Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703560X/ci2413sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703560X/ci2413Isup2.hkl |
CCDC reference: 659100
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.049
- wR factor = 0.169
- Data-to-parameter ratio = 12.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of C2 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C4 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C5 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C19 = ... S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was synthesized according to the method reported in the literature (Ramesh et al., 2007). A solution of the Baylis–Hilman adduct of ninhydrin (1 mmol), proline (1 mmol) and ninhydrin (1 mmol) in methonol was refluxed. After completion of the reaction, as monitored by thin-layer chromatographic analysis, the solvent was removed under vacuum, and the crude product was subjected to column chromatography on silica gel (100–200 mesh) using petroleum ether/ethyl acetate (7:3) as eluent. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a ethanol solution.
H atoms were positioned geometrically (O—H = 0.82 Å and C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C,O) for the methyl and OH groups.
Pyrrolizidine alkaloids represent a group of compounds present in a variety of plants throughout the world. The pyrrolizidine alkaloids are well documented for their mutagenic, antineoplastic, carcinogenic, hepatoxic and many pharmacological activities. Substituted pyrrolidine compounds have been found to have antimicrobial and antifungal activity against various pathogens (Amalraj et al., 2003). Several optically active pyrrolidine compounds have been used as intermediates in controlled asymmetric synthesis (Suzuki et al., 1994). The spiro-indole-pyrrolidine ring system is a frequently encountered structural motif in many biologically important and pharmacologically relevant alkaloids, e.g. vincrinstine, vinblastine and Spirotypostatins (Cordell, 1981). Against this background and in order to obtain detailed information on its molecular conformation, the structure determination of the title compound has been carried out and the results are presented here.
The title compound (Fig.1) consists of a pyrrolizine ring system (rings A and B) connected to a indane dione group (rings C and D) at C2, hydroxyl indane dione group (rings E and F) and methoxy carbonyl group at C4. All the five-membered rings A, B, C and E adopt envelope conformations. The puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) for the pyrrolidine ring A are q2 = 0.245 (2) Å, φ = 187.8 (5)° and Δs(N1) = 4.7 (2)°, for the pyrrolidine ring B are q2 = 0.399 (2) Å, φ = 318.6 (4)° and Δs(C8) = 3.2 (2)°, for the ring C are q2 = 0.141 (2) Å, φ = 5.0 (10)° and Δs(C2) = 1.7 (3)°, and for the ring E are q2 = 0.090 (3) Å, φ = 356.8 (17)° and Δs(C19) = 0.7 (3)°.
The molecule is stabilized by the intramolecular O5—H5···O4 hydrogen bond which generates an S(8) motif (Bernstein et al., 1995). The crystal packing is stabilized by intermolecular C—H···O hydrogen bonds. Atom C22 in the molecule at (x, y, z) donates one proton to atom O7 in the molecule at (x, 1 + y, z), forming a C(6) chain along the b axis. Also, atoms C8 and C16 in the molecule at (x, y, z) donate one proton each to atom O4 and O3 in the molecule at (x, 1 - y, 1/2 + z) and (x, 1 - y, -1/2 + z), respectively, forming a chain along the c axis. These hydrogen bonds generate an R22(11) ring motif. The molecules at (x, y, z) and (-x, 2 - y, -z) are linked by C23—H23···O1 hydrogen bonds into cyclic centrosymmetric R22(18) dimers. Thus, the symmetry-related molecules are cross-linked by these hydrogen bonds to generate a three-dimensional network.
For general background, see: Amalraj et al. (2003); Cordell (1981); Suzuki et al. (1994). For synthesis, see: Ramesh et al. (2007). For ring conformations, see: Cremer & Pople (1975); Nardelli (1983). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Data collection: CAD-4 Software (Enraf–Nonius, 1988); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
C26H21NO7 | F(000) = 1920 |
Mr = 459.44 | Dx = 1.390 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 39.580 (5) Å | θ = 2.3–68.0° |
b = 7.6690 (15) Å | µ = 0.85 mm−1 |
c = 14.868 (3) Å | T = 293 K |
β = 103.291 (16)° | Block, colourless |
V = 4392.0 (14) Å3 | 0.37 × 0.24 × 0.15 mm |
Z = 8 |
Enraf–Nonius CAD-4 diffractometer | 3118 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
Graphite monochromator | θmax = 68.0°, θmin = 2.3° |
ω/2θ scans | h = 0→47 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→9 |
Tmin = 0.784, Tmax = 0.881 | l = −17→17 |
4055 measured reflections | 2 standard reflections every 60 min |
3994 independent reflections | intensity decay: 4% |
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)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.169 | w = 1/[σ2(Fo2) + (0.1055P)2 + 3.9632P] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
3994 reflections | Δρmax = 0.26 e Å−3 |
309 parameters | Δρmin = −0.22 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: 0.00074 (11) |
C26H21NO7 | V = 4392.0 (14) Å3 |
Mr = 459.44 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 39.580 (5) Å | µ = 0.85 mm−1 |
b = 7.6690 (15) Å | T = 293 K |
c = 14.868 (3) Å | 0.37 × 0.24 × 0.15 mm |
β = 103.291 (16)° |
Enraf–Nonius CAD-4 diffractometer | 3118 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.052 |
Tmin = 0.784, Tmax = 0.881 | 2 standard reflections every 60 min |
4055 measured reflections | intensity decay: 4% |
3994 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.26 e Å−3 |
3994 reflections | Δρmin = −0.22 e Å−3 |
309 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 | ||
O1 | 0.07308 (5) | 0.7325 (3) | 0.11713 (13) | 0.0797 (7) | |
O2 | 0.12466 (4) | 0.7130 (2) | 0.21385 (11) | 0.0554 (4) | |
O3 | 0.22421 (4) | 0.6868 (3) | 0.21202 (11) | 0.0619 (5) | |
O4 | 0.17375 (4) | 0.5356 (3) | −0.09529 (11) | 0.0693 (6) | |
O5 | 0.10878 (5) | 0.6593 (3) | −0.11651 (11) | 0.0674 (6) | |
H5 | 0.1292 | 0.6292 | −0.1003 | 0.101* | |
O6 | 0.10669 (5) | 1.0111 (2) | −0.03087 (14) | 0.0685 (5) | |
O7 | 0.05550 (6) | 0.4526 (3) | −0.0507 (2) | 0.1019 (9) | |
N1 | 0.16725 (4) | 0.4251 (2) | 0.09413 (11) | 0.0388 (4) | |
C2 | 0.18367 (5) | 0.5860 (3) | 0.07124 (13) | 0.0387 (5) | |
C3 | 0.15739 (5) | 0.7337 (3) | 0.06648 (15) | 0.0404 (5) | |
H3A | 0.1577 | 0.8093 | 0.0144 | 0.048* | |
H3B | 0.1629 | 0.8027 | 0.1226 | 0.048* | |
C4 | 0.12111 (5) | 0.6473 (3) | 0.05505 (13) | 0.0379 (5) | |
C5 | 0.12937 (5) | 0.4442 (3) | 0.06061 (15) | 0.0401 (5) | |
H5A | 0.1227 | 0.3958 | −0.0020 | 0.048* | |
C6 | 0.11382 (6) | 0.3280 (3) | 0.12542 (18) | 0.0537 (6) | |
H6A | 0.1010 | 0.3976 | 0.1608 | 0.064* | |
H6B | 0.0983 | 0.2414 | 0.0904 | 0.064* | |
C7 | 0.14515 (7) | 0.2410 (3) | 0.18904 (18) | 0.0582 (6) | |
H7A | 0.1412 | 0.2232 | 0.2504 | 0.070* | |
H7B | 0.1502 | 0.1295 | 0.1642 | 0.070* | |
C8 | 0.17429 (6) | 0.3687 (3) | 0.19145 (15) | 0.0506 (6) | |
H8A | 0.1731 | 0.4658 | 0.2325 | 0.061* | |
H8B | 0.1968 | 0.3129 | 0.2103 | 0.061* | |
C9 | 0.10343 (5) | 0.7037 (3) | 0.13072 (15) | 0.0438 (5) | |
C10 | 0.10900 (8) | 0.7620 (4) | 0.28863 (19) | 0.0719 (8) | |
H10A | 0.0999 | 0.8781 | 0.2785 | 0.108* | |
H10B | 0.1262 | 0.7580 | 0.3459 | 0.108* | |
H10C | 0.0905 | 0.6824 | 0.2913 | 0.108* | |
C11 | 0.21928 (6) | 0.6158 (3) | 0.13721 (15) | 0.0444 (5) | |
C12 | 0.24625 (5) | 0.5492 (3) | 0.09159 (15) | 0.0433 (5) | |
C13 | 0.28137 (6) | 0.5255 (3) | 0.1270 (2) | 0.0581 (6) | |
H13 | 0.2915 | 0.5499 | 0.1885 | 0.070* | |
C14 | 0.30097 (6) | 0.4644 (4) | 0.0679 (2) | 0.0663 (7) | |
H14 | 0.3247 | 0.4472 | 0.0903 | 0.080* | |
C15 | 0.28613 (7) | 0.4280 (3) | −0.0240 (2) | 0.0603 (7) | |
H15 | 0.3000 | 0.3872 | −0.0621 | 0.072* | |
C16 | 0.25130 (6) | 0.4510 (3) | −0.05965 (18) | 0.0519 (6) | |
H16 | 0.2414 | 0.4279 | −0.1215 | 0.062* | |
C17 | 0.23135 (5) | 0.5101 (3) | −0.00032 (15) | 0.0417 (5) | |
C18 | 0.19387 (5) | 0.5440 (3) | −0.01998 (14) | 0.0429 (5) | |
C19 | 0.09585 (5) | 0.6972 (3) | −0.03765 (15) | 0.0432 (5) | |
C20 | 0.08603 (6) | 0.8913 (3) | −0.04602 (15) | 0.0461 (5) | |
C21 | 0.04821 (6) | 0.9050 (3) | −0.08045 (16) | 0.0509 (6) | |
C22 | 0.02816 (8) | 1.0539 (4) | −0.1044 (2) | 0.0666 (7) | |
H22 | 0.0382 | 1.1641 | −0.0999 | 0.080* | |
C23 | −0.00700 (8) | 1.0321 (5) | −0.1347 (2) | 0.0837 (10) | |
H23 | −0.0210 | 1.1295 | −0.1517 | 0.100* | |
C24 | −0.02206 (8) | 0.8695 (6) | −0.1408 (3) | 0.0916 (11) | |
H24 | −0.0460 | 0.8592 | −0.1618 | 0.110* | |
C25 | −0.00228 (7) | 0.7217 (5) | −0.1162 (2) | 0.0813 (9) | |
H25 | −0.0125 | 0.6120 | −0.1196 | 0.098* | |
C26 | 0.03318 (6) | 0.7415 (4) | −0.08649 (18) | 0.0572 (6) | |
C27 | 0.06007 (6) | 0.6068 (3) | −0.05542 (19) | 0.0596 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0564 (11) | 0.1316 (19) | 0.0562 (11) | 0.0390 (11) | 0.0233 (8) | 0.0113 (11) |
O2 | 0.0560 (9) | 0.0683 (11) | 0.0452 (9) | 0.0027 (8) | 0.0184 (7) | −0.0102 (8) |
O3 | 0.0600 (10) | 0.0793 (12) | 0.0442 (9) | −0.0009 (9) | 0.0073 (7) | −0.0162 (8) |
O4 | 0.0507 (9) | 0.1217 (17) | 0.0359 (9) | 0.0137 (10) | 0.0108 (7) | −0.0045 (9) |
O5 | 0.0641 (11) | 0.0972 (15) | 0.0397 (9) | 0.0275 (10) | 0.0093 (7) | −0.0066 (9) |
O6 | 0.0660 (11) | 0.0474 (10) | 0.0853 (14) | −0.0032 (8) | 0.0033 (10) | 0.0134 (9) |
O7 | 0.0690 (13) | 0.0490 (12) | 0.166 (3) | −0.0109 (10) | −0.0172 (14) | 0.0075 (13) |
N1 | 0.0420 (9) | 0.0408 (9) | 0.0358 (9) | 0.0042 (7) | 0.0136 (7) | 0.0006 (7) |
C2 | 0.0387 (10) | 0.0439 (11) | 0.0362 (10) | 0.0013 (8) | 0.0139 (8) | 0.0003 (8) |
C3 | 0.0422 (11) | 0.0379 (11) | 0.0436 (11) | 0.0000 (8) | 0.0151 (8) | −0.0009 (9) |
C4 | 0.0384 (10) | 0.0381 (11) | 0.0390 (11) | 0.0030 (8) | 0.0128 (8) | 0.0003 (8) |
C5 | 0.0421 (11) | 0.0353 (10) | 0.0451 (11) | 0.0015 (8) | 0.0146 (8) | −0.0030 (8) |
C6 | 0.0578 (14) | 0.0404 (12) | 0.0708 (16) | −0.0016 (10) | 0.0307 (12) | 0.0032 (11) |
C7 | 0.0731 (16) | 0.0492 (13) | 0.0587 (14) | 0.0032 (12) | 0.0281 (12) | 0.0118 (11) |
C8 | 0.0598 (13) | 0.0521 (13) | 0.0414 (11) | 0.0080 (11) | 0.0151 (10) | 0.0081 (10) |
C9 | 0.0462 (12) | 0.0416 (12) | 0.0472 (12) | 0.0082 (9) | 0.0179 (9) | 0.0033 (9) |
C10 | 0.090 (2) | 0.0815 (19) | 0.0528 (15) | 0.0068 (16) | 0.0352 (14) | −0.0064 (14) |
C11 | 0.0455 (11) | 0.0468 (12) | 0.0411 (11) | 0.0001 (9) | 0.0106 (9) | −0.0008 (9) |
C12 | 0.0415 (11) | 0.0397 (11) | 0.0497 (12) | −0.0023 (9) | 0.0128 (9) | 0.0004 (9) |
C13 | 0.0409 (12) | 0.0566 (15) | 0.0734 (17) | −0.0021 (10) | 0.0061 (11) | −0.0038 (12) |
C14 | 0.0386 (12) | 0.0605 (16) | 0.102 (2) | 0.0028 (11) | 0.0202 (13) | 0.0014 (15) |
C15 | 0.0531 (14) | 0.0488 (13) | 0.090 (2) | 0.0010 (11) | 0.0390 (13) | −0.0045 (13) |
C16 | 0.0556 (13) | 0.0488 (13) | 0.0601 (14) | −0.0022 (10) | 0.0317 (11) | −0.0023 (10) |
C17 | 0.0437 (11) | 0.0392 (11) | 0.0462 (11) | −0.0008 (8) | 0.0184 (9) | 0.0019 (9) |
C18 | 0.0427 (11) | 0.0526 (12) | 0.0358 (11) | 0.0009 (9) | 0.0139 (9) | 0.0011 (9) |
C19 | 0.0431 (11) | 0.0439 (12) | 0.0431 (11) | 0.0060 (9) | 0.0113 (9) | −0.0026 (9) |
C20 | 0.0502 (12) | 0.0463 (12) | 0.0418 (11) | 0.0024 (10) | 0.0103 (9) | 0.0040 (9) |
C21 | 0.0505 (13) | 0.0565 (14) | 0.0469 (12) | 0.0122 (10) | 0.0136 (10) | 0.0036 (10) |
C22 | 0.0699 (17) | 0.0660 (17) | 0.0646 (16) | 0.0251 (14) | 0.0170 (13) | 0.0096 (13) |
C23 | 0.0645 (18) | 0.104 (3) | 0.088 (2) | 0.0416 (18) | 0.0273 (16) | 0.0277 (19) |
C24 | 0.0455 (15) | 0.129 (3) | 0.101 (2) | 0.0209 (18) | 0.0179 (15) | 0.034 (2) |
C25 | 0.0469 (14) | 0.094 (2) | 0.098 (2) | −0.0011 (15) | 0.0061 (14) | 0.0195 (19) |
C26 | 0.0462 (12) | 0.0637 (16) | 0.0612 (15) | 0.0041 (11) | 0.0112 (11) | 0.0069 (12) |
C27 | 0.0494 (13) | 0.0533 (15) | 0.0696 (16) | −0.0003 (11) | 0.0007 (11) | 0.0003 (12) |
O1—C9 | 1.192 (3) | C10—H10A | 0.96 |
O2—C9 | 1.327 (3) | C10—H10B | 0.96 |
O2—C10 | 1.442 (3) | C10—H10C | 0.96 |
O3—C11 | 1.213 (3) | C11—C12 | 1.481 (3) |
O4—C18 | 1.217 (3) | C12—C13 | 1.380 (3) |
O5—C19 | 1.413 (3) | C12—C17 | 1.391 (3) |
O5—H5 | 0.82 | C13—C14 | 1.380 (4) |
O6—C20 | 1.216 (3) | C13—H13 | 0.93 |
O7—C27 | 1.201 (3) | C14—C15 | 1.386 (4) |
N1—C2 | 1.470 (3) | C14—H14 | 0.93 |
N1—C8 | 1.474 (3) | C15—C16 | 1.370 (4) |
N1—C5 | 1.475 (3) | C15—H15 | 0.93 |
C2—C3 | 1.528 (3) | C16—C17 | 1.388 (3) |
C2—C18 | 1.535 (3) | C16—H16 | 0.93 |
C2—C11 | 1.538 (3) | C17—C18 | 1.468 (3) |
C3—C4 | 1.555 (3) | C18—O4 | 1.217 (3) |
C3—H3A | 0.97 | C19—C20 | 1.537 (3) |
C3—H3B | 0.97 | C19—C27 | 1.544 (3) |
C4—C9 | 1.518 (3) | C20—O6 | 1.216 (3) |
C4—C19 | 1.553 (3) | C20—C21 | 1.470 (3) |
C4—C5 | 1.590 (3) | C21—C26 | 1.382 (4) |
C5—C6 | 1.541 (3) | C21—C22 | 1.389 (3) |
C5—H5A | 0.98 | C22—C23 | 1.371 (4) |
C6—C7 | 1.529 (4) | C22—H22 | 0.93 |
C6—H6A | 0.97 | C23—C24 | 1.376 (5) |
C6—H6B | 0.97 | C23—H23 | 0.93 |
C7—C8 | 1.508 (4) | C24—C25 | 1.378 (5) |
C7—H7A | 0.97 | C24—H24 | 0.93 |
C7—H7B | 0.97 | C25—C26 | 1.379 (4) |
C8—H8A | 0.97 | C25—H25 | 0.93 |
C8—H8B | 0.97 | C26—C27 | 1.479 (4) |
C9—O2—C10 | 116.08 (19) | H10B—C10—H10C | 109.5 |
C19—O5—H5 | 109.5 | O3—C11—C12 | 126.4 (2) |
C2—N1—C8 | 118.65 (17) | O3—C11—C2 | 125.6 (2) |
C2—N1—C5 | 107.91 (15) | C12—C11—C2 | 107.93 (17) |
C8—N1—C5 | 108.00 (16) | C13—C12—C17 | 120.5 (2) |
N1—C2—C3 | 107.47 (15) | C13—C12—C11 | 129.8 (2) |
N1—C2—C18 | 104.38 (16) | C17—C12—C11 | 109.70 (18) |
C3—C2—C18 | 115.39 (17) | C12—C13—C14 | 117.8 (2) |
N1—C2—C11 | 111.49 (16) | C12—C13—H13 | 121.1 |
C3—C2—C11 | 115.68 (17) | C14—C13—H13 | 121.1 |
C18—C2—C11 | 101.89 (16) | C13—C14—C15 | 121.5 (2) |
C2—C3—C4 | 106.92 (17) | C13—C14—H14 | 119.2 |
C2—C3—H3A | 110.3 | C15—C14—H14 | 119.2 |
C4—C3—H3A | 110.3 | C16—C15—C14 | 121.1 (2) |
C2—C3—H3B | 110.3 | C16—C15—H15 | 119.5 |
C4—C3—H3B | 110.3 | C14—C15—H15 | 119.5 |
H3A—C3—H3B | 108.6 | C15—C16—C17 | 117.7 (2) |
C9—C4—C19 | 105.97 (16) | C15—C16—H16 | 121.1 |
C9—C4—C3 | 111.66 (17) | C17—C16—H16 | 121.1 |
C19—C4—C3 | 112.47 (17) | C16—C17—C12 | 121.3 (2) |
C9—C4—C5 | 111.40 (16) | C16—C17—C18 | 128.9 (2) |
C19—C4—C5 | 111.72 (16) | C12—C17—C18 | 109.77 (18) |
C3—C4—C5 | 103.77 (15) | O4—C18—C17 | 126.24 (19) |
N1—C5—C6 | 104.63 (17) | O4—C18—C2 | 125.06 (19) |
N1—C5—C4 | 107.21 (16) | C17—C18—C2 | 108.67 (17) |
C6—C5—C4 | 119.49 (17) | O5—C19—C20 | 105.39 (18) |
N1—C5—H5A | 108.4 | O5—C19—C27 | 104.98 (19) |
C6—C5—H5A | 108.4 | C20—C19—C27 | 102.48 (17) |
C4—C5—H5A | 108.4 | O5—C19—C4 | 113.81 (16) |
C7—C6—C5 | 104.81 (18) | C20—C19—C4 | 114.18 (18) |
C7—C6—H6A | 110.8 | C27—C19—C4 | 114.79 (19) |
C5—C6—H6A | 110.8 | O6—C20—C21 | 126.8 (2) |
C7—C6—H6B | 110.8 | O6—C20—C19 | 124.8 (2) |
C5—C6—H6B | 110.8 | C21—C20—C19 | 108.40 (19) |
H6A—C6—H6B | 108.9 | C26—C21—C22 | 121.1 (2) |
C8—C7—C6 | 103.77 (19) | C26—C21—C20 | 110.3 (2) |
C8—C7—H7A | 111.0 | C22—C21—C20 | 128.6 (2) |
C6—C7—H7A | 111.0 | C23—C22—C21 | 117.4 (3) |
C8—C7—H7B | 111.0 | C23—C22—H22 | 121.3 |
C6—C7—H7B | 111.0 | C21—C22—H22 | 121.3 |
H7A—C7—H7B | 109.0 | C22—C23—C24 | 121.6 (3) |
N1—C8—C7 | 101.33 (18) | C22—C23—H23 | 119.2 |
N1—C8—H8A | 111.5 | C24—C23—H23 | 119.2 |
C7—C8—H8A | 111.5 | C23—C24—C25 | 121.1 (3) |
N1—C8—H8B | 111.5 | C23—C24—H24 | 119.4 |
C7—C8—H8B | 111.5 | C25—C24—H24 | 119.4 |
H8A—C8—H8B | 109.3 | C24—C25—C26 | 117.9 (3) |
O1—C9—O2 | 123.1 (2) | C24—C25—H25 | 121.0 |
O1—C9—C4 | 123.0 (2) | C26—C25—H25 | 121.0 |
O2—C9—C4 | 113.85 (17) | C25—C26—C21 | 120.8 (2) |
O2—C10—H10A | 109.5 | C25—C26—C27 | 129.0 (3) |
O2—C10—H10B | 109.5 | C21—C26—C27 | 110.2 (2) |
H10A—C10—H10B | 109.5 | O7—C27—C26 | 126.8 (2) |
O2—C10—H10C | 109.5 | O7—C27—C19 | 125.2 (2) |
H10A—C10—H10C | 109.5 | C26—C27—C19 | 107.8 (2) |
C8—N1—C2—C3 | −96.3 (2) | C11—C12—C17—C16 | 177.7 (2) |
C5—N1—C2—C3 | 26.8 (2) | C13—C12—C17—C18 | 179.1 (2) |
C8—N1—C2—C18 | 140.68 (18) | C11—C12—C17—C18 | −1.5 (2) |
C5—N1—C2—C18 | −96.18 (17) | C16—C17—C18—O4 | −4.9 (4) |
C8—N1—C2—C11 | 31.4 (2) | C12—C17—C18—O4 | 174.1 (2) |
C5—N1—C2—C11 | 154.57 (16) | C16—C17—C18—C2 | 173.1 (2) |
N1—C2—C3—C4 | −18.4 (2) | C12—C17—C18—C2 | −7.8 (2) |
C18—C2—C3—C4 | 97.5 (2) | N1—C2—C18—O4 | 75.0 (3) |
C11—C2—C3—C4 | −143.72 (17) | C3—C2—C18—O4 | −42.6 (3) |
C2—C3—C4—C9 | 123.77 (18) | C11—C2—C18—O4 | −168.8 (2) |
C2—C3—C4—C19 | −117.25 (18) | N1—C2—C18—C17 | −102.99 (19) |
C2—C3—C4—C5 | 3.7 (2) | C3—C2—C18—C17 | 139.32 (18) |
C2—N1—C5—C6 | −152.10 (17) | C11—C2—C18—C17 | 13.2 (2) |
C8—N1—C5—C6 | −22.7 (2) | C9—C4—C19—O5 | 177.89 (19) |
C2—N1—C5—C4 | −24.3 (2) | C3—C4—C19—O5 | 55.6 (2) |
C8—N1—C5—C4 | 105.14 (18) | C5—C4—C19—O5 | −60.6 (2) |
C9—C4—C5—N1 | −108.08 (18) | C9—C4—C19—C20 | 56.8 (2) |
C19—C4—C5—N1 | 133.60 (17) | C3—C4—C19—C20 | −65.4 (2) |
C3—C4—C5—N1 | 12.2 (2) | C5—C4—C19—C20 | 178.33 (17) |
C9—C4—C5—C6 | 10.5 (3) | C9—C4—C19—C27 | −61.1 (2) |
C19—C4—C5—C6 | −107.8 (2) | C3—C4—C19—C27 | 176.63 (18) |
C3—C4—C5—C6 | 130.8 (2) | C5—C4—C19—C27 | 60.4 (2) |
N1—C5—C6—C7 | −3.4 (2) | O5—C19—C20—O6 | −75.5 (3) |
C4—C5—C6—C7 | −123.3 (2) | C27—C19—C20—O6 | 174.9 (2) |
C5—C6—C7—C8 | 27.2 (2) | C4—C19—C20—O6 | 50.2 (3) |
C2—N1—C8—C7 | 162.84 (18) | O5—C19—C20—C21 | 101.1 (2) |
C5—N1—C8—C7 | 39.7 (2) | C27—C19—C20—C21 | −8.5 (2) |
C6—C7—C8—N1 | −40.4 (2) | C4—C19—C20—C21 | −133.28 (19) |
C10—O2—C9—O1 | −0.5 (4) | O6—C20—C21—C26 | −178.2 (2) |
C10—O2—C9—C4 | −178.6 (2) | C19—C20—C21—C26 | 5.3 (3) |
C19—C4—C9—O1 | 18.5 (3) | O6—C20—C21—C22 | 1.2 (4) |
C3—C4—C9—O1 | 141.3 (2) | C19—C20—C21—C22 | −175.3 (2) |
C5—C4—C9—O1 | −103.2 (3) | C26—C21—C22—C23 | −0.5 (4) |
C19—C4—C9—O2 | −163.39 (18) | C20—C21—C22—C23 | −179.8 (3) |
C3—C4—C9—O2 | −40.6 (2) | C21—C22—C23—C24 | 0.5 (5) |
C5—C4—C9—O2 | 74.9 (2) | C22—C23—C24—C25 | 0.1 (6) |
N1—C2—C11—O3 | −85.2 (3) | C23—C24—C25—C26 | −0.8 (5) |
C3—C2—C11—O3 | 37.9 (3) | C24—C25—C26—C21 | 0.9 (5) |
C18—C2—C11—O3 | 163.9 (2) | C24—C25—C26—C27 | 179.3 (3) |
N1—C2—C11—C12 | 96.95 (19) | C22—C21—C26—C25 | −0.2 (4) |
C3—C2—C11—C12 | −139.87 (18) | C20—C21—C26—C25 | 179.2 (3) |
C18—C2—C11—C12 | −13.9 (2) | C22—C21—C26—C27 | −178.9 (2) |
O3—C11—C12—C13 | 11.7 (4) | C20—C21—C26—C27 | 0.6 (3) |
C2—C11—C12—C13 | −170.5 (2) | C25—C26—C27—O7 | 0.0 (5) |
O3—C11—C12—C17 | −167.6 (2) | C21—C26—C27—O7 | 178.6 (3) |
C2—C11—C12—C17 | 10.2 (2) | C25—C26—C27—C19 | 175.3 (3) |
C17—C12—C13—C14 | 0.8 (4) | C21—C26—C27—C19 | −6.2 (3) |
C11—C12—C13—C14 | −178.5 (2) | O5—C19—C27—O7 | 74.2 (4) |
C12—C13—C14—C15 | 0.1 (4) | C20—C19—C27—O7 | −175.9 (3) |
C13—C14—C15—C16 | −0.2 (4) | C4—C19—C27—O7 | −51.5 (4) |
C14—C15—C16—C17 | −0.7 (4) | O5—C19—C27—C26 | −101.1 (2) |
C15—C16—C17—C12 | 1.7 (3) | C20—C19—C27—C26 | 8.8 (3) |
C15—C16—C17—C18 | −179.4 (2) | C4—C19—C27—C26 | 133.2 (2) |
C13—C12—C17—C16 | −1.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O4 | 0.82 | 1.89 | 2.691 (2) | 165 |
C8—H8A···O4i | 0.97 | 2.56 | 3.259 (3) | 130 |
C16—H16···O3ii | 0.93 | 2.57 | 3.481 (3) | 168 |
C22—H22···O7iii | 0.93 | 2.38 | 3.280 (4) | 163 |
C23—H23···O1iv | 0.93 | 2.47 | 3.238 (3) | 140 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2; (iii) x, y+1, z; (iv) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C26H21NO7 |
Mr | 459.44 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 39.580 (5), 7.6690 (15), 14.868 (3) |
β (°) | 103.291 (16) |
V (Å3) | 4392.0 (14) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 0.85 |
Crystal size (mm) | 0.37 × 0.24 × 0.15 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.784, 0.881 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4055, 3994, 3118 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.169, 0.99 |
No. of reflections | 3994 |
No. of parameters | 309 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.22 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1988), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97 and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O4 | 0.82 | 1.89 | 2.691 (2) | 165 |
C8—H8A···O4i | 0.97 | 2.56 | 3.259 (3) | 130 |
C16—H16···O3ii | 0.93 | 2.57 | 3.481 (3) | 168 |
C22—H22···O7iii | 0.93 | 2.38 | 3.280 (4) | 163 |
C23—H23···O1iv | 0.93 | 2.47 | 3.238 (3) | 140 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2; (iii) x, y+1, z; (iv) −x, −y+2, −z. |
Pyrrolizidine alkaloids represent a group of compounds present in a variety of plants throughout the world. The pyrrolizidine alkaloids are well documented for their mutagenic, antineoplastic, carcinogenic, hepatoxic and many pharmacological activities. Substituted pyrrolidine compounds have been found to have antimicrobial and antifungal activity against various pathogens (Amalraj et al., 2003). Several optically active pyrrolidine compounds have been used as intermediates in controlled asymmetric synthesis (Suzuki et al., 1994). The spiro-indole-pyrrolidine ring system is a frequently encountered structural motif in many biologically important and pharmacologically relevant alkaloids, e.g. vincrinstine, vinblastine and Spirotypostatins (Cordell, 1981). Against this background and in order to obtain detailed information on its molecular conformation, the structure determination of the title compound has been carried out and the results are presented here.
The title compound (Fig.1) consists of a pyrrolizine ring system (rings A and B) connected to a indane dione group (rings C and D) at C2, hydroxyl indane dione group (rings E and F) and methoxy carbonyl group at C4. All the five-membered rings A, B, C and E adopt envelope conformations. The puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) for the pyrrolidine ring A are q2 = 0.245 (2) Å, φ = 187.8 (5)° and Δs(N1) = 4.7 (2)°, for the pyrrolidine ring B are q2 = 0.399 (2) Å, φ = 318.6 (4)° and Δs(C8) = 3.2 (2)°, for the ring C are q2 = 0.141 (2) Å, φ = 5.0 (10)° and Δs(C2) = 1.7 (3)°, and for the ring E are q2 = 0.090 (3) Å, φ = 356.8 (17)° and Δs(C19) = 0.7 (3)°.
The molecule is stabilized by the intramolecular O5—H5···O4 hydrogen bond which generates an S(8) motif (Bernstein et al., 1995). The crystal packing is stabilized by intermolecular C—H···O hydrogen bonds. Atom C22 in the molecule at (x, y, z) donates one proton to atom O7 in the molecule at (x, 1 + y, z), forming a C(6) chain along the b axis. Also, atoms C8 and C16 in the molecule at (x, y, z) donate one proton each to atom O4 and O3 in the molecule at (x, 1 - y, 1/2 + z) and (x, 1 - y, -1/2 + z), respectively, forming a chain along the c axis. These hydrogen bonds generate an R22(11) ring motif. The molecules at (x, y, z) and (-x, 2 - y, -z) are linked by C23—H23···O1 hydrogen bonds into cyclic centrosymmetric R22(18) dimers. Thus, the symmetry-related molecules are cross-linked by these hydrogen bonds to generate a three-dimensional network.