supplementary materials


ld2092 scheme

Acta Cryst. (2013). E69, o833    [ doi:10.1107/S1600536813011604 ]

15-Methoxy-14,15-dihydroandranginine

D.-L. Wang, X.-H. Cai, P. Huang and H.-P. Huang

Abstract top

The title polycyclic alkaloid, C22H26N2O3, 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 0.756 (3) (methylene C) and -0.802 (3) Å (methine C). In the crystal, pairs of N-H...O hydrogen bonds connect the molecules into centrosymmetric dimers.

Comment top

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).

Related literature top

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)

Experimental top

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 9–10. 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.

Refinement top

All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95-1.00 Å and Uiso(H) = 1.2 Ueq. Positions of hydrogen atoms of methyl groups were rotationally optimized. Atom H of amino group was refined isotropically without restrictions.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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
[Figure 1] Fig. 1. : The molecular structure of the title molecule(I) with atom labels and 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. : packing diagram of (I). Hydrogen bonds shown as dashed lines.
15-Methoxy-14,15-dihydroandranginine top
Crystal data top
C22H26N2O3Z = 2
Mr = 366.45F(000) = 392
Triclinic, P1Dx = 1.361 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.914 (3) ÅCell parameters from 2653 reflections
b = 11.232 (4) Åθ = 3.0–27.5°
c = 11.806 (4) ŵ = 0.09 mm1
α = 91.079 (6)°T = 153 K
β = 100.737 (5)°Prism, colorless
γ = 96.317 (6)°0.43 × 0.23 × 0.13 mm
V = 894.5 (6) Å3
Data collection top
Rigaku AFC10/Saturn724+
diffractometer
2868 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.030
Graphite monochromatorθmax = 27.5°, θmin = 3.0°
Detector resolution: 28.5714 pixels mm-1h = 88
phi and ω scansk = 1414
8672 measured reflectionsl = 1415
4028 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0318P)2 + 0.160P]
where P = (Fo2 + 2Fc2)/3
4028 reflections(Δ/σ)max = 0.001
250 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C22H26N2O3γ = 96.317 (6)°
Mr = 366.45V = 894.5 (6) Å3
Triclinic, P1Z = 2
a = 6.914 (3) ÅMo Kα radiation
b = 11.232 (4) ŵ = 0.09 mm1
c = 11.806 (4) ÅT = 153 K
α = 91.079 (6)°0.43 × 0.23 × 0.13 mm
β = 100.737 (5)°
Data collection top
Rigaku AFC10/Saturn724+
diffractometer
2868 reflections with I > 2σ(I)
8672 measured reflectionsRint = 0.030
4028 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089Δρmax = 0.27 e Å3
S = 1.00Δρmin = 0.19 e Å3
4028 reflectionsAbsolute structure: ?
250 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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
xyzUiso*/Ueq
O10.60683 (16)0.85999 (9)0.01190 (9)0.0277 (3)
O20.46541 (15)0.48350 (9)0.27560 (8)0.0239 (2)
O30.67895 (15)0.46849 (9)0.44057 (8)0.0244 (2)
N11.00622 (18)0.69322 (12)0.50300 (10)0.0205 (3)
N40.42553 (17)0.72717 (10)0.24809 (9)0.0185 (3)
C20.8300 (2)0.71262 (13)0.43152 (11)0.0175 (3)
C30.3346 (2)0.81220 (14)0.16762 (12)0.0229 (3)
H3A0.42080.88950.17580.028*
H3B0.20480.82690.18560.028*
C50.4122 (2)0.75869 (13)0.36721 (11)0.0194 (3)
H5A0.42150.68540.41230.023*
H5B0.27930.78400.36690.023*
C60.5671 (2)0.85711 (13)0.43018 (12)0.0215 (3)
H6A0.58760.92230.37690.026*
H6B0.51760.89110.49590.026*
C70.7607 (2)0.81020 (13)0.47397 (12)0.0189 (3)
C80.8993 (2)0.85448 (13)0.57542 (12)0.0201 (3)
C90.9085 (2)0.95044 (14)0.65452 (12)0.0246 (3)
H90.80691.00190.64570.030*
C101.0671 (2)0.96896 (14)0.74531 (13)0.0275 (4)
H101.07391.03360.79960.033*
C111.2176 (2)0.89460 (14)0.75890 (13)0.0280 (4)
H111.32610.91020.82170.034*
C121.2125 (2)0.79874 (14)0.68306 (12)0.0262 (4)
H121.31490.74780.69290.031*
C131.0515 (2)0.77946 (13)0.59135 (12)0.0202 (3)
C140.3065 (2)0.76125 (15)0.04513 (12)0.0259 (4)
H14A0.21990.68410.03710.031*
H14B0.24140.81730.00920.031*
C150.5046 (2)0.74198 (14)0.01609 (12)0.0235 (3)
H150.48460.69940.06110.028*
C160.7451 (2)0.63502 (12)0.32228 (11)0.0168 (3)
C170.9184 (2)0.59056 (13)0.27308 (12)0.0214 (3)
H17A1.01060.66080.26050.026*
H17B0.99200.54110.33080.026*
C180.8514 (2)0.51737 (14)0.16040 (12)0.0242 (3)
H18A0.96850.50190.12760.029*
H18B0.78120.43920.17500.029*
C190.7168 (2)0.58305 (13)0.07633 (12)0.0231 (3)
H190.69870.56060.00330.028*
C200.6212 (2)0.67091 (13)0.10661 (12)0.0200 (3)
C210.6292 (2)0.71353 (12)0.23085 (11)0.0177 (3)
H210.70390.79570.24040.021*
C220.7679 (3)0.86269 (17)0.04602 (15)0.0386 (4)
H22A0.83270.94500.04400.046*
H22B0.71990.83420.12640.046*
H22C0.86320.81070.00790.046*
C230.6256 (2)0.52135 (12)0.35387 (12)0.0174 (3)
C240.3361 (2)0.38405 (13)0.30607 (13)0.0250 (3)
H24A0.22270.36450.24270.030*
H24B0.28880.40610.37600.030*
H24C0.40920.31420.32020.030*
H1N1.078 (2)0.6370 (16)0.4959 (14)0.032 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0297 (6)0.0267 (6)0.0277 (6)0.0001 (5)0.0091 (5)0.0057 (5)
O20.0229 (6)0.0209 (6)0.0248 (6)0.0055 (4)0.0007 (5)0.0038 (4)
O30.0259 (6)0.0219 (6)0.0249 (6)0.0035 (4)0.0028 (5)0.0062 (4)
N10.0180 (7)0.0223 (7)0.0209 (7)0.0044 (5)0.0020 (5)0.0000 (5)
N40.0168 (6)0.0219 (7)0.0172 (6)0.0036 (5)0.0031 (5)0.0027 (5)
C20.0161 (7)0.0182 (7)0.0174 (7)0.0001 (6)0.0020 (6)0.0035 (6)
C30.0193 (8)0.0253 (8)0.0249 (8)0.0061 (6)0.0035 (6)0.0064 (6)
C50.0181 (7)0.0198 (8)0.0211 (7)0.0036 (6)0.0052 (6)0.0018 (6)
C60.0225 (8)0.0188 (8)0.0232 (8)0.0039 (6)0.0036 (6)0.0007 (6)
C70.0196 (7)0.0170 (7)0.0194 (7)0.0000 (6)0.0032 (6)0.0018 (6)
C80.0215 (8)0.0205 (8)0.0175 (7)0.0021 (6)0.0039 (6)0.0021 (6)
C90.0278 (9)0.0212 (8)0.0243 (8)0.0013 (6)0.0063 (7)0.0001 (6)
C100.0338 (9)0.0250 (8)0.0213 (8)0.0062 (7)0.0050 (7)0.0028 (6)
C110.0268 (9)0.0341 (9)0.0183 (8)0.0078 (7)0.0016 (7)0.0023 (7)
C120.0217 (8)0.0311 (9)0.0244 (8)0.0006 (7)0.0017 (7)0.0042 (7)
C130.0203 (8)0.0209 (8)0.0188 (7)0.0016 (6)0.0045 (6)0.0015 (6)
C140.0218 (8)0.0328 (9)0.0216 (8)0.0025 (7)0.0003 (6)0.0063 (7)
C150.0237 (8)0.0266 (8)0.0190 (7)0.0003 (6)0.0030 (6)0.0014 (6)
C160.0164 (7)0.0161 (7)0.0176 (7)0.0021 (6)0.0030 (6)0.0007 (5)
C170.0178 (7)0.0238 (8)0.0226 (8)0.0022 (6)0.0038 (6)0.0012 (6)
C180.0245 (8)0.0246 (8)0.0250 (8)0.0036 (6)0.0084 (7)0.0023 (6)
C190.0245 (8)0.0267 (8)0.0178 (7)0.0008 (6)0.0054 (6)0.0023 (6)
C200.0174 (7)0.0223 (8)0.0190 (7)0.0031 (6)0.0035 (6)0.0002 (6)
C210.0169 (7)0.0160 (7)0.0199 (7)0.0009 (6)0.0033 (6)0.0021 (6)
C220.0347 (10)0.0414 (11)0.0410 (10)0.0059 (8)0.0162 (8)0.0048 (8)
C230.0176 (7)0.0160 (7)0.0200 (7)0.0048 (6)0.0061 (6)0.0011 (6)
C240.0223 (8)0.0193 (8)0.0332 (9)0.0031 (6)0.0083 (7)0.0009 (6)
Geometric parameters (Å, º) top
O1—C221.4091 (19)C11—C121.381 (2)
O1—C151.4381 (18)C11—H110.9500
O2—C231.3274 (17)C12—C131.396 (2)
O2—C241.4461 (17)C12—H120.9500
O3—C231.2109 (16)C14—C151.509 (2)
N1—C131.3775 (19)C14—H14A0.9900
N1—C21.3881 (18)C14—H14B0.9900
N1—H1N0.859 (17)C15—C201.5105 (19)
N4—C51.4657 (18)C15—H151.0000
N4—C31.4675 (17)C16—C231.5337 (19)
N4—C211.4836 (18)C16—C171.549 (2)
C2—C71.366 (2)C16—C211.5665 (18)
C2—C161.5265 (19)C17—C181.518 (2)
C3—C141.515 (2)C17—H17A0.9900
C3—H3A0.9900C17—H17B0.9900
C3—H3B0.9900C18—C191.493 (2)
C5—C61.527 (2)C18—H18A0.9900
C5—H5A0.9900C18—H18B0.9900
C5—H5B0.9900C19—C201.325 (2)
C6—C71.498 (2)C19—H190.9500
C6—H6A0.9900C20—C211.523 (2)
C6—H6B0.9900C21—H211.0000
C7—C81.430 (2)C22—H22A0.9800
C8—C91.401 (2)C22—H22B0.9800
C8—C131.407 (2)C22—H22C0.9800
C9—C101.378 (2)C24—H24A0.9800
C9—H90.9500C24—H24B0.9800
C10—C111.393 (2)C24—H24C0.9800
C10—H100.9500
C22—O1—C15113.67 (12)C3—C14—H14B109.7
C23—O2—C24116.57 (11)H14A—C14—H14B108.2
C13—N1—C2109.27 (12)O1—C15—C14105.53 (12)
C13—N1—H1N123.4 (11)O1—C15—C20110.41 (12)
C2—N1—H1N127.3 (11)C14—C15—C20111.29 (12)
C5—N4—C3111.16 (11)O1—C15—H15109.8
C5—N4—C21114.27 (10)C14—C15—H15109.8
C3—N4—C21110.72 (11)C20—C15—H15109.8
C7—C2—N1108.82 (12)C2—C16—C23109.26 (11)
C7—C2—C16129.33 (12)C2—C16—C17108.93 (11)
N1—C2—C16121.80 (12)C23—C16—C17105.34 (11)
N4—C3—C14109.50 (12)C2—C16—C21108.70 (11)
N4—C3—H3A109.8C23—C16—C21115.68 (11)
C14—C3—H3A109.8C17—C16—C21108.74 (11)
N4—C3—H3B109.8C18—C17—C16113.48 (12)
C14—C3—H3B109.8C18—C17—H17A108.9
H3A—C3—H3B108.2C16—C17—H17A108.9
N4—C5—C6116.69 (12)C18—C17—H17B108.9
N4—C5—H5A108.1C16—C17—H17B108.9
C6—C5—H5A108.1H17A—C17—H17B107.7
N4—C5—H5B108.1C19—C18—C17110.25 (12)
C6—C5—H5B108.1C19—C18—H18A109.6
H5A—C5—H5B107.3C17—C18—H18A109.6
C7—C6—C5111.61 (12)C19—C18—H18B109.6
C7—C6—H6A109.3C17—C18—H18B109.6
C5—C6—H6A109.3H18A—C18—H18B108.1
C7—C6—H6B109.3C20—C19—C18123.64 (13)
C5—C6—H6B109.3C20—C19—H19118.2
H6A—C6—H6B108.0C18—C19—H19118.2
C2—C7—C8107.44 (12)C19—C20—C15120.65 (13)
C2—C7—C6127.05 (13)C19—C20—C21124.21 (13)
C8—C7—C6125.29 (13)C15—C20—C21115.03 (12)
C9—C8—C13119.11 (13)N4—C21—C20109.21 (11)
C9—C8—C7133.72 (14)N4—C21—C16113.89 (11)
C13—C8—C7107.18 (13)C20—C21—C16113.54 (11)
C10—C9—C8118.96 (15)N4—C21—H21106.6
C10—C9—H9120.5C20—C21—H21106.6
C8—C9—H9120.5C16—C21—H21106.6
C9—C10—C11121.12 (15)O1—C22—H22A109.5
C9—C10—H10119.4O1—C22—H22B109.5
C11—C10—H10119.4H22A—C22—H22B109.5
C12—C11—C10121.44 (14)O1—C22—H22C109.5
C12—C11—H11119.3H22A—C22—H22C109.5
C10—C11—H11119.3H22B—C22—H22C109.5
C11—C12—C13117.53 (15)O3—C23—O2123.37 (13)
C11—C12—H12121.2O3—C23—C16122.35 (12)
C13—C12—H12121.2O2—C23—C16114.20 (11)
N1—C13—C12130.87 (14)O2—C24—H24A109.5
N1—C13—C8107.29 (12)O2—C24—H24B109.5
C12—C13—C8121.84 (14)H24A—C24—H24B109.5
C15—C14—C3109.99 (12)O2—C24—H24C109.5
C15—C14—H14A109.7H24A—C24—H24C109.5
C3—C14—H14A109.7H24B—C24—H24C109.5
C15—C14—H14B109.7
C13—N1—C2—C70.53 (16)C7—C2—C16—C17146.69 (14)
C13—N1—C2—C16177.13 (12)N1—C2—C16—C1730.45 (17)
C5—N4—C3—C14166.45 (12)C7—C2—C16—C2128.35 (19)
C21—N4—C3—C1465.41 (15)N1—C2—C16—C21148.79 (12)
C3—N4—C5—C681.17 (15)C2—C16—C17—C18177.04 (11)
C21—N4—C5—C645.04 (16)C23—C16—C17—C1865.86 (14)
N4—C5—C6—C779.41 (15)C21—C16—C17—C1858.73 (15)
N1—C2—C7—C80.47 (15)C16—C17—C18—C1950.95 (16)
C16—C2—C7—C8176.97 (13)C17—C18—C19—C2019.8 (2)
N1—C2—C7—C6174.43 (13)C18—C19—C20—C15173.52 (13)
C16—C2—C7—C68.1 (2)C18—C19—C20—C212.4 (2)
C5—C6—C7—C224.9 (2)O1—C15—C20—C19106.75 (16)
C5—C6—C7—C8149.13 (13)C14—C15—C20—C19136.40 (15)
C2—C7—C8—C9180.00 (15)O1—C15—C20—C2169.54 (15)
C6—C7—C8—C95.0 (2)C14—C15—C20—C2147.31 (17)
C2—C7—C8—C130.24 (15)C5—N4—C21—C20175.36 (11)
C6—C7—C8—C13174.77 (13)C3—N4—C21—C2058.20 (14)
C13—C8—C9—C100.4 (2)C5—N4—C21—C1647.27 (15)
C7—C8—C9—C10179.88 (15)C3—N4—C21—C16173.71 (11)
C8—C9—C10—C110.4 (2)C19—C20—C21—N4134.12 (14)
C9—C10—C11—C120.9 (2)C15—C20—C21—N449.74 (15)
C10—C11—C12—C130.5 (2)C19—C20—C21—C165.84 (19)
C2—N1—C13—C12179.14 (14)C15—C20—C21—C16178.02 (12)
C2—N1—C13—C80.37 (15)C2—C16—C21—N481.24 (14)
C11—C12—C13—N1179.70 (14)C23—C16—C21—N442.06 (16)
C11—C12—C13—C80.3 (2)C17—C16—C21—N4160.30 (12)
C9—C8—C13—N1179.72 (12)C2—C16—C21—C20152.92 (11)
C7—C8—C13—N10.08 (15)C23—C16—C21—C2083.78 (14)
C9—C8—C13—C120.7 (2)C17—C16—C21—C2034.46 (15)
C7—C8—C13—C12179.48 (13)C24—O2—C23—O39.3 (2)
N4—C3—C14—C1561.07 (16)C24—O2—C23—C16173.83 (12)
C22—O1—C15—C14162.46 (12)C2—C16—C23—O339.04 (18)
C22—O1—C15—C2077.17 (15)C17—C16—C23—O377.84 (16)
C3—C14—C15—O168.38 (14)C21—C16—C23—O3162.05 (12)
C3—C14—C15—C2051.41 (17)C2—C16—C23—O2144.01 (12)
C7—C2—C16—C2398.72 (16)C17—C16—C23—O299.11 (13)
N1—C2—C16—C2384.13 (16)C21—C16—C23—O220.99 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O3i0.859 (17)2.187 (16)2.9759 (18)152.6 (15)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O3i0.859 (17)2.187 (16)2.9759 (18)152.6 (15)
Symmetry code: (i) x+2, y+1, z+1.
Acknowledgements top

This work was supported financially by the National Natural Science Foundation of China (2107298, 81001592) and the Natural Science Foundation of th Education Committee of Anhui Province (KJ2010A210).

references
References top

Danieli, B., Lesma, G., Luzzani, M., Passarella, D. & Silvani, A. (1977b). Tetrahedron, 34, 11291–11296.

Danieli, B., Lesma, G., Martinelli, M., Passarella, D. & Silvani, A. (1977a). J. Org. Chem. 19, 6519–6523.

Kanfan, C., Massiot, G., Ahond, A., Das, B. C., Husson, H. P. & Potier, P. (1974). J. Chem. Soc. Chem Commun. pp. 164–165.

Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.