(1R,3S,4R,4aS,7R,7aS,10R,12aR)-3-Azido-4,7,10-trimethyl-1,10-epidioxy­per­hydropyrano[4,3-j][1,2]benzodiox­epine

Xie, L.; Zhai, X.; Zuo, J.; Zhao, Y.; Gong, P.

doi:10.1107/S1600536810024566

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1839

doi:10.1107/S1600536810024566

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(1R,3S,4R,4aS,7R,7aS,10R,12aR)-3-Azido-4,7,10-trimethyl-1,10-epidioxyperhydropyrano[4,3-j][1,2]benzodioxepine

Lijun Xie,^a Xin Zhai,^a Jian Zuo,^b Yanfang Zhao ^a and Ping Gong ^a ^*

^aKey Laboratory of Original New Drug Design and Discovery of the Ministry of Education, Shenyang Pharmaceutical University, Shenyang, Liaoning 110016, People's Republic of China, and ^bKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100, People's Republic of China
^*Correspondence e-mail: gongpinggp@126.com

(Received 15 June 2010; accepted 23 June 2010; online 26 June 2010)

In the title compound, C₁₅H₂₃N₃O₄, the six-membered pyran, cyclohexane and trioxane rings adopt chair, chair and boat conformations, respectively, while the seven-membered rings adopt distorted boat and very distorted chair conformations. In the crystal, adjacent molecules are connected by weak C—H⋯N and C—H⋯O interactions.

Related literature

For general background to artemisinin, a sesquiterpene endoperoxide widely used to treat drug-resistant malaria, see: Liu et al. (1979 ). For the anticancer properties of the title compound, see: Efferth et al. (1996 ); Chadwick et al. (2009 ); Galal et al. (2009 ). For structural analyses of highly related compounds, see: Gul et al. (2009 ); Jasinskiet al. (2008 ).

Experimental

Crystal data

C₁₅H₂₃N₃O₄
M_r = 309.36
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.9938 (9) Å
b = 11.207 (1) Å
c = 17.984 (2) Å
V = 1611.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.50 × 0.40 × 0.38 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.955, T_max = 0.965
7585 measured reflections
1657 independent reflections
1130 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.103
S = 1.09
1657 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯N3ⁱ	0.97	2.68	3.628 (6)	167
C10—H10⋯O3ⁱⁱ	0.98	2.67	3.535 (5)	148
C12—H12A⋯O3ⁱⁱ	0.97	2.65	3.508 (5)	147
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810024566/im2212sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024566/im2212Isup2.hkl

checkCIF report

Comment top

Artemisinin, a sesquiterpene endoperoxide isolated from Artemisia annua L, is being widely used to treat drug-resistant malaria (Liu et al., 1979). In addition, Artemisinin and its derivatives also showed potent and broad anticancer properties in different human cancer cell lines and animal models (Efferth et al., 1996). These compounds contain an endoperoxide bridge (R—O—O—R) which is required for their biological activities. Recently, there are many reports about significant anticancer activities of artemisinin derivatives, which were expected to be more stable toward the metabolism process (Chadwick et al., 2009; Galal et al., 2009). Herein, we present the synthesis and structure of an artemisinin derivatives, (1R,3S,4R,4aS,7R,7aS,10R,12aR)-3-Azido- 4,7,10-trimethyl-1,10-epoxy-decahydro- 12H-pyrano[4,3-j]-1,2-benzodioxepin.

The crystal structure of the title compound is given in Fig. 1. The bond lengths and angles in the title compound are found to have normal values with respect to highly related compounds (Gul et al., 2009; Jasinski et al., 2008). The six membered rings A, B and C adopt chair, chair and boat conformations, respectively. In the crystal, adjacent molecules are connected by non-classical C—H···N and C—H···O hydrogen bonding, with the distance of 3.628 (6), 3.508 (5) and 3.535 (5) Å (Table 1), respectively.

Related literature top

For general background to Artemisinin, a sesquiterpene endoperoxide widely used to treat drug-resistant malaria, see: Liu et al. (1979). For the anticancer properties of the title compound, see: Efferth et al. (1996); Chadwick et al. (2009); Galal et al. (2009). For structural analyses of highly related compounds, see: Gul et al. (2009); Jasinski et al. (2008).

Experimental top

Trimethylchlorosilane (300 mmol, 38.1 ml) was added gradually to a solution of dihydroartemisinin (200 mmol, 56.8 g, diastereomeric mixture with R and S configuration at C(3)) and sodium azide (300 mmol, 19.5 g) in CH₂Cl₂(300 ml). Then sodium iodide (20 mmol, 3.0 g) was added to the reaction mixture at low temperature. The reaction mixture was stirred at room temperature for 28 h. The mixture was quenched with a saturated NaHCO₃ solution (100 ml) and diluted with CH₂Cl₂. Two phases were separated and the organic phase was washed with brine, dried over MgSO₄, filtered, and concentrated under reduced pressure. The crude mixture was purified by column chromatography (silica, 1%-5% EtOAc/hexanes) to furnish the product (94 mmol, 29.0 g) and it's diastereomer with R configuration at C(3). Colorless single crystals of the title compound was obtained in CH₂Cl₂ solution after 10 days by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

(1R,3S,4R,4aS,7R,7aS,10R, 12aR)-3-Azido-4,7,10-trimethyl-1,10-epidioxyperhydropyrano[4,3- j][1,2]benzodioxepine top

Crystal data top

C₁₅H₂₃N₃O₄	F(000) = 664
M_r = 309.36	D_x = 1.275 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2309 reflections
a = 7.9938 (9) Å	θ = 2.3–21.4°
b = 11.207 (1) Å	µ = 0.09 mm⁻¹
c = 17.984 (2) Å	T = 298 K
V = 1611.1 (3) Å³	Block, colorless
Z = 4	0.50 × 0.40 × 0.38 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1657 independent reflections
Radiation source: fine-focus sealed tube	1130 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
phi and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→7
T_min = 0.955, T_max = 0.965	k = −13→13
7585 measured reflections	l = −16→21

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0312P)² + 0.4488P] where P = (F_o² + 2F_c²)/3
1657 reflections	(Δ/σ)_max < 0.001
202 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₅H₂₃N₃O₄	V = 1611.1 (3) Å³
M_r = 309.36	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.9938 (9) Å	µ = 0.09 mm⁻¹
b = 11.207 (1) Å	T = 298 K
c = 17.984 (2) Å	0.50 × 0.40 × 0.38 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1657 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1130 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.965	R_int = 0.043
7585 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.09	Δρ_max = 0.12 e Å⁻³
1657 reflections	Δρ_min = −0.16 e Å⁻³
202 parameters

Special details top

Experimental. We took dihydroartemisinin (mixture of 3R and 3S isomers of hydroxyl group) as the starting material in our experiment. During the course of synthesis, we got a mixture of two diastereomers with 3S and 3R and all other stereogenic centers are known and still in the configuration as they were in the starting compound. The mixture was separated by silica gel column chromatography and the title compound with 3S was crystallized under our conditions, while the other one (3R) was obtained as amorphous powder.

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
N1	0.4489 (5)	0.4264 (3)	0.41235 (17)	0.0737 (10)
N2	0.3162 (6)	0.4810 (3)	0.41854 (19)	0.0756 (10)
N3	0.2016 (6)	0.5395 (4)	0.4253 (3)	0.1117 (15)
O1	0.3528 (3)	0.3297 (2)	0.30143 (11)	0.0583 (6)
O2	0.3573 (3)	0.3910 (2)	0.18223 (12)	0.0601 (7)
O3	0.4236 (3)	0.1895 (2)	0.17929 (14)	0.0726 (8)
O4	0.5935 (3)	0.2044 (2)	0.20749 (13)	0.0669 (7)
C1	0.4297 (5)	0.3114 (3)	0.37062 (18)	0.0656 (10)
H1	0.3554	0.2601	0.3999	0.079*
C2	0.5957 (5)	0.2491 (4)	0.3652 (2)	0.0738 (12)
H2	0.5712	0.1695	0.3454	0.089*
C3	0.7131 (5)	0.3075 (4)	0.3087 (2)	0.0670 (11)
H3	0.8021	0.2495	0.2989	0.080*
C4	0.6214 (4)	0.3259 (3)	0.23485 (17)	0.0528 (9)
C5	0.4547 (4)	0.3878 (3)	0.24650 (17)	0.0495 (9)
H5	0.4759	0.4699	0.2627	0.059*
C6	0.3823 (5)	0.2889 (4)	0.13467 (19)	0.0683 (11)
C7	0.5171 (5)	0.3170 (4)	0.0778 (2)	0.0789 (12)
H7A	0.5780	0.2444	0.0667	0.095*
H7B	0.4638	0.3435	0.0322	0.095*
C8	0.6406 (6)	0.4117 (4)	0.1028 (2)	0.0765 (12)
H8A	0.5809	0.4867	0.1075	0.092*
H8B	0.7234	0.4218	0.0639	0.092*
C9	0.7325 (5)	0.3881 (3)	0.1758 (2)	0.0653 (10)
H9	0.8227	0.3319	0.1640	0.078*
C10	0.8171 (5)	0.5007 (4)	0.2052 (2)	0.0798 (12)
H10	0.7293	0.5586	0.2172	0.096*
C11	0.9123 (5)	0.4740 (5)	0.2759 (3)	0.0973 (16)
H11A	0.9621	0.5470	0.2945	0.117*
H11B	1.0020	0.4184	0.2650	0.117*
C12	0.7998 (5)	0.4211 (4)	0.3354 (2)	0.0840 (13)
H12A	0.7159	0.4795	0.3493	0.101*
H12B	0.8661	0.4032	0.3791	0.101*
C13	0.6724 (7)	0.2282 (5)	0.4424 (2)	0.1150 (19)
H13A	0.6936	0.3037	0.4659	0.173*
H13B	0.7756	0.1851	0.4374	0.173*
H13C	0.5960	0.1828	0.4724	0.173*
C14	0.2153 (6)	0.2572 (5)	0.1011 (3)	0.1060 (17)
H14A	0.2293	0.1929	0.0665	0.159*
H14B	0.1704	0.3255	0.0758	0.159*
H14C	0.1398	0.2332	0.1398	0.159*
C15	0.9352 (6)	0.5587 (5)	0.1476 (3)	0.124 (2)
H15A	0.9829	0.6300	0.1683	0.186*
H15B	0.8730	0.5785	0.1036	0.186*
H15C	1.0229	0.5038	0.1351	0.186*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.085 (2)	0.083 (2)	0.0530 (19)	−0.002 (2)	0.003 (2)	−0.0156 (19)
N2	0.094 (3)	0.079 (3)	0.055 (2)	−0.016 (2)	0.017 (2)	−0.015 (2)
N3	0.105 (3)	0.112 (3)	0.117 (4)	0.005 (3)	0.021 (3)	−0.037 (3)
O1	0.0652 (14)	0.0705 (16)	0.0393 (12)	−0.0044 (13)	0.0041 (11)	−0.0011 (12)
O2	0.0722 (15)	0.0672 (15)	0.0410 (13)	0.0191 (14)	−0.0084 (13)	−0.0062 (13)
O3	0.101 (2)	0.0608 (16)	0.0560 (14)	−0.0006 (16)	−0.0084 (15)	−0.0067 (15)
O4	0.0912 (19)	0.0523 (15)	0.0572 (14)	0.0182 (14)	0.0006 (14)	−0.0024 (13)
C1	0.095 (3)	0.065 (2)	0.0366 (17)	−0.013 (2)	0.0044 (19)	−0.0005 (19)
C2	0.107 (3)	0.070 (3)	0.044 (2)	0.014 (3)	−0.011 (2)	0.005 (2)
C3	0.068 (2)	0.071 (3)	0.062 (2)	0.019 (2)	−0.010 (2)	0.002 (2)
C4	0.061 (2)	0.051 (2)	0.0465 (18)	0.0126 (19)	0.0015 (17)	−0.0009 (17)
C5	0.058 (2)	0.054 (2)	0.0362 (16)	0.0069 (19)	−0.0015 (18)	−0.0046 (17)
C6	0.094 (3)	0.068 (3)	0.0431 (19)	0.013 (2)	−0.011 (2)	−0.008 (2)
C7	0.111 (3)	0.083 (3)	0.043 (2)	0.025 (3)	0.003 (2)	−0.002 (2)
C8	0.099 (3)	0.082 (3)	0.048 (2)	0.013 (3)	0.022 (2)	0.010 (2)
C9	0.065 (2)	0.068 (2)	0.063 (2)	0.017 (2)	0.016 (2)	−0.001 (2)
C10	0.067 (3)	0.083 (3)	0.090 (3)	−0.003 (2)	0.016 (2)	0.000 (3)
C11	0.063 (3)	0.118 (4)	0.111 (4)	−0.008 (3)	−0.001 (3)	−0.011 (3)
C12	0.076 (3)	0.103 (3)	0.073 (3)	0.007 (3)	−0.018 (2)	−0.006 (3)
C13	0.160 (5)	0.127 (4)	0.057 (3)	0.039 (4)	−0.024 (3)	0.018 (3)
C14	0.120 (4)	0.124 (4)	0.074 (3)	0.003 (4)	−0.035 (3)	−0.030 (3)
C15	0.108 (4)	0.121 (4)	0.143 (5)	−0.028 (4)	0.040 (4)	0.010 (4)

Geometric parameters (Å, º) top

N1—N2	1.229 (5)	C7—H7A	0.9700
N1—C1	1.499 (5)	C7—H7B	0.9700
N2—N3	1.133 (5)	C8—C9	1.528 (5)
O1—C1	1.403 (4)	C8—H8A	0.9700
O1—C5	1.437 (4)	C8—H8B	0.9700
O2—C5	1.394 (4)	C9—C10	1.526 (5)
O2—C6	1.442 (4)	C9—H9	0.9800
O3—C6	1.412 (4)	C10—C11	1.511 (6)
O3—O4	1.459 (3)	C10—C15	1.545 (6)
O4—C4	1.464 (4)	C10—H10	0.9800
C1—C2	1.503 (6)	C11—C12	1.518 (6)
C1—H1	0.9800	C11—H11A	0.9700
C2—C3	1.530 (5)	C11—H11B	0.9700
C2—C13	1.536 (5)	C12—H12A	0.9700
C2—H2	0.9800	C12—H12B	0.9700
C3—C12	1.527 (5)	C13—H13A	0.9600
C3—C4	1.531 (4)	C13—H13B	0.9600
C3—H3	0.9800	C13—H13C	0.9600
C4—C5	1.517 (5)	C14—H14A	0.9600
C4—C9	1.550 (5)	C14—H14B	0.9600
C5—H5	0.9800	C14—H14C	0.9600
C6—C14	1.507 (5)	C15—H15A	0.9600
C6—C7	1.518 (5)	C15—H15B	0.9600
C7—C8	1.518 (6)	C15—H15C	0.9600

N2—N1—C1	112.6 (3)	C7—C8—C9	116.5 (3)
N3—N2—N1	174.3 (4)	C7—C8—H8A	108.2
C1—O1—C5	115.3 (3)	C9—C8—H8A	108.2
C5—O2—C6	113.2 (3)	C7—C8—H8B	108.2
C6—O3—O4	108.9 (3)	C9—C8—H8B	108.2
O3—O4—C4	111.4 (2)	H8A—C8—H8B	107.3
O1—C1—N1	111.3 (3)	C10—C9—C8	111.6 (3)
O1—C1—C2	113.4 (3)	C10—C9—C4	112.8 (3)
N1—C1—C2	110.0 (3)	C8—C9—C4	113.0 (3)
O1—C1—H1	107.3	C10—C9—H9	106.3
N1—C1—H1	107.3	C8—C9—H9	106.3
C2—C1—H1	107.3	C4—C9—H9	106.3
C1—C2—C3	112.7 (3)	C11—C10—C9	110.6 (4)
C1—C2—C13	111.4 (3)	C11—C10—C15	109.9 (4)
C3—C2—C13	114.9 (4)	C9—C10—C15	112.7 (4)
C1—C2—H2	105.7	C11—C10—H10	107.9
C3—C2—H2	105.7	C9—C10—H10	107.9
C13—C2—H2	105.7	C15—C10—H10	107.9
C12—C3—C2	115.3 (3)	C10—C11—C12	111.8 (3)
C12—C3—C4	112.2 (3)	C10—C11—H11A	109.3
C2—C3—C4	109.9 (3)	C12—C11—H11A	109.3
C12—C3—H3	106.3	C10—C11—H11B	109.3
C2—C3—H3	106.3	C12—C11—H11B	109.3
C4—C3—H3	106.3	H11A—C11—H11B	107.9
O4—C4—C5	109.7 (3)	C11—C12—C3	111.9 (4)
O4—C4—C3	103.9 (3)	C11—C12—H12A	109.2
C5—C4—C3	111.2 (3)	C3—C12—H12A	109.2
O4—C4—C9	106.0 (3)	C11—C12—H12B	109.2
C5—C4—C9	113.1 (3)	C3—C12—H12B	109.2
C3—C4—C9	112.4 (3)	H12A—C12—H12B	107.9
O2—C5—O1	105.4 (3)	C2—C13—H13A	109.5
O2—C5—C4	112.8 (3)	C2—C13—H13B	109.5
O1—C5—C4	112.7 (3)	H13A—C13—H13B	109.5
O2—C5—H5	108.6	C2—C13—H13C	109.5
O1—C5—H5	108.6	H13A—C13—H13C	109.5
C4—C5—H5	108.6	H13B—C13—H13C	109.5
O3—C6—O2	108.7 (3)	C6—C14—H14A	109.5
O3—C6—C14	104.4 (4)	C6—C14—H14B	109.5
O2—C6—C14	107.5 (3)	H14A—C14—H14B	109.5
O3—C6—C7	112.4 (3)	C6—C14—H14C	109.5
O2—C6—C7	109.5 (3)	H14A—C14—H14C	109.5
C14—C6—C7	114.1 (3)	H14B—C14—H14C	109.5
C8—C7—C6	114.0 (3)	C10—C15—H15A	109.5
C8—C7—H7A	108.7	C10—C15—H15B	109.5
C6—C7—H7A	108.7	H15A—C15—H15B	109.5
C8—C7—H7B	108.7	C10—C15—H15C	109.5
C6—C7—H7B	108.7	H15A—C15—H15C	109.5
H7A—C7—H7B	107.6	H15B—C15—H15C	109.5

C1—N1—N2—N3	−159 (4)	O4—C4—C5—O1	62.1 (3)
C6—O3—O4—C4	44.7 (3)	C3—C4—C5—O1	−52.3 (4)
C5—O1—C1—N1	72.1 (4)	C9—C4—C5—O1	−179.9 (3)
C5—O1—C1—C2	−52.6 (4)	O4—O3—C6—O2	−72.3 (3)
N2—N1—C1—O1	53.7 (4)	O4—O3—C6—C14	173.2 (3)
N2—N1—C1—C2	−179.8 (3)	O4—O3—C6—C7	49.0 (4)
O1—C1—C2—C3	50.7 (4)	C5—O2—C6—O3	30.7 (4)
N1—C1—C2—C3	−74.6 (4)	C5—O2—C6—C14	143.2 (3)
O1—C1—C2—C13	−178.5 (4)	C5—O2—C6—C7	−92.4 (3)
N1—C1—C2—C13	56.2 (5)	O3—C6—C7—C8	−95.2 (4)
C1—C2—C3—C12	78.1 (4)	O2—C6—C7—C8	25.7 (4)
C13—C2—C3—C12	−50.9 (5)	C14—C6—C7—C8	146.2 (4)
C1—C2—C3—C4	−49.8 (4)	C6—C7—C8—C9	56.2 (5)
C13—C2—C3—C4	−178.8 (3)	C7—C8—C9—C10	−165.3 (3)
O3—O4—C4—C5	16.4 (3)	C7—C8—C9—C4	−36.8 (5)
O3—O4—C4—C3	135.4 (3)	O4—C4—C9—C10	−162.7 (3)
O3—O4—C4—C9	−106.0 (3)	C5—C4—C9—C10	77.1 (4)
C12—C3—C4—O4	162.9 (3)	C3—C4—C9—C10	−49.8 (4)
C2—C3—C4—O4	−67.5 (4)	O4—C4—C9—C8	69.6 (4)
C12—C3—C4—C5	−79.1 (4)	C5—C4—C9—C8	−50.7 (4)
C2—C3—C4—C5	50.5 (4)	C3—C4—C9—C8	−177.6 (3)
C12—C3—C4—C9	48.8 (4)	C8—C9—C10—C11	−177.9 (3)
C2—C3—C4—C9	178.4 (3)	C4—C9—C10—C11	53.5 (4)
C6—O2—C5—O1	−91.5 (3)	C8—C9—C10—C15	−54.6 (5)
C6—O2—C5—C4	31.9 (4)	C4—C9—C10—C15	176.9 (3)
C1—O1—C5—O2	177.1 (3)	C9—C10—C11—C12	−57.2 (5)
C1—O1—C5—C4	53.7 (4)	C15—C10—C11—C12	177.8 (4)
O4—C4—C5—O2	−57.1 (4)	C10—C11—C12—C3	57.2 (5)
C3—C4—C5—O2	−171.5 (3)	C2—C3—C12—C11	−179.4 (3)
C9—C4—C5—O2	61.0 (4)	C4—C3—C12—C11	−52.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···N3ⁱ	0.97	2.68	3.628 (6)	167
C10—H10···O3ⁱⁱ	0.98	2.67	3.535 (5)	148
C12—H12A···O3ⁱⁱ	0.97	2.65	3.508 (5)	147

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

Experimental details

Crystal data
Chemical formula	C₁₅H₂₃N₃O₄
M_r	309.36
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.9938 (9), 11.207 (1), 17.984 (2)
V (Å³)	1611.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.40 × 0.38

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.955, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	7585, 1657, 1130
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.103, 1.09
No. of reflections	1657
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.16

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···N3ⁱ	0.97	2.68	3.628 (6)	166.8
C10—H10···O3ⁱⁱ	0.98	2.67	3.535 (5)	147.8
C12—H12A···O3ⁱⁱ	0.97	2.65	3.508 (5)	146.9

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

Acknowledgements

The authors thank Liaocheng University for providing research facilities. This work was supported by the National S&T Major Project of China (No. 2009ZX09103–099) and the Science Project of Liaoning Province Education Department (No. L2010532).

References

Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chadwick, J., Mercer, A. E. & Park, B. K. (2009). Bioorg. Med. Chem. 17, 1325–1338. Web of Science CrossRef PubMed CAS Google Scholar
Efferth, T., Rucker, G. & Falkenberg, M. (1996). Arzneimittelforschung, 46, 196–200. CAS PubMed Web of Science Google Scholar
Galal, A. M., Gul, W. & Slade, D. (2009). Bioorg. Med. Chem. 17, 741–745. Web of Science CrossRef PubMed CAS Google Scholar
Gul, W., Carvalho, P., Galal, A., Avery, M. A. & El Sohly, M. A. (2009). Acta Cryst. E65, o358–o359. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jasinski, J. P., Butcher, R. J., Yathirajan, H. S., Narayana, B. & Sreevidya, T. V. (2008). Acta Cryst. E64, o585–o586. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, J. M., Ni, M. Y. & Fan, Y. (1979). Acta Chim. Sin. 37, 129–141. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 66| Part 7| July 2010| Page o1839

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(1R,3S,4R,4aS,7R,7aS,10R,12aR)-3-Azido-4,7,10-tri­methyl-1,10-epi­dioxy­per­hydro­pyrano[4,3-j][1,2]benzodiox­epine

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(1R,3S,4R,4aS,7R,7aS,10R,12aR)-3-Azido-4,7,10-trimethyl-1,10-epidioxyperhydropyrano[4,3-j][1,2]benzodioxepine