Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010001252X/sx1108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010001252X/sx1108Isup2.hkl |
CCDC reference: 158251
(–)-Argemonine was isolated from Argemone platyceras Link et Otto (Slavík & Slavíková, 1963), crystallized from ether and recrystallized from aqueous methanol (m.p. 427–428 K), [α]D21 = -208° (0.5 M in CHCl3).
The absolute structure could not be established from the present data (Flack, 1983) because of the weak anomalous scattering signal. Friedel reflections were merged for the final refinement. The absolute configuration shown, the 6S,12S isomer, is based on the absolute stereochemistry established previously (Červinka et al., 1966; Kaneda et al., 1976). All argemonine H atoms were treated as riding, with C—H = 0.93–0.98 Å. The H atom (H30A) of the water molecule was postioned from a difference map and allowed to refine isotropically.
Data collection: KM-4 Software (Kuma, 1992); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson & Burnett, 1996).
C21H25NO4·0.5H2O | F(000) = 780 |
Mr = 364.43 | Dx = 1.337 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
a = 18.169 (4) Å | Cell parameters from 50 reflections |
b = 9.801 (2) Å | θ = 11.0–20.8° |
c = 12.726 (3) Å | µ = 0.09 mm−1 |
β = 126.96 (3)° | T = 130 K |
V = 1810.8 (7) Å3 | Trigonal bipyramid, colourless |
Z = 4 | 0.70 × 0.50 × 0.50 mm |
Kuma KM-4 CCD diffractometer | 2201 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 28.5°, θmin = 4.0° |
ω scans | h = −23→23 |
6415 measured reflections | k = −12→13 |
2254 independent reflections | l = −16→15 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.054P)2 + 0.4286P] where P = (Fo2 + 2Fc2)/3 |
2254 reflections | (Δ/σ)max < 0.001 |
249 parameters | Δρmax = 0.23 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C21H25NO4·0.5H2O | V = 1810.8 (7) Å3 |
Mr = 364.43 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 18.169 (4) Å | µ = 0.09 mm−1 |
b = 9.801 (2) Å | T = 130 K |
c = 12.726 (3) Å | 0.70 × 0.50 × 0.50 mm |
β = 126.96 (3)° |
Kuma KM-4 CCD diffractometer | 2201 reflections with I > 2σ(I) |
6415 measured reflections | Rint = 0.021 |
2254 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 1 restraint |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.23 e Å−3 |
2254 reflections | Δρmin = −0.21 e Å−3 |
249 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O18 | 0.20462 (7) | −0.02808 (11) | 0.71574 (10) | 0.0185 (2) | |
O19 | 0.11674 (7) | 0.16177 (13) | 0.54123 (11) | 0.0231 (2) | |
O20 | 0.59998 (8) | 0.67489 (12) | 0.89583 (11) | 0.0222 (2) | |
O21 | 0.64642 (8) | 0.55233 (12) | 1.11413 (11) | 0.0241 (2) | |
N1 | 0.50822 (8) | 0.09674 (14) | 0.66303 (12) | 0.0167 (2) | |
C1 | 0.34395 (9) | 0.00897 (14) | 0.73301 (13) | 0.0147 (3) | |
H1 | 0.3760 | −0.0616 | 0.7963 | 0.018* | |
C2 | 0.25372 (9) | 0.03771 (15) | 0.68216 (13) | 0.0153 (3) | |
C3 | 0.20607 (9) | 0.14204 (15) | 0.58740 (13) | 0.0170 (3) | |
C4 | 0.25100 (9) | 0.21543 (16) | 0.54884 (13) | 0.0172 (3) | |
H4 | 0.2192 | 0.2864 | 0.4859 | 0.021* | |
C4A | 0.34288 (10) | 0.18693 (14) | 0.60110 (13) | 0.0159 (3) | |
C5 | 0.38981 (10) | 0.26917 (16) | 0.55722 (13) | 0.0179 (3) | |
H5A | 0.3774 | 0.3674 | 0.5580 | 0.021* | |
H5B | 0.3645 | 0.2437 | 0.4660 | 0.021* | |
C6 | 0.49433 (10) | 0.24432 (14) | 0.64784 (13) | 0.0157 (3) | |
H6 | 0.5207 | 0.2798 | 0.6032 | 0.019* | |
C6A | 0.53892 (9) | 0.32075 (15) | 0.77685 (13) | 0.0151 (3) | |
C7 | 0.55162 (10) | 0.46154 (15) | 0.77932 (14) | 0.0168 (3) | |
H7 | 0.5348 | 0.5069 | 0.7018 | 0.020* | |
C8 | 0.58810 (10) | 0.53527 (15) | 0.89255 (15) | 0.0177 (3) | |
C9 | 0.61269 (9) | 0.46963 (16) | 1.00783 (14) | 0.0176 (3) | |
C10 | 0.60070 (9) | 0.33018 (15) | 1.00613 (14) | 0.0165 (3) | |
H10 | 0.6173 | 0.2850 | 1.0836 | 0.020* | |
C10A | 0.56435 (9) | 0.25494 (14) | 0.89111 (13) | 0.0142 (3) | |
C11 | 0.55449 (9) | 0.10271 (15) | 0.89139 (13) | 0.0152 (3) | |
H11A | 0.5317 | 0.0791 | 0.9428 | 0.018* | |
H11B | 0.6156 | 0.0594 | 0.9345 | 0.018* | |
C12 | 0.48756 (9) | 0.04657 (15) | 0.75113 (13) | 0.0148 (3) | |
H12 | 0.4931 | −0.0551 | 0.7553 | 0.018* | |
C12A | 0.38865 (9) | 0.08291 (14) | 0.69218 (12) | 0.0144 (3) | |
C13 | 0.25171 (10) | −0.13501 (17) | 0.80910 (15) | 0.0209 (3) | |
H13A | 0.2687 | −0.2061 | 0.7731 | 0.031* | |
H13B | 0.2114 | −0.1741 | 0.8285 | 0.031* | |
H13C | 0.3075 | −0.0987 | 0.8901 | 0.031* | |
C14 | 0.06546 (10) | 0.25843 (18) | 0.43721 (15) | 0.0254 (3) | |
H14A | 0.0920 | 0.3495 | 0.4696 | 0.038* | |
H14B | 0.0012 | 0.2586 | 0.4058 | 0.038* | |
H14C | 0.0680 | 0.2335 | 0.3648 | 0.038* | |
C15 | 0.67676 (11) | 0.71114 (17) | 0.89810 (16) | 0.0238 (3) | |
H15A | 0.7327 | 0.6694 | 0.9748 | 0.036* | |
H15B | 0.6837 | 0.8106 | 0.9034 | 0.036* | |
H15C | 0.6668 | 0.6784 | 0.8176 | 0.036* | |
C16 | 0.66980 (13) | 0.4889 (2) | 1.23151 (16) | 0.0303 (4) | |
H16A | 0.6149 | 0.4459 | 1.2145 | 0.045* | |
H16B | 0.6934 | 0.5579 | 1.3006 | 0.045* | |
H16C | 0.7172 | 0.4195 | 1.2601 | 0.045* | |
C17 | 0.59854 (10) | 0.05447 (16) | 0.70245 (16) | 0.0212 (3) | |
H17A | 0.6058 | 0.0826 | 0.6352 | 0.032* | |
H17B | 0.6040 | −0.0450 | 0.7121 | 0.032* | |
H17C | 0.6466 | 0.0974 | 0.7865 | 0.032* | |
O30 | 0.5000 | 0.8061 (2) | 1.0000 | 0.0331 (4) | |
H30A | 0.533 (2) | 0.757 (4) | 0.983 (3) | 0.084 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O18 | 0.0174 (4) | 0.0170 (5) | 0.0222 (5) | 0.0010 (4) | 0.0125 (4) | 0.0032 (4) |
O19 | 0.0159 (5) | 0.0238 (6) | 0.0248 (5) | 0.0053 (4) | 0.0097 (4) | 0.0063 (5) |
O20 | 0.0298 (5) | 0.0109 (5) | 0.0297 (5) | −0.0011 (4) | 0.0199 (5) | −0.0013 (4) |
O21 | 0.0338 (6) | 0.0171 (5) | 0.0199 (5) | −0.0059 (5) | 0.0154 (5) | −0.0045 (4) |
N1 | 0.0209 (5) | 0.0130 (5) | 0.0202 (5) | 0.0004 (5) | 0.0144 (5) | 0.0003 (4) |
C1 | 0.0157 (6) | 0.0127 (6) | 0.0135 (5) | 0.0007 (5) | 0.0075 (5) | 0.0005 (5) |
C2 | 0.0171 (6) | 0.0134 (6) | 0.0153 (6) | −0.0020 (5) | 0.0096 (5) | −0.0021 (5) |
C3 | 0.0154 (6) | 0.0156 (6) | 0.0158 (6) | 0.0016 (5) | 0.0073 (5) | −0.0009 (5) |
C4 | 0.0183 (6) | 0.0143 (6) | 0.0144 (6) | 0.0022 (5) | 0.0074 (5) | 0.0014 (5) |
C4A | 0.0186 (6) | 0.0140 (6) | 0.0136 (5) | −0.0004 (5) | 0.0089 (5) | −0.0001 (5) |
C5 | 0.0225 (6) | 0.0155 (6) | 0.0159 (6) | 0.0012 (5) | 0.0117 (5) | 0.0026 (5) |
C6 | 0.0219 (6) | 0.0124 (6) | 0.0169 (6) | −0.0010 (5) | 0.0138 (5) | 0.0004 (5) |
C6A | 0.0167 (6) | 0.0131 (6) | 0.0179 (6) | 0.0000 (5) | 0.0116 (5) | 0.0001 (5) |
C7 | 0.0207 (6) | 0.0137 (6) | 0.0192 (6) | 0.0005 (5) | 0.0136 (6) | 0.0019 (5) |
C8 | 0.0204 (6) | 0.0121 (6) | 0.0227 (7) | −0.0007 (5) | 0.0141 (6) | −0.0002 (5) |
C9 | 0.0177 (6) | 0.0163 (7) | 0.0182 (6) | −0.0021 (5) | 0.0105 (5) | −0.0023 (5) |
C10 | 0.0167 (6) | 0.0164 (7) | 0.0158 (6) | −0.0007 (5) | 0.0094 (5) | 0.0011 (5) |
C10A | 0.0143 (5) | 0.0111 (6) | 0.0174 (6) | −0.0006 (5) | 0.0096 (5) | 0.0000 (5) |
C11 | 0.0159 (6) | 0.0127 (6) | 0.0159 (6) | 0.0003 (5) | 0.0090 (5) | 0.0028 (5) |
C12 | 0.0174 (6) | 0.0111 (6) | 0.0175 (6) | 0.0005 (5) | 0.0114 (5) | 0.0013 (5) |
C12A | 0.0167 (6) | 0.0123 (6) | 0.0132 (6) | −0.0012 (5) | 0.0084 (5) | −0.0010 (5) |
C13 | 0.0184 (6) | 0.0191 (7) | 0.0228 (7) | −0.0020 (6) | 0.0111 (6) | 0.0052 (6) |
C14 | 0.0199 (6) | 0.0223 (7) | 0.0243 (7) | 0.0065 (6) | 0.0080 (6) | 0.0046 (6) |
C15 | 0.0276 (7) | 0.0150 (6) | 0.0293 (7) | −0.0045 (6) | 0.0173 (6) | −0.0005 (6) |
C16 | 0.0430 (9) | 0.0274 (8) | 0.0202 (7) | −0.0090 (8) | 0.0188 (7) | −0.0056 (7) |
C17 | 0.0237 (7) | 0.0185 (7) | 0.0289 (7) | 0.0007 (6) | 0.0198 (6) | 0.0012 (6) |
O30 | 0.0294 (9) | 0.0193 (8) | 0.0492 (11) | 0.000 | 0.0228 (9) | 0.000 |
O18—C2 | 1.3611 (16) | C7—H7 | 0.9500 |
O18—C13 | 1.4211 (18) | C8—C9 | 1.406 (2) |
O19—C3 | 1.3675 (17) | C9—C10 | 1.382 (2) |
O19—C14 | 1.4264 (19) | C10—C10A | 1.4000 (19) |
O20—C8 | 1.3820 (18) | C10—H10 | 0.9500 |
O20—C15 | 1.4230 (19) | C10A—C11 | 1.5029 (19) |
O21—C9 | 1.3659 (18) | C11—C12 | 1.535 (2) |
O21—C16 | 1.426 (2) | C11—H11A | 0.9900 |
N1—C6 | 1.4610 (18) | C11—H11B | 0.9900 |
N1—C12 | 1.4648 (17) | C12—C12A | 1.5159 (18) |
N1—C17 | 1.4582 (18) | C12—H12 | 1.0000 |
C1—C2 | 1.3821 (19) | C13—H13A | 0.9800 |
C1—C12A | 1.4008 (19) | C13—H13B | 0.9800 |
C1—H1 | 0.9500 | C13—H13C | 0.9800 |
C2—C3 | 1.4120 (19) | C14—H14A | 0.9800 |
C3—C4 | 1.381 (2) | C14—H14B | 0.9800 |
C4—C4A | 1.404 (2) | C14—H14C | 0.9800 |
C4—H4 | 0.9500 | C15—H15A | 0.9800 |
C4A—C12A | 1.3839 (19) | C15—H15B | 0.9800 |
C4A—C5 | 1.5037 (19) | C15—H15C | 0.9800 |
C5—C6 | 1.537 (2) | C16—H16A | 0.9800 |
C5—H5A | 0.9900 | C16—H16B | 0.9800 |
C5—H5B | 0.9900 | C16—H16C | 0.9800 |
C6—C6A | 1.5209 (19) | C17—H17A | 0.9800 |
C6—H6 | 1.0000 | C17—H17B | 0.9800 |
C6A—C10A | 1.3914 (19) | C17—H17C | 0.9800 |
C6A—C7 | 1.3963 (19) | O30—H30A | 0.90 (4) |
C7—C8 | 1.375 (2) | ||
C2—O18—C13 | 115.67 (11) | C6A—C10A—C10 | 119.99 (13) |
C3—O19—C14 | 115.91 (12) | C6A—C10A—C11 | 119.83 (13) |
C8—O20—C15 | 112.41 (12) | C10—C10A—C11 | 120.17 (12) |
C9—O21—C16 | 116.90 (13) | C10A—C11—C12 | 111.42 (11) |
C17—N1—C6 | 113.32 (12) | C10A—C11—H11A | 109.3 |
C17—N1—C12 | 113.24 (12) | C12—C11—H11A | 109.3 |
C6—N1—C12 | 109.29 (11) | C10A—C11—H11B | 109.3 |
C2—C1—C12A | 120.66 (12) | C12—C11—H11B | 109.3 |
C2—C1—H1 | 119.7 | H11A—C11—H11B | 108.0 |
C12A—C1—H1 | 119.7 | N1—C12—C12A | 108.39 (11) |
O18—C2—C1 | 124.98 (12) | N1—C12—C11 | 112.41 (11) |
O18—C2—C3 | 115.47 (12) | C12A—C12—C11 | 111.45 (11) |
C1—C2—C3 | 119.54 (12) | N1—C12—H12 | 108.2 |
O19—C3—C4 | 125.18 (13) | C12A—C12—H12 | 108.2 |
O19—C3—C2 | 115.42 (13) | C11—C12—H12 | 108.2 |
C4—C3—C2 | 119.40 (13) | C4A—C12A—C1 | 120.09 (12) |
C3—C4—C4A | 121.10 (13) | C4A—C12A—C12 | 121.61 (12) |
C3—C4—H4 | 119.5 | C1—C12A—C12 | 118.30 (12) |
C4A—C4—H4 | 119.5 | O18—C13—H13A | 109.5 |
C12A—C4A—C4 | 119.20 (13) | O18—C13—H13B | 109.5 |
C12A—C4A—C5 | 121.10 (12) | H13A—C13—H13B | 109.5 |
C4—C4A—C5 | 119.70 (13) | O18—C13—H13C | 109.5 |
C4A—C5—C6 | 110.93 (11) | H13A—C13—H13C | 109.5 |
C4A—C5—H5A | 109.5 | H13B—C13—H13C | 109.5 |
C6—C5—H5A | 109.5 | O19—C14—H14A | 109.5 |
C4A—C5—H5B | 109.5 | O19—C14—H14B | 109.5 |
C6—C5—H5B | 109.5 | H14A—C14—H14B | 109.5 |
H5A—C5—H5B | 108.0 | O19—C14—H14C | 109.5 |
N1—C6—C6A | 114.03 (12) | H14A—C14—H14C | 109.5 |
N1—C6—C5 | 107.05 (11) | H14B—C14—H14C | 109.5 |
C6A—C6—C5 | 110.35 (12) | O20—C15—H15A | 109.5 |
N1—C6—H6 | 108.4 | O20—C15—H15B | 109.5 |
C6A—C6—H6 | 108.4 | H15A—C15—H15B | 109.5 |
C5—C6—H6 | 108.4 | O20—C15—H15C | 109.5 |
C10A—C6A—C7 | 119.21 (13) | H15A—C15—H15C | 109.5 |
C10A—C6A—C6 | 121.77 (13) | H15B—C15—H15C | 109.5 |
C7—C6A—C6 | 118.98 (12) | O21—C16—H16A | 109.5 |
C8—C7—C6A | 120.81 (13) | O21—C16—H16B | 109.5 |
C8—C7—H7 | 119.6 | H16A—C16—H16B | 109.5 |
C6A—C7—H7 | 119.6 | O21—C16—H16C | 109.5 |
C7—C8—O20 | 121.35 (13) | H16A—C16—H16C | 109.5 |
C7—C8—C9 | 120.24 (14) | H16B—C16—H16C | 109.5 |
O20—C8—C9 | 118.40 (13) | N1—C17—H17A | 109.5 |
O21—C9—C10 | 125.10 (13) | N1—C17—H17B | 109.5 |
O21—C9—C8 | 115.70 (13) | H17A—C17—H17B | 109.5 |
C10—C9—C8 | 119.20 (14) | N1—C17—H17C | 109.5 |
C9—C10—C10A | 120.54 (13) | H17A—C17—H17C | 109.5 |
C9—C10—H10 | 119.7 | H17B—C17—H17C | 109.5 |
C10A—C10—H10 | 119.7 | H30A—O30—H30Ai | 115 (4) |
C13—O18—C2—C1 | −0.9 (2) | C16—O21—C9—C10 | −0.8 (2) |
C13—O18—C2—C3 | 178.77 (12) | C16—O21—C9—C8 | 178.50 (14) |
C12A—C1—C2—O18 | −179.88 (13) | C7—C8—C9—O21 | −178.61 (12) |
C12A—C1—C2—C3 | 0.5 (2) | O20—C8—C9—O21 | 0.2 (2) |
C14—O19—C3—C4 | 5.6 (2) | C7—C8—C9—C10 | 0.7 (2) |
C14—O19—C3—C2 | −174.66 (13) | O20—C8—C9—C10 | 179.56 (13) |
O18—C2—C3—O19 | −0.67 (18) | O21—C9—C10—C10A | 179.15 (13) |
C1—C2—C3—O19 | 179.02 (12) | C8—C9—C10—C10A | −0.1 (2) |
O18—C2—C3—C4 | 179.12 (12) | C7—C6A—C10A—C10 | 1.1 (2) |
C1—C2—C3—C4 | −1.2 (2) | C6—C6A—C10A—C10 | −176.60 (12) |
O19—C3—C4—C4A | −179.45 (13) | C7—C6A—C10A—C11 | −177.65 (13) |
C2—C3—C4—C4A | 0.8 (2) | C6—C6A—C10A—C11 | 4.7 (2) |
C3—C4—C4A—C12A | 0.4 (2) | C9—C10—C10A—C6A | −0.8 (2) |
C3—C4—C4A—C5 | −179.81 (13) | C9—C10—C10A—C11 | 177.96 (13) |
C12A—C4A—C5—C6 | −13.16 (18) | C6A—C10A—C11—C12 | −18.97 (17) |
C4—C4A—C5—C6 | 167.03 (12) | C10—C10A—C11—C12 | 162.29 (12) |
C17—N1—C6—C6A | −79.59 (15) | C17—N1—C12—C12A | −173.65 (12) |
C12—N1—C6—C6A | 47.71 (15) | C6—N1—C12—C12A | 59.01 (14) |
C17—N1—C6—C5 | 158.06 (11) | C17—N1—C12—C11 | 62.72 (16) |
C12—N1—C6—C5 | −74.64 (14) | C6—N1—C12—C11 | −64.63 (15) |
C4A—C5—C6—N1 | 48.37 (15) | C10A—C11—C12—N1 | 49.41 (15) |
C4A—C5—C6—C6A | −76.25 (15) | C10A—C11—C12—C12A | −72.50 (14) |
N1—C6—C6A—C10A | −19.05 (19) | C4—C4A—C12A—C1 | −1.11 (19) |
C5—C6—C6A—C10A | 101.48 (15) | C5—C4A—C12A—C1 | 179.07 (12) |
N1—C6—C6A—C7 | 163.25 (12) | C4—C4A—C12A—C12 | 179.45 (12) |
C5—C6—C6A—C7 | −76.23 (16) | C5—C4A—C12A—C12 | −0.4 (2) |
C10A—C6A—C7—C8 | −0.5 (2) | C2—C1—C12A—C4A | 0.7 (2) |
C6—C6A—C7—C8 | 177.27 (12) | C2—C1—C12A—C12 | −179.85 (12) |
C6A—C7—C8—O20 | −179.21 (13) | N1—C12—C12A—C4A | −21.45 (18) |
C6A—C7—C8—C9 | −0.4 (2) | C11—C12—C12A—C4A | 102.76 (14) |
C15—O20—C8—C7 | −75.56 (18) | N1—C12—C12A—C1 | 159.10 (12) |
C15—O20—C8—C9 | 105.63 (15) | C11—C12—C12A—C1 | −76.69 (16) |
Symmetry code: (i) −x+1, y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O30—H30A···O20 | 0.90 (4) | 2.23 (3) | 3.0997 (15) | 164 (3) |
Experimental details
Crystal data | |
Chemical formula | C21H25NO4·0.5H2O |
Mr | 364.43 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 130 |
a, b, c (Å) | 18.169 (4), 9.801 (2), 12.726 (3) |
β (°) | 126.96 (3) |
V (Å3) | 1810.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.70 × 0.50 × 0.50 |
Data collection | |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6415, 2254, 2201 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.671 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.077, 1.06 |
No. of reflections | 2254 |
No. of parameters | 249 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Computer programs: KM-4 Software (Kuma, 1992), KM-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Johnson & Burnett, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
O30—H30A···O20 | 0.90 (4) | 2.23 (3) | 3.0997 (15) | 164 (3) |
(–)-Argemonine hemihydrate, (I), is a member of a relatively small group of pavinane alkaloids occurring in some plant species of the genera Argemone (Papaveraceae), Thalictrum (Ranunculaceae), and Berberis and some Leontice (Berberidaceae) (Gözler et al., 1983). In the Leontice species, argemonine occurs as the dextrorotatory enantiomer (Gözler et al., 1983). (–)-Argemonine has been isolated for the first time from Argemone hispida Gray (Soine & Gisvold, 1944; Schermerhorn & Soine, 1951) and later found in some other Argemone species which occur naturally in the southern regions of North America. The structure of argemonine was determined by Martell et al. (1963) and Stermitz et al. (1963), and the identity with N-methylpavine, a semisynthetic derivative of papaverine, was proved (Schöpf, 1949; Battersby & Binks, 1955). The absolute configuration was established as 6S,12S (Červinka et al., 1966) and confirmed by the X-ray study of (–)-argemonine methiodide (Kaneda et al., 1976). \scheme
Argemonine possesses an azabicyclo[3.3.1]nonadiene system fused with two benzene rings each of them bearing two methoxyl groups (Fig. 1). All bond lengths and angles are within normal range. The bond lengths involving trivalent nitrogen N1—C6, N1—C12 and N1—C17 are 1.4610 (18), 1.4648 (18) and 1.4582 (18) Å, respectively. They are shorter than the corresponding distances involving tetravalent nitrogen in argemonine methiodide (Kaneda et al., 1976). The bond angles C12—N1—C17 [113.24 (12)°] and C6—N1—C17 [113.32 (12)°] are somewhat enlarged probably due to sterical repulsion of the N-methyl group within a rigid azabicyclononadiene. The bond angles around the O atoms O18, O19 and O21 are enlarged [average value 116.2 (5)°] compared with the C8—O20—C15 angle [112.41 (12)°]. Similar findings were made in (–)-argemonine methiodide (Kaneda et al., 1976). The three methoxyl groups (C2—OMe, C3—OMe and C9—OMe) essentially lie in the planes of the adjacent aromatic rings [cis-torsion angles -0.9 (2), -0.8 (2) and 5.6 (2)°, respectively]. The remaining methoxyl (O20—C15, attached to C8 atom) is almost perpendicular to the aromatic plane [torsion angle C15—O20—C8—C7 - 75.56 (18)°]. The angle between the two aromatic rings is 86.90 (5)° (Fig. 2). Both partially saturated nitrogen heterocycles adopt twisted half-chair conformations, with atoms N1, C6 and C12 deviating significantly from the planes of the aromatic rings. Both the last mentioned methoxy and the N-methyl group deviate most from molecular twofold symmetry. As they rotate freely, their position can be most easily affected by packing interactions, including hydrogen bonding interactions. The conformation is nearly identical to the structure of argemonine methiodide, with the r.m.s. deviation of the superimposition being only 0.08 Å.
The water O atom of this hemihydrate lies on a twofold axis and takes part in O—H···O hydrogen bonding to symmetry-related argemonine molecules (Table 1). Their mutual orientation can be described as two crossed L letters (Fig. 2). This finding is in contrast with the previously published structure of (–)-argemonine methiodide (Kaneda et al., 1976) where the crystal packing revealed molecules aligned in a sandwich-like arrangement.