Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014055/gs1056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014055/gs1056Isup2.hkl |
CCDC reference: 142766
Leurosine (0.5 g) was added portionwise to iodomethane (5 ml). The solution was stirred at room temperature for 1 h and the solvent was then removed under reduced pressure. Suitable crystals of (I) were obtained by slow evaporation of a methanol-water-tetrahydrofuran solution.
H atoms (except those of the solvent molecules) were introduced at calculated positions as riding atoms, with an isotropic displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. Solvent H atoms? The I atom was found disordered on two positions, with occupancy factors of 0.755 (4) and 0.241 (4). The maximum peak in the difference map was found 1.83 Å from C30 and the minimum 1.12 Å from I1.
Data collection: DENZO-SMN (Otwinowski & Minor, 1997); cell refinement: DENZO-SMN; data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms and the solvent molecules are omitted for clarity. |
C47H59IN4O9·3CH3OH·2H2O | Dx = 1.352 Mg m−3 |
Mr = 1083.04 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from about 10000 reflections |
a = 9.5567 (19) Å | θ = 3–30° |
b = 20.491 (4) Å | µ = 0.67 mm−1 |
c = 27.169 (5) Å | T = 123 K |
V = 5320.5 (18) Å3 | Irregular, colourless |
Z = 4 | 0.30 × 0.20 × 0.15 mm |
F(000) = 2272 |
Nonius Kappa CCD diffractometer | 8109 independent reflections |
Radiation source: fine-focus sealed tube | 5893 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ϕ rotation scans with 2° steps | θmax = 25.1°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (MULABS in PLATON; Spek, 1998) | h = −11→11 |
Tmin = 0.867, Tmax = 0.905 | k = −24→24 |
17090 measured reflections | l = −32→32 |
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)] = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.211 | w = 1/[σ2(Fo2) + (0.1266P)2 + 8.9316P] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.022 |
8109 reflections | Δρmax = 1.11 e Å−3 |
633 parameters | Δρmin = −0.78 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (3) |
C47H59IN4O9·3CH3OH·2H2O | V = 5320.5 (18) Å3 |
Mr = 1083.04 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.5567 (19) Å | µ = 0.67 mm−1 |
b = 20.491 (4) Å | T = 123 K |
c = 27.169 (5) Å | 0.30 × 0.20 × 0.15 mm |
Nonius Kappa CCD diffractometer | 8109 independent reflections |
Absorption correction: empirical (using intensity measurements) (MULABS in PLATON; Spek, 1998) | 5893 reflections with I > 2σ(I) |
Tmin = 0.867, Tmax = 0.905 | Rint = 0.055 |
17090 measured reflections |
R[F2 > 2σ(F2)] = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.211 | Δρmax = 1.11 e Å−3 |
S = 0.97 | Δρmin = −0.78 e Å−3 |
8109 reflections | Absolute structure: Flack (1983) |
633 parameters | Absolute structure parameter: −0.06 (3) |
1 restraint |
Experimental. Unit-cell dimensions were determined from more than a thousand reflections in all the angular range, taken from ten frames with ϕ steps of 2°. A 180° range in ϕ was scanned during data collection with 2°ϕ steps and 10 s exposure by frame·The crystal to detector distance was 40 mm. |
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 on F2 for ALL reflections except for 132 with very negative F2 or flagged by the user for potential systematic errors. The structure was solved by direct methods and refined by full matrix least-squares on F2 with anisotropic displacement parameters for all non-H atoms. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
I1 | −0.3577 (3) | 1.65982 (5) | −0.03593 (4) | 0.1004 (9) | 0.755 (4) |
I2 | −0.2269 (8) | 1.6360 (2) | −0.03578 (14) | 0.106 (3) | 0.241 (4) |
O3 | −0.2062 (4) | 1.4326 (2) | 0.12419 (17) | 0.0328 (11) | |
H3A | −0.2308 | 1.4211 | 0.1518 | 0.049* | |
O4' | 0.4984 (5) | 1.2773 (2) | 0.33745 (19) | 0.0375 (12) | |
O4 | −0.3129 (4) | 1.3267 (2) | 0.06436 (17) | 0.0351 (11) | |
O16 | 0.3840 (4) | 1.1367 (2) | 0.14360 (15) | 0.0282 (10) | |
O22' | 0.3778 (5) | 1.0197 (2) | 0.21295 (17) | 0.0362 (11) | |
O23' | 0.1891 (5) | 1.0381 (2) | 0.16549 (16) | 0.0346 (11) | |
O23 | −0.0577 (6) | 1.4712 (2) | 0.05166 (18) | 0.0496 (14) | |
O24 | −0.0651 (5) | 1.3720 (2) | 0.01648 (18) | 0.0381 (11) | |
O26 | −0.2506 (5) | 1.2366 (3) | 0.0220 (2) | 0.0560 (16) | |
O28 | 0.3328 (16) | 1.4743 (7) | 0.3939 (6) | 0.081 (5) | |
O29 | 0.8775 (7) | 1.0473 (4) | 0.1354 (2) | 0.080 (2) | |
O30 | −0.4125 (8) | 1.5118 (4) | 0.0816 (4) | 0.108 (3) | |
O31 | 0.0442 (17) | 1.6789 (5) | 0.0085 (6) | 0.218 (9) | |
O32 | 0.7683 (12) | 0.8955 (5) | 0.0262 (4) | 0.135 (4) | |
N1 | 0.1195 (5) | 1.3349 (2) | 0.10677 (18) | 0.0265 (11) | |
N6' | 0.2726 (6) | 1.1972 (3) | 0.3737 (2) | 0.0340 (13) | |
N9 | −0.2212 (5) | 1.3787 (3) | 0.2112 (2) | 0.0284 (12) | |
N16' | −0.0156 (5) | 1.0795 (2) | 0.23463 (19) | 0.0260 (12) | |
H16A | −0.0262 | 1.0827 | 0.2033 | 0.031* | |
C1' | 0.3608 (7) | 1.1363 (3) | 0.2613 (2) | 0.0256 (13) | |
H1'A | 0.3695 | 1.1059 | 0.2884 | 0.031* | |
H1'B | 0.4444 | 1.1321 | 0.2413 | 0.031* | |
C2' | 0.3568 (7) | 1.2066 (3) | 0.2827 (2) | 0.0306 (15) | |
H2'A | 0.3388 | 1.2359 | 0.2549 | 0.037* | |
C2 | 0.0134 (6) | 1.3717 (3) | 0.1349 (2) | 0.0250 (14) | |
H2A | 0.0529 | 1.4141 | 0.1440 | 0.030* | |
C3' | 0.4949 (7) | 1.2243 (3) | 0.3022 (3) | 0.0328 (16) | |
H3'A | 0.5725 | 1.2229 | 0.2787 | 0.039* | |
C3 | −0.1243 (7) | 1.3835 (3) | 0.1028 (2) | 0.0277 (14) | |
C4' | 0.5313 (7) | 1.2118 (3) | 0.3529 (3) | 0.0369 (17) | |
C4 | −0.1993 (6) | 1.3178 (3) | 0.0985 (2) | 0.0267 (14) | |
H4A | −0.1338 | 1.2861 | 0.0845 | 0.032* | |
C5' | 0.4235 (7) | 1.1769 (4) | 0.3841 (3) | 0.0394 (18) | |
H5'A | 0.4439 | 1.1851 | 0.4185 | 0.047* | |
H5'B | 0.4322 | 1.1303 | 0.3786 | 0.047* | |
C5 | −0.2539 (6) | 1.2907 (3) | 0.1473 (2) | 0.0289 (15) | |
C6 | −0.4098 (7) | 1.3082 (4) | 0.1566 (3) | 0.0364 (17) | |
H6A | −0.4755 | 1.2939 | 0.1338 | 0.044* | |
C7' | 0.1783 (7) | 1.1412 (3) | 0.3869 (2) | 0.0330 (15) | |
H7'A | 0.0830 | 1.1574 | 0.3878 | 0.040* | |
H7'B | 0.2018 | 1.1273 | 0.4201 | 0.040* | |
C7 | −0.4555 (7) | 1.3422 (4) | 0.1949 (3) | 0.0398 (17) | |
H7A | −0.5517 | 1.3463 | 0.1991 | 0.048* | |
C8' | 0.1809 (7) | 1.0821 (3) | 0.3544 (2) | 0.0274 (14) | |
H8'A | 0.1573 | 1.0444 | 0.3744 | 0.033* | |
H8'B | 0.2762 | 1.0760 | 0.3429 | 0.033* | |
C8 | −0.3643 (7) | 1.3737 (3) | 0.2311 (3) | 0.0361 (16) | |
H8A | −0.3634 | 1.3485 | 0.2613 | 0.043* | |
H8B | −0.3997 | 1.4170 | 0.2386 | 0.043* | |
C9' | 0.0843 (6) | 1.0821 (3) | 0.3092 (2) | 0.0259 (14) | |
C10' | −0.0586 (7) | 1.0612 (3) | 0.3142 (2) | 0.0255 (14) | |
C10 | −0.1152 (7) | 1.4033 (3) | 0.2460 (3) | 0.0348 (16) | |
H10A | −0.1389 | 1.3913 | 0.2795 | 0.042* | |
H10B | −0.1082 | 1.4505 | 0.2440 | 0.042* | |
C11' | −0.1405 (8) | 1.0422 (3) | 0.3548 (3) | 0.0346 (16) | |
H11'A | −0.1028 | 1.0426 | 0.3864 | 0.042* | |
C11 | 0.0230 (6) | 1.3710 (3) | 0.2301 (3) | 0.0305 (15) | |
H11A | 0.0579 | 1.3423 | 0.2557 | 0.037* | |
H11B | 0.0936 | 1.4037 | 0.2229 | 0.037* | |
C12' | −0.2766 (8) | 1.0230 (3) | 0.3475 (3) | 0.0400 (18) | |
H12'A | −0.3320 | 1.0121 | 0.3744 | 0.048* | |
C12 | −0.0145 (6) | 1.3317 (3) | 0.1831 (2) | 0.0252 (14) | |
C13' | −0.3332 (7) | 1.0196 (3) | 0.2998 (3) | 0.0378 (17) | |
H13'A | −0.4245 | 1.0051 | 0.2954 | 0.045* | |
C13 | 0.0776 (6) | 1.2720 (3) | 0.1759 (2) | 0.0214 (13) | |
C14' | −0.2540 (7) | 1.0377 (3) | 0.2593 (3) | 0.0371 (17) | |
H14'A | −0.2908 | 1.0357 | 0.2276 | 0.044* | |
C14 | 0.0960 (5) | 1.2177 (3) | 0.2053 (2) | 0.0188 (12) | |
H14A | 0.0409 | 1.2122 | 0.2332 | 0.023* | |
C15' | −0.1180 (7) | 1.0588 (3) | 0.2674 (2) | 0.0278 (14) | |
C15 | 0.1972 (6) | 1.1708 (3) | 0.1932 (2) | 0.0225 (13) | |
C16 | 0.2789 (6) | 1.1808 (3) | 0.1511 (2) | 0.0257 (14) | |
C17' | 0.1043 (6) | 1.0942 (3) | 0.2597 (2) | 0.0236 (13) | |
C17 | 0.2575 (6) | 1.2337 (3) | 0.1195 (2) | 0.0253 (14) | |
H17A | 0.3093 | 1.2379 | 0.0907 | 0.030* | |
C18' | 0.2323 (6) | 1.1152 (3) | 0.2294 (2) | 0.0228 (13) | |
C18 | 0.1561 (6) | 1.2800 (3) | 0.1321 (2) | 0.0213 (13) | |
C19' | 0.2437 (7) | 1.2214 (3) | 0.3216 (2) | 0.0304 (15) | |
H19'A | 0.2303 | 1.2683 | 0.3229 | 0.036* | |
H19'B | 0.1563 | 1.2023 | 0.3106 | 0.036* | |
C19 | −0.1677 (7) | 1.3154 (3) | 0.1923 (2) | 0.0286 (15) | |
H19A | −0.1734 | 1.2828 | 0.2187 | 0.034* | |
C20' | 0.6800 (8) | 1.2018 (4) | 0.3722 (3) | 0.049 (2) | |
H20'A | 0.6881 | 1.2229 | 0.4041 | 0.059* | |
H20'B | 0.6956 | 1.1555 | 0.3770 | 0.059* | |
C20 | −0.2441 (7) | 1.2158 (3) | 0.1443 (3) | 0.0319 (15) | |
H20A | −0.2893 | 1.2022 | 0.1140 | 0.038* | |
H20B | −0.1459 | 1.2044 | 0.1415 | 0.038* | |
C21' | 0.7933 (8) | 1.2282 (5) | 0.3386 (4) | 0.055 (2) | |
H21'A | 0.8833 | 1.2205 | 0.3531 | 0.083* | |
H21'B | 0.7800 | 1.2743 | 0.3341 | 0.083* | |
H21'C | 0.7883 | 1.2066 | 0.3073 | 0.083* | |
C21 | −0.3055 (8) | 1.1759 (4) | 0.1858 (3) | 0.0450 (19) | |
H21A | −0.2927 | 1.1304 | 0.1790 | 0.067* | |
H21B | −0.4036 | 1.1852 | 0.1887 | 0.067* | |
H21C | −0.2592 | 1.1869 | 0.2161 | 0.067* | |
C22' | 0.2786 (7) | 1.0526 (3) | 0.2019 (2) | 0.0272 (14) | |
C22 | 0.2258 (7) | 1.3693 (3) | 0.0783 (3) | 0.0350 (16) | |
H22A | 0.1847 | 1.4069 | 0.0629 | 0.053* | |
H22B | 0.2627 | 1.3407 | 0.0535 | 0.053* | |
H22C | 0.3000 | 1.3830 | 0.0998 | 0.053* | |
C23' | 0.2264 (9) | 0.9830 (4) | 0.1352 (3) | 0.053 (2) | |
H23'A | 0.1560 | 0.9766 | 0.1104 | 0.079* | |
H23'B | 0.2329 | 0.9446 | 0.1553 | 0.079* | |
H23'C | 0.3150 | 0.9910 | 0.1197 | 0.079* | |
C23 | −0.0803 (8) | 1.4065 (3) | 0.0517 (2) | 0.0349 (17) | |
C24' | 0.2395 (8) | 1.2532 (4) | 0.4085 (3) | 0.0452 (19) | |
H24'A | 0.2984 | 1.2898 | 0.4009 | 0.068* | |
H24'B | 0.2558 | 1.2397 | 0.4418 | 0.068* | |
H24'C | 0.1432 | 1.2656 | 0.4047 | 0.068* | |
C24 | −0.0153 (13) | 1.4978 (4) | 0.0050 (3) | 0.070 (3) | |
H24A | −0.0024 | 1.5441 | 0.0081 | 0.106* | |
H24B | −0.0863 | 1.4892 | −0.0191 | 0.106* | |
H24C | 0.0710 | 1.4779 | −0.0051 | 0.106* | |
C25 | 0.4345 (7) | 1.1280 (3) | 0.0949 (2) | 0.0321 (15) | |
H25A | 0.5079 | 1.0960 | 0.0950 | 0.048* | |
H25B | 0.4703 | 1.1687 | 0.0828 | 0.048* | |
H25C | 0.3596 | 1.1134 | 0.0741 | 0.048* | |
C26 | −0.3224 (8) | 1.2841 (4) | 0.0260 (3) | 0.0438 (19) | |
C27 | −0.4343 (8) | 1.3036 (5) | −0.0087 (3) | 0.061 (3) | |
H27A | −0.4785 | 1.3428 | 0.0030 | 0.092* | |
H27B | −0.5025 | 1.2693 | −0.0109 | 0.092* | |
H27C | −0.3945 | 1.3113 | −0.0406 | 0.092* | |
C28 | 0.3893 (17) | 1.4277 (6) | 0.3569 (7) | 0.131 (6) | |
C29 | 0.9269 (16) | 1.0763 (8) | 0.0885 (5) | 0.116 (5) | |
C30 | −0.4594 (16) | 1.4906 (6) | 0.0397 (4) | 0.101 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.210 (2) | 0.0504 (6) | 0.0410 (5) | −0.0262 (9) | 0.0166 (7) | −0.0050 (4) |
I2 | 0.172 (6) | 0.084 (3) | 0.062 (2) | −0.030 (3) | −0.025 (2) | −0.0045 (19) |
O3 | 0.039 (3) | 0.024 (2) | 0.036 (3) | 0.0077 (19) | −0.006 (2) | −0.003 (2) |
O4' | 0.043 (3) | 0.022 (2) | 0.047 (3) | 0.000 (2) | −0.014 (2) | −0.002 (2) |
O4 | 0.033 (3) | 0.037 (3) | 0.035 (3) | 0.007 (2) | −0.010 (2) | −0.015 (2) |
O16 | 0.028 (2) | 0.034 (2) | 0.022 (2) | 0.0095 (19) | 0.0041 (18) | 0.0049 (19) |
O22' | 0.050 (3) | 0.026 (2) | 0.033 (3) | 0.008 (2) | 0.007 (2) | 0.002 (2) |
O23' | 0.042 (3) | 0.029 (2) | 0.032 (3) | −0.002 (2) | 0.003 (2) | −0.010 (2) |
O23 | 0.090 (4) | 0.026 (3) | 0.032 (3) | −0.009 (3) | −0.010 (3) | 0.005 (2) |
O24 | 0.057 (3) | 0.031 (3) | 0.026 (3) | −0.003 (2) | −0.006 (2) | 0.002 (2) |
O26 | 0.046 (3) | 0.057 (4) | 0.065 (4) | −0.006 (3) | −0.003 (3) | −0.037 (3) |
O28 | 0.091 (11) | 0.057 (9) | 0.095 (12) | 0.030 (8) | −0.032 (9) | −0.004 (8) |
O29 | 0.072 (4) | 0.136 (6) | 0.032 (3) | 0.009 (4) | −0.005 (3) | −0.012 (4) |
O30 | 0.090 (5) | 0.069 (5) | 0.163 (9) | 0.032 (4) | −0.078 (5) | −0.043 (5) |
O31 | 0.291 (16) | 0.079 (7) | 0.286 (18) | 0.001 (8) | 0.215 (15) | 0.007 (9) |
O32 | 0.159 (8) | 0.122 (8) | 0.125 (9) | −0.026 (7) | −0.019 (7) | 0.036 (7) |
N1 | 0.031 (3) | 0.024 (3) | 0.025 (3) | −0.004 (2) | 0.000 (2) | 0.002 (2) |
N6' | 0.049 (4) | 0.032 (3) | 0.022 (3) | 0.004 (3) | −0.003 (3) | −0.004 (2) |
N9 | 0.030 (3) | 0.025 (3) | 0.031 (3) | 0.001 (2) | 0.001 (2) | −0.008 (2) |
N16' | 0.031 (3) | 0.025 (3) | 0.022 (3) | −0.002 (2) | −0.002 (2) | 0.006 (2) |
C1' | 0.034 (4) | 0.024 (3) | 0.018 (3) | −0.001 (3) | 0.002 (3) | 0.002 (2) |
C2' | 0.034 (4) | 0.025 (3) | 0.032 (4) | −0.004 (3) | −0.001 (3) | 0.003 (3) |
C2 | 0.028 (3) | 0.022 (3) | 0.025 (3) | 0.001 (3) | −0.005 (3) | 0.001 (3) |
C3' | 0.033 (4) | 0.028 (3) | 0.038 (4) | 0.002 (3) | 0.003 (3) | −0.008 (3) |
C3 | 0.035 (4) | 0.021 (3) | 0.027 (3) | 0.000 (3) | −0.011 (3) | −0.003 (3) |
C4' | 0.046 (4) | 0.026 (4) | 0.038 (4) | 0.004 (3) | −0.015 (3) | −0.005 (3) |
C4 | 0.021 (3) | 0.025 (3) | 0.034 (4) | 0.004 (2) | −0.007 (3) | −0.004 (3) |
C5' | 0.044 (4) | 0.037 (4) | 0.037 (4) | 0.007 (3) | −0.017 (3) | 0.000 (3) |
C5 | 0.027 (4) | 0.030 (4) | 0.030 (4) | −0.002 (3) | −0.009 (3) | −0.009 (3) |
C6 | 0.026 (4) | 0.038 (4) | 0.046 (4) | 0.005 (3) | −0.004 (3) | 0.000 (3) |
C7' | 0.043 (4) | 0.032 (4) | 0.023 (3) | −0.002 (3) | 0.002 (3) | −0.003 (3) |
C7 | 0.026 (4) | 0.041 (4) | 0.052 (5) | 0.009 (3) | 0.001 (3) | −0.001 (4) |
C8' | 0.037 (4) | 0.018 (3) | 0.027 (3) | −0.002 (3) | 0.003 (3) | 0.003 (3) |
C8 | 0.028 (4) | 0.032 (4) | 0.048 (4) | 0.008 (3) | 0.002 (3) | −0.009 (3) |
C9' | 0.032 (4) | 0.021 (3) | 0.024 (3) | 0.005 (3) | −0.005 (3) | 0.003 (3) |
C10' | 0.033 (4) | 0.019 (3) | 0.024 (3) | 0.000 (3) | 0.002 (3) | 0.002 (3) |
C10 | 0.042 (4) | 0.026 (3) | 0.037 (4) | −0.002 (3) | −0.003 (3) | −0.003 (3) |
C11' | 0.046 (5) | 0.028 (3) | 0.030 (4) | 0.009 (3) | 0.008 (3) | 0.008 (3) |
C11 | 0.031 (4) | 0.026 (3) | 0.034 (4) | 0.008 (3) | −0.003 (3) | −0.001 (3) |
C12' | 0.042 (5) | 0.030 (4) | 0.048 (5) | 0.009 (3) | 0.011 (3) | 0.020 (3) |
C12 | 0.029 (4) | 0.022 (3) | 0.024 (3) | −0.002 (3) | −0.003 (3) | −0.005 (3) |
C13' | 0.030 (4) | 0.030 (4) | 0.054 (5) | −0.001 (3) | 0.008 (3) | 0.012 (3) |
C13 | 0.019 (3) | 0.025 (3) | 0.021 (3) | −0.002 (2) | −0.001 (2) | −0.005 (3) |
C14' | 0.043 (4) | 0.030 (4) | 0.039 (4) | −0.002 (3) | −0.006 (3) | 0.007 (3) |
C14 | 0.016 (3) | 0.021 (3) | 0.019 (3) | −0.005 (2) | 0.004 (2) | −0.004 (2) |
C15' | 0.035 (4) | 0.018 (3) | 0.030 (3) | −0.002 (3) | 0.005 (3) | 0.002 (3) |
C15 | 0.028 (3) | 0.020 (3) | 0.020 (3) | −0.002 (2) | −0.001 (3) | 0.004 (3) |
C16 | 0.030 (4) | 0.026 (3) | 0.021 (3) | −0.002 (3) | −0.001 (3) | 0.002 (3) |
C17' | 0.025 (3) | 0.021 (3) | 0.025 (3) | 0.000 (2) | 0.005 (3) | −0.002 (3) |
C17 | 0.025 (3) | 0.030 (3) | 0.021 (3) | −0.002 (3) | 0.002 (3) | 0.007 (3) |
C18' | 0.032 (4) | 0.014 (3) | 0.022 (3) | 0.001 (2) | −0.004 (3) | 0.001 (2) |
C18 | 0.030 (3) | 0.014 (3) | 0.020 (3) | −0.003 (2) | −0.007 (3) | 0.004 (2) |
C19' | 0.037 (4) | 0.022 (3) | 0.031 (4) | 0.004 (3) | −0.006 (3) | −0.005 (3) |
C19 | 0.031 (4) | 0.022 (3) | 0.033 (4) | 0.000 (3) | 0.001 (3) | −0.006 (3) |
C20' | 0.051 (5) | 0.036 (4) | 0.061 (5) | 0.004 (3) | −0.025 (4) | −0.010 (4) |
C20 | 0.024 (4) | 0.026 (3) | 0.046 (4) | −0.005 (3) | −0.002 (3) | −0.008 (3) |
C21' | 0.038 (5) | 0.056 (5) | 0.071 (6) | 0.008 (4) | −0.007 (4) | −0.007 (5) |
C21 | 0.050 (5) | 0.034 (4) | 0.051 (5) | −0.014 (3) | −0.008 (4) | 0.003 (4) |
C22' | 0.037 (4) | 0.023 (3) | 0.022 (3) | 0.002 (3) | 0.008 (3) | 0.003 (3) |
C22 | 0.050 (4) | 0.028 (3) | 0.027 (4) | −0.013 (3) | 0.008 (3) | 0.002 (3) |
C23' | 0.083 (6) | 0.038 (4) | 0.037 (4) | −0.003 (4) | 0.006 (4) | −0.024 (4) |
C23 | 0.055 (5) | 0.023 (3) | 0.026 (4) | 0.003 (3) | −0.017 (3) | 0.000 (3) |
C24' | 0.060 (5) | 0.039 (4) | 0.036 (4) | 0.003 (4) | −0.001 (4) | −0.008 (3) |
C24 | 0.138 (9) | 0.045 (5) | 0.028 (4) | −0.021 (5) | −0.007 (5) | 0.004 (4) |
C25 | 0.040 (4) | 0.034 (4) | 0.023 (4) | 0.008 (3) | 0.005 (3) | −0.002 (3) |
C26 | 0.036 (4) | 0.049 (5) | 0.046 (5) | −0.009 (4) | −0.006 (3) | −0.019 (4) |
C27 | 0.042 (5) | 0.105 (8) | 0.037 (5) | 0.009 (5) | −0.007 (4) | −0.027 (5) |
C28 | 0.137 (11) | 0.045 (6) | 0.213 (18) | 0.005 (7) | 0.072 (12) | 0.014 (9) |
C29 | 0.137 (12) | 0.137 (13) | 0.073 (9) | 0.005 (9) | 0.004 (8) | −0.030 (9) |
C30 | 0.158 (12) | 0.093 (8) | 0.052 (6) | 0.020 (8) | −0.024 (7) | −0.011 (7) |
I1—O31i | 3.516 (12) | N16'—C17' | 1.367 (8) |
I1—O32ii | 3.759 (12) | N16'—C15' | 1.390 (8) |
I2—O31 | 2.99 (2) | N16'—C10' | 2.233 (8) |
O3—C3 | 1.401 (8) | N16'—C9' | 2.241 (8) |
O3—C23 | 2.370 (9) | N16'—C18' | 2.484 (8) |
O3—C4 | 2.454 (7) | N16'—C14' | 2.524 (9) |
O3—C2 | 2.460 (7) | N16'—O29iv | 2.959 (8) |
O3—O23 | 2.554 (7) | N16'—C15 | 2.983 (8) |
O3—N9 | 2.614 (7) | N16'—C22' | 3.000 (8) |
O3—O30 | 2.804 (8) | N16'—C14 | 3.128 (7) |
O3—O4 | 2.897 (6) | C1'—C2' | 1.554 (8) |
O3—C5 | 3.009 (8) | C1'—C18' | 1.564 (9) |
O3—C19 | 3.054 (8) | C2'—C3' | 1.469 (10) |
O3—C8'iii | 3.127 (7) | C2'—C19' | 1.542 (9) |
O3—C12 | 3.193 (7) | C2—C12 | 1.567 (9) |
O4'—C4' | 1.442 (8) | C2—C3 | 1.598 (8) |
O4'—C3' | 1.449 (8) | C3'—C4' | 1.443 (10) |
O4—C26 | 1.362 (8) | C3—C23 | 1.525 (9) |
O4—C4 | 1.440 (7) | C3—C4 | 1.530 (9) |
O16—C16 | 1.367 (7) | C4'—C5' | 1.514 (11) |
O16—C25 | 1.419 (7) | C4'—C20' | 1.528 (10) |
O22'—C22' | 1.201 (8) | C4—C5 | 1.529 (10) |
O23'—C22' | 1.341 (8) | C5—C20 | 1.539 (9) |
O23'—C23' | 1.442 (8) | C5—C6 | 1.554 (10) |
O23'—N16' | 2.842 (7) | C5—C19 | 1.559 (9) |
O23'—O29iv | 3.095 (8) | C6—C7 | 1.327 (10) |
O23—C23 | 1.343 (8) | C7'—C8' | 1.500 (9) |
O23—C24 | 1.438 (10) | C7—C8 | 1.464 (10) |
O24—C23 | 1.198 (8) | C8'—C9' | 1.535 (9) |
O26—C26 | 1.197 (9) | C8'—O3xii | 3.127 (7) |
O28—C28 | 1.49 (2) | C8'—O30xii | 3.162 (9) |
O28—O29v | 2.628 (15) | C9'—C17' | 1.381 (9) |
O28—O32v | 2.87 (2) | C9'—C10' | 1.438 (9) |
O29—C29 | 1.483 (16) | C10'—C15' | 1.394 (9) |
O29—O28vi | 2.628 (15) | C10'—C11' | 1.408 (9) |
O29—N16'vii | 2.959 (8) | C10—C11 | 1.540 (9) |
O29—O23'vii | 3.095 (8) | C11'—C12' | 1.373 (11) |
O29—O32 | 4.423 (14) | C11—C12 | 1.551 (9) |
O30—C30 | 1.297 (13) | C12'—C13' | 1.405 (11) |
O30—C8'iii | 3.162 (9) | C12—C13 | 1.520 (8) |
O31—O32viii | 2.792 (16) | C12—C19 | 1.522 (10) |
O31—I1ix | 3.516 (12) | C13'—C14' | 1.386 (10) |
O32—O31x | 2.792 (16) | C13—C14 | 1.382 (8) |
O32—O28vi | 2.87 (2) | C13—C18 | 1.415 (8) |
O32—I1xi | 3.759 (12) | C14'—C15' | 1.387 (10) |
N1—C18 | 1.364 (7) | C14—C15 | 1.402 (8) |
N1—C22 | 1.458 (8) | C15—C16 | 1.400 (8) |
N1—C2 | 1.476 (8) | C15—C18' | 1.540 (8) |
N6'—C7' | 1.503 (9) | C16—C17 | 1.399 (9) |
N6'—C24' | 1.520 (9) | C17'—C18' | 1.537 (9) |
N6'—C5' | 1.527 (9) | C17—C18 | 1.400 (9) |
N6'—C19' | 1.525 (9) | C18'—C22' | 1.549 (9) |
N9—C8 | 1.474 (9) | C20'—C21' | 1.517 (12) |
N9—C19 | 1.485 (8) | C20—C21 | 1.511 (10) |
N9—C10 | 1.474 (9) | C26—C27 | 1.481 (11) |
O31i—I1—O32ii | 90.9 (3) | C10'—N16'—C22' | 115.3 (3) |
C3—O3—C23 | 37.7 (3) | C9'—N16'—C22' | 82.7 (2) |
C3—O3—C4 | 34.8 (3) | C18'—N16'—C22' | 31.03 (19) |
C23—O3—C4 | 62.2 (2) | C14'—N16'—C22' | 149.5 (3) |
C3—O3—C2 | 37.6 (3) | O23'—N16'—C22' | 26.37 (16) |
C23—O3—C2 | 63.3 (2) | O29iv—N16'—C22' | 90.7 (2) |
C4—O3—C2 | 61.6 (2) | C15—N16'—C22' | 50.56 (18) |
C3—O3—O23 | 65.9 (3) | C17'—N16'—C14 | 69.1 (3) |
C23—O3—O23 | 31.4 (2) | C15'—N16'—C14 | 132.9 (4) |
C4—O3—O23 | 93.6 (2) | C10'—N16'—C14 | 117.5 (3) |
C2—O3—O23 | 77.0 (2) | C9'—N16'—C14 | 93.6 (2) |
C3—O3—N9 | 95.9 (3) | C18'—N16'—C14 | 52.67 (18) |
C23—O3—N9 | 133.2 (3) | C14'—N16'—C14 | 133.1 (3) |
C4—O3—N9 | 81.6 (2) | O23'—N16'—C14 | 82.36 (19) |
C2—O3—N9 | 74.0 (2) | O29iv—N16'—C14 | 95.0 (2) |
O23—O3—N9 | 149.2 (2) | C15—N16'—C14 | 26.40 (16) |
C3—O3—O30 | 129.5 (4) | C22'—N16'—C14 | 76.80 (19) |
C23—O3—O30 | 98.3 (3) | C2'—C1'—C18' | 116.4 (5) |
C4—O3—O30 | 117.2 (3) | C3'—C2'—C19' | 109.5 (6) |
C2—O3—O30 | 160.5 (3) | C3'—C2'—C1' | 110.0 (5) |
O23—O3—O30 | 83.8 (3) | C19'—C2'—C1' | 117.2 (5) |
N9—O3—O30 | 125.5 (3) | N1—C2—C12 | 106.4 (5) |
C3—O3—O4 | 55.0 (3) | N1—C2—C3 | 111.1 (5) |
C23—O3—O4 | 62.8 (2) | C12—C2—C3 | 113.3 (5) |
C4—O3—O4 | 29.77 (17) | N1—C2—O3 | 141.6 (4) |
C2—O3—O4 | 89.2 (2) | C12—C2—O3 | 102.6 (4) |
O23—O3—O4 | 89.7 (2) | C3—C2—O3 | 32.3 (3) |
N9—O3—O4 | 99.9 (2) | C4'—C3'—O4' | 59.8 (4) |
O30—O3—O4 | 87.4 (2) | C4'—C3'—C2' | 121.2 (6) |
C3—O3—C5 | 58.5 (3) | O4'—C3'—C2' | 116.4 (5) |
C23—O3—C5 | 91.9 (2) | O3—C3—C23 | 108.1 (5) |
C4—O3—C5 | 30.4 (2) | O3—C3—C4 | 113.7 (5) |
C2—O3—C5 | 67.3 (2) | C23—C3—C4 | 109.4 (5) |
O23—O3—C5 | 123.0 (2) | O3—C3—C2 | 110.0 (5) |
N9—O3—C5 | 52.73 (18) | C23—C3—C2 | 108.5 (5) |
O30—O3—C5 | 122.6 (3) | C4—C3—C2 | 107.0 (5) |
O4—O3—C5 | 48.71 (17) | O4'—C4'—C3' | 60.3 (4) |
C3—O3—C19 | 67.7 (3) | O4'—C4'—C5' | 117.1 (6) |
C23—O3—C19 | 105.4 (2) | C3'—C4'—C5' | 117.0 (6) |
C4—O3—C19 | 54.2 (2) | O4'—C4'—C20' | 115.3 (6) |
C2—O3—C19 | 55.0 (2) | C3'—C4'—C20' | 125.1 (7) |
O23—O3—C19 | 130.1 (2) | C5'—C4'—C20' | 112.2 (6) |
N9—O3—C19 | 29.06 (17) | O4—C4—C5 | 110.3 (5) |
O30—O3—C19 | 142.2 (3) | O4—C4—C3 | 106.9 (5) |
O4—O3—C19 | 78.09 (18) | C5—C4—C3 | 114.4 (5) |
C5—O3—C19 | 29.78 (17) | O4—C4—O3 | 92.4 (4) |
C3—O3—C8'iii | 137.5 (4) | C5—C4—O3 | 95.3 (4) |
C23—O3—C8'iii | 109.7 (3) | C3—C4—O3 | 31.5 (3) |
C4—O3—C8'iii | 171.7 (3) | C4'—C5'—N6' | 114.2 (6) |
C2—O3—C8'iii | 114.2 (2) | C20—C5—C4 | 107.2 (5) |
O23—O3—C8'iii | 78.3 (2) | C20—C5—C6 | 107.3 (5) |
N9—O3—C8'iii | 104.5 (2) | C4—C5—C6 | 112.6 (5) |
O30—O3—C8'iii | 64.2 (2) | C20—C5—C19 | 109.5 (5) |
O4—O3—C8'iii | 149.9 (2) | C4—C5—C19 | 112.5 (5) |
C5—O3—C8'iii | 156.8 (2) | C6—C5—C19 | 107.7 (5) |
C19—O3—C8'iii | 130.4 (2) | C20—C5—O3 | 160.5 (5) |
C3—O3—C12 | 54.7 (3) | C4—C5—O3 | 54.3 (3) |
C23—O3—C12 | 88.8 (2) | C6—C5—O3 | 87.5 (4) |
C4—O3—C12 | 60.4 (2) | C19—C5—O3 | 76.7 (3) |
C2—O3—C12 | 28.62 (19) | C7—C6—C5 | 124.3 (6) |
O23—O3—C12 | 105.6 (2) | N6'—C7'—C8' | 117.7 (5) |
N9—O3—C12 | 45.91 (17) | C6—C7—C8 | 124.3 (6) |
O30—O3—C12 | 170.2 (3) | C7'—C8'—C9' | 117.4 (5) |
O4—O3—C12 | 89.88 (17) | C7'—C8'—O3xii | 133.0 (4) |
C5—O3—C12 | 49.93 (17) | C9'—C8'—O3xii | 101.3 (4) |
C19—O3—C12 | 28.09 (18) | C7'—C8'—O30xii | 93.1 (4) |
C8'iii—O3—C12 | 119.8 (2) | C9'—C8'—O30xii | 149.4 (4) |
C4'—O4'—C3' | 59.9 (4) | O3xii—C8'—O30xii | 52.95 (18) |
C26—O4—C4 | 117.5 (5) | C7—C8—N9 | 109.7 (6) |
C26—O4—O3 | 158.9 (4) | C17'—C9'—C10' | 106.0 (5) |
C4—O4—O3 | 57.8 (3) | C17'—C9'—C8' | 134.1 (6) |
C16—O16—C25 | 118.2 (5) | C10'—C9'—C8' | 119.7 (6) |
C22'—O23'—C23' | 115.9 (6) | C17'—C9'—N16' | 35.1 (3) |
C22'—O23'—N16' | 83.4 (3) | C10'—C9'—N16' | 70.9 (4) |
C23'—O23'—N16' | 141.3 (4) | C8'—C9'—N16' | 168.2 (5) |
C22'—O23'—O29iv | 142.7 (4) | C15'—C10'—C11' | 118.6 (6) |
C23'—O23'—O29iv | 97.7 (4) | C15'—C10'—C9' | 108.2 (5) |
N16'—O23'—O29iv | 59.61 (17) | C11'—C10'—C9' | 133.2 (6) |
C23—O23—C24 | 114.8 (6) | C15'—C10'—N16' | 36.6 (3) |
C23—O23—O3 | 66.7 (4) | C11'—C10'—N16' | 155.2 (5) |
C24—O23—O3 | 162.6 (6) | C9'—C10'—N16' | 71.6 (4) |
C28—O28—O29v | 115.9 (11) | N9—C10—C11 | 105.2 (5) |
C28—O28—O32v | 105.8 (9) | C12'—C11'—C10' | 119.5 (7) |
O29v—O28—O32v | 106.9 (6) | C10—C11—C12 | 104.8 (5) |
C29—O29—O28vi | 102.2 (7) | C11'—C12'—C13' | 120.9 (7) |
C29—O29—N16'vii | 125.7 (7) | C13—C12—C19 | 113.7 (5) |
O28vi—O29—N16'vii | 131.9 (5) | C13—C12—C11 | 112.9 (5) |
C29—O29—O23'vii | 86.8 (7) | C19—C12—C11 | 101.5 (5) |
O28vi—O29—O23'vii | 141.4 (5) | C13—C12—C2 | 102.4 (5) |
N16'vii—O29—O23'vii | 55.95 (17) | C19—C12—C2 | 114.6 (5) |
C29—O29—O32 | 77.3 (6) | C11—C12—C2 | 112.1 (5) |
O28vi—O29—O32 | 38.4 (4) | C13—C12—O3 | 142.1 (4) |
N16'vii—O29—O32 | 148.2 (3) | C19—C12—O3 | 70.9 (3) |
O23'vii—O29—O32 | 111.2 (3) | C11—C12—O3 | 102.0 (4) |
C30—O30—O3 | 114.3 (7) | C2—C12—O3 | 48.7 (3) |
C30—O30—C8'iii | 151.2 (10) | C14'—C13'—C12' | 120.6 (7) |
O3—O30—C8'iii | 62.88 (19) | C14—C13—C18 | 120.8 (5) |
O32viii—O31—I2 | 111.6 (6) | C14—C13—C12 | 130.3 (5) |
O32viii—O31—I1ix | 112.3 (5) | C18—C13—C12 | 108.8 (5) |
I2—O31—I1ix | 126.3 (5) | C15'—C14'—C13' | 117.9 (7) |
O31x—O32—O28vi | 107.7 (6) | C15'—C14'—N16' | 24.7 (3) |
O31x—O32—I1xi | 126.0 (5) | C13'—C14'—N16' | 142.5 (6) |
O28vi—O32—I1xi | 115.9 (4) | C13—C14—C15 | 120.3 (5) |
O31x—O32—O29 | 142.3 (6) | C13—C14—N16' | 146.4 (4) |
O28vi—O32—O29 | 34.6 (3) | C15—C14—N16' | 71.0 (3) |
I1xi—O32—O29 | 86.6 (2) | C14'—C15'—N16' | 130.7 (6) |
C18—N1—C22 | 119.2 (5) | C14'—C15'—C10' | 122.6 (6) |
C18—N1—C2 | 109.6 (5) | N16'—C15'—C10' | 106.7 (5) |
C22—N1—C2 | 120.4 (5) | C14—C15—C16 | 118.4 (5) |
C7'—N6'—C24' | 107.6 (5) | C14—C15—C18' | 120.5 (5) |
C7'—N6'—C5' | 108.3 (5) | C16—C15—C18' | 120.5 (5) |
C24'—N6'—C5' | 106.7 (5) | C14—C15—N16' | 82.6 (3) |
C7'—N6'—C19' | 111.2 (5) | C16—C15—N16' | 141.3 (4) |
C24'—N6'—C19' | 107.0 (5) | C18'—C15—N16' | 56.3 (3) |
C5'—N6'—C19' | 115.6 (5) | O16—C16—C17 | 121.9 (5) |
C8—N9—C19 | 112.7 (5) | O16—C16—C15 | 115.8 (5) |
C8—N9—C10 | 115.2 (5) | C17—C16—C15 | 122.3 (6) |
C19—N9—C10 | 106.5 (5) | N16'—C17'—C9' | 109.3 (5) |
C8—N9—O3 | 114.3 (4) | N16'—C17'—C18' | 117.5 (5) |
C19—N9—O3 | 92.1 (4) | C9'—C17'—C18' | 133.1 (6) |
C10—N9—O3 | 113.4 (4) | C16—C17—C18 | 118.4 (5) |
C17'—N16'—C15' | 109.8 (5) | C17'—C18'—C15 | 112.1 (5) |
C17'—N16'—C10' | 73.0 (4) | C17'—C18'—C22' | 104.6 (5) |
C15'—N16'—C10' | 36.7 (3) | C15—C18'—C22' | 111.6 (5) |
C17'—N16'—C9' | 35.6 (3) | C17'—C18'—C1' | 113.9 (5) |
C15'—N16'—C9' | 74.2 (4) | C15—C18'—C1' | 108.7 (5) |
C10'—N16'—C9' | 37.5 (3) | C22'—C18'—C1' | 105.7 (5) |
C17'—N16'—C18' | 33.3 (3) | C17'—C18'—N16' | 29.2 (3) |
C15'—N16'—C18' | 143.0 (4) | C15—C18'—N16' | 92.7 (4) |
C10'—N16'—C18' | 106.3 (3) | C22'—C18'—N16' | 93.2 (4) |
C9'—N16'—C18' | 68.8 (2) | C1'—C18'—N16' | 143.0 (4) |
C17'—N16'—C14' | 134.4 (4) | N1—C18—C17 | 127.8 (5) |
C15'—N16'—C14' | 24.6 (3) | N1—C18—C13 | 112.6 (5) |
C10'—N16'—C14' | 61.3 (3) | C17—C18—C13 | 119.6 (5) |
C9'—N16'—C14' | 98.8 (3) | N6'—C19'—C2' | 116.5 (5) |
C18'—N16'—C14' | 167.5 (3) | N9—C19—C12 | 101.4 (5) |
C17'—N16'—O23' | 79.5 (3) | N9—C19—C5 | 111.9 (5) |
C15'—N16'—O23' | 144.8 (4) | C12—C19—C5 | 116.7 (5) |
C10'—N16'—O23' | 135.8 (3) | N9—C19—O3 | 58.8 (3) |
C9'—N16'—O23' | 108.1 (3) | C12—C19—O3 | 81.0 (4) |
C18'—N16'—O23' | 52.63 (19) | C5—C19—O3 | 73.5 (4) |
C14'—N16'—O23' | 134.0 (3) | C21'—C20'—C4' | 114.2 (7) |
C17'—N16'—O29iv | 142.5 (4) | C21—C20—C5 | 118.4 (6) |
C15'—N16'—O29iv | 105.8 (4) | O22'—C22'—O23' | 124.3 (6) |
C10'—N16'—O29iv | 141.4 (3) | O22'—C22'—C18' | 124.8 (6) |
C9'—N16'—O29iv | 167.6 (3) | O23'—C22'—C18' | 110.9 (5) |
C18'—N16'—O29iv | 110.0 (3) | O22'—C22'—N16' | 140.3 (4) |
C14'—N16'—O29iv | 81.6 (3) | O23'—C22'—N16' | 70.2 (3) |
O23'—N16'—O29iv | 64.44 (19) | C18'—C22'—N16' | 55.8 (3) |
C17'—N16'—C15 | 58.6 (3) | O24—C23—O23 | 124.3 (7) |
C15'—N16'—C15 | 156.0 (4) | O24—C23—C3 | 125.2 (6) |
C10'—N16'—C15 | 126.6 (3) | O23—C23—C3 | 110.4 (6) |
C9'—N16'—C15 | 92.0 (3) | O24—C23—O3 | 149.1 (6) |
C18'—N16'—C15 | 31.05 (18) | O23—C23—O3 | 81.9 (4) |
C14'—N16'—C15 | 158.2 (3) | C3—C23—O3 | 34.2 (3) |
O23'—N16'—C15 | 57.89 (17) | O26—C26—O4 | 123.6 (7) |
O29iv—N16'—C15 | 91.8 (2) | O26—C26—C27 | 125.1 (7) |
C17'—N16'—C22' | 53.3 (3) | O4—C26—C27 | 111.2 (7) |
C15'—N16'—C22' | 142.5 (4) |
Symmetry codes: (i) x−1/2, −y+7/2, −z; (ii) x−3/2, −y+5/2, −z; (iii) −x, y+1/2, −z+1/2; (iv) x−1, y, z; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x+1, y, z; (viii) x−1/2, −y+5/2, −z; (ix) x+1/2, −y+7/2, −z; (x) x+1/2, −y+5/2, −z; (xi) x+3/2, −y+5/2, −z; (xii) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C47H59IN4O9·3CH3OH·2H2O |
Mr | 1083.04 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 123 |
a, b, c (Å) | 9.5567 (19), 20.491 (4), 27.169 (5) |
V (Å3) | 5320.5 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (MULABS in PLATON; Spek, 1998) |
Tmin, Tmax | 0.867, 0.905 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17090, 8109, 5893 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.211, 0.97 |
No. of reflections | 8109 |
No. of parameters | 633 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.11, −0.78 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.06 (3) |
Computer programs: DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), SHELXTL (Sheldrick, 1997), SHELXTL.
Leurosine is the most abundant dimeric antitumour alkaloid isolated from the Madagascar periwinkle (Catharanthus Roseus). It belongs to the family of Vinca alkaloids which includes, amongst others, vinblastine (Magnus et al., 1990), vincristine (Mangeney et al., 1979) and anhydrovinblastine (Scott et al., 1978). These compounds and vinorelbine (Brossi et al., 1990), a semisynthetic derivative, inhibit mitosis by binding to tubuline, thus allowing a broad spectrum of activity in the treatment of various carcinomas. The identification of leurosine was achieved by spectroscopic comparison with related alkaloids and by chemical synthesis. Indeed, the mild oxidation of anhydrovinblastine furnished, as the major product, the corresponding epoxidized leurosine (Langlois & Potier, 1979). However, no X-ray data have yet been reported for leurosine and the present study was initiated to resolve the solid state conformation of leurosine methiodide as the methanol-water solvate, (I).
The structure of (I) is ionic, (leurosine-CH3)+ I−·3CH3OH·2H2O, and the cation structure is shown in Fig. 1. The central six-membered ring of the vindoline moiety, C2/C12/C19/C5/C4/C3, is in a boat conformation, the C3 and C19 atoms being 0.694 (9) and 0.439 (9) Å from the plane defined within ±0.087 Å by the four remaining atoms. The other six-membered ring of the vindoline moiety, N9/C8/C7/C6/C5/C19, is in a sofa conformation: atoms C19, C5, C6 and C7 are coplanar within ±0.016 Å and the N9 and C8 atoms are on the same side at 0.78 (1) and 0.23 (1) Å from this plane. The O3—N9 bond length of 2.614 (7) Å is indicative of a short intramolecular hydrogen bond between the tertiary N and the hydroxyl group: H3A···N9 1.84 Å and O3—H3A···N9 157.8°. The five-membered ring N9/C10/C11/C12/C19 adopts an envelope conformation, with atom C19 deviating by 0.657 (9) Å from the plane formed by the remaining four atoms at ± 0.018 Å. Comparison of the vindoline moiety of leurosine and of 18'-epivinblastine (Lynch et al., 1991) shows that the conformation of these three rings is similar in both compounds.
The piperidine ring of the upper part of the molecule adopts a sofa conformation. Atoms C2', C3', C4' and C5' are coplanar to within 0.010 Å, with atoms C19' and N6' being 0.97 (1) and 0.81 (1) Å out of this plane; the oxiran atom O4' is on the same side at 1.206 (8) Å, leading to a boat conformation for the seven-membered ring. In 18'-epivinblastine the corresponding piperidine ring has a chair conformation. On the other hand, a similar boat-chair conformation is observed in both compounds for the azacyclononene ring.
The structure of (I) is stabilized by hydrogen bonds between methanol and water molecules [O···O 2.63 (1)–2.87 (2) Å], between a water molecule and the I atom [I1···O31(x − 1/2, 7/2 − y, −z) 3.52 (1) and I2···O31 2.99 (2) Å] and between the indolino N16'H and a methanol molecule [N16'···O29(x − 1, y, z) 2.959 (8) Å and N16'-H16A···O29(x − 1, y, z) 149.3°].