Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003249/gg1038sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003249/gg1038IIsup2.hkl |
CCDC reference: 164690
Protopine, (I), isolated from Chelidonium majus L. (Slavík et al., 1965), was dissolved in hot 3% hydrochloric acid and the solution allowed to stand at ambient temperature. After three weeks colourless crystals of protopine hydrochloride, (II), were collected, washed and dried, m.p. 534–537 K (decomposition).
Data collection: KUMA KM-4 Software (Kuma, 1992); cell refinement: KUMA KM-4 Software; data reduction: KUMA 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); software used to prepare material for publication: SHELXL97.
Fig. 1. A perspective view of compound (II). Displacement ellipsoids are drawn with 50% probability. |
C20H20NO5+·Cl− | F(000) = 816 |
Mr = 389.82 | Dx = 1.567 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.940 (1) Å | Cell parameters from 1967 reflections |
b = 17.755 (1) Å | θ = 3.3–23.0° |
c = 13.829 (2) Å | µ = 0.27 mm−1 |
β = 104.18 (1)° | T = 150 K |
V = 1652.1 (3) Å3 | Prism, colourless |
Z = 4 | 0.50 × 0.40 × 0.35 mm |
KUMA KM-4 with CCD diffractometer | 2546 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
Detector resolution: 0.06 mm pixels mm-1 | h = −8→8 |
ω scans | k = −21→10 |
11498 measured reflections | l = −16→16 |
2900 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0382P)2 + 1.9P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max = 0.001 |
2900 reflections | Δρmax = 0.29 e Å−3 |
246 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0064 (9) |
C20H20NO5+·Cl− | V = 1652.1 (3) Å3 |
Mr = 389.82 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.940 (1) Å | µ = 0.27 mm−1 |
b = 17.755 (1) Å | T = 150 K |
c = 13.829 (2) Å | 0.50 × 0.40 × 0.35 mm |
β = 104.18 (1)° |
KUMA KM-4 with CCD diffractometer | 2546 reflections with I > 2σ(I) |
11498 measured reflections | Rint = 0.020 |
2900 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.29 e Å−3 |
2900 reflections | Δρmin = −0.30 e Å−3 |
246 parameters |
Experimental. All H atoms except the oxygen bonded one were added according to geometry and refined using riding model. The oxygen bound hydrogen was found from difference Fourier map, and treated using riding model subsequently. |
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 | ||
C1 | 0.5681 (3) | −0.16359 (11) | 0.93414 (14) | 0.0159 (4) | |
H1 | 0.6691 | −0.1979 | 0.9656 | 0.019* | |
C2 | 0.6081 (3) | −0.08890 (11) | 0.92558 (15) | 0.0170 (4) | |
C3 | 0.4618 (3) | −0.03741 (11) | 0.88243 (14) | 0.0164 (4) | |
C4 | 0.2672 (3) | −0.05854 (11) | 0.84939 (14) | 0.0170 (4) | |
H4 | 0.1663 | −0.0225 | 0.8243 | 0.020* | |
C4A | 0.2212 (3) | −0.13571 (11) | 0.85385 (14) | 0.0159 (4) | |
C5 | 0.0087 (3) | −0.15928 (11) | 0.81031 (16) | 0.0190 (4) | |
H5A | −0.0810 | −0.1236 | 0.8327 | 0.023* | |
H5B | −0.0199 | −0.1563 | 0.7367 | 0.023* | |
C6 | −0.0342 (3) | −0.23803 (11) | 0.84002 (15) | 0.0164 (4) | |
H6A | −0.1654 | −0.2545 | 0.7992 | 0.020* | |
H6B | −0.0395 | −0.2384 | 0.9109 | 0.020* | |
N7 | 0.1245 (2) | −0.29212 (9) | 0.82523 (12) | 0.0140 (4) | |
C8 | 0.0608 (3) | −0.36941 (11) | 0.84789 (15) | 0.0162 (4) | |
H8A | 0.0144 | −0.3676 | 0.9101 | 0.019* | |
H8B | −0.0523 | −0.3857 | 0.7933 | 0.019* | |
C8A | 0.2249 (3) | −0.42593 (11) | 0.85970 (14) | 0.0154 (4) | |
C9 | 0.1845 (3) | −0.50161 (11) | 0.86441 (14) | 0.0165 (4) | |
C10 | 0.3302 (3) | −0.55618 (11) | 0.88120 (14) | 0.0166 (4) | |
C11 | 0.5266 (3) | −0.53805 (11) | 0.89188 (15) | 0.0182 (4) | |
H11 | 0.6272 | −0.5755 | 0.9026 | 0.022* | |
C12 | 0.5712 (3) | −0.46139 (11) | 0.88623 (15) | 0.0177 (4) | |
H12 | 0.7053 | −0.4469 | 0.8919 | 0.021* | |
C12A | 0.4253 (3) | −0.40573 (11) | 0.87259 (14) | 0.0153 (4) | |
C13 | 0.4833 (3) | −0.32315 (11) | 0.87550 (14) | 0.0152 (4) | |
H13A | 0.5030 | −0.3084 | 0.8096 | 0.018* | |
H13B | 0.6112 | −0.3161 | 0.9254 | 0.018* | |
C14 | 0.3270 (3) | −0.27198 (11) | 0.90168 (14) | 0.0143 (4) | |
C14A | 0.3697 (3) | −0.18793 (11) | 0.89415 (14) | 0.0156 (4) | |
C15 | 0.7536 (3) | 0.02127 (12) | 0.91057 (17) | 0.0227 (5) | |
H15A | 0.8071 | 0.0225 | 0.8505 | 0.027* | |
H15B | 0.8204 | 0.0609 | 0.9572 | 0.027* | |
C16 | 0.1405 (3) | −0.28998 (11) | 0.71829 (14) | 0.0179 (4) | |
H16A | 0.2170 | −0.3336 | 0.7053 | 0.027* | |
H16B | 0.2078 | −0.2435 | 0.7067 | 0.027* | |
H16C | 0.0071 | −0.2914 | 0.6735 | 0.027* | |
C17 | 0.0363 (3) | −0.61402 (11) | 0.85651 (16) | 0.0212 (5) | |
H17A | −0.0304 | −0.6401 | 0.9026 | 0.025* | |
H17B | −0.0171 | −0.6343 | 0.7885 | 0.025* | |
O18 | 0.7867 (2) | −0.05142 (8) | 0.95742 (11) | 0.0215 (3) | |
O19 | 0.5418 (2) | 0.03335 (8) | 0.88356 (11) | 0.0203 (3) | |
O20 | 0.0008 (2) | −0.53373 (8) | 0.85779 (12) | 0.0224 (3) | |
O21 | 0.2464 (2) | −0.62578 (8) | 0.88711 (11) | 0.0219 (3) | |
O22 | 0.3069 (2) | −0.29289 (7) | 0.99584 (10) | 0.0167 (3) | |
H22 | 0.2445 | −0.2546 | 1.0277 | 0.025* | |
Cl | 0.08851 (7) | −0.20199 (3) | 1.11743 (4) | 0.02114 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0149 (9) | 0.0157 (10) | 0.0169 (10) | 0.0010 (8) | 0.0035 (8) | 0.0000 (8) |
C2 | 0.0156 (9) | 0.0175 (10) | 0.0180 (10) | −0.0024 (8) | 0.0045 (8) | −0.0040 (8) |
C3 | 0.0225 (10) | 0.0114 (9) | 0.0163 (10) | −0.0025 (8) | 0.0071 (8) | −0.0020 (7) |
C4 | 0.0200 (10) | 0.0131 (10) | 0.0185 (10) | 0.0025 (8) | 0.0061 (8) | 0.0001 (8) |
C4A | 0.0176 (10) | 0.0164 (10) | 0.0148 (9) | 0.0001 (8) | 0.0063 (8) | −0.0007 (8) |
C5 | 0.0138 (9) | 0.0144 (10) | 0.0281 (11) | 0.0020 (8) | 0.0038 (8) | 0.0025 (8) |
C6 | 0.0128 (9) | 0.0160 (10) | 0.0208 (10) | 0.0006 (8) | 0.0048 (8) | 0.0003 (8) |
N7 | 0.0124 (8) | 0.0136 (8) | 0.0159 (8) | −0.0006 (6) | 0.0030 (6) | 0.0007 (6) |
C8 | 0.0153 (9) | 0.0118 (10) | 0.0213 (10) | −0.0017 (8) | 0.0044 (8) | 0.0001 (8) |
C8A | 0.0174 (10) | 0.0138 (10) | 0.0155 (9) | 0.0000 (8) | 0.0047 (8) | −0.0012 (7) |
C9 | 0.0194 (10) | 0.0150 (10) | 0.0157 (9) | −0.0015 (8) | 0.0053 (8) | −0.0014 (8) |
C10 | 0.0227 (10) | 0.0101 (9) | 0.0172 (10) | −0.0019 (8) | 0.0053 (8) | −0.0021 (8) |
C11 | 0.0217 (10) | 0.0144 (10) | 0.0189 (10) | 0.0038 (8) | 0.0056 (8) | −0.0014 (8) |
C12 | 0.0157 (10) | 0.0193 (11) | 0.0190 (10) | 0.0009 (8) | 0.0056 (8) | −0.0014 (8) |
C12A | 0.0186 (10) | 0.0135 (10) | 0.0139 (9) | 0.0003 (8) | 0.0044 (8) | −0.0005 (7) |
C13 | 0.0146 (9) | 0.0124 (10) | 0.0185 (10) | −0.0008 (8) | 0.0039 (8) | 0.0003 (7) |
C14 | 0.0115 (9) | 0.0157 (10) | 0.0151 (9) | −0.0018 (7) | 0.0020 (7) | 0.0000 (7) |
C14A | 0.0184 (10) | 0.0140 (10) | 0.0153 (9) | 0.0006 (8) | 0.0060 (8) | 0.0003 (7) |
C15 | 0.0211 (10) | 0.0160 (10) | 0.0300 (12) | −0.0049 (8) | 0.0044 (9) | 0.0001 (9) |
C16 | 0.0201 (10) | 0.0209 (10) | 0.0128 (9) | 0.0002 (8) | 0.0041 (8) | −0.0001 (8) |
C17 | 0.0224 (11) | 0.0133 (10) | 0.0279 (11) | −0.0016 (8) | 0.0063 (9) | −0.0005 (8) |
O18 | 0.0189 (7) | 0.0146 (7) | 0.0287 (8) | −0.0040 (6) | 0.0012 (6) | 0.0003 (6) |
O19 | 0.0207 (7) | 0.0118 (7) | 0.0268 (8) | −0.0021 (6) | 0.0027 (6) | −0.0003 (6) |
O20 | 0.0177 (7) | 0.0133 (7) | 0.0359 (9) | −0.0021 (6) | 0.0064 (6) | 0.0000 (6) |
O21 | 0.0215 (8) | 0.0115 (7) | 0.0311 (8) | −0.0003 (6) | 0.0034 (6) | 0.0002 (6) |
O22 | 0.0204 (7) | 0.0154 (7) | 0.0147 (7) | 0.0019 (5) | 0.0054 (6) | 0.0031 (5) |
Cl | 0.0234 (3) | 0.0192 (3) | 0.0223 (3) | 0.00144 (19) | 0.0087 (2) | 0.00052 (19) |
C1—C2 | 1.366 (3) | C10—C11 | 1.372 (3) |
C1—C14A | 1.419 (3) | C10—O21 | 1.377 (2) |
C2—O18 | 1.381 (2) | C11—C12 | 1.402 (3) |
C2—C3 | 1.388 (3) | C12—C12A | 1.394 (3) |
C3—C4 | 1.368 (3) | C12A—C13 | 1.518 (3) |
C3—O19 | 1.372 (2) | C13—C14 | 1.525 (3) |
C4—C4A | 1.412 (3) | C14—O22 | 1.394 (2) |
C4A—C5 | 1.509 (3) | C14—C14A | 1.530 (3) |
C4A—C14A | 1.397 (3) | C15—O18 | 1.437 (3) |
C5—C6 | 1.507 (3) | C15—O19 | 1.441 (3) |
N7—C6 | 1.513 (2) | C17—O21 | 1.431 (3) |
N7—C8 | 1.498 (2) | C17—O20 | 1.447 (2) |
N7—C14 | 1.579 (2) | Cl—H22 | 2.0595 |
N7—C16 | 1.510 (2) | Cl—H6Ai | 2.7807 |
C8—C8A | 1.497 (3) | Cl—H16Ci | 2.8197 |
C8A—C9 | 1.377 (3) | Cl—H17Aii | 2.8367 |
C8A—C12A | 1.404 (3) | Cl—H15Biii | 2.8385 |
C9—C10 | 1.379 (3) | Cl—H6B | 2.8497 |
C9—O20 | 1.379 (2) | Cl—H13Aiv | 2.8667 |
C2—C1—C14A | 117.39 (18) | O22—C14—C14A | 112.88 (15) |
C1—C2—O18 | 128.76 (18) | C13—C14—C14A | 113.85 (16) |
C1—C2—C3 | 122.28 (18) | O22—C14—N7 | 106.77 (14) |
O18—C2—C3 | 108.94 (17) | C13—C14—N7 | 105.92 (15) |
C4—C3—O19 | 128.21 (18) | C14A—C14—N7 | 109.31 (15) |
C4—C3—C2 | 121.42 (18) | C4A—C14A—C1 | 120.25 (18) |
O19—C3—C2 | 110.31 (17) | C4A—C14A—C14 | 122.58 (17) |
C3—C4—C4A | 117.84 (18) | C1—C14A—C14 | 117.12 (17) |
C14A—C4A—C4 | 120.59 (18) | O18—C15—O19 | 106.89 (15) |
C14A—C4A—C5 | 121.90 (18) | O21—C17—O20 | 107.70 (15) |
C4—C4A—C5 | 117.47 (17) | C2—O18—C15 | 104.91 (15) |
C6—C5—C4A | 112.81 (16) | C3—O19—C15 | 104.52 (15) |
C5—C6—N7 | 110.65 (15) | C9—O20—C17 | 104.54 (15) |
C6—N7—C8 | 106.93 (14) | C10—O21—C17 | 105.46 (15) |
C6—N7—C14 | 108.91 (14) | H22—Cl—H6Ai | 97.0 |
C8—N7—C14 | 109.11 (14) | H22—Cl—H16Ci | 59.3 |
C6—N7—C16 | 110.30 (15) | H6Ai—Cl—H16Ci | 51.4 |
C8—N7—C16 | 108.90 (15) | H22—Cl—H17Aii | 64.9 |
C14—N7—C16 | 112.53 (14) | H6Ai—Cl—H17Aii | 81.6 |
C8A—C8—N7 | 112.41 (16) | H16Ci—Cl—H17Aii | 95.6 |
C9—C8A—C12A | 116.73 (18) | H22—Cl—H15Biii | 89.1 |
C9—C8A—C8 | 120.06 (17) | H6Ai—Cl—H15Biii | 115.6 |
C12A—C8A—C8 | 123.09 (17) | H16Ci—Cl—H15Biii | 80.2 |
C8A—C9—C10 | 122.97 (19) | H17Aii—Cl—H15Biii | 151.1 |
C8A—C9—O20 | 126.58 (18) | H22—Cl—H6B | 51.2 |
C10—C9—O20 | 110.40 (17) | H6Ai—Cl—H6B | 144.6 |
C11—C10—O21 | 128.85 (18) | H16Ci—Cl—H6B | 108.3 |
C11—C10—C9 | 121.42 (18) | H17Aii—Cl—H6B | 71.1 |
O21—C10—C9 | 109.72 (17) | H15Biii—Cl—H6B | 83.0 |
C10—C11—C12 | 116.66 (18) | H22—Cl—H13Aiv | 147.8 |
C12A—C12—C11 | 122.18 (19) | H6Ai—Cl—H13Aiv | 53.2 |
C12—C12A—C8A | 119.98 (18) | H16Ci—Cl—H13Aiv | 100.4 |
C12—C12A—C13 | 120.11 (17) | H17Aii—Cl—H13Aiv | 95.6 |
C8A—C12A—C13 | 119.87 (17) | H15Biii—Cl—H13Aiv | 113.3 |
C12A—C13—C14 | 112.47 (16) | H6B—Cl—H13Aiv | 149.2 |
O22—C14—C13 | 107.65 (15) | ||
C14A—C1—C2—O18 | −179.67 (18) | C12—C12A—C13—C14 | −156.61 (17) |
C14A—C1—C2—C3 | 1.9 (3) | C8A—C12A—C13—C14 | 21.1 (2) |
C1—C2—C3—C4 | 2.5 (3) | C12A—C13—C14—O22 | 60.4 (2) |
O18—C2—C3—C4 | −176.22 (17) | C12A—C13—C14—C14A | −173.68 (15) |
C1—C2—C3—O19 | 179.86 (18) | C12A—C13—C14—N7 | −53.5 (2) |
O18—C2—C3—O19 | 1.1 (2) | C8—N7—C14—O22 | −45.32 (18) |
O19—C3—C4—C4A | 178.64 (18) | C16—N7—C14—O22 | −166.31 (15) |
C2—C3—C4—C4A | −4.5 (3) | C6—N7—C14—O22 | 71.07 (18) |
C3—C4—C4A—C14A | 2.2 (3) | C8—N7—C14—C13 | 69.22 (18) |
C3—C4—C4A—C5 | −175.60 (18) | C16—N7—C14—C13 | −51.77 (19) |
C14A—C4A—C5—C6 | 15.7 (3) | C6—N7—C14—C13 | −174.40 (15) |
C4—C4A—C5—C6 | −166.49 (17) | C8—N7—C14—C14A | −167.73 (15) |
C4A—C5—C6—N7 | −47.8 (2) | C16—N7—C14—C14A | 71.28 (19) |
C5—C6—N7—C8 | −175.16 (16) | C6—N7—C14—C14A | −51.34 (19) |
C5—C6—N7—C16 | −56.9 (2) | C4—C4A—C14A—C1 | 2.0 (3) |
C5—C6—N7—C14 | 67.07 (19) | C5—C4A—C14A—C1 | 179.79 (18) |
C16—N7—C8—C8A | 74.33 (19) | C4—C4A—C14A—C14 | 179.32 (17) |
C6—N7—C8—C8A | −166.49 (16) | C5—C4A—C14A—C14 | −2.9 (3) |
C14—N7—C8—C8A | −48.8 (2) | C2—C1—C14A—C4A | −4.1 (3) |
N7—C8—C8A—C9 | −169.35 (17) | C2—C1—C14A—C14 | 178.52 (17) |
N7—C8—C8A—C12A | 14.7 (3) | O22—C14—C14A—C4A | −97.9 (2) |
C12A—C8A—C9—C10 | 0.2 (3) | C13—C14—C14A—C4A | 138.95 (19) |
C8—C8A—C9—C10 | −176.00 (18) | N7—C14—C14A—C4A | 20.7 (2) |
C12A—C8A—C9—O20 | 177.29 (18) | O22—C14—C14A—C1 | 79.4 (2) |
C8—C8A—C9—O20 | 1.1 (3) | C13—C14—C14A—C1 | −43.7 (2) |
C8A—C9—C10—C11 | −1.7 (3) | N7—C14—C14A—C1 | −161.89 (16) |
O20—C9—C10—C11 | −179.15 (18) | C1—C2—O18—C15 | 167.8 (2) |
C8A—C9—C10—O21 | 176.87 (18) | C3—C2—O18—C15 | −13.6 (2) |
O20—C9—C10—O21 | −0.6 (2) | O19—C15—O18—C2 | 20.7 (2) |
O21—C10—C11—C12 | −177.38 (19) | C4—C3—O19—C15 | −171.1 (2) |
C9—C10—C11—C12 | 0.9 (3) | C2—C3—O19—C15 | 11.8 (2) |
C10—C11—C12—C12A | 1.3 (3) | O18—C15—O19—C3 | −20.0 (2) |
C11—C12—C12A—C8A | −2.8 (3) | C8A—C9—O20—C17 | 174.2 (2) |
C11—C12—C12A—C13 | 174.96 (18) | C10—C9—O20—C17 | −8.4 (2) |
C9—C8A—C12A—C12 | 1.9 (3) | O21—C17—O20—C9 | 14.1 (2) |
C8—C8A—C12A—C12 | 178.02 (18) | C11—C10—O21—C17 | −172.1 (2) |
C9—C8A—C12A—C13 | −175.82 (17) | C9—C10—O21—C17 | 9.5 (2) |
C8—C8A—C12A—C13 | 0.3 (3) | O20—C17—O21—C10 | −14.6 (2) |
Symmetry codes: (i) x+1/2, −y−1/2, z+1/2; (ii) −x, −y−1, −z+2; (iii) −x+1, −y, −z+2; (iv) x−1/2, −y−1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C20H20NO5+·Cl− |
Mr | 389.82 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 6.940 (1), 17.755 (1), 13.829 (2) |
β (°) | 104.18 (1) |
V (Å3) | 1652.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.50 × 0.40 × 0.35 |
Data collection | |
Diffractometer | KUMA KM-4 with CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11498, 2900, 2546 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.102, 1.16 |
No. of reflections | 2900 |
No. of parameters | 246 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.30 |
Computer programs: KUMA KM-4 Software (Kuma, 1992), KUMA KM-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Johnson & Burnett, 1996), SHELXL97.
C2—O18 | 1.381 (2) | C9—O20 | 1.379 (2) |
C3—O19 | 1.372 (2) | C10—O21 | 1.377 (2) |
C4A—C5 | 1.509 (3) | C12A—C13 | 1.518 (3) |
C4A—C14A | 1.397 (3) | C13—C14 | 1.525 (3) |
C5—C6 | 1.507 (3) | C14—O22 | 1.394 (2) |
N7—C6 | 1.513 (2) | C14—C14A | 1.530 (3) |
N7—C8 | 1.498 (2) | C15—O18 | 1.437 (3) |
N7—C14 | 1.579 (2) | C15—O19 | 1.441 (3) |
N7—C16 | 1.510 (2) | C17—O21 | 1.431 (3) |
C8—C8A | 1.497 (3) | C17—O20 | 1.447 (2) |
C8A—C12A | 1.404 (3) | ||
C5—C6—N7 | 110.65 (15) | C14—N7—C16 | 112.53 (14) |
C6—N7—C8 | 106.93 (14) | C8A—C8—N7 | 112.41 (16) |
C6—N7—C14 | 108.91 (14) | O22—C14—N7 | 106.77 (14) |
C8—N7—C14 | 109.11 (14) | C13—C14—N7 | 105.92 (15) |
C6—N7—C16 | 110.30 (15) | C14A—C14—N7 | 109.31 (15) |
C8—N7—C16 | 108.90 (15) |
Protopine is an isoquinoline alkaloid of the protopine group which is common in the plants of the Papaveraceae, Fumariaceae, and other families (Guinaudeau & Shamma, 1982). The free base of protopine (I) with a ten-membered nitrogen heterocycle has already been investigated by X-ray analysis (Hall & Ahmed, 1968a) as well as the free bases of the related alkaloids cryptopine (Hall & Ahmed, 1968b), allocryptopine (Sakai et al., 1988; Marek et al., 1998), and corycavine (Kamigauchi et al., 1987). All the cited papers reported a strong electrostatic interaction between the nitrogen and the carbonyl carbon across the ten-membered ring. In an acidic environment, a fundamental alteration of the skeleton occurs and protopines take the forms of tetracyclic structures corresponding to the tetrahydroprotoberberines. Compound (II) has already been described using spectral data (UV, IR, NMR) and investigated by diffraction analysis (Luo et al., 1985). However, that report afforded neither complete geometric and crystal data parameters nor packing data. The detailed molecular study of protopine hydrochloride may be of interest in biosynthetic considerations and especially in pharmacological studies. Protopine has been shown to have multiple actions on cardiovascular system including anti-arrhythmic effects (Song et al., 2000) as well as anti-thrombotic activities (Saeed et al., 1997). Generally, it is known that the medically active forms of alkaloids are as salts rather than their free bases (Dostál, 2000). \sch
The title compound, protopine hydrochloride, (II), is the salt of protopine. NMR studies of protopine salts indicated the presence of two (cis, trans) isomers in solutions (Iwasa et al., 1982; Hussain et al., 1983). The crystal of (II), examined in the present paper, is a trans-isomer with respect to the position of the N-methyl and the hydroxyl group (Fig. 1). The dihedral angle along the C16—N7—C14—O22 junction is -166.31 (15)°. In the tetrahydroprotoberberine alkaloids canadinium camphorsulfonate (Sakai et al., 1987) and tetrahydropalmatine (Ribár et al., 1993), both the central rings also were found to be trans-fused. On the other hand, corycavinium camphorsulfonate, structurally close to protopine hydrochloride, is cis-configurated (Kamigauchi et al., 1994). The six-membered nitrogen heterocycles in (II) adopt distorted half-chair conformations. The angle between the mean planes of both aromatic rings is 17.10 (5)°.
Selected geometric parameters are given in Table 1. The central N7—C14 bond in the quinolizine ring is unusually long [1.579 (2) Å] and similar to coulteropine hydrobromide where the length of central bond was 1.58 Å (Stermitz et al., 1968). This finding implies that this particular bond easily breaks under the action of hydroxide ion to provide a ten-membered ring of the free base (I). The mean of the bond angles around the nitrogen is 109.5° (sp3 hybridization). The molecule bears two chiral centers (C14, N7) and from the centrosymmetric space group it follows that the crystal is a racemate. From plant extracts, protopines are usually obtained in the form of optically inactive free bases (type I) because they are stable and easy to crystallize. However, in plant tissues, protopine alkaloids occur as salts of type II (Kamigauchi et al., 1994). To the best of our knowledge, a natural salt of protopine has probably not yet been isolated from plant material directly without being alkalized. Thus, the in vitro prepared protopine hydrochloride (I) is obviously racemic whereas the configuration of the protopine salt generated in vivo still remains an open question. There are numerous contacts between the chloride ion and H atoms in the range of 2.78–2.87 Å, the shortest one being O22—H22···Cl (2.06 Å). The molecules are packed in a chain-like arrangement with chloride ions in between.