Experimental. Crystal data. C 22 H 26 N 2 O 3 M r = Triclinic, P1 a = (3) Å b = (4) Å c = (4) Å = (6) = 100.

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1 Acta Crystallographica Section E Structure Reports Online ISSN Methoxy-14,15-dihydroandranginine Dian-Lei Wang, a Xiang-Hai Cai, b Peng Huang a * and He-Ping Huang a * a School of Pharmacy, Anhui University of Traditional Chinese Medicine, Hefei , People s Republic of China, and b State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming , People s Republic of China Correspondence great7701@126.com, hhp760222@126.com Received 11 January 2013; accepted 28 April 2013 Key indicators: single-crystal X-ray study; T = 153 K; mean (C C) = Å; R factor = 0.041; wr factor = 0.089; data-to-parameter ratio = Experimental Crystal data C 22 H 26 N 2 O 3 M r = Triclinic, P1 a = (3) Å b = (4) Å c = (4) Å = (6) = (5) Data collection Rigaku AFC10/Saturn724+ diffractometer 8672 measured reflections Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 250 parameters organic compounds = (6) V = (6) Å 3 Z =2 Mo K radiation = 0.09 mm 1 T = 153 K mm 4028 independent reflections 2868 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.27 e Å 3 min = 0.19 e Å 3 The title polycyclic alkaloid, C 22 H 26 N 2 O 3, an indole derivative obtained from Melodinus yunnanensis, comprises three chiral C atoms and crystallizes as a racemate. Its seven-membered heterocyclic ring has a twisted conformation, with the N atom within the plane of the indole moiety and with two adjacent C atoms deviating in opposite directions from its plane by (3) (methylene C) and (3) Å (methine C). In the crystal, pairs of N HO hydrogen bonds connect the molecules into centrosymmetric dimers. Related literature Indole alkaloid derivatives obtained from Melodinus yunnanensis have been investigated due to their antimalarial and anticancer properties, see: Kanfan et al. (1974). For the structures of related compounds, see: Danieli et al. (1977a) and for applications of similar compounds see: Danieli et al. (1977a,b) Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA N1 H1NO3 i (17) (16) (18) (15) Symmetry code: (i) x þ 2; y þ 1; z þ 1. Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; 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. This work was supported financially by the National Natural Science Foundation of China ( , ) and the Natural Science Foundation of th Education Committee of Anhui Province (KJ2010A210). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LD2092). References Danieli, B., Lesma, G., Luzzani, M., Passarella, D. & Silvani, A. (1977b). Tetrahedron, 34, Danieli, B., Lesma, G., Martinelli, M., Passarella, D. & Silvani, A. (1977a). J. Org. Chem. 19, Kanfan, C., Massiot, G., Ahond, A., Das, B. C., Husson, H. P. & Potier, P. (1974). J. Chem. Soc. Chem Commun. pp Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Sheldrick, G. M. (2008). Acta Cryst. A64, doi: /s Wang et al. o833

2 supporting information [doi: /s ] 15-Methoxy-14,15-dihydroandranginine Dian-Lei Wang, Xiang-Hai Cai, Peng Huang and He-Ping Huang S1. Comment The indole alkaloid derivatives of the title compound, (I), are obtained from Melodinus yunnanensis leaves and twigs by column chromatography. These indole alkaloid derivatives have been investigated due to their antimalarial and anticancer properties (Kanfan et al. 1974). Herewith we present the crystal structure of (I). S2. Experimental Dried and powdered leaves and twigs of Melodinus yunnanensis (20 kg) were extracted three times with methanol at room temperature and the solvent evaporated in vacuo. The residue was dissolved in 0.3% aqueous hydrochloric acid, and the solution subsequently basified using ammonia water to ph The basic solution was partitioned with EtOAc, producing an aqueous and EtOAc phase. The resulting EtOAc fraction (105 g) was collected and then subjected to column chromatography over silica gel and eluted with a chloroform-acetone gradient (1/0 to 3/1, v/v) to afford the title compound (500 mg). The product was purified by recrystalliaztion from methanol to give colorless crystals. S3. Refinement All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C H = Å and U iso (H) = 1.2 U eq. Positions of hydrogen atoms of methyl groups were rotationally optimized. Atom H of amino group was refined isotropically without restrictions. sup-1

3 Figure 1 The molecular structure of the title molecule(i) with atom labels and 30% probability displacement ellipsoids. sup-2

4 Figure 2 packing diagram of (I). Hydrogen bonds shown as dashed lines. 15-Methoxy-14,15-dihydroandranginine Crystal data C 22 H 26 N 2 O 3 M r = Triclinic, P1 Hall symbol: -P 1 a = (3) Å b = (4) Å c = (4) Å α = (6) β = (5) γ = (6) V = (6) Å 3 Data collection Rigaku AFC10/Saturn724+ diffractometer Radiation source: Rotating Anode Z = 2 F(000) = 392 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 2653 reflections θ = µ = 0.09 mm 1 T = 153 K Prism, colorless mm Graphite monochromator Detector resolution: pixels mm -1 phi and ω scans sup-3

5 8672 measured reflections 4028 independent reflections 2868 reflections with I > 2σ(I) R int = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 250 parameters 0 restraints Primary atom site location: structure-invariant direct methods θ max = 27.5, θ min = 3.0 h = 8 8 k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0318P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.27 e Å 3 Δρ min = 0.19 e Å 3 Special details 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq O (16) (9) (9) (3) O (15) (9) (8) (2) O (15) (9) (8) (2) N (18) (12) (10) (3) N (17) (10) (9) (3) C (2) (13) (11) (3) C (2) (14) (12) (3) H3A * H3B * C (2) (13) (11) (3) H5A * H5B * C (2) (13) (12) (3) H6A * H6B * C (2) (13) (12) (3) C (2) (13) (12) (3) C (2) (14) (12) (3) H * C (2) (14) (13) (4) sup-4

6 H * C (2) (14) (13) (4) H * C (2) (14) (12) (4) H * C (2) (13) (12) (3) C (2) (15) (12) (4) H14A * H14B * C (2) (14) (12) (3) H * C (2) (12) (11) (3) C (2) (13) (12) (3) H17A * H17B * C (2) (14) (12) (3) H18A * H18B * C (2) (13) (12) (3) H * C (2) (13) (12) (3) C (2) (12) (11) (3) H * C (3) (17) (15) (4) H22A * H22B * H22C * C (2) (12) (12) (3) C (2) (13) (13) (3) H24A * H24B * H24C * H1N (2) (16) (14) (5)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O (6) (6) (6) (5) (5) (5) O (6) (6) (6) (4) (5) (4) O (6) (6) (6) (4) (5) (4) N (7) (7) (7) (5) (5) (5) N (6) (7) (6) (5) (5) (5) C (7) (7) (7) (6) (6) (6) C (8) (8) (8) (6) (6) (6) C (7) (8) (7) (6) (6) (6) C (8) (8) (8) (6) (6) (6) C (7) (7) (7) (6) (6) (6) C (8) (8) (7) (6) (6) (6) sup-5

7 C (9) (8) (8) (6) (7) (6) C (9) (8) (8) (7) (7) (6) C (9) (9) (8) (7) (7) (7) C (8) (9) (8) (7) (7) (7) C (8) (8) (7) (6) (6) (6) C (8) (9) (8) (7) (6) (7) C (8) (8) (7) (6) (6) (6) C (7) (7) (7) (6) (6) (5) C (7) (8) (8) (6) (6) (6) C (8) (8) (8) (6) (7) (6) C (8) (8) (7) (6) (6) (6) C (7) (8) (7) (6) (6) (6) C (7) (7) (7) (6) (6) (6) C (10) (11) (10) (8) (8) (8) C (7) (7) (7) (6) (6) (6) C (8) (8) (9) (6) (7) (6) Geometric parameters (Å, º) O1 C (19) C11 C (2) O1 C (18) C11 H O2 C (17) C12 C (2) O2 C (17) C12 H O3 C (16) C14 C (2) N1 C (19) C14 H14A N1 C (18) C14 H14B N1 H1N (17) C15 C (19) N4 C (18) C15 H N4 C (17) C16 C (19) N4 C (18) C16 C (2) C2 C (2) C16 C (18) C2 C (19) C17 C (2) C3 C (2) C17 H17A C3 H3A C17 H17B C3 H3B C18 C (2) C5 C (2) C18 H18A C5 H5A C18 H18B C5 H5B C19 C (2) C6 C (2) C19 H C6 H6A C20 C (2) C6 H6B C21 H C7 C (2) C22 H22A C8 C (2) C22 H22B C8 C (2) C22 H22C C9 C (2) C24 H24A C9 H C24 H24B C10 C (2) C24 H24C C10 H sup-6

8 C22 O1 C (12) C3 C14 H14B C23 O2 C (11) H14A C14 H14B C13 N1 C (12) O1 C15 C (12) C13 N1 H1N (11) O1 C15 C (12) C2 N1 H1N (11) C14 C15 C (12) C5 N4 C (11) O1 C15 H C5 N4 C (10) C14 C15 H C3 N4 C (11) C20 C15 H C7 C2 N (12) C2 C16 C (11) C7 C2 C (12) C2 C16 C (11) N1 C2 C (12) C23 C16 C (11) N4 C3 C (12) C2 C16 C (11) N4 C3 H3A C23 C16 C (11) C14 C3 H3A C17 C16 C (11) N4 C3 H3B C18 C17 C (12) C14 C3 H3B C18 C17 H17A H3A C3 H3B C16 C17 H17A N4 C5 C (12) C18 C17 H17B N4 C5 H5A C16 C17 H17B C6 C5 H5A H17A C17 H17B N4 C5 H5B C19 C18 C (12) C6 C5 H5B C19 C18 H18A H5A C5 H5B C17 C18 H18A C7 C6 C (12) C19 C18 H18B C7 C6 H6A C17 C18 H18B C5 C6 H6A H18A C18 H18B C7 C6 H6B C20 C19 C (13) C5 C6 H6B C20 C19 H H6A C6 H6B C18 C19 H C2 C7 C (12) C19 C20 C (13) C2 C7 C (13) C19 C20 C (13) C8 C7 C (13) C15 C20 C (12) C9 C8 C (13) N4 C21 C (11) C9 C8 C (14) N4 C21 C (11) C13 C8 C (13) C20 C21 C (11) C10 C9 C (15) N4 C21 H C10 C9 H C20 C21 H C8 C9 H C16 C21 H C9 C10 C (15) O1 C22 H22A C9 C10 H O1 C22 H22B C11 C10 H H22A C22 H22B C12 C11 C (14) O1 C22 H22C C12 C11 H H22A C22 H22C C10 C11 H H22B C22 H22C C11 C12 C (15) O3 C23 O (13) C11 C12 H O3 C23 C (12) C13 C12 H O2 C23 C (11) sup-7

9 N1 C13 C (14) O2 C24 H24A N1 C13 C (12) O2 C24 H24B C12 C13 C (14) H24A C24 H24B C15 C14 C (12) O2 C24 H24C C15 C14 H14A H24A C24 H24C C3 C14 H14A H24B C24 H24C C15 C14 H14B C13 N1 C2 C (16) C7 C2 C16 C (14) C13 N1 C2 C (12) N1 C2 C16 C (17) C5 N4 C3 C (12) C7 C2 C16 C (19) C21 N4 C3 C (15) N1 C2 C16 C (12) C3 N4 C5 C (15) C2 C16 C17 C (11) C21 N4 C5 C (16) C23 C16 C17 C (14) N4 C5 C6 C (15) C21 C16 C17 C (15) N1 C2 C7 C (15) C16 C17 C18 C (16) C16 C2 C7 C (13) C17 C18 C19 C (2) N1 C2 C7 C (13) C18 C19 C20 C (13) C16 C2 C7 C6 8.1 (2) C18 C19 C20 C (2) C5 C6 C7 C (2) O1 C15 C20 C (16) C5 C6 C7 C (13) C14 C15 C20 C (15) C2 C7 C8 C (15) O1 C15 C20 C (15) C6 C7 C8 C9 5.0 (2) C14 C15 C20 C (17) C2 C7 C8 C (15) C5 N4 C21 C (11) C6 C7 C8 C (13) C3 N4 C21 C (14) C13 C8 C9 C (2) C5 N4 C21 C (15) C7 C8 C9 C (15) C3 N4 C21 C (11) C8 C9 C10 C (2) C19 C20 C21 N (14) C9 C10 C11 C (2) C15 C20 C21 N (15) C10 C11 C12 C (2) C19 C20 C21 C (19) C2 N1 C13 C (14) C15 C20 C21 C (12) C2 N1 C13 C (15) C2 C16 C21 N (14) C11 C12 C13 N (14) C23 C16 C21 N (16) C11 C12 C13 C8 0.3 (2) C17 C16 C21 N (12) C9 C8 C13 N (12) C2 C16 C21 C (11) C7 C8 C13 N (15) C23 C16 C21 C (14) C9 C8 C13 C (2) C17 C16 C21 C (15) C7 C8 C13 C (13) C24 O2 C23 O3 9.3 (2) N4 C3 C14 C (16) C24 O2 C23 C (12) C22 O1 C15 C (12) C2 C16 C23 O (18) C22 O1 C15 C (15) C17 C16 C23 O (16) C3 C14 C15 O (14) C21 C16 C23 O (12) C3 C14 C15 C (17) C2 C16 C23 O (12) C7 C2 C16 C (16) C17 C16 C23 O (13) N1 C2 C16 C (16) C21 C16 C23 O (17) sup-8

10 Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N1 H1N O3 i (17) (16) (18) (15) Symmetry code: (i) x+2, y+1, z+1. sup-9