O1—C8—C7	177.38 (19)	C13—O4—C20—C19	−179.81 (19)
C1—O1—C8—C3	−0.4 (2)	C13—O4—C20—C15	1.3 (2)
C2—C3—C8—C7	−177.94 (19)	C14—C15—C20—C19	179.97 (19)
C4—C3—C8—C7	−0.6 (3)	C16—C15—C20—C19	−2.5 (3)
C2—C3—C8—O1	−0.2 (2)	C14—C15—C20—O4	−1.2 (2)
C4—C3—C8—O1	177.12 (17)	C16—C15—C20—O4	176.29 (16)
C8—C7—C10—C12	116.2 (2)	C20—C19—C22—C23	−132.3 (2)
C6—C7—C10—C12	−65.5 (3)	C18—C19—C22—C23	46.9 (3)
C8—C7—C10—C11	−120.9 (2)	C20—C19—C22—C24	104.0 (3)
C6—C7—C10—C11	57.4 (3)	C18—C19—C22—C24	−76.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱ	0.87 (3)	1.81 (3)	2.627 (2)	157 (3)
O6—H6···O2ⁱⁱ	0.84 (3)	1.93 (3)	2.727 (2)	156 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱ	0.87 (3)	1.81 (3)	2.627 (2)	157 (3)
O6—H6···O2ⁱⁱ	0.84 (3)	1.93 (3)	2.727 (2)	156 (3)

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

Acknowledgements

This work was financed by DID–USB (project S1–IN–CB–005–12).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Almeida, L. C., Teixeira, R. R., Fontes, P., Álvares, C. R. & Demuner, A. J. (2010). Quim. Nova, 33, 5, 1163–1174. Google Scholar
Bruker (2002). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker–Nonius (2002). COLLECT. Bruker–Nonius, Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst. 36, 220–229. Web of Science CrossRef CAS IUCr Journals Google Scholar
Langer, P., Eckardt, T., Saleh, N. N. R., Karime, I. & Müller, P. (2001). Eur. J. Org. Chem. 19, 3657–3667. CrossRef Google Scholar
Langer, P. & Saleh, N. N. R. (2000). Org. Lett. 2, 3333–3336. Web of Science CrossRef PubMed CAS Google Scholar
Langer, P., Schneider, T. & Stoll, M. (2000). Chem. Eur. J. 6, 17, 3204–3214. Google Scholar
Ma, S., Shi, Z. & Yu, Z. (1999). Tetrahedron, 55, 12137–12148. Web of Science CrossRef CAS Google Scholar
Park, B. R., Kim, K. H., Lim, J. W. & Kim, J. N. (2012). Tetrahedron Lett. 53, 36–40. Web of Science CrossRef CAS Google Scholar
Rao, Y. S. (1964). Chem. Rev. 64, 353–388. CrossRef CAS Web of Science Google Scholar
Schneider, D. F. & Viljoen, M. S. (1997). Synth. Commun. 27, 3349–3360. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, H.-W., Wang, J.-F., Liu, G.-Z., Hong, G.-F. & Liu, H.-M. (2007). Org. Biomol. Chem. 5, 1247–1250. Web of Science CrossRef PubMed CAS Google Scholar

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