8-{[(E)-3-(2-Chloro­phen­yl)acrylo­yloxy]imino}-12,13-ep­oxy­trichethec-9-en-4-yl (E)-3-(2-chloro­phen­yl)acrylate

Xu, X.-J.; Li, X.-L.; Cheng, J.; Zhao, J.

doi:10.1107/S1600536811039638

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2834

doi:10.1107/S1600536811039638

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8-{[(E)-3-(2-Chlorophenyl)acryloyloxy]imino}-12,13-epoxytrichethec-9-en-4-yl (E)-3-(2-chlorophenyl)acrylate

Xiao-Jun Xu,^a Xiao-Liang Li,^b Jing-li Cheng ^c and Jin-hao Zhao ^c ^*

^aCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310032, People's Republic of China, ^bDepartment of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China, and ^cInstitute of Pesticide and Environmental Toxicology, Zhejiang University, Hangzhou 310029, People's Republic of China
^*Correspondence e-mail: jinhaozhao@zju.edu.cn

(Received 19 September 2011; accepted 27 September 2011; online 5 October 2011)

In the title compound, C₃₃H₃₁Cl₂NO₆, the five-membered ring displays an envelope conformation, whereas the two six-membered rings both exhibit a chair conformation. As for the seven-membered ring, the dihedral angle between the mean planes formed by the four C atoms of the envelope unit and the three C and one O atoms of the six-membered chair is 69.08 (4)°, and these two mean planes are nearly perpendicular to the epoxy ring, making dihedral angles of 87.53 (4) and 88.67 (4)°, respectively.

Related literature

The endophytic fungi Trichoderma taxi sp. nov. from Taxus mairei S. Y. Hu can produce a compound with fungicidal activity, Trichodermin (Zhang et al., 2007 ), which is a member of the 4β-acetoxy-12,13-epoxytrichothecene family (Nielsen et al., 2005 ). For a related Trichodermin structure, see: Chen et al. (2008 ). For structures of Trichodermin derivatives, see: Cheng et al. (2009 ); Xu et al. (2010 ).

Experimental

Crystal data

C₃₃H₃₁Cl₂NO₆
M_r = 608.49
Monoclinic, P 2₁
a = 7.2302 (4) Å
b = 14.4055 (6) Å
c = 14.6663 (6) Å
β = 94.414 (1)°
V = 1523.03 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.41 × 0.36 × 0.29 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.895, T_max = 0.929
15059 measured reflections
6713 independent reflections
3890 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.130
S = 1.00
6713 reflections
384 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 3099 Friedel pairs
Flack parameter: 0.02 (8)

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811039638/zq2124sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811039638/zq2124Isup2.hkl

checkCIF report

Comment top

The endophytic fungi Trichoderma taxi sp. nov. from Taxus mairei S. Y. Hu can produce a compound with fungicidal activity - Trichodermin (Zhang et al., 2007), which is a member of the 4β-acetoxy-12,13-epoxytrichothecene family (Nielsen et al., 2005). Bioassays showed Trichodermin strongly inhibited Rhizoctonia solani and Botrytis cinere. In order to find the relationship between the conjugated double bonds at 8 and 4 positions and biological activities, we designed to take the esterification reaction, thus, the title compound had been synthesized. Its molecular structure is shown in Fig. 1. In the molecule, the five membered ring displays an envelope conformation with atom C12 at the flap position 0.694 (5) Å out of the mean plane formed by C2, C3, C4 and C5. The pyranyl ring displays a chair conformation with the C11 and C12 atoms deviating by -0.578 (5) and 0.843 (5) Å from the mean plane formed by O1, C2, C5 and C6. It is interesting to note that the C8–C9–C10 bond angle is smaller than in the structure of Trichodermin (Chen et al., 2008) and Trichodermol (4α-hydroxy-12,13-epoxytrichothec-9-ene) (Cheng et al., 2009), two hydrogen bonds being displaced by the presence of the carbon-nitrogen double bond in the title compound. As for the seven-membered ring, the dihedral angle between the mean planes formed by C2–C3–C4–C5 and C2–C5–C6–O1 is 69.08 (4) °, two planes which are nearly perpendicular to the three-membered ring with angles of 87.53 (4) and 88.67 (4)°, respectively.

Related literature top

The endophytic fungi Trichoderma taxi sp. nov. from Taxus mairei S. Y. Hu can produce a compound with fungicidal activity, Trichodermin (Zhang et al., 2007), which is a member of the 4β-acetoxy-12,13-epoxytrichothecene family (Nielsen et al., 2005). For a related Trichodermin structure, see: Chen et al. (2008). For structures of Trichodermin derivatives, see: Cheng et al. (2009); Xu et al. (2010).

Experimental top

In a flask, a solution of trichodermin (4.00 g, 13.70 mmoL) in 30 ml 1,4-dioxane was added dropwise over a period of 90 min to a refluxing solution of selenium dioxide (2.00 g, 18.02 mmoL) in 20 ml of 1,4-dioxane. After refluxing 12 h, the reaction was cooled and concentrated. Then 50 ml of ethyl acetate was added, and was washed with 5% aqueous sodium bicarbonate, dried, and concentrated in vacuum to 3.50 g of yellow liquid. The crude product was purified by flash column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (5: 1 by volume) as the eluent to give trichodermin-8-one (1.10 g, 26.2%) as colorless crystals. Then a mixture of trichodermin-8-one (1.00 g, 3.27 mmoL), hydroxylammonium chloride (0.45 g, 6.52 mmoL), and 30 ml methanol was stirred at 80 °C for 0.2 h. After the mixture was dissolved, a solution of potassium carbonate (4.00 g, 13.70 mmoL) in 20 ml water was added dropwise. The solution was stirred for 2.5 h, and concentrated, then extracted by ethyl acetate (10 ml) for three times, evaporated, and the crude product was purified via silica gel column chromatography using a 1: 2 (v/v) mixture of ethyl acetate and petroleum ether (boiling point range 60–90 °C) as the eluting solution to obtain (E)-trichodermin-8-hydroxy oxime as colorless crystals (0.89 g, 85.0%). At last, (E)-3-(2-chlorophenyl)acryloyl chloride (1.11 g, 5.54 mmoL) with 5 ml dichloromethane was added dropwise into a mixture of (E)-trichodermin-8-hydroxy oxime (0.89 g, 2.77 mmoL), triethylamine (33.8 mg, 0.28 mmoL), and N,N-dimethylpyridin-4-amine (0.56 g, 5.54 mmoL). The solution was stirred at room temperature and monitored by TLC. After 0.5 h, the mixture was washed with 1 N HCl, sat. NaHCO₃ and dried over anhydrous Na₂SO₄. The solvent was evaporated in vacuo to afford the crude product, which was purified by column chromatography to give the title compound (1.35 g, 80%) as a colorless solid. The solid was filtrated and recrystallized with acetone to get colourless blocks.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Reaction scheme.

8-{[(E)-3-(2-Chlorophenyl)acryloyloxy]imino}-12,13-epoxytrichethec- 9-en-4-yl (E)-3-(2-chlorophenyl)acrylate top

Crystal data top

C₃₃H₃₁Cl₂NO₆	F(000) = 636
M_r = 608.49	D_x = 1.327 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9966 reflections
a = 7.2302 (4) Å	θ = 3.1–27.4°
b = 14.4055 (6) Å	µ = 0.26 mm⁻¹
c = 14.6663 (6) Å	T = 296 K
β = 94.414 (1)°	Chunk, colourless
V = 1523.03 (12) Å³	0.41 × 0.36 × 0.29 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	6713 independent reflections
Radiation source: rolling anode	3890 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −18→18
T_min = 0.895, T_max = 0.929	l = −18→18
15059 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0437P)² + 0.8334P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.130	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.40 e Å⁻³
6713 reflections	Δρ_min = −0.30 e Å⁻³
384 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
7 restraints	Extinction coefficient: 0.0140 (15)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 3099 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.02 (8)

Crystal data top

C₃₃H₃₁Cl₂NO₆	V = 1523.03 (12) Å³
M_r = 608.49	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.2302 (4) Å	µ = 0.26 mm⁻¹
b = 14.4055 (6) Å	T = 296 K
c = 14.6663 (6) Å	0.41 × 0.36 × 0.29 mm
β = 94.414 (1)°

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	6713 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3890 reflections with I > 2σ(I)
T_min = 0.895, T_max = 0.929	R_int = 0.026
15059 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.130	Δρ_max = 0.40 e Å⁻³
S = 1.00	Δρ_min = −0.30 e Å⁻³
6713 reflections	Absolute structure: Flack (1983), 3099 Friedel pairs
384 parameters	Absolute structure parameter: 0.02 (8)
7 restraints

Special details top

Experimental. ESI-MS: 631.5 (M+Na)+ (100%); ¹H-NMR (500 MHz, CDCl₃): 8.27–8.15 (2H, dd, J1 = J2 = 16.0 Hz, 2H-CH—Ar), 7.72–7.64 (2H, m, 2H-3-Ar), 7.47–7.43 (2H, m, 2H-6-Ar), 7.38–7.28 (4H, m, 4H-4,5-Ar), 6.66–6.48 (2H, dd, J1 = J2 = 16.0 Hz, 2H-COCH), 6.10–6.08 (1H, dd, J = 3.5, 7.5 Hz, H4), 5.69–5.67 (1H, d, J = 5.5 Hz, H-10), 3.65 (1H, d, J = 5.5 Hz, H11), 3.86 (1H, d, J = 7.5 Hz, H2), 3.22–3.21 (1H, d, J = 4.0 Hz, H13), 3.18–3.15 (1H, d, J = 15.5 Hz, H7), 2.99–2.98 (1H, d, J = 4.0 Hz, H13), 2.71–2.67 (1H, m, H-3), 2.66–2.63 (1H, d, J = 15.5 Hz, H7), 2.21–2.16 (1H, m, H-3), 2.08 (3H, s, H-16), 1.06 (3H, s, H-14), 0.89 (3H, s, H-15).

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
Cl1	−0.06472 (18)	0.61733 (11)	0.92949 (9)	0.0927 (4)
Cl2	0.1261 (2)	0.79377 (10)	0.29996 (11)	0.1019 (5)
O1	1.0020 (3)	0.56786 (16)	0.48929 (17)	0.0504 (6)
O2	0.7296 (4)	0.76494 (16)	0.56209 (17)	0.0543 (6)
O3	0.6673 (3)	0.63093 (17)	0.72185 (16)	0.0536 (6)
O4	0.4986 (5)	0.5146 (2)	0.7750 (3)	0.1002 (12)
O5	0.3826 (4)	0.4871 (2)	0.24887 (18)	0.0630 (7)
O6	0.3161 (6)	0.4193 (4)	0.1137 (3)	0.129 (2)
N1	0.5490 (4)	0.4323 (2)	0.2564 (2)	0.0595 (8)
C2	0.9633 (4)	0.6377 (2)	0.5546 (2)	0.0491 (8)
H2	1.0539	0.6883	0.5547	0.059*
C3	0.9472 (5)	0.6005 (3)	0.6506 (3)	0.0551 (9)
H3A	0.9799	0.6481	0.6958	0.066*
H3B	1.0285	0.5476	0.6623	0.066*
C4	0.7444 (5)	0.5718 (3)	0.6541 (2)	0.0496 (8)
H4	0.7331	0.5060	0.6696	0.060*
C5	0.6473 (4)	0.5939 (2)	0.5573 (2)	0.0424 (7)
C6	0.6787 (4)	0.5101 (2)	0.4915 (2)	0.0440 (8)
C7	0.6125 (5)	0.5343 (2)	0.3920 (2)	0.0507 (9)
H7A	0.4800	0.5462	0.3881	0.061*
H7B	0.6740	0.5905	0.3742	0.061*
C9	0.8307 (5)	0.4096 (2)	0.3412 (3)	0.0529 (9)
C8	0.6522 (5)	0.4579 (2)	0.3274 (3)	0.0499 (8)
C10	0.9381 (5)	0.4258 (3)	0.4174 (3)	0.0557 (9)
H10	1.0537	0.3973	0.4234	0.067*
C11	0.8862 (5)	0.4870 (2)	0.4945 (2)	0.0482 (8)
H11	0.9211	0.4551	0.5523	0.058*
C12	0.7696 (5)	0.6729 (2)	0.5303 (2)	0.0420 (7)
C13	0.7247 (6)	0.7472 (3)	0.4653 (3)	0.0580 (10)
H13A	0.8243	0.7723	0.4321	0.070*
H13B	0.6044	0.7455	0.4312	0.070*
C14	0.4438 (5)	0.6208 (3)	0.5593 (3)	0.0581 (9)
H14A	0.4343	0.6772	0.5934	0.087*
H14B	0.3783	0.5721	0.5879	0.087*
H14C	0.3908	0.6298	0.4979	0.087*
C15	0.5706 (6)	0.4250 (3)	0.5197 (3)	0.0618 (10)
H15A	0.6037	0.3724	0.4843	0.093*
H15B	0.4400	0.4367	0.5091	0.093*
H15C	0.6002	0.4126	0.5835	0.093*
C16	0.8876 (6)	0.3440 (3)	0.2685 (3)	0.0720 (12)
H16A	1.0136	0.3247	0.2828	0.108*
H16B	0.8776	0.3748	0.2103	0.108*
H16C	0.8079	0.2906	0.2661	0.108*
C17	0.5438 (6)	0.5955 (3)	0.7761 (3)	0.0633 (10)
C18	0.4717 (6)	0.6688 (3)	0.8326 (3)	0.0615 (10)
H18	0.5244	0.7276	0.8317	0.074*
C19	0.3334 (6)	0.6537 (3)	0.8852 (3)	0.0608 (10)
H19	0.2873	0.5935	0.8873	0.073*
C20	0.2477 (6)	0.7241 (3)	0.9399 (2)	0.0585 (10)
C21	0.3411 (7)	0.8050 (3)	0.9676 (3)	0.0729 (12)
H21	0.4628	0.8137	0.9530	0.087*
C22	0.2555 (9)	0.8728 (4)	1.0165 (3)	0.0877 (15)
H22	0.3199	0.9264	1.0346	0.105*
C23	0.0763 (10)	0.8608 (4)	1.0381 (4)	0.0973 (18)
H23	0.0196	0.9063	1.0714	0.117*
C24	−0.0192 (8)	0.7831 (4)	1.0113 (3)	0.0857 (15)
H24	−0.1418	0.7759	1.0251	0.103*
C25	0.0657 (6)	0.7153 (3)	0.9640 (3)	0.0656 (11)
C26	0.2778 (6)	0.4734 (4)	0.1713 (3)	0.0763 (14)
C27	0.1139 (6)	0.5335 (3)	0.1633 (3)	0.0686 (12)
H27	0.0286	0.5240	0.1134	0.082*
C28	0.0775 (5)	0.5998 (3)	0.2207 (3)	0.0583 (9)
H28	0.1621	0.6087	0.2710	0.070*
C29	−0.0846 (5)	0.6608 (3)	0.2125 (2)	0.0576 (10)
C30	−0.2520 (6)	0.6318 (4)	0.1689 (3)	0.0698 (11)
H30	−0.2623	0.5720	0.1454	0.084*
C31	−0.4065 (6)	0.6916 (4)	0.1599 (4)	0.0813 (14)
H31	−0.5183	0.6711	0.1314	0.098*
C32	−0.3908 (8)	0.7799 (4)	0.1935 (4)	0.0892 (16)
H32	−0.4923	0.8197	0.1870	0.107*
C33	−0.2279 (8)	0.8105 (4)	0.2363 (3)	0.0842 (14)
H33	−0.2183	0.8706	0.2591	0.101*
C34	−0.0785 (6)	0.7516 (3)	0.2454 (3)	0.0672 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0732 (8)	0.1191 (11)	0.0855 (8)	−0.0194 (8)	0.0046 (6)	0.0097 (8)
Cl2	0.0834 (9)	0.1012 (10)	0.1193 (11)	−0.0005 (7)	−0.0035 (7)	−0.0454 (9)
O1	0.0376 (13)	0.0466 (13)	0.0668 (15)	−0.0018 (10)	0.0037 (10)	−0.0122 (12)
O2	0.0618 (16)	0.0385 (12)	0.0630 (15)	0.0037 (11)	0.0075 (12)	−0.0072 (11)
O3	0.0580 (15)	0.0511 (14)	0.0526 (13)	−0.0015 (12)	0.0095 (11)	−0.0035 (12)
O4	0.128 (3)	0.059 (2)	0.122 (3)	−0.014 (2)	0.064 (2)	0.0020 (19)
O5	0.0541 (16)	0.0694 (17)	0.0616 (15)	0.0174 (14)	−0.0214 (12)	−0.0176 (13)
O6	0.114 (3)	0.152 (3)	0.114 (3)	0.059 (2)	−0.038 (2)	−0.073 (2)
N1	0.0535 (19)	0.0534 (17)	0.068 (2)	0.0142 (15)	−0.0163 (15)	−0.0115 (16)
C2	0.0325 (17)	0.0462 (18)	0.069 (2)	−0.0056 (15)	0.0032 (15)	−0.0147 (17)
C3	0.042 (2)	0.060 (2)	0.061 (2)	0.0008 (17)	−0.0074 (16)	−0.0075 (19)
C4	0.053 (2)	0.0473 (19)	0.0482 (19)	0.0009 (16)	−0.0013 (16)	−0.0035 (16)
C5	0.0335 (16)	0.0460 (18)	0.0472 (17)	−0.0020 (14)	0.0000 (13)	−0.0008 (14)
C6	0.0365 (18)	0.0396 (17)	0.0544 (19)	−0.0002 (14)	−0.0064 (14)	0.0004 (15)
C7	0.046 (2)	0.0465 (19)	0.058 (2)	0.0080 (15)	−0.0101 (16)	−0.0104 (17)
C9	0.052 (2)	0.0402 (18)	0.065 (2)	0.0086 (16)	−0.0057 (17)	−0.0101 (17)
C8	0.049 (2)	0.0427 (18)	0.056 (2)	0.0040 (15)	−0.0092 (16)	−0.0032 (16)
C10	0.049 (2)	0.0450 (19)	0.070 (2)	0.0134 (17)	−0.0114 (18)	−0.0118 (19)
C11	0.0438 (19)	0.0410 (18)	0.058 (2)	0.0047 (15)	−0.0089 (15)	−0.0017 (16)
C12	0.0410 (19)	0.0313 (15)	0.0537 (19)	0.0006 (13)	0.0028 (14)	−0.0070 (15)
C13	0.069 (3)	0.049 (2)	0.056 (2)	0.0059 (18)	0.0074 (18)	0.0017 (18)
C14	0.0392 (19)	0.069 (2)	0.066 (2)	0.0027 (19)	0.0039 (16)	−0.007 (2)
C15	0.061 (2)	0.050 (2)	0.073 (3)	−0.0163 (19)	−0.0029 (19)	0.004 (2)
C16	0.076 (3)	0.058 (2)	0.079 (3)	0.020 (2)	−0.010 (2)	−0.019 (2)
C17	0.071 (3)	0.060 (2)	0.060 (2)	−0.005 (2)	0.016 (2)	0.006 (2)
C18	0.066 (3)	0.063 (2)	0.056 (2)	0.002 (2)	0.0101 (19)	−0.001 (2)
C19	0.061 (2)	0.064 (2)	0.059 (2)	−0.001 (2)	0.0131 (18)	0.0076 (19)
C20	0.063 (3)	0.068 (2)	0.045 (2)	0.005 (2)	0.0067 (18)	0.0137 (19)
C21	0.080 (3)	0.072 (3)	0.068 (3)	−0.002 (3)	0.012 (2)	0.010 (2)
C22	0.118 (5)	0.069 (3)	0.078 (3)	0.003 (3)	0.021 (3)	0.003 (3)
C23	0.131 (5)	0.081 (4)	0.085 (4)	0.019 (4)	0.046 (3)	0.012 (3)
C24	0.083 (3)	0.098 (4)	0.080 (3)	0.023 (3)	0.031 (3)	0.018 (3)
C25	0.066 (3)	0.078 (3)	0.053 (2)	0.006 (2)	0.008 (2)	0.016 (2)
C26	0.063 (3)	0.094 (3)	0.068 (3)	0.027 (2)	−0.021 (2)	−0.031 (3)
C27	0.055 (2)	0.086 (3)	0.061 (2)	0.016 (2)	−0.0186 (19)	−0.016 (2)
C28	0.047 (2)	0.072 (3)	0.054 (2)	0.0062 (19)	−0.0057 (16)	−0.0058 (19)
C29	0.051 (2)	0.072 (3)	0.0490 (19)	0.0049 (19)	0.0008 (16)	0.0027 (19)
C30	0.057 (2)	0.083 (3)	0.068 (2)	0.001 (2)	−0.0038 (19)	0.016 (2)
C31	0.052 (3)	0.105 (4)	0.086 (3)	0.010 (3)	0.000 (2)	0.030 (3)
C32	0.074 (4)	0.107 (5)	0.088 (3)	0.029 (3)	0.019 (3)	0.023 (3)
C33	0.083 (4)	0.094 (4)	0.077 (3)	0.029 (3)	0.017 (3)	0.001 (3)
C34	0.068 (3)	0.076 (3)	0.058 (2)	0.013 (2)	0.007 (2)	−0.005 (2)

Geometric parameters (Å, º) top

Cl1—C25	1.750 (5)	C14—H14A	0.9600
Cl2—C34	1.736 (5)	C14—H14B	0.9600
O1—C2	1.432 (4)	C14—H14C	0.9600
O1—C11	1.441 (4)	C15—H15A	0.9600
O2—C13	1.440 (4)	C15—H15B	0.9600
O2—C12	1.442 (4)	C15—H15C	0.9600
O3—C17	1.342 (5)	C16—H16A	0.9600
O3—C4	1.451 (4)	C16—H16B	0.9600
O4—C17	1.210 (5)	C16—H16C	0.9600
O5—C26	1.332 (4)	C17—C18	1.463 (6)
O5—N1	1.437 (4)	C18—C19	1.327 (5)
O6—C26	1.197 (5)	C18—H18	0.9300
N1—C8	1.286 (4)	C19—C20	1.461 (6)
C2—C12	1.506 (5)	C19—H19	0.9300
C2—C3	1.520 (5)	C20—C21	1.392 (6)
C2—H2	0.9800	C20—C25	1.394 (6)
C3—C4	1.528 (5)	C21—C22	1.385 (7)
C3—H3A	0.9700	C21—H21	0.9300
C3—H3B	0.9700	C22—C23	1.368 (8)
C4—C5	1.568 (5)	C22—H22	0.9300
C4—H4	0.9800	C23—C24	1.358 (8)
C5—C12	1.512 (4)	C23—H23	0.9300
C5—C14	1.523 (5)	C24—C25	1.371 (6)
C5—C6	1.574 (5)	C24—H24	0.9300
C6—C15	1.527 (5)	C26—C27	1.465 (6)
C6—C11	1.534 (5)	C27—C28	1.313 (5)
C6—C7	1.540 (5)	C27—H27	0.9300
C7—C8	1.495 (5)	C28—C29	1.462 (5)
C7—H7A	0.9700	C28—H28	0.9300
C7—H7B	0.9700	C29—C30	1.389 (6)
C9—C10	1.332 (5)	C29—C34	1.394 (6)
C9—C8	1.467 (5)	C30—C31	1.408 (6)
C9—C16	1.505 (5)	C30—H30	0.9300
C10—C11	1.503 (5)	C31—C32	1.365 (8)
C10—H10	0.9300	C31—H31	0.9300
C11—H11	0.9800	C32—C33	1.364 (8)
C12—C13	1.453 (5)	C32—H32	0.9300
C13—H13A	0.9700	C33—C34	1.371 (6)
C13—H13B	0.9700	C33—H33	0.9300

C2—O1—C11	112.9 (3)	H14A—C14—H14B	109.5
C13—O2—C12	60.6 (2)	C5—C14—H14C	109.5
C17—O3—C4	119.4 (3)	H14A—C14—H14C	109.5
C26—O5—N1	113.7 (3)	H14B—C14—H14C	109.5
C8—N1—O5	109.5 (3)	C6—C15—H15A	109.5
O1—C2—C12	107.7 (3)	C6—C15—H15B	109.5
O1—C2—C3	113.9 (3)	H15A—C15—H15B	109.5
C12—C2—C3	101.6 (3)	C6—C15—H15C	109.5
O1—C2—H2	111.1	H15A—C15—H15C	109.5
C12—C2—H2	111.1	H15B—C15—H15C	109.5
C3—C2—H2	111.1	C9—C16—H16A	109.5
C2—C3—C4	105.6 (3)	C9—C16—H16B	109.5
C2—C3—H3A	110.6	H16A—C16—H16B	109.5
C4—C3—H3A	110.6	C9—C16—H16C	109.5
C2—C3—H3B	110.6	H16A—C16—H16C	109.5
C4—C3—H3B	110.6	H16B—C16—H16C	109.5
H3A—C3—H3B	108.8	O4—C17—O3	123.4 (4)
O3—C4—C3	106.5 (3)	O4—C17—C18	126.5 (4)
O3—C4—C5	109.4 (3)	O3—C17—C18	110.1 (3)
C3—C4—C5	106.2 (3)	C19—C18—C17	121.9 (4)
O3—C4—H4	111.5	C19—C18—H18	119.1
C3—C4—H4	111.5	C17—C18—H18	119.1
C5—C4—H4	111.5	C18—C19—C20	125.2 (4)
C12—C5—C14	113.5 (3)	C18—C19—H19	117.4
C12—C5—C4	99.2 (3)	C20—C19—H19	117.4
C14—C5—C4	113.6 (3)	C21—C20—C25	116.6 (4)
C12—C5—C6	107.5 (2)	C21—C20—C19	121.7 (4)
C14—C5—C6	113.1 (3)	C25—C20—C19	121.6 (4)
C4—C5—C6	108.9 (3)	C22—C21—C20	121.0 (5)
C15—C6—C11	109.7 (3)	C22—C21—H21	119.5
C15—C6—C7	108.1 (3)	C20—C21—H21	119.5
C11—C6—C7	108.0 (3)	C23—C22—C21	120.0 (5)
C15—C6—C5	110.4 (3)	C23—C22—H22	120.0
C11—C6—C5	109.7 (3)	C21—C22—H22	120.0
C7—C6—C5	111.0 (3)	C24—C23—C22	120.4 (5)
C8—C7—C6	111.9 (3)	C24—C23—H23	119.8
C8—C7—H7A	109.2	C22—C23—H23	119.8
C6—C7—H7A	109.2	C23—C24—C25	119.8 (5)
C8—C7—H7B	109.2	C23—C24—H24	120.1
C6—C7—H7B	109.2	C25—C24—H24	120.1
H7A—C7—H7B	107.9	C24—C25—C20	122.1 (5)
C10—C9—C8	118.9 (3)	C24—C25—Cl1	117.9 (4)
C10—C9—C16	122.1 (3)	C20—C25—Cl1	119.9 (4)
C8—C9—C16	119.0 (3)	O6—C26—O5	123.5 (4)
N1—C8—C9	115.2 (3)	O6—C26—C27	123.9 (4)
N1—C8—C7	126.6 (3)	O5—C26—C27	112.6 (4)
C9—C8—C7	118.1 (3)	C28—C27—C26	125.4 (4)
C9—C10—C11	124.8 (3)	C28—C27—H27	117.3
C9—C10—H10	117.6	C26—C27—H27	117.3
C11—C10—H10	117.6	C27—C28—C29	125.7 (4)
O1—C11—C10	104.7 (3)	C27—C28—H28	117.2
O1—C11—C6	113.2 (3)	C29—C28—H28	117.2
C10—C11—C6	114.0 (3)	C30—C29—C34	116.4 (4)
O1—C11—H11	108.2	C30—C29—C28	121.5 (4)
C10—C11—H11	108.2	C34—C29—C28	122.1 (4)
C6—C11—H11	108.2	C29—C30—C31	121.1 (5)
O2—C12—C13	59.6 (2)	C29—C30—H30	119.5
O2—C12—C2	116.0 (3)	C31—C30—H30	119.5
C13—C12—C2	124.0 (3)	C32—C31—C30	119.5 (5)
O2—C12—C5	118.1 (3)	C32—C31—H31	120.2
C13—C12—C5	128.3 (3)	C30—C31—H31	120.2
C2—C12—C5	103.7 (3)	C33—C32—C31	120.7 (5)
O2—C13—C12	59.8 (2)	C33—C32—H32	119.6
O2—C13—H13A	117.8	C31—C32—H32	119.6
C12—C13—H13A	117.8	C32—C33—C34	119.4 (5)
O2—C13—H13B	117.8	C32—C33—H33	120.3
C12—C13—H13B	117.8	C34—C33—H33	120.3
H13A—C13—H13B	114.9	C33—C34—C29	122.8 (5)
C5—C14—H14A	109.5	C33—C34—Cl2	117.8 (4)
C5—C14—H14B	109.5	C29—C34—Cl2	119.4 (3)

C26—O5—N1—C8	172.1 (4)	O1—C2—C12—C13	−86.7 (4)
C11—O1—C2—C12	−65.2 (3)	C3—C2—C12—C13	153.4 (3)
C11—O1—C2—C3	46.7 (4)	O1—C2—C12—C5	72.6 (3)
O1—C2—C3—C4	−87.5 (3)	C3—C2—C12—C5	−47.4 (3)
C12—C2—C3—C4	28.0 (3)	C14—C5—C12—O2	37.1 (4)
C17—O3—C4—C3	−143.0 (3)	C4—C5—C12—O2	−83.8 (3)
C17—O3—C4—C5	102.6 (4)	C6—C5—C12—O2	162.9 (3)
C2—C3—C4—O3	−116.5 (3)	C14—C5—C12—C13	−34.9 (5)
C2—C3—C4—C5	0.1 (4)	C4—C5—C12—C13	−155.8 (3)
O3—C4—C5—C12	86.8 (3)	C6—C5—C12—C13	90.9 (4)
C3—C4—C5—C12	−27.8 (3)	C14—C5—C12—C2	167.0 (3)
O3—C4—C5—C14	−34.0 (4)	C4—C5—C12—C2	46.2 (3)
C3—C4—C5—C14	−148.6 (3)	C6—C5—C12—C2	−67.1 (3)
O3—C4—C5—C6	−161.0 (3)	C2—C12—C13—O2	−102.6 (3)
C3—C4—C5—C6	84.4 (3)	C5—C12—C13—O2	103.4 (4)
C12—C5—C6—C15	175.6 (3)	C4—O3—C17—O4	3.8 (6)
C14—C5—C6—C15	−58.3 (4)	C4—O3—C17—C18	−174.6 (3)
C4—C5—C6—C15	69.0 (3)	O4—C17—C18—C19	−5.6 (7)
C12—C5—C6—C11	54.6 (3)	O3—C17—C18—C19	172.8 (4)
C14—C5—C6—C11	−179.3 (3)	C17—C18—C19—C20	−176.8 (4)
C4—C5—C6—C11	−52.0 (3)	C18—C19—C20—C21	−22.9 (6)
C12—C5—C6—C7	−64.7 (3)	C18—C19—C20—C25	154.5 (4)
C14—C5—C6—C7	61.5 (4)	C25—C20—C21—C22	0.0 (6)
C4—C5—C6—C7	−171.2 (3)	C19—C20—C21—C22	177.5 (4)
C15—C6—C7—C8	−62.5 (4)	C20—C21—C22—C23	−0.2 (7)
C11—C6—C7—C8	56.1 (4)	C21—C22—C23—C24	−0.5 (8)
C5—C6—C7—C8	176.3 (3)	C22—C23—C24—C25	1.4 (8)
O5—N1—C8—C9	−177.8 (3)	C23—C24—C25—C20	−1.6 (7)
O5—N1—C8—C7	−1.6 (5)	C23—C24—C25—Cl1	−179.0 (4)
C10—C9—C8—N1	−173.9 (4)	C21—C20—C25—C24	0.9 (6)
C16—C9—C8—N1	6.7 (6)	C19—C20—C25—C24	−176.6 (4)
C10—C9—C8—C7	9.6 (6)	C21—C20—C25—Cl1	178.3 (3)
C16—C9—C8—C7	−169.8 (4)	C19—C20—C25—Cl1	0.8 (5)
C6—C7—C8—N1	143.3 (4)	N1—O5—C26—O6	1.4 (7)
C6—C7—C8—C9	−40.6 (5)	N1—O5—C26—C27	−177.1 (4)
C8—C9—C10—C11	3.5 (6)	O6—C26—C27—C28	−172.9 (6)
C16—C9—C10—C11	−177.1 (4)	O5—C26—C27—C28	5.6 (7)
C2—O1—C11—C10	176.1 (3)	C26—C27—C28—C29	179.2 (4)
C2—O1—C11—C6	51.4 (4)	C27—C28—C29—C30	28.8 (6)
C9—C10—C11—O1	−108.8 (4)	C27—C28—C29—C34	−149.4 (4)
C9—C10—C11—C6	15.4 (5)	C34—C29—C30—C31	−0.6 (6)
C15—C6—C11—O1	−166.7 (3)	C28—C29—C30—C31	−178.9 (4)
C7—C6—C11—O1	75.8 (3)	C29—C30—C31—C32	0.9 (7)
C5—C6—C11—O1	−45.3 (4)	C30—C31—C32—C33	−0.6 (7)
C15—C6—C11—C10	73.8 (4)	C31—C32—C33—C34	0.1 (8)
C7—C6—C11—C10	−43.8 (4)	C32—C33—C34—C29	0.2 (7)
C5—C6—C11—C10	−164.8 (3)	C32—C33—C34—Cl2	179.7 (4)
C13—O2—C12—C2	115.8 (4)	C30—C29—C34—C33	0.1 (6)
C13—O2—C12—C5	−120.1 (4)	C28—C29—C34—C33	178.4 (4)
O1—C2—C12—O2	−156.3 (3)	C30—C29—C34—Cl2	−179.5 (3)
C3—C2—C12—O2	83.8 (3)	C28—C29—C34—Cl2	−1.2 (6)

Experimental details

Crystal data
Chemical formula	C₃₃H₃₁Cl₂NO₆
M_r	608.49
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	7.2302 (4), 14.4055 (6), 14.6663 (6)
β (°)	94.414 (1)
V (Å³)	1523.03 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.41 × 0.36 × 0.29

Data collection
Diffractometer	Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.895, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	15059, 6713, 3890
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.130, 1.00
No. of reflections	6713
No. of parameters	384
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.30
Absolute structure	Flack (1983), 3099 Friedel pairs
Absolute structure parameter	0.02 (8)

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

This project was supported by grants from the National Key Technology R&D Program of China (2011BAE06B04–10). The authors are grateful to Professor Jianming Gu for the crystal analysis.

References

Chen, S.-Y., Zhang, C.-L., Chen, Y.-Z. & Lin, F.-C. (2008). Acta Cryst. E64, o702. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cheng, J.-L., Zhou, Y., Lin, F.-C., Zhao, J.-H. & Zhu, G.-N. (2009). Acta Cryst. E65, o2879. Web of Science CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Nielsen, K. F., Grafenhan, T., Zafari, D. & Thrane, U. (2005). J. Agric. Food Chem. 53, 8190–8196. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2007). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, X., Wang, Z., Cheng, J., Zhou, Y. & Zhao, J. (2010). Acta Cryst. E66, o2097. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, C., Liu, S., Lin, F., Kubicek, C. P. & Druzhinina, I. S. (2007). Microbiol. Lett. 270, 90–96. Web of Science CrossRef CAS Google Scholar

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