Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102015202/fr1384sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015202/fr1384Isup2.hkl |
CCDC reference: 197336
Zanthoxylum rhoifolium was collected in March 1998, in the town of Jaguari, Rio Grande do Sul, Brazil, and was identified by Professor Ana Zélia Silva. The voucher specimen (No. 1150) is in the Herbário Ático Seabra of Federal University of Maranhão. The compounds were extracted from the bark with methanol. The crude extract was dissolved in water, acidified and washed with diethyl ether. The aqueous solution was basified and partitioned with n-hexane and diethyl ether. The products were isolated by column and thin-layer chromatography of the organic fractions. Complete details of the purification and antibacterial assay are given in the _exptl_special_details section of the deposited CIF.
H atoms were constrained to geometric positions, with distances fixed to 0.99 (CH), 0.98 (CH2), 0.94 (aromatic H) or 0.97 Å (CH3). Isotropic displacement parameters for the H atoms were set at 150% of that of the parent atom for CH3 groups and at 120% for the other groups. The methyl H atoms were located on regions of highest electron density and the methyl groups allowed to rotate while maintaining a tetrahedral geometry.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: HELENA (Spek, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. View of (I) with the atom-numbering scheme and 50% probability displacement ellipsoids for non-H atoms. H atoms are represented by spheres of arbitrary size. |
C23H19NO5 | Z = 2 |
Mr = 389.39 | F(000) = 408 |
Triclinic, P1 | Dx = 1.419 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.5418 Å |
a = 8.2525 (7) Å | Cell parameters from 25 reflections |
b = 8.2653 (6) Å | θ = 8.9–27.1° |
c = 13.9594 (6) Å | µ = 0.83 mm−1 |
α = 94.191 (6)° | T = 213 K |
β = 93.879 (6)° | Needle, colorless |
γ = 105.293 (6)° | 0.25 × 0.10 × 0.10 mm |
V = 912.25 (10) Å3 |
Enraf-Nonius CAD-4 diffractometer | 2287 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
Graphite monochromator | θmax = 65.0°, θmin = 5.6° |
ω scans | h = −1→9 |
Absorption correction: ψ scan with 5 reflections using the ABSPSI routine in PLATON (Spek, 1995) | k = −9→9 |
Tmin = 0.864, Tmax = 0.921 | l = −16→16 |
3809 measured reflections | 3 standard reflections every 60 min |
3107 independent reflections | intensity decay: <2% |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0627P)2 + 0.1711P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3107 reflections | Δρmax = 0.23 e Å−3 |
267 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0064 (8) |
C23H19NO5 | γ = 105.293 (6)° |
Mr = 389.39 | V = 912.25 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.2525 (7) Å | Cu Kα radiation |
b = 8.2653 (6) Å | µ = 0.83 mm−1 |
c = 13.9594 (6) Å | T = 213 K |
α = 94.191 (6)° | 0.25 × 0.10 × 0.10 mm |
β = 93.879 (6)° |
Enraf-Nonius CAD-4 diffractometer | 2287 reflections with I > 2σ(I) |
Absorption correction: ψ scan with 5 reflections using the ABSPSI routine in PLATON (Spek, 1995) | Rint = 0.045 |
Tmin = 0.864, Tmax = 0.921 | 3 standard reflections every 60 min |
3809 measured reflections | intensity decay: <2% |
3107 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.23 e Å−3 |
3107 reflections | Δρmin = −0.20 e Å−3 |
267 parameters |
Experimental. Dried and powdered bark (650 g) was exhaustively extracted with MeOH at room temperature. Solvent was evaporated in vacuum to obtain 98 g of the crude extract. To this extract, H2O/Et2O (1:1, v/v) (1 l) was added and acidified with 2M HCl to pH 2.0. The organic phase was separated and the H2O layer extracted 3x with Et2O. The Et2O phases were not analysed. The aq. acidic solution was made basic with NH4OH to pH 9.0 and successively partitioned with n-hexane (yield 0.9 g) and Et2O (yield 2.4 g). A portion of the hexane fraction (0.9 g) was chromatographed on silica gel column (30 g) and eluted with CHCl3 (500 ml), Rf 0.54, to afford 1 (20 mg). The Et2O fraction (2.4 g) was submitted to CC on silica gel (100 g) with a gradient of CHCl3—MeOH (99:1) to MeOH (20 fractions, 150 ml each). Fractions 2–6 were combined and further purified with a preparative TLC [CHCl3: MeOH (98:2), two runs] to afford 1 (170 mg) and 2 (90 mg). Crystallization of fractions 8–10 (Et2O: MeOH) yielded 3 (30 mg) and crystallization of fractions 12–16 (MeOH) yielded 4 (300 mg). The antibacterial activity of alkaloids 1 and 2 against two Gram-positive bacteria: Staphylococcus aureus (ATCC 6538p), Staphylococcus epidermidis (ATCC 12228), the three gram-negative bacteria: Klebsiela pneumoniae (ATCC 10031), Salmonella setubal (ATCC 19196) and Escherichia coli (ATCC 11103), using the bioautographie technique. The microorganisms used in the antibacterial assay have been maintained at the Departamento de Química da Universidade Federal de Santa Maria, RS, Brasil. For the antimicrobial assay, 50.0, 25.0, 12.5, 6.25, 3.12, 1.06 µg of 1 and 2 were applied to pre-coated TLC plates. TLC plates were developed with CHCl3 and dried for complete removal of solvents. The inoculum was prepared by culturing each organism in tryptone soya agar (TSA, Oxoid) at 37 °C to a turbidity equivalent to McFarland 0.5 standard (1.5 × 108 CFU/ml). One microliter of each diluted inoculum (104 – 106 CFU) was applied onto Mueller Agar (MHA-DIFCO) plates. Amoxicillin (0.5 µg) was used as positive control. #Table S1. Bioautography assay results of 6-acetonyldihydroavicine (1) #against bacteriasa #__________________________________________________________________________ #Microorganismsb | Antibacterial activityc (mg) #Staphylococcus aureus ATCC 6538p | 1.0 #Staphylococcus epidermidis ATCC 12228 | 3.5 #Klebsiella pneumonial ATCC 10031 | 1.0 #Salmonella setubal ATCC 19196 | 3.5 #Escherichia coli ATCC 11103 | 3.5 # #a Positive controls. Amoxicillin (0.5 mg) #b ATCC (American Type Culture Collection). #c Minimum amount required for inhibition on bacteria growth on TLC #plates. #__________________________________________________________________________ |
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 > 2σ(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 | 0.9251 (2) | 0.4457 (2) | 0.26085 (15) | 0.0364 (5) | |
C2 | 0.9819 (3) | 0.6139 (2) | 0.30341 (16) | 0.0403 (5) | |
H2 | 1.0524 | 0.6958 | 0.2705 | 0.048* | |
C3 | 0.9362 (3) | 0.6592 (2) | 0.39108 (16) | 0.0415 (5) | |
H3 | 0.9786 | 0.7713 | 0.4182 | 0.050* | |
C4 | 0.8266 (2) | 0.5420 (2) | 0.44253 (16) | 0.0385 (5) | |
C5 | 0.7771 (3) | 0.5901 (3) | 0.53340 (16) | 0.0438 (5) | |
H5 | 0.8162 | 0.7016 | 0.5619 | 0.053* | |
C6 | 0.6722 (3) | 0.4705 (3) | 0.57735 (16) | 0.0435 (5) | |
O7 | 0.6093 (2) | 0.4861 (2) | 0.66507 (12) | 0.0593 (5) | |
C8 | 0.4987 (3) | 0.3258 (3) | 0.67673 (17) | 0.0521 (6) | |
H8A | 0.3833 | 0.3351 | 0.6802 | 0.063* | |
H8B | 0.5338 | 0.2845 | 0.7366 | 0.063* | |
O9 | 0.5051 (2) | 0.2119 (2) | 0.59622 (12) | 0.0597 (5) | |
C10 | 0.6093 (3) | 0.3045 (3) | 0.53547 (16) | 0.0429 (5) | |
C11 | 0.6499 (3) | 0.2506 (3) | 0.44921 (16) | 0.0414 (5) | |
H11 | 0.6058 | 0.1384 | 0.4225 | 0.050* | |
C12 | 0.7636 (2) | 0.3726 (2) | 0.40005 (15) | 0.0368 (5) | |
C13 | 0.8160 (2) | 0.3272 (2) | 0.30921 (15) | 0.0357 (5) | |
N14 | 0.75781 (19) | 0.15470 (19) | 0.27038 (12) | 0.0355 (4) | |
C15 | 0.7375 (2) | 0.1346 (2) | 0.16421 (15) | 0.0359 (5) | |
H15 | 0.7260 | 0.0145 | 0.1439 | 0.043* | |
C16 | 0.8894 (2) | 0.2369 (2) | 0.11996 (15) | 0.0362 (5) | |
C17 | 0.9359 (2) | 0.1753 (3) | 0.03309 (16) | 0.0390 (5) | |
H17 | 0.8728 | 0.0725 | 0.0000 | 0.047* | |
C18 | 1.0772 (2) | 0.2715 (3) | −0.00166 (16) | 0.0390 (5) | |
O19 | 1.14947 (19) | 0.23701 (18) | −0.08428 (11) | 0.0518 (4) | |
C20 | 1.3022 (3) | 0.3695 (3) | −0.08225 (17) | 0.0469 (6) | |
H20A | 1.3999 | 0.3235 | −0.0755 | 0.056* | |
H20B | 1.3052 | 0.4235 | −0.1426 | 0.056* | |
O21 | 1.30803 (18) | 0.48984 (18) | −0.00258 (11) | 0.0493 (4) | |
C22 | 1.1708 (2) | 0.4225 (2) | 0.04670 (15) | 0.0367 (5) | |
C23 | 1.1264 (2) | 0.4872 (2) | 0.13053 (15) | 0.0374 (5) | |
H23 | 1.1897 | 0.5918 | 0.1616 | 0.045* | |
C24 | 0.9815 (2) | 0.3910 (2) | 0.16891 (15) | 0.0352 (5) | |
C25 | 0.8613 (3) | 0.0526 (3) | 0.31112 (16) | 0.0440 (5) | |
H25A | 0.9765 | 0.0944 | 0.2950 | 0.066* | |
H25B | 0.8166 | −0.0638 | 0.2846 | 0.066* | |
H25C | 0.8593 | 0.0596 | 0.3807 | 0.066* | |
C26 | 0.5723 (2) | 0.1717 (3) | 0.12994 (17) | 0.0405 (5) | |
H26A | 0.5716 | 0.2842 | 0.1571 | 0.048 (6)* | |
H26B | 0.5624 | 0.1696 | 0.0595 | 0.065 (8)* | |
C27 | 0.4248 (2) | 0.0414 (3) | 0.16143 (16) | 0.0399 (5) | |
C28 | 0.3008 (3) | 0.1003 (3) | 0.2164 (2) | 0.0683 (8) | |
H28A | 0.2119 | 0.0040 | 0.2301 | 0.102* | |
H28B | 0.2524 | 0.1728 | 0.1786 | 0.102* | |
H28C | 0.3566 | 0.1626 | 0.2765 | 0.102* | |
O29 | 0.41039 (18) | −0.10772 (18) | 0.14154 (12) | 0.0524 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0304 (10) | 0.0332 (10) | 0.0447 (13) | 0.0073 (8) | 0.0012 (9) | 0.0047 (9) |
C2 | 0.0345 (10) | 0.0317 (10) | 0.0529 (14) | 0.0049 (8) | 0.0045 (9) | 0.0065 (9) |
C3 | 0.0382 (11) | 0.0308 (10) | 0.0525 (14) | 0.0061 (9) | 0.0001 (10) | 0.0006 (9) |
C4 | 0.0329 (10) | 0.0369 (11) | 0.0462 (13) | 0.0108 (9) | 0.0014 (9) | 0.0040 (9) |
C5 | 0.0426 (12) | 0.0398 (12) | 0.0483 (14) | 0.0123 (10) | 0.0007 (10) | −0.0003 (10) |
C6 | 0.0395 (12) | 0.0509 (13) | 0.0426 (13) | 0.0168 (10) | 0.0047 (10) | 0.0031 (10) |
O7 | 0.0691 (11) | 0.0592 (10) | 0.0498 (11) | 0.0150 (9) | 0.0184 (8) | 0.0026 (8) |
C8 | 0.0535 (14) | 0.0632 (15) | 0.0425 (14) | 0.0179 (12) | 0.0128 (11) | 0.0082 (11) |
O9 | 0.0710 (12) | 0.0548 (10) | 0.0510 (11) | 0.0072 (9) | 0.0280 (9) | 0.0051 (8) |
C10 | 0.0379 (11) | 0.0461 (12) | 0.0454 (14) | 0.0096 (10) | 0.0078 (10) | 0.0105 (10) |
C11 | 0.0376 (11) | 0.0392 (11) | 0.0473 (13) | 0.0087 (9) | 0.0080 (10) | 0.0060 (9) |
C12 | 0.0320 (10) | 0.0355 (11) | 0.0435 (13) | 0.0100 (8) | 0.0013 (9) | 0.0056 (9) |
C13 | 0.0302 (10) | 0.0316 (10) | 0.0444 (13) | 0.0076 (8) | −0.0001 (9) | 0.0043 (9) |
N14 | 0.0330 (9) | 0.0290 (8) | 0.0433 (10) | 0.0061 (7) | 0.0028 (7) | 0.0049 (7) |
C15 | 0.0317 (10) | 0.0307 (10) | 0.0422 (12) | 0.0020 (8) | 0.0050 (9) | 0.0058 (8) |
C16 | 0.0295 (10) | 0.0331 (10) | 0.0453 (13) | 0.0060 (8) | 0.0041 (9) | 0.0073 (9) |
C17 | 0.0324 (10) | 0.0347 (10) | 0.0460 (13) | 0.0019 (8) | 0.0043 (9) | 0.0039 (9) |
C18 | 0.0357 (11) | 0.0375 (11) | 0.0440 (13) | 0.0081 (9) | 0.0081 (9) | 0.0067 (9) |
O19 | 0.0490 (9) | 0.0438 (9) | 0.0555 (10) | −0.0025 (7) | 0.0216 (8) | −0.0002 (7) |
C20 | 0.0415 (12) | 0.0420 (12) | 0.0538 (15) | 0.0029 (10) | 0.0141 (10) | 0.0052 (10) |
O21 | 0.0420 (8) | 0.0423 (8) | 0.0584 (11) | −0.0009 (7) | 0.0214 (7) | 0.0023 (7) |
C22 | 0.0289 (10) | 0.0350 (10) | 0.0457 (13) | 0.0045 (8) | 0.0076 (9) | 0.0115 (9) |
C23 | 0.0305 (10) | 0.0319 (10) | 0.0468 (13) | 0.0028 (8) | 0.0026 (9) | 0.0063 (9) |
C24 | 0.0294 (10) | 0.0317 (10) | 0.0432 (12) | 0.0054 (8) | 0.0024 (9) | 0.0063 (9) |
C25 | 0.0457 (12) | 0.0376 (11) | 0.0507 (14) | 0.0139 (9) | 0.0025 (10) | 0.0086 (9) |
C26 | 0.0315 (10) | 0.0382 (11) | 0.0484 (14) | 0.0024 (9) | 0.0035 (9) | 0.0088 (9) |
C27 | 0.0312 (11) | 0.0392 (12) | 0.0469 (13) | 0.0054 (9) | −0.0014 (9) | 0.0089 (9) |
C28 | 0.0549 (15) | 0.0610 (16) | 0.095 (2) | 0.0176 (13) | 0.0324 (15) | 0.0157 (15) |
O29 | 0.0429 (9) | 0.0365 (9) | 0.0707 (12) | −0.0013 (7) | 0.0045 (8) | 0.0040 (7) |
C1—C13 | 1.393 (3) | C20—O21 | 1.426 (3) |
C1—C2 | 1.415 (3) | O21—C22 | 1.377 (2) |
C1—C24 | 1.475 (3) | C22—C23 | 1.364 (3) |
C2—C3 | 1.360 (3) | C23—C24 | 1.413 (3) |
C3—C4 | 1.414 (3) | C26—C27 | 1.511 (3) |
C4—C5 | 1.420 (3) | C27—O29 | 1.216 (2) |
C4—C12 | 1.427 (3) | C27—C28 | 1.479 (3) |
C5—C6 | 1.347 (3) | C2—H2 | 0.9400 |
C6—O7 | 1.373 (3) | C3—H3 | 0.9400 |
C6—C10 | 1.400 (3) | C5—H5 | 0.9400 |
O7—C8 | 1.424 (3) | C8—H8A | 0.9800 |
C8—O9 | 1.425 (3) | C8—H8B | 0.9800 |
O9—C10 | 1.375 (3) | C11—H11 | 0.9400 |
C10—C11 | 1.347 (3) | C15—H15 | 0.9900 |
C11—C12 | 1.435 (3) | C17—H17 | 0.9400 |
C12—C13 | 1.423 (3) | C20—H20A | 0.9800 |
C13—N14 | 1.431 (2) | C20—H20B | 0.9800 |
N14—C25 | 1.466 (2) | C23—H23 | 0.9400 |
N14—C15 | 1.472 (3) | C25—H25A | 0.9700 |
C15—C16 | 1.513 (3) | C25—H25B | 0.9700 |
C15—C26 | 1.528 (3) | C25—H25C | 0.9700 |
C16—C17 | 1.397 (3) | C26—H26A | 0.9800 |
C16—C24 | 1.400 (3) | C26—H26B | 0.9800 |
C17—C18 | 1.368 (3) | C28—H28A | 0.9700 |
C18—O19 | 1.379 (2) | C28—H28B | 0.9700 |
C18—C22 | 1.381 (3) | C28—H28C | 0.9700 |
O19—C20 | 1.432 (2) | ||
C13—C1—C2 | 118.5 (2) | C23—C24—C1 | 122.11 (18) |
C13—C1—C24 | 119.14 (18) | C27—C26—C15 | 109.83 (16) |
C2—C1—C24 | 122.30 (18) | O29—C27—C28 | 121.6 (2) |
C3—C2—C1 | 121.3 (2) | O29—C27—C26 | 120.00 (19) |
C2—C3—C4 | 121.69 (19) | C28—C27—C26 | 118.39 (19) |
C3—C4—C5 | 121.60 (19) | C3—C2—H2 | 119.4 |
C3—C4—C12 | 118.2 (2) | C1—C2—H2 | 119.4 |
C5—C4—C12 | 120.16 (19) | C2—C3—H3 | 119.2 |
C6—C5—C4 | 117.7 (2) | C4—C3—H3 | 119.2 |
C5—C6—O7 | 128.2 (2) | C6—C5—H5 | 121.2 |
C5—C6—C10 | 122.2 (2) | C4—C5—H5 | 121.2 |
O7—C6—C10 | 109.6 (2) | O7—C8—H8A | 110.0 |
C6—O7—C8 | 106.32 (17) | O9—C8—H8A | 110.0 |
O7—C8—O9 | 108.43 (18) | O7—C8—H8B | 110.0 |
C10—O9—C8 | 106.39 (18) | O9—C8—H8B | 110.0 |
C11—C10—O9 | 127.6 (2) | H8A—C8—H8B | 108.4 |
C11—C10—C6 | 123.2 (2) | C10—C11—H11 | 121.6 |
O9—C10—C6 | 109.18 (19) | C12—C11—H11 | 121.6 |
C10—C11—C12 | 116.8 (2) | N14—C15—H15 | 107.1 |
C13—C12—C4 | 119.09 (19) | C16—C15—H15 | 107.1 |
C13—C12—C11 | 120.97 (18) | C26—C15—H15 | 107.1 |
C4—C12—C11 | 119.9 (2) | C18—C17—H17 | 121.5 |
C1—C13—C12 | 121.15 (18) | C16—C17—H17 | 121.5 |
C1—C13—N14 | 120.78 (19) | O21—C20—H20A | 110.0 |
C12—C13—N14 | 118.04 (18) | O19—C20—H20A | 110.0 |
C13—N14—C25 | 111.69 (15) | O21—C20—H20B | 110.0 |
C13—N14—C15 | 112.94 (15) | O19—C20—H20B | 110.0 |
C25—N14—C15 | 112.83 (16) | H20A—C20—H20B | 108.4 |
N14—C15—C16 | 112.70 (16) | C22—C23—H23 | 121.3 |
N14—C15—C26 | 108.82 (16) | C24—C23—H23 | 121.3 |
C16—C15—C26 | 113.55 (16) | N14—C25—H25A | 109.5 |
C17—C16—C24 | 121.73 (18) | N14—C25—H25B | 109.5 |
C17—C16—C15 | 119.88 (17) | H25A—C25—H25B | 109.5 |
C24—C16—C15 | 118.38 (19) | N14—C25—H25C | 109.5 |
C18—C17—C16 | 117.01 (18) | H25A—C25—H25C | 109.5 |
C17—C18—O19 | 127.87 (19) | H25B—C25—H25C | 109.5 |
C17—C18—C22 | 121.8 (2) | C27—C26—H26A | 109.7 |
O19—C18—C22 | 110.29 (17) | C15—C26—H26A | 109.7 |
C18—O19—C20 | 105.23 (15) | C27—C26—H26B | 109.7 |
O21—C20—O19 | 108.59 (16) | C15—C26—H26B | 109.7 |
C22—O21—C20 | 105.94 (15) | H26A—C26—H26B | 108.2 |
C23—C22—O21 | 127.98 (18) | C27—C28—H28A | 109.5 |
C23—C22—C18 | 122.41 (18) | C27—C28—H28B | 109.5 |
O21—C22—C18 | 109.61 (18) | H28A—C28—H28B | 109.5 |
C22—C23—C24 | 117.38 (18) | C27—C28—H28C | 109.5 |
C16—C24—C23 | 119.62 (19) | H28A—C28—H28C | 109.5 |
C16—C24—C1 | 118.26 (18) | H28B—C28—H28C | 109.5 |
C13—C1—C2—C3 | 2.2 (3) | C13—N14—C15—C16 | 48.3 (2) |
C24—C1—C2—C3 | −175.95 (19) | C25—N14—C15—C16 | −79.60 (19) |
C1—C2—C3—C4 | −1.8 (3) | C13—N14—C15—C26 | −78.62 (19) |
C2—C3—C4—C5 | −179.03 (19) | C25—N14—C15—C26 | 153.53 (16) |
C2—C3—C4—C12 | −0.1 (3) | N14—C15—C16—C17 | 146.43 (18) |
C3—C4—C5—C6 | 179.90 (19) | C26—C15—C16—C17 | −89.3 (2) |
C12—C4—C5—C6 | 1.0 (3) | N14—C15—C16—C24 | −32.5 (2) |
C4—C5—C6—O7 | 179.11 (19) | C26—C15—C16—C24 | 91.8 (2) |
C4—C5—C6—C10 | −1.4 (3) | C24—C16—C17—C18 | 0.8 (3) |
C5—C6—O7—C8 | 177.5 (2) | C15—C16—C17—C18 | −178.12 (18) |
C10—C6—O7—C8 | −2.1 (2) | C16—C17—C18—O19 | 178.93 (19) |
C6—O7—C8—O9 | 3.3 (2) | C16—C17—C18—C22 | 0.2 (3) |
O7—C8—O9—C10 | −3.3 (2) | C17—C18—O19—C20 | −174.8 (2) |
C8—O9—C10—C11 | −178.4 (2) | C22—C18—O19—C20 | 4.1 (2) |
C8—O9—C10—C6 | 2.0 (2) | C18—O19—C20—O21 | −5.9 (2) |
C5—C6—C10—C11 | 0.9 (3) | O19—C20—O21—C22 | 5.5 (2) |
O7—C6—C10—C11 | −179.5 (2) | C20—O21—C22—C23 | 176.8 (2) |
C5—C6—C10—O9 | −179.52 (19) | C20—O21—C22—C18 | −3.0 (2) |
O7—C6—C10—O9 | 0.0 (2) | C17—C18—C22—C23 | −1.6 (3) |
O9—C10—C11—C12 | −179.36 (19) | O19—C18—C22—C23 | 179.47 (18) |
C6—C10—C11—C12 | 0.1 (3) | C17—C18—C22—O21 | 178.22 (18) |
C3—C4—C12—C13 | 1.4 (3) | O19—C18—C22—O21 | −0.7 (2) |
C5—C4—C12—C13 | −179.61 (18) | O21—C22—C23—C24 | −177.97 (18) |
C3—C4—C12—C11 | −178.96 (18) | C18—C22—C23—C24 | 1.9 (3) |
C5—C4—C12—C11 | 0.0 (3) | C17—C16—C24—C23 | −0.5 (3) |
C10—C11—C12—C13 | 179.06 (18) | C15—C16—C24—C23 | 178.41 (17) |
C10—C11—C12—C4 | −0.6 (3) | C17—C16—C24—C1 | −179.20 (18) |
C2—C1—C13—C12 | −0.8 (3) | C15—C16—C24—C1 | −0.2 (3) |
C24—C1—C13—C12 | 177.39 (17) | C22—C23—C24—C16 | −0.8 (3) |
C2—C1—C13—N14 | −178.60 (17) | C22—C23—C24—C1 | 177.82 (18) |
C24—C1—C13—N14 | −0.4 (3) | C13—C1—C24—C16 | 17.8 (3) |
C4—C12—C13—C1 | −1.0 (3) | C2—C1—C24—C16 | −164.11 (18) |
C11—C12—C13—C1 | 179.41 (18) | C13—C1—C24—C23 | −160.86 (18) |
C4—C12—C13—N14 | 176.87 (16) | C2—C1—C24—C23 | 17.3 (3) |
C11—C12—C13—N14 | −2.7 (3) | N14—C15—C26—C27 | −64.9 (2) |
C1—C13—N14—C25 | 95.4 (2) | C16—C15—C26—C27 | 168.73 (17) |
C12—C13—N14—C25 | −82.5 (2) | C15—C26—C27—O29 | −53.6 (3) |
C1—C13—N14—C15 | −33.1 (2) | C15—C26—C27—C28 | 126.3 (2) |
C12—C13—N14—C15 | 149.04 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O29i | 0.98 | 2.42 | 3.372 (3) | 164 |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C23H19NO5 |
Mr | 389.39 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 213 |
a, b, c (Å) | 8.2525 (7), 8.2653 (6), 13.9594 (6) |
α, β, γ (°) | 94.191 (6), 93.879 (6), 105.293 (6) |
V (Å3) | 912.25 (10) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.83 |
Crystal size (mm) | 0.25 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan with 5 reflections using the ABSPSI routine in PLATON (Spek, 1995) |
Tmin, Tmax | 0.864, 0.921 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3809, 3107, 2287 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.588 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.125, 1.04 |
No. of reflections | 3107 |
No. of parameters | 267 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.20 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1992), CAD-4 EXPRESS, HELENA (Spek, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
C1—C24 | 1.475 (3) | N14—C15 | 1.472 (3) |
C6—O7 | 1.373 (3) | C16—C24 | 1.400 (3) |
C6—C10 | 1.400 (3) | C18—O19 | 1.379 (2) |
O7—C8 | 1.424 (3) | C18—C22 | 1.381 (3) |
C8—O9 | 1.425 (3) | O19—C20 | 1.432 (2) |
O9—C10 | 1.375 (3) | C20—O21 | 1.426 (3) |
C13—N14 | 1.431 (2) | O21—C22 | 1.377 (2) |
N14—C25 | 1.466 (2) | ||
C13—N14—C25 | 111.69 (15) | N14—C15—C26 | 108.82 (16) |
C13—N14—C15 | 112.94 (15) | C16—C15—C26 | 113.55 (16) |
C25—N14—C15 | 112.83 (16) | C27—C26—C15 | 109.83 (16) |
N14—C15—C16 | 112.70 (16) | ||
C24—C1—C13—N14 | −0.4 (3) | C15—C16—C24—C1 | −0.2 (3) |
C1—C13—N14—C15 | −33.1 (2) | C13—C1—C24—C16 | 17.8 (3) |
C13—N14—C15—C16 | 48.3 (2) | C15—C26—C27—C28 | 126.3 (2) |
N14—C15—C16—C24 | −32.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O29i | 0.98 | 2.42 | 3.372 (3) | 164 |
Symmetry code: (i) −x+1, −y, −z+1. |
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Zanthoxylum rhoifolium (Rutaceae), locally called `mamica-de-cadela, mamica-de-porca, jujevê', is a plant that grows in South America (Brazil, Uruguay, Paraguay and Argentina). It has been used in Brazilian folk medicine as teas or infusions against a variety of diseases (Tin-Wa et al., 1974). Its medicinal properties may be related to its alkaloid composition (Tin-Wa et al., 1974; Odebiyl & Sotowara, 1979; Lenfeld et al., 1981; Nowick, 1983; Cushman et al., 1984). As a continuation of our chemical studies on Rutaceae plants (Morel et al., 1997), we now report the structure determination of a dihydrobenzophenanthridine alkaloid, 6-acetonyldihydroavicine, (I) isolated from Z. rhoifolium. This alkaloid, which has been previously isolated from Zanthoxylum tetraspermum (Nissanka et al., 2001), was found together with three other known benzophenantridine alkaloids, 6-acetonyldihydronitidine, (II), 6-acetonyldihydrochelerythrine, (III) (Decaudain et al., 1974; Waterman & Khalid, 1981; Desai et al., 1967), and xanthoxyline, (IV) (Morel et al., 1997). All were identified by mass and 1/13C multidimensional NMR spectroscopic methods. To determine whether compounds (I), (II) and (III) were artifacts from the extraction and isolation procedure, the same plant material was extracted with MeOH at room temperature, followed by extraction under neutral conditions (absence of acetone). From this procedure, alkaloids (I), (II) and (III) were still present.
The single-crystal X-ray study on (I) confirms that the compound exists as a racemate, as suggested by its low specific rotary power, [α]25D = -1° (c 0.35, MeOH). The structure shows two planar systems, consisting of aromatic rings with attached five-membered dioxolo rings (C1–C13 and C16–C24), bent at an angle of 18.42 (6)° to each other by the N-containing ring. The N-containing ring adopts a screw–boat form, with Cremer & Pople (1975) puckering values of θ = 68.2° and ϕ = 329.1°, and a puckering amplitude Q = 0.417 Å. The near planarity of the core of the molecule gives rise to a graphite-type packing arrangement. The molecules form sheets parallel to the (111) plane, spaced 3.533 (6) Å apart, staggered so that the two groups (C25 and C26/C27/O29/C28) that are out of the plane fit in spaces between the rings packed above and below. There is a hydrogen-bonding interaction C8—H8B···O29.
The antimicrobial activity of alkaloids (I) and (II) was evaluated by means of direct bioautography in a thin-layer chromatography biossay. Alkaloids (I) and (II) show a strong activity against the two Gram-positive bacteria Staphylococcus aureus (ATCC 6538p), Staphylococcus epidermidis (ATCC 12228), and the three Gram-negative bacteria Klebsiela pneumoniae (ATCC 10031), Salmonella setubal (ATCC 19196) and Escherichia coli (ATCC 11103). Both were inactive against Micrococcus luteus (ATCC 9341).