Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703348X/pr2006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703348X/pr2006Isup2.hkl |
CCDC reference: 657758
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.050
- wR factor = 0.122
- Data-to-parameter ratio = 9.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.97 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C61 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C57
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.06 From the CIF: _reflns_number_total 6482 Count of symmetry unique reflns 6624 Completeness (_total/calc) 97.86% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT792_ALERT_1_G Check the Absolute Configuration of C1 = ... R PLAT792_ALERT_1_G Check the Absolute Configuration of C2 = ... S PLAT792_ALERT_1_G Check the Absolute Configuration of C3 = ... R PLAT792_ALERT_1_G Check the Absolute Configuration of C4 = ... R PLAT792_ALERT_1_G Check the Absolute Configuration of C35 = ... S PLAT792_ALERT_1_G Check the Absolute Configuration of C36 = ... R PLAT792_ALERT_1_G Check the Absolute Configuration of C37 = ... S PLAT792_ALERT_1_G Check the Absolute Configuration of C38 = ... S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 12 ALERT level G = General alerts; check 10 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of isoquinolic aicd (0.186 g, 1 mmol), isatin (0.147 g, 1 mmol), bis-benzylidine acetone (0.224 g, 1 mmol) and triethyl amine (0.252 g, 2.5 mmol) was refluxed in acetonitrile for 12 h. The reaction was monitored by TLC and after completion, the solvent was removed at reduced pressure. The crude product was subjected to column chromatrography (Silica gel, 100–200 mesh) using Hexane/Ethyl acetate (9:1) as eluent. The compound was recrystallized from Hexane/Ethyl acetate (1:1) by slow evaporation.
All H-atoms were refined using a riding model with d(C—H) = 0.93 Å, Uiso = 1.2Ueq (C) for aromatic, 0.98 Å, Uiso = 1.2Ueq (C) for CH, 0.97 Å, Uiso = 1.2Ueq (C) for CH2, 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms and 0.86 Å, Uiso = 1.2Ueq (N) for the NH group.
Pyrrolidine occurs widely in nature and is a structural part of porphyrin heme, chlorophyll and vitamin B12. Pyrrolidine compounds have antifungal and antimicrobial activity (Amal Raj et al., 2003). The spiro ring system is a frequently encountered structural motif in many pharmacologically relevant alkaloids. Synthetic spiro-pyrrolidine derivatives have activity against the aldose reductase enzyme which controls influenza (Stylianakis et al., 2003). As spiropyrrolidine compounds are of great pharmaceutical importance, we have undertaken the three dimensional crystal structure determination of the title compound, C34 H28 N2 O2, by X-ray diffraction (Fig.1).
The bond lengths and angles are comparable with the literature values (Allen et al., 1987). The sum of the bond angles around N1 (339.5 (6)°) and N3 (336.0 (6)°) indicates the sp3 hybridization. The pyrrolidine ring in molecule A adopts a twisted conformation with a pseudo twofold axis passing through atom C1 and C3—C4 bond. In molecule B, it adopts an envelope conformation with atom C38 deviating by -0.608 (2)Å from the plane of rest of the atoms in the ring. The six membered rings N1/C4—C6/C11/C12 and N3/C38—C40/C45/C46 in molecules A and B, respectively, are non-planar. The oxindole ring in molecules A and B is planar with the dihedral angle between five and six membered rings being 2.3 (1) and 1.8 (1)°, respectively. Oxygen atoms O1 and O3 lie below the plane of the five membered rings in the oxindole moiety in molecule A and B by 0.021 (2) and 0.049 (2) Å, respectively.
The puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) for pyrrolidine ring N1/C1—C4 in the molecule A are q2 = 0.392 (3) Å, φ = 310.6 (4)° and Δ 2(C1) = 7.5 (2), for pyrrolidine ring N3/C35—C38 in the molecule B are q2 = 0.400 (3) Å, φ = 152.0 (4)° and Δ s(C38) = 9.7 (2), for six memebered rings (N1/C4—C6/C11/C12 and N3/C38—C40/C45/C46) in molecule A and B are q2 = 0.394 (3) Å; 0.369 (3) Å, q3 = 0.328 (3) Å; -0.314 (3) Å, QT = 0.513 (3) Å; 0.485 (3)Å and θ = 50.2 (3)°; s130.4(3)°, respectively.
The molecule is stabilized by weak C—H···O intramolecular interactions. The crystal packing is stabilized by two N—H···O intermolecular interactions. Atoms N2 and N4 act as donors to O4 (1/2 + x,1 - y,z) and O2 (-1/2 + x,-y,z), generating a chain running along b axis.
For related literature, see: Allen et al. (1987); Amal Raj et al. (2003); Cremer & Pople (1975); Nardelli (1983); Stylianakis et al. (2003).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
C34H28N2O2 | F(000) = 2096 |
Mr = 496.58 | Dx = 1.249 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 3158 reflections |
a = 19.301 (4) Å | θ = 1.4–25.0° |
b = 14.725 (3) Å | µ = 0.08 mm−1 |
c = 18.583 (4) Å | T = 293 K |
V = 5281 (2) Å3 | Block, colourless |
Z = 8 | 0.28 × 0.24 × 0.23 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5365 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 28.1°, θmin = 1.4° |
ω scans | h = −25→25 |
44375 measured reflections | k = −19→19 |
6482 independent reflections | l = −23→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0723P)2 + 0.0694P] where P = (Fo2 + 2Fc2)/3 |
6482 reflections | (Δ/σ)max < 0.001 |
685 parameters | Δρmax = 0.26 e Å−3 |
1 restraint | Δρmin = −0.13 e Å−3 |
C34H28N2O2 | V = 5281 (2) Å3 |
Mr = 496.58 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 19.301 (4) Å | µ = 0.08 mm−1 |
b = 14.725 (3) Å | T = 293 K |
c = 18.583 (4) Å | 0.28 × 0.24 × 0.23 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5365 reflections with I > 2σ(I) |
44375 measured reflections | Rint = 0.030 |
6482 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 1 restraint |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.26 e Å−3 |
6482 reflections | Δρmin = −0.13 e Å−3 |
685 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 | ||
N1 | 0.46079 (10) | 0.50133 (13) | 0.42242 (11) | 0.0422 (4) | |
N2 | 0.62533 (12) | 0.58129 (15) | 0.45090 (14) | 0.0587 (6) | |
H2 | 0.6587 | 0.6178 | 0.4406 | 0.070* | |
O1 | 0.59608 (10) | 0.53639 (13) | 0.33659 (12) | 0.0601 (5) | |
O2 | 0.54648 (10) | 0.24727 (13) | 0.49803 (11) | 0.0581 (5) | |
C1 | 0.53286 (12) | 0.47841 (16) | 0.44209 (13) | 0.0403 (5) | |
C2 | 0.53957 (12) | 0.37561 (14) | 0.42011 (13) | 0.0403 (5) | |
H2A | 0.5671 | 0.3732 | 0.3758 | 0.048* | |
C3 | 0.46564 (12) | 0.34610 (15) | 0.40080 (13) | 0.0402 (5) | |
H3 | 0.4416 | 0.3289 | 0.4452 | 0.048* | |
C4 | 0.43374 (12) | 0.43268 (15) | 0.37264 (13) | 0.0432 (5) | |
H4 | 0.4503 | 0.4449 | 0.3237 | 0.052* | |
C5 | 0.35535 (13) | 0.43692 (18) | 0.37494 (16) | 0.0526 (6) | |
H5A | 0.3364 | 0.3977 | 0.3379 | 0.063* | |
H5B | 0.3392 | 0.4150 | 0.4212 | 0.063* | |
C6 | 0.32979 (13) | 0.53207 (18) | 0.36345 (14) | 0.0512 (6) | |
C7 | 0.26194 (15) | 0.5487 (2) | 0.34094 (17) | 0.0632 (7) | |
H7 | 0.2320 | 0.5000 | 0.3337 | 0.076* | |
C8 | 0.23858 (17) | 0.6352 (3) | 0.32928 (19) | 0.0743 (9) | |
H8 | 0.1934 | 0.6447 | 0.3136 | 0.089* | |
C9 | 0.28120 (18) | 0.7074 (3) | 0.3405 (2) | 0.0788 (10) | |
H9 | 0.2650 | 0.7662 | 0.3335 | 0.095* | |
C10 | 0.34873 (17) | 0.6929 (2) | 0.36238 (18) | 0.0659 (8) | |
H10 | 0.3781 | 0.7423 | 0.3688 | 0.079* | |
C11 | 0.37348 (14) | 0.60568 (18) | 0.37491 (14) | 0.0513 (6) | |
C12 | 0.44767 (14) | 0.59353 (17) | 0.39869 (18) | 0.0550 (6) | |
H12A | 0.4784 | 0.6081 | 0.3590 | 0.066* | |
H12B | 0.4576 | 0.6352 | 0.4378 | 0.066* | |
C13 | 0.58798 (12) | 0.53482 (15) | 0.40082 (16) | 0.0467 (5) | |
C14 | 0.60314 (14) | 0.56264 (18) | 0.52101 (16) | 0.0542 (6) | |
C15 | 0.62925 (19) | 0.5944 (3) | 0.5859 (2) | 0.0797 (10) | |
H15 | 0.6656 | 0.6358 | 0.5873 | 0.096* | |
C16 | 0.5996 (2) | 0.5626 (3) | 0.6476 (2) | 0.0880 (11) | |
H16 | 0.6165 | 0.5830 | 0.6916 | 0.106* | |
C17 | 0.54584 (18) | 0.5018 (3) | 0.64710 (18) | 0.0746 (9) | |
H17 | 0.5273 | 0.4810 | 0.6902 | 0.090* | |
C18 | 0.51918 (14) | 0.47146 (19) | 0.58210 (16) | 0.0543 (6) | |
H18 | 0.4822 | 0.4310 | 0.5811 | 0.065* | |
C19 | 0.54836 (12) | 0.50215 (16) | 0.51922 (14) | 0.0445 (5) | |
C20 | 0.57527 (12) | 0.31515 (16) | 0.47504 (13) | 0.0434 (5) | |
C21 | 0.64594 (12) | 0.33979 (16) | 0.49544 (14) | 0.0468 (6) | |
H21 | 0.6688 | 0.3841 | 0.4688 | 0.056* | |
C22 | 0.67879 (13) | 0.30178 (18) | 0.55021 (15) | 0.0494 (6) | |
H22 | 0.6552 | 0.2560 | 0.5745 | 0.059* | |
C23 | 0.74793 (14) | 0.32391 (17) | 0.57657 (14) | 0.0497 (6) | |
C24 | 0.78893 (15) | 0.3894 (2) | 0.54376 (17) | 0.0622 (7) | |
H24 | 0.7723 | 0.4202 | 0.5037 | 0.075* | |
C25 | 0.85405 (16) | 0.4092 (2) | 0.56991 (19) | 0.0698 (8) | |
H25 | 0.8810 | 0.4531 | 0.5473 | 0.084* | |
C26 | 0.87937 (17) | 0.3645 (2) | 0.62915 (19) | 0.0689 (8) | |
H26 | 0.9231 | 0.3784 | 0.6470 | 0.083* | |
C27 | 0.83963 (17) | 0.2994 (2) | 0.66163 (18) | 0.0705 (8) | |
H27 | 0.8568 | 0.2686 | 0.7015 | 0.085* | |
C28 | 0.77457 (15) | 0.2788 (2) | 0.63601 (17) | 0.0626 (7) | |
H28 | 0.7483 | 0.2342 | 0.6587 | 0.075* | |
C29 | 0.46236 (12) | 0.26695 (15) | 0.34907 (13) | 0.0419 (5) | |
C30 | 0.49026 (15) | 0.27250 (18) | 0.28099 (14) | 0.0513 (6) | |
H30 | 0.5118 | 0.3258 | 0.2663 | 0.062* | |
C31 | 0.48653 (17) | 0.1997 (2) | 0.23432 (16) | 0.0645 (8) | |
H31 | 0.5053 | 0.2045 | 0.1884 | 0.077* | |
C32 | 0.45541 (18) | 0.1202 (2) | 0.2553 (2) | 0.0717 (9) | |
H32 | 0.4529 | 0.0712 | 0.2238 | 0.086* | |
C33 | 0.42797 (19) | 0.1138 (2) | 0.3231 (2) | 0.0755 (9) | |
H33 | 0.4072 | 0.0600 | 0.3380 | 0.091* | |
C34 | 0.43110 (16) | 0.18685 (19) | 0.36949 (17) | 0.0605 (7) | |
H34 | 0.4118 | 0.1820 | 0.4152 | 0.073* | |
N3 | 0.30081 (10) | 0.01027 (14) | 0.48973 (11) | 0.0431 (4) | |
N4 | 0.13746 (12) | −0.08201 (15) | 0.46957 (14) | 0.0538 (5) | |
H4A | 0.1044 | −0.1181 | 0.4817 | 0.065* | |
O3 | 0.17250 (10) | −0.03839 (14) | 0.58196 (11) | 0.0622 (5) | |
O4 | 0.22277 (11) | 0.26153 (13) | 0.42423 (12) | 0.0629 (5) | |
C35 | 0.22770 (12) | 0.02546 (15) | 0.47260 (13) | 0.0404 (5) | |
C36 | 0.21591 (12) | 0.12748 (15) | 0.49559 (13) | 0.0415 (5) | |
H36 | 0.1801 | 0.1271 | 0.5330 | 0.050* | |
C37 | 0.28381 (12) | 0.15756 (16) | 0.53213 (13) | 0.0419 (5) | |
H37 | 0.3125 | 0.1880 | 0.4959 | 0.050* | |
C38 | 0.31875 (12) | 0.06702 (15) | 0.55144 (13) | 0.0423 (5) | |
H38 | 0.2978 | 0.0420 | 0.5952 | 0.051* | |
C39 | 0.39667 (14) | 0.07150 (18) | 0.56000 (16) | 0.0546 (6) | |
H39A | 0.4155 | 0.1128 | 0.5243 | 0.066* | |
H39B | 0.4076 | 0.0957 | 0.6072 | 0.066* | |
C40 | 0.43057 (12) | −0.02032 (19) | 0.55155 (14) | 0.0514 (6) | |
C41 | 0.49887 (14) | −0.0325 (2) | 0.57275 (16) | 0.0615 (7) | |
H41 | 0.5236 | 0.0162 | 0.5917 | 0.074* | |
C42 | 0.53040 (15) | −0.1157 (3) | 0.56606 (17) | 0.0717 (9) | |
H42 | 0.5763 | −0.1229 | 0.5803 | 0.086* | |
C43 | 0.49443 (17) | −0.1884 (3) | 0.53838 (19) | 0.0723 (9) | |
H43 | 0.5158 | −0.2448 | 0.5344 | 0.087* | |
C44 | 0.42672 (16) | −0.1777 (2) | 0.51665 (17) | 0.0646 (8) | |
H44 | 0.4024 | −0.2268 | 0.4979 | 0.078* | |
C45 | 0.39465 (14) | −0.09327 (19) | 0.52270 (14) | 0.0517 (6) | |
C46 | 0.31998 (14) | −0.08480 (18) | 0.49940 (17) | 0.0564 (7) | |
H46A | 0.3133 | −0.1173 | 0.4545 | 0.068* | |
H46B | 0.2902 | −0.1121 | 0.5354 | 0.068* | |
C47 | 0.17671 (12) | −0.03513 (16) | 0.51703 (15) | 0.0459 (5) | |
C48 | 0.15689 (13) | −0.06487 (17) | 0.39832 (16) | 0.0503 (6) | |
C49 | 0.12964 (18) | −0.1014 (2) | 0.3361 (2) | 0.0708 (9) | |
H49 | 0.0932 | −0.1426 | 0.3375 | 0.085* | |
C50 | 0.1583 (2) | −0.0746 (3) | 0.2723 (2) | 0.0866 (11) | |
H50 | 0.1403 | −0.0974 | 0.2295 | 0.104* | |
C51 | 0.2136 (2) | −0.0145 (3) | 0.26936 (19) | 0.0803 (10) | |
H51 | 0.2331 | 0.0010 | 0.2253 | 0.096* | |
C52 | 0.23952 (17) | 0.02232 (19) | 0.33228 (16) | 0.0598 (7) | |
H52 | 0.2761 | 0.0635 | 0.3308 | 0.072* | |
C53 | 0.21077 (13) | −0.00253 (16) | 0.39683 (14) | 0.0452 (5) | |
C54 | 0.19103 (13) | 0.19223 (16) | 0.43715 (14) | 0.0446 (5) | |
C55 | 0.12545 (13) | 0.17004 (17) | 0.40118 (15) | 0.0487 (6) | |
H55 | 0.0979 | 0.1239 | 0.4199 | 0.058* | |
C56 | 0.10429 (14) | 0.21369 (19) | 0.34293 (16) | 0.0547 (6) | |
H56 | 0.1323 | 0.2612 | 0.3275 | 0.066* | |
C57 | 0.04232 (16) | 0.1963 (2) | 0.29999 (16) | 0.0574 (7) | |
C58 | −0.00864 (18) | 0.1359 (2) | 0.3203 (2) | 0.0738 (9) | |
H58 | −0.0046 | 0.1045 | 0.3635 | 0.089* | |
C59 | −0.0659 (2) | 0.1219 (2) | 0.2767 (3) | 0.0885 (12) | |
H59 | −0.1006 | 0.0821 | 0.2913 | 0.106* | |
C60 | −0.0717 (2) | 0.1664 (3) | 0.2121 (2) | 0.0898 (13) | |
H60 | −0.1091 | 0.1548 | 0.1819 | 0.108* | |
C61 | −0.0228 (3) | 0.2269 (4) | 0.1927 (2) | 0.1200 (18) | |
H61 | −0.0274 | 0.2585 | 0.1497 | 0.144* | |
C62 | 0.0339 (2) | 0.2423 (3) | 0.2362 (2) | 0.0962 (13) | |
H62 | 0.0670 | 0.2847 | 0.2221 | 0.115* | |
C63 | 0.27609 (13) | 0.22087 (17) | 0.59528 (15) | 0.0483 (6) | |
C64 | 0.23529 (16) | 0.1990 (2) | 0.65397 (16) | 0.0600 (7) | |
H64 | 0.2100 | 0.1452 | 0.6535 | 0.072* | |
C65 | 0.2313 (2) | 0.2548 (3) | 0.71295 (19) | 0.0781 (10) | |
H65 | 0.2038 | 0.2385 | 0.7519 | 0.094* | |
C66 | 0.2676 (2) | 0.3339 (3) | 0.7146 (2) | 0.0886 (12) | |
H66 | 0.2651 | 0.3714 | 0.7548 | 0.106* | |
C67 | 0.3075 (2) | 0.3580 (2) | 0.6576 (3) | 0.0885 (12) | |
H67 | 0.3320 | 0.4124 | 0.6587 | 0.106* | |
C68 | 0.31184 (16) | 0.3019 (2) | 0.5973 (2) | 0.0668 (8) | |
H68 | 0.3390 | 0.3192 | 0.5584 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0385 (10) | 0.0402 (10) | 0.0480 (11) | 0.0028 (8) | −0.0090 (8) | −0.0060 (8) |
N2 | 0.0500 (13) | 0.0505 (13) | 0.0755 (17) | −0.0118 (10) | −0.0073 (11) | −0.0034 (12) |
O1 | 0.0590 (11) | 0.0635 (12) | 0.0577 (12) | −0.0005 (9) | 0.0036 (9) | 0.0076 (9) |
O2 | 0.0575 (11) | 0.0499 (10) | 0.0669 (12) | −0.0013 (8) | −0.0082 (9) | 0.0105 (9) |
C1 | 0.0405 (12) | 0.0371 (11) | 0.0432 (12) | 0.0030 (9) | −0.0041 (9) | −0.0039 (9) |
C2 | 0.0429 (12) | 0.0361 (11) | 0.0420 (12) | 0.0009 (9) | 0.0000 (9) | −0.0036 (9) |
C3 | 0.0409 (11) | 0.0416 (11) | 0.0380 (11) | −0.0013 (9) | 0.0004 (9) | −0.0026 (10) |
C4 | 0.0460 (13) | 0.0426 (12) | 0.0409 (12) | 0.0029 (10) | −0.0060 (10) | −0.0043 (10) |
C5 | 0.0439 (13) | 0.0541 (14) | 0.0599 (16) | −0.0005 (11) | −0.0101 (11) | −0.0085 (12) |
C6 | 0.0465 (13) | 0.0630 (15) | 0.0440 (13) | 0.0062 (12) | −0.0032 (11) | −0.0068 (12) |
C7 | 0.0487 (15) | 0.0853 (19) | 0.0555 (16) | 0.0106 (14) | −0.0086 (13) | −0.0087 (15) |
C8 | 0.0513 (17) | 0.103 (3) | 0.069 (2) | 0.0255 (18) | −0.0135 (15) | 0.0011 (19) |
C9 | 0.074 (2) | 0.082 (2) | 0.080 (2) | 0.0339 (19) | −0.0092 (18) | 0.0144 (19) |
C10 | 0.0651 (18) | 0.0601 (16) | 0.072 (2) | 0.0130 (14) | −0.0058 (15) | 0.0103 (15) |
C11 | 0.0525 (14) | 0.0536 (14) | 0.0479 (14) | 0.0106 (12) | −0.0055 (11) | −0.0009 (11) |
C12 | 0.0515 (14) | 0.0408 (12) | 0.0729 (17) | 0.0055 (11) | −0.0098 (13) | −0.0023 (13) |
C13 | 0.0442 (13) | 0.0383 (12) | 0.0575 (16) | 0.0033 (10) | −0.0041 (11) | 0.0019 (11) |
C14 | 0.0520 (14) | 0.0497 (14) | 0.0609 (16) | 0.0032 (11) | −0.0098 (12) | −0.0133 (13) |
C15 | 0.070 (2) | 0.081 (2) | 0.088 (3) | −0.0124 (17) | −0.0209 (19) | −0.026 (2) |
C16 | 0.087 (2) | 0.119 (3) | 0.058 (2) | −0.006 (2) | −0.0176 (18) | −0.028 (2) |
C17 | 0.074 (2) | 0.100 (3) | 0.0504 (18) | 0.0078 (19) | −0.0034 (15) | −0.0125 (17) |
C18 | 0.0539 (15) | 0.0588 (15) | 0.0504 (15) | 0.0049 (12) | −0.0047 (12) | −0.0076 (12) |
C19 | 0.0433 (12) | 0.0403 (12) | 0.0498 (14) | 0.0072 (10) | −0.0104 (10) | −0.0093 (11) |
C20 | 0.0469 (13) | 0.0387 (12) | 0.0447 (13) | 0.0053 (10) | −0.0010 (10) | −0.0039 (10) |
C21 | 0.0454 (12) | 0.0423 (12) | 0.0527 (14) | 0.0041 (10) | −0.0005 (11) | 0.0055 (11) |
C22 | 0.0484 (13) | 0.0522 (14) | 0.0476 (13) | −0.0023 (11) | −0.0003 (11) | 0.0047 (11) |
C23 | 0.0470 (13) | 0.0557 (14) | 0.0462 (14) | 0.0022 (12) | −0.0014 (11) | 0.0016 (11) |
C24 | 0.0584 (16) | 0.0696 (17) | 0.0585 (17) | −0.0050 (13) | −0.0082 (13) | 0.0161 (14) |
C25 | 0.0584 (17) | 0.0731 (19) | 0.078 (2) | −0.0158 (15) | −0.0037 (15) | 0.0087 (16) |
C26 | 0.0549 (16) | 0.083 (2) | 0.0691 (19) | −0.0074 (15) | −0.0147 (15) | −0.0039 (17) |
C27 | 0.0664 (19) | 0.090 (2) | 0.0546 (17) | 0.0014 (17) | −0.0169 (14) | 0.0131 (16) |
C28 | 0.0600 (17) | 0.0762 (19) | 0.0517 (16) | −0.0079 (14) | −0.0040 (13) | 0.0137 (14) |
C29 | 0.0421 (12) | 0.0396 (12) | 0.0440 (13) | −0.0008 (9) | −0.0014 (10) | −0.0034 (10) |
C30 | 0.0642 (16) | 0.0461 (13) | 0.0437 (14) | −0.0075 (12) | 0.0018 (12) | −0.0009 (11) |
C31 | 0.080 (2) | 0.0680 (18) | 0.0454 (15) | −0.0018 (16) | 0.0021 (14) | −0.0125 (13) |
C32 | 0.084 (2) | 0.0561 (17) | 0.075 (2) | −0.0078 (15) | −0.0017 (17) | −0.0282 (16) |
C33 | 0.085 (2) | 0.0482 (15) | 0.093 (3) | −0.0221 (15) | 0.0184 (19) | −0.0138 (16) |
C34 | 0.0669 (18) | 0.0528 (15) | 0.0617 (17) | −0.0094 (13) | 0.0158 (14) | −0.0052 (13) |
N3 | 0.0380 (9) | 0.0465 (11) | 0.0449 (11) | 0.0043 (8) | −0.0035 (8) | 0.0017 (8) |
N4 | 0.0482 (12) | 0.0454 (11) | 0.0679 (14) | −0.0106 (9) | 0.0023 (10) | 0.0045 (10) |
O3 | 0.0646 (12) | 0.0704 (13) | 0.0515 (12) | −0.0062 (10) | 0.0080 (9) | 0.0138 (10) |
O4 | 0.0633 (12) | 0.0512 (11) | 0.0742 (14) | −0.0054 (9) | −0.0162 (10) | 0.0170 (10) |
C35 | 0.0390 (12) | 0.0408 (12) | 0.0415 (12) | −0.0024 (9) | −0.0006 (10) | 0.0038 (10) |
C36 | 0.0409 (12) | 0.0437 (12) | 0.0398 (12) | −0.0020 (9) | 0.0014 (9) | 0.0026 (9) |
C37 | 0.0416 (12) | 0.0439 (12) | 0.0402 (12) | −0.0018 (9) | −0.0007 (9) | 0.0045 (10) |
C38 | 0.0430 (12) | 0.0442 (12) | 0.0399 (12) | −0.0008 (9) | −0.0021 (10) | 0.0042 (10) |
C39 | 0.0479 (14) | 0.0581 (15) | 0.0578 (16) | −0.0028 (11) | −0.0100 (12) | 0.0070 (13) |
C40 | 0.0419 (13) | 0.0687 (16) | 0.0436 (13) | 0.0046 (11) | 0.0018 (10) | 0.0126 (12) |
C41 | 0.0417 (13) | 0.087 (2) | 0.0553 (16) | 0.0042 (14) | 0.0023 (12) | 0.0156 (15) |
C42 | 0.0424 (14) | 0.113 (3) | 0.0598 (18) | 0.0214 (17) | 0.0077 (13) | 0.0180 (18) |
C43 | 0.0666 (19) | 0.090 (2) | 0.0602 (18) | 0.0373 (18) | 0.0085 (15) | 0.0073 (16) |
C44 | 0.0651 (17) | 0.0672 (18) | 0.0616 (17) | 0.0219 (14) | 0.0024 (14) | −0.0005 (14) |
C45 | 0.0482 (13) | 0.0626 (15) | 0.0444 (13) | 0.0119 (12) | 0.0033 (11) | 0.0058 (12) |
C46 | 0.0514 (15) | 0.0485 (14) | 0.0692 (18) | 0.0086 (11) | −0.0094 (13) | −0.0040 (13) |
C47 | 0.0406 (12) | 0.0412 (12) | 0.0558 (15) | 0.0031 (10) | 0.0012 (11) | 0.0086 (11) |
C48 | 0.0468 (13) | 0.0425 (12) | 0.0617 (15) | −0.0005 (11) | −0.0073 (12) | −0.0001 (12) |
C49 | 0.077 (2) | 0.0605 (17) | 0.075 (2) | −0.0126 (15) | −0.0192 (18) | −0.0099 (16) |
C50 | 0.110 (3) | 0.082 (2) | 0.067 (2) | −0.009 (2) | −0.028 (2) | −0.0163 (19) |
C51 | 0.105 (3) | 0.085 (2) | 0.0504 (18) | −0.005 (2) | −0.0063 (17) | 0.0003 (16) |
C52 | 0.0709 (18) | 0.0601 (16) | 0.0483 (15) | −0.0069 (14) | −0.0005 (13) | 0.0013 (13) |
C53 | 0.0452 (12) | 0.0418 (12) | 0.0485 (13) | 0.0039 (10) | −0.0063 (10) | −0.0015 (11) |
C54 | 0.0481 (13) | 0.0409 (13) | 0.0449 (13) | 0.0060 (10) | −0.0016 (10) | 0.0010 (10) |
C55 | 0.0444 (13) | 0.0466 (13) | 0.0551 (14) | 0.0035 (10) | −0.0042 (11) | 0.0045 (11) |
C56 | 0.0590 (15) | 0.0524 (14) | 0.0525 (15) | 0.0034 (12) | −0.0055 (12) | 0.0037 (12) |
C57 | 0.0609 (17) | 0.0590 (16) | 0.0523 (15) | 0.0122 (13) | −0.0124 (12) | −0.0038 (12) |
C58 | 0.078 (2) | 0.0532 (16) | 0.091 (2) | 0.0015 (15) | −0.0312 (18) | 0.0114 (16) |
C59 | 0.082 (2) | 0.0533 (17) | 0.130 (4) | 0.0014 (16) | −0.046 (2) | −0.002 (2) |
C60 | 0.097 (3) | 0.085 (2) | 0.087 (3) | 0.018 (2) | −0.050 (2) | −0.016 (2) |
C61 | 0.111 (4) | 0.179 (5) | 0.071 (3) | −0.002 (4) | −0.042 (3) | 0.028 (3) |
C62 | 0.089 (3) | 0.133 (4) | 0.067 (2) | −0.011 (2) | −0.0248 (19) | 0.028 (2) |
C63 | 0.0493 (14) | 0.0438 (13) | 0.0519 (15) | 0.0064 (10) | −0.0107 (11) | 0.0011 (11) |
C64 | 0.0723 (19) | 0.0588 (16) | 0.0488 (15) | 0.0069 (14) | −0.0019 (14) | −0.0012 (13) |
C65 | 0.091 (2) | 0.089 (2) | 0.0540 (18) | 0.027 (2) | −0.0041 (16) | −0.0077 (17) |
C66 | 0.099 (3) | 0.087 (3) | 0.080 (3) | 0.021 (2) | −0.017 (2) | −0.036 (2) |
C67 | 0.084 (2) | 0.059 (2) | 0.123 (4) | −0.0040 (17) | −0.020 (2) | −0.029 (2) |
C68 | 0.0649 (18) | 0.0544 (16) | 0.081 (2) | −0.0040 (13) | −0.0079 (16) | −0.0097 (15) |
N1—C12 | 1.450 (3) | N3—C46 | 1.459 (3) |
N1—C4 | 1.466 (3) | N3—C38 | 1.461 (3) |
N1—C1 | 1.477 (3) | N3—C35 | 1.464 (3) |
N2—C13 | 1.362 (4) | N4—C47 | 1.352 (4) |
N2—C14 | 1.399 (4) | N4—C48 | 1.399 (4) |
N2—H2 | 0.8600 | N4—H4A | 0.8600 |
O1—C13 | 1.204 (3) | O3—C47 | 1.210 (3) |
O2—C20 | 1.221 (3) | O4—C54 | 1.214 (3) |
C1—C19 | 1.505 (3) | C35—C53 | 1.503 (4) |
C1—C13 | 1.552 (4) | C35—C47 | 1.564 (3) |
C1—C2 | 1.573 (3) | C35—C36 | 1.578 (3) |
C2—C20 | 1.520 (3) | C36—C54 | 1.523 (3) |
C2—C3 | 1.534 (3) | C36—C37 | 1.541 (3) |
C2—H2A | 0.9800 | C36—H36 | 0.9800 |
C3—C4 | 1.510 (3) | C37—C63 | 1.506 (3) |
C3—C29 | 1.512 (3) | C37—C38 | 1.537 (3) |
C3—H3 | 0.9800 | C37—H37 | 0.9800 |
C4—C5 | 1.515 (4) | C38—C39 | 1.514 (3) |
C4—H4 | 0.9800 | C38—H38 | 0.9800 |
C5—C6 | 1.501 (4) | C39—C40 | 1.510 (4) |
C5—H5A | 0.9700 | C39—H39A | 0.9700 |
C5—H5B | 0.9700 | C39—H39B | 0.9700 |
C6—C11 | 1.390 (4) | C40—C45 | 1.386 (4) |
C6—C7 | 1.397 (4) | C40—C41 | 1.387 (4) |
C7—C8 | 1.368 (4) | C41—C42 | 1.374 (5) |
C7—H7 | 0.9300 | C41—H41 | 0.9300 |
C8—C9 | 1.361 (5) | C42—C43 | 1.376 (5) |
C8—H8 | 0.9300 | C42—H42 | 0.9300 |
C9—C10 | 1.382 (4) | C43—C44 | 1.377 (5) |
C9—H9 | 0.9300 | C43—H43 | 0.9300 |
C10—C11 | 1.390 (4) | C44—C45 | 1.393 (4) |
C10—H10 | 0.9300 | C44—H44 | 0.9300 |
C11—C12 | 1.509 (4) | C45—C46 | 1.510 (4) |
C12—H12A | 0.9700 | C46—H46A | 0.9700 |
C12—H12B | 0.9700 | C46—H46B | 0.9700 |
C14—C19 | 1.383 (4) | C48—C49 | 1.380 (4) |
C14—C15 | 1.388 (4) | C48—C53 | 1.388 (4) |
C15—C16 | 1.364 (6) | C49—C50 | 1.367 (6) |
C15—H15 | 0.9300 | C49—H49 | 0.9300 |
C16—C17 | 1.371 (6) | C50—C51 | 1.387 (6) |
C16—H16 | 0.9300 | C50—H50 | 0.9300 |
C17—C18 | 1.387 (4) | C51—C52 | 1.383 (5) |
C17—H17 | 0.9300 | C51—H51 | 0.9300 |
C18—C19 | 1.374 (4) | C52—C53 | 1.371 (4) |
C18—H18 | 0.9300 | C52—H52 | 0.9300 |
C20—C21 | 1.462 (3) | C54—C55 | 1.468 (4) |
C21—C22 | 1.323 (4) | C55—C56 | 1.323 (4) |
C21—H21 | 0.9300 | C55—H55 | 0.9300 |
C22—C23 | 1.459 (4) | C56—C57 | 1.460 (4) |
C22—H22 | 0.9300 | C56—H56 | 0.9300 |
C23—C28 | 1.388 (4) | C57—C62 | 1.375 (5) |
C23—C24 | 1.388 (4) | C57—C58 | 1.378 (5) |
C24—C25 | 1.379 (4) | C58—C59 | 1.386 (5) |
C24—H24 | 0.9300 | C58—H58 | 0.9300 |
C25—C26 | 1.372 (5) | C59—C60 | 1.373 (6) |
C25—H25 | 0.9300 | C59—H59 | 0.9300 |
C26—C27 | 1.369 (5) | C60—C61 | 1.346 (7) |
C26—H26 | 0.9300 | C60—H60 | 0.9300 |
C27—C28 | 1.377 (4) | C61—C62 | 1.379 (6) |
C27—H27 | 0.9300 | C61—H61 | 0.9300 |
C28—H28 | 0.9300 | C62—H62 | 0.9300 |
C29—C30 | 1.377 (4) | C63—C68 | 1.379 (4) |
C29—C34 | 1.378 (4) | C63—C64 | 1.383 (4) |
C30—C31 | 1.381 (4) | C64—C65 | 1.372 (5) |
C30—H30 | 0.9300 | C64—H64 | 0.9300 |
C31—C32 | 1.371 (5) | C65—C66 | 1.359 (6) |
C31—H31 | 0.9300 | C65—H65 | 0.9300 |
C32—C33 | 1.371 (5) | C66—C67 | 1.357 (6) |
C32—H32 | 0.9300 | C66—H66 | 0.9300 |
C33—C34 | 1.379 (4) | C67—C68 | 1.395 (5) |
C33—H33 | 0.9300 | C67—H67 | 0.9300 |
C34—H34 | 0.9300 | C68—H68 | 0.9300 |
C12—N1—C4 | 113.0 (2) | C46—N3—C38 | 113.1 (2) |
C12—N1—C1 | 117.0 (2) | C46—N3—C35 | 114.7 (2) |
C4—N1—C1 | 109.5 (2) | C38—N3—C35 | 108.2 (2) |
C13—N2—C14 | 112.1 (2) | C47—N4—C48 | 112.0 (2) |
C13—N2—H2 | 124.0 | C47—N4—H4A | 124.0 |
C14—N2—H2 | 124.0 | C48—N4—H4A | 124.0 |
N1—C1—C19 | 111.70 (19) | N3—C35—C53 | 111.8 (2) |
N1—C1—C13 | 113.62 (19) | N3—C35—C47 | 113.88 (19) |
C19—C1—C13 | 102.1 (2) | C53—C35—C47 | 101.61 (19) |
N1—C1—C2 | 103.47 (17) | N3—C35—C36 | 103.04 (18) |
C19—C1—C2 | 117.0 (2) | C53—C35—C36 | 118.90 (19) |
C13—C1—C2 | 109.28 (19) | C47—C35—C36 | 108.01 (18) |
C20—C2—C3 | 114.39 (19) | C54—C36—C37 | 113.74 (19) |
C20—C2—C1 | 115.25 (19) | C54—C36—C35 | 116.6 (2) |
C3—C2—C1 | 104.88 (18) | C37—C36—C35 | 105.67 (18) |
C20—C2—H2A | 107.3 | C54—C36—H36 | 106.7 |
C3—C2—H2A | 107.3 | C37—C36—H36 | 106.7 |
C1—C2—H2A | 107.3 | C35—C36—H36 | 106.7 |
C4—C3—C29 | 114.4 (2) | C63—C37—C38 | 113.5 (2) |
C4—C3—C2 | 102.78 (18) | C63—C37—C36 | 115.9 (2) |
C29—C3—C2 | 113.96 (19) | C38—C37—C36 | 103.11 (18) |
C4—C3—H3 | 108.5 | C63—C37—H37 | 108.0 |
C29—C3—H3 | 108.5 | C38—C37—H37 | 108.0 |
C2—C3—H3 | 108.5 | C36—C37—H37 | 108.0 |
N1—C4—C3 | 102.61 (18) | N3—C38—C39 | 110.1 (2) |
N1—C4—C5 | 108.03 (19) | N3—C38—C37 | 102.06 (18) |
C3—C4—C5 | 115.6 (2) | C39—C38—C37 | 115.0 (2) |
N1—C4—H4 | 110.1 | N3—C38—H38 | 109.8 |
C3—C4—H4 | 110.1 | C39—C38—H38 | 109.8 |
C5—C4—H4 | 110.1 | C37—C38—H38 | 109.8 |
C6—C5—C4 | 111.3 (2) | C40—C39—C38 | 112.4 (2) |
C6—C5—H5A | 109.4 | C40—C39—H39A | 109.1 |
C4—C5—H5A | 109.4 | C38—C39—H39A | 109.1 |
C6—C5—H5B | 109.4 | C40—C39—H39B | 109.1 |
C4—C5—H5B | 109.4 | C38—C39—H39B | 109.1 |
H5A—C5—H5B | 108.0 | H39A—C39—H39B | 107.9 |
C11—C6—C7 | 118.6 (3) | C45—C40—C41 | 119.0 (3) |
C11—C6—C5 | 120.5 (2) | C45—C40—C39 | 121.1 (2) |
C7—C6—C5 | 121.0 (3) | C41—C40—C39 | 119.8 (3) |
C8—C7—C6 | 121.3 (3) | C42—C41—C40 | 120.7 (3) |
C8—C7—H7 | 119.3 | C42—C41—H41 | 119.7 |
C6—C7—H7 | 119.3 | C40—C41—H41 | 119.7 |
C9—C8—C7 | 120.3 (3) | C41—C42—C43 | 120.3 (3) |
C9—C8—H8 | 119.9 | C41—C42—H42 | 119.9 |
C7—C8—H8 | 119.9 | C43—C42—H42 | 119.9 |
C8—C9—C10 | 119.6 (3) | C42—C43—C44 | 119.9 (3) |
C8—C9—H9 | 120.2 | C42—C43—H43 | 120.0 |
C10—C9—H9 | 120.2 | C44—C43—H43 | 120.0 |
C9—C10—C11 | 121.1 (3) | C43—C44—C45 | 120.0 (3) |
C9—C10—H10 | 119.4 | C43—C44—H44 | 120.0 |
C11—C10—H10 | 119.4 | C45—C44—H44 | 120.0 |
C10—C11—C6 | 119.1 (3) | C40—C45—C44 | 120.0 (3) |
C10—C11—C12 | 119.0 (3) | C40—C45—C46 | 121.6 (2) |
C6—C11—C12 | 121.9 (2) | C44—C45—C46 | 118.3 (3) |
N1—C12—C11 | 111.5 (2) | N3—C46—C45 | 110.9 (2) |
N1—C12—H12A | 109.3 | N3—C46—H46A | 109.5 |
C11—C12—H12A | 109.3 | C45—C46—H46A | 109.5 |
N1—C12—H12B | 109.3 | N3—C46—H46B | 109.5 |
C11—C12—H12B | 109.3 | C45—C46—H46B | 109.5 |
H12A—C12—H12B | 108.0 | H46A—C46—H46B | 108.0 |
O1—C13—N2 | 126.8 (3) | O3—C47—N4 | 126.3 (2) |
O1—C13—C1 | 126.1 (2) | O3—C47—C35 | 126.2 (2) |
N2—C13—C1 | 107.1 (2) | N4—C47—C35 | 107.4 (2) |
C19—C14—C15 | 121.0 (3) | C49—C48—C53 | 121.8 (3) |
C19—C14—N2 | 109.8 (2) | C49—C48—N4 | 128.4 (3) |
C15—C14—N2 | 129.2 (3) | C53—C48—N4 | 109.8 (2) |
C16—C15—C14 | 117.6 (3) | C50—C49—C48 | 117.4 (3) |
C16—C15—H15 | 121.2 | C50—C49—H49 | 121.3 |
C14—C15—H15 | 121.2 | C48—C49—H49 | 121.3 |
C15—C16—C17 | 122.4 (3) | C49—C50—C51 | 121.9 (3) |
C15—C16—H16 | 118.8 | C49—C50—H50 | 119.0 |
C17—C16—H16 | 118.8 | C51—C50—H50 | 119.0 |
C16—C17—C18 | 119.8 (3) | C52—C51—C50 | 119.7 (3) |
C16—C17—H17 | 120.1 | C52—C51—H51 | 120.1 |
C18—C17—H17 | 120.1 | C50—C51—H51 | 120.1 |
C19—C18—C17 | 118.8 (3) | C53—C52—C51 | 119.2 (3) |
C19—C18—H18 | 120.6 | C53—C52—H52 | 120.4 |
C17—C18—H18 | 120.6 | C51—C52—H52 | 120.4 |
C18—C19—C14 | 120.3 (2) | C52—C53—C48 | 119.8 (2) |
C18—C19—C1 | 130.7 (2) | C52—C53—C35 | 131.2 (2) |
C14—C19—C1 | 108.9 (2) | C48—C53—C35 | 109.0 (2) |
O2—C20—C21 | 122.5 (2) | O4—C54—C55 | 122.1 (2) |
O2—C20—C2 | 120.6 (2) | O4—C54—C36 | 120.5 (2) |
C21—C20—C2 | 116.9 (2) | C55—C54—C36 | 117.2 (2) |
C22—C21—C20 | 122.8 (2) | C56—C55—C54 | 122.0 (2) |
C22—C21—H21 | 118.6 | C56—C55—H55 | 119.0 |
C20—C21—H21 | 118.6 | C54—C55—H55 | 119.0 |
C21—C22—C23 | 127.0 (2) | C55—C56—C57 | 127.9 (3) |
C21—C22—H22 | 116.5 | C55—C56—H56 | 116.0 |
C23—C22—H22 | 116.5 | C57—C56—H56 | 116.0 |
C28—C23—C24 | 118.1 (3) | C62—C57—C58 | 118.0 (3) |
C28—C23—C22 | 119.9 (2) | C62—C57—C56 | 118.8 (3) |
C24—C23—C22 | 122.0 (2) | C58—C57—C56 | 123.2 (3) |
C25—C24—C23 | 120.8 (3) | C57—C58—C59 | 120.4 (3) |
C25—C24—H24 | 119.6 | C57—C58—H58 | 119.8 |
C23—C24—H24 | 119.6 | C59—C58—H58 | 119.8 |
C26—C25—C24 | 120.4 (3) | C60—C59—C58 | 120.3 (4) |
C26—C25—H25 | 119.8 | C60—C59—H59 | 119.8 |
C24—C25—H25 | 119.8 | C58—C59—H59 | 119.8 |
C27—C26—C25 | 119.4 (3) | C61—C60—C59 | 119.5 (4) |
C27—C26—H26 | 120.3 | C61—C60—H60 | 120.3 |
C25—C26—H26 | 120.3 | C59—C60—H60 | 120.3 |
C26—C27—C28 | 120.9 (3) | C60—C61—C62 | 120.6 (4) |
C26—C27—H27 | 119.6 | C60—C61—H61 | 119.7 |
C28—C27—H27 | 119.6 | C62—C61—H61 | 119.7 |
C27—C28—C23 | 120.5 (3) | C57—C62—C61 | 121.1 (4) |
C27—C28—H28 | 119.8 | C57—C62—H62 | 119.4 |
C23—C28—H28 | 119.8 | C61—C62—H62 | 119.4 |
C30—C29—C34 | 118.3 (2) | C68—C63—C64 | 117.7 (3) |
C30—C29—C3 | 121.5 (2) | C68—C63—C37 | 120.5 (3) |
C34—C29—C3 | 120.2 (2) | C64—C63—C37 | 121.7 (2) |
C29—C30—C31 | 120.7 (3) | C65—C64—C63 | 121.4 (3) |
C29—C30—H30 | 119.7 | C65—C64—H64 | 119.3 |
C31—C30—H30 | 119.7 | C63—C64—H64 | 119.3 |
C32—C31—C30 | 120.4 (3) | C66—C65—C64 | 120.2 (4) |
C32—C31—H31 | 119.8 | C66—C65—H65 | 119.9 |
C30—C31—H31 | 119.8 | C64—C65—H65 | 119.9 |
C33—C32—C31 | 119.3 (3) | C67—C66—C65 | 119.9 (3) |
C33—C32—H32 | 120.3 | C67—C66—H66 | 120.1 |
C31—C32—H32 | 120.3 | C65—C66—H66 | 120.1 |
C32—C33—C34 | 120.2 (3) | C66—C67—C68 | 120.4 (3) |
C32—C33—H33 | 119.9 | C66—C67—H67 | 119.8 |
C34—C33—H33 | 119.9 | C68—C67—H67 | 119.8 |
C29—C34—C33 | 121.0 (3) | C63—C68—C67 | 120.3 (4) |
C29—C34—H34 | 119.5 | C63—C68—H68 | 119.8 |
C33—C34—H34 | 119.5 | C67—C68—H68 | 119.8 |
C12—N1—C1—C19 | 85.8 (3) | C46—N3—C35—C53 | −72.9 (3) |
C4—N1—C1—C19 | −143.9 (2) | C38—N3—C35—C53 | 159.84 (19) |
C12—N1—C1—C13 | −29.1 (3) | C46—N3—C35—C47 | 41.5 (3) |
C4—N1—C1—C13 | 101.2 (2) | C38—N3—C35—C47 | −85.7 (2) |
C12—N1—C1—C2 | −147.5 (2) | C46—N3—C35—C36 | 158.3 (2) |
C4—N1—C1—C2 | −17.2 (2) | C38—N3—C35—C36 | 31.0 (2) |
N1—C1—C2—C20 | −135.5 (2) | N3—C35—C36—C54 | 121.4 (2) |
C19—C1—C2—C20 | −12.2 (3) | C53—C35—C36—C54 | −2.9 (3) |
C13—C1—C2—C20 | 103.1 (2) | C47—C35—C36—C54 | −117.8 (2) |
N1—C1—C2—C3 | −8.8 (2) | N3—C35—C36—C37 | −6.1 (2) |
C19—C1—C2—C3 | 114.5 (2) | C53—C35—C36—C37 | −130.4 (2) |
C13—C1—C2—C3 | −130.2 (2) | C47—C35—C36—C37 | 114.7 (2) |
C20—C2—C3—C4 | 157.62 (19) | C54—C36—C37—C63 | 87.3 (2) |
C1—C2—C3—C4 | 30.4 (2) | C35—C36—C37—C63 | −143.5 (2) |
C20—C2—C3—C29 | −78.0 (3) | C54—C36—C37—C38 | −148.1 (2) |
C1—C2—C3—C29 | 154.8 (2) | C35—C36—C37—C38 | −18.9 (2) |
C12—N1—C4—C3 | 169.2 (2) | C46—N3—C38—C39 | 65.6 (3) |
C1—N1—C4—C3 | 36.9 (2) | C35—N3—C38—C39 | −166.3 (2) |
C12—N1—C4—C5 | −68.2 (3) | C46—N3—C38—C37 | −171.9 (2) |
C1—N1—C4—C5 | 159.5 (2) | C35—N3—C38—C37 | −43.7 (2) |
C29—C3—C4—N1 | −164.70 (19) | C63—C37—C38—N3 | 163.32 (19) |
C2—C3—C4—N1 | −40.6 (2) | C36—C37—C38—N3 | 37.1 (2) |
C29—C3—C4—C5 | 78.0 (3) | C63—C37—C38—C39 | −77.6 (3) |
C2—C3—C4—C5 | −157.9 (2) | C36—C37—C38—C39 | 156.2 (2) |
N1—C4—C5—C6 | 51.7 (3) | N3—C38—C39—C40 | −44.3 (3) |
C3—C4—C5—C6 | 166.0 (2) | C37—C38—C39—C40 | −158.9 (2) |
C4—C5—C6—C11 | −20.3 (4) | C38—C39—C40—C45 | 14.0 (4) |
C4—C5—C6—C7 | 159.6 (3) | C38—C39—C40—C41 | −166.2 (2) |
C11—C6—C7—C8 | 0.9 (5) | C45—C40—C41—C42 | −0.7 (4) |
C5—C6—C7—C8 | −179.0 (3) | C39—C40—C41—C42 | 179.4 (3) |
C6—C7—C8—C9 | −0.9 (5) | C40—C41—C42—C43 | −0.2 (5) |
C7—C8—C9—C10 | 1.3 (6) | C41—C42—C43—C44 | 0.6 (5) |
C8—C9—C10—C11 | −1.6 (5) | C42—C43—C44—C45 | 0.0 (5) |
C9—C10—C11—C6 | 1.6 (5) | C41—C40—C45—C44 | 1.3 (4) |
C9—C10—C11—C12 | 180.0 (3) | C39—C40—C45—C44 | −178.9 (3) |
C7—C6—C11—C10 | −1.2 (4) | C41—C40—C45—C46 | 179.3 (3) |
C5—C6—C11—C10 | 178.7 (3) | C39—C40—C45—C46 | −0.9 (4) |
C7—C6—C11—C12 | −179.5 (3) | C43—C44—C45—C40 | −0.9 (4) |
C5—C6—C11—C12 | 0.3 (4) | C43—C44—C45—C46 | −179.0 (3) |
C4—N1—C12—C11 | 47.0 (3) | C38—N3—C46—C45 | −50.7 (3) |
C1—N1—C12—C11 | 175.6 (2) | C35—N3—C46—C45 | −175.4 (2) |
C10—C11—C12—N1 | 169.0 (3) | C40—C45—C46—N3 | 18.2 (4) |
C6—C11—C12—N1 | −12.7 (4) | C44—C45—C46—N3 | −163.8 (3) |
C14—N2—C13—O1 | −178.8 (3) | C48—N4—C47—O3 | −178.2 (3) |
C14—N2—C13—C1 | 0.8 (3) | C48—N4—C47—C35 | 2.8 (3) |
N1—C1—C13—O1 | −60.6 (3) | N3—C35—C47—O3 | 57.4 (3) |
C19—C1—C13—O1 | 179.0 (2) | C53—C35—C47—O3 | 177.8 (3) |
C2—C1—C13—O1 | 54.4 (3) | C36—C35—C47—O3 | −56.4 (3) |
N1—C1—C13—N2 | 119.8 (2) | N3—C35—C47—N4 | −123.6 (2) |
C19—C1—C13—N2 | −0.6 (2) | C53—C35—C47—N4 | −3.2 (2) |
C2—C1—C13—N2 | −125.2 (2) | C36—C35—C47—N4 | 122.6 (2) |
C13—N2—C14—C19 | −0.6 (3) | C47—N4—C48—C49 | 178.8 (3) |
C13—N2—C14—C15 | 178.0 (3) | C47—N4—C48—C53 | −1.1 (3) |
C19—C14—C15—C16 | 1.0 (5) | C53—C48—C49—C50 | 0.7 (5) |
N2—C14—C15—C16 | −177.4 (3) | N4—C48—C49—C50 | −179.1 (3) |
C14—C15—C16—C17 | −0.2 (6) | C48—C49—C50—C51 | 1.2 (6) |
C15—C16—C17—C18 | −0.8 (6) | C49—C50—C51—C52 | −2.2 (6) |
C16—C17—C18—C19 | 1.1 (5) | C50—C51—C52—C53 | 1.1 (5) |
C17—C18—C19—C14 | −0.3 (4) | C51—C52—C53—C48 | 0.8 (4) |
C17—C18—C19—C1 | 177.0 (3) | C51—C52—C53—C35 | 179.9 (3) |
C15—C14—C19—C18 | −0.7 (4) | C49—C48—C53—C52 | −1.8 (4) |
N2—C14—C19—C18 | 178.0 (2) | N4—C48—C53—C52 | 178.1 (2) |
C15—C14—C19—C1 | −178.6 (3) | C49—C48—C53—C35 | 179.0 (3) |
N2—C14—C19—C1 | 0.1 (3) | N4—C48—C53—C35 | −1.2 (3) |
N1—C1—C19—C18 | 61.0 (3) | N3—C35—C53—C52 | −54.7 (3) |
C13—C1—C19—C18 | −177.2 (3) | C47—C35—C53—C52 | −176.6 (3) |
C2—C1—C19—C18 | −58.0 (3) | C36—C35—C53—C52 | 65.2 (4) |
N1—C1—C19—C14 | −121.5 (2) | N3—C35—C53—C48 | 124.4 (2) |
C13—C1—C19—C14 | 0.3 (2) | C47—C35—C53—C48 | 2.6 (2) |
C2—C1—C19—C14 | 119.6 (2) | C36—C35—C53—C48 | −115.7 (2) |
C3—C2—C20—O2 | 2.9 (3) | C37—C36—C54—O4 | −2.0 (3) |
C1—C2—C20—O2 | 124.6 (2) | C35—C36—C54—O4 | −125.4 (3) |
C3—C2—C20—C21 | 179.9 (2) | C37—C36—C54—C55 | −178.1 (2) |
C1—C2—C20—C21 | −58.4 (3) | C35—C36—C54—C55 | 58.5 (3) |
O2—C20—C21—C22 | −13.8 (4) | O4—C54—C55—C56 | 14.1 (4) |
C2—C20—C21—C22 | 169.3 (2) | C36—C54—C55—C56 | −169.8 (2) |
C20—C21—C22—C23 | −177.4 (2) | C54—C55—C56—C57 | 177.0 (3) |
C21—C22—C23—C28 | 178.6 (3) | C55—C56—C57—C62 | −172.2 (3) |
C21—C22—C23—C24 | −1.6 (5) | C55—C56—C57—C58 | 8.0 (5) |
C28—C23—C24—C25 | −0.4 (5) | C62—C57—C58—C59 | 0.8 (5) |
C22—C23—C24—C25 | 179.8 (3) | C56—C57—C58—C59 | −179.4 (3) |
C23—C24—C25—C26 | −0.2 (5) | C57—C58—C59—C60 | 1.5 (6) |
C24—C25—C26—C27 | 0.7 (5) | C58—C59—C60—C61 | −2.9 (7) |
C25—C26—C27—C28 | −0.5 (5) | C59—C60—C61—C62 | 2.0 (8) |
C26—C27—C28—C23 | −0.1 (5) | C58—C57—C62—C61 | −1.8 (7) |
C24—C23—C28—C27 | 0.5 (5) | C56—C57—C62—C61 | 178.4 (4) |
C22—C23—C28—C27 | −179.7 (3) | C60—C61—C62—C57 | 0.4 (9) |
C4—C3—C29—C30 | 56.8 (3) | C38—C37—C63—C68 | 114.1 (3) |
C2—C3—C29—C30 | −61.0 (3) | C36—C37—C63—C68 | −126.8 (3) |
C4—C3—C29—C34 | −123.3 (3) | C38—C37—C63—C64 | −63.6 (3) |
C2—C3—C29—C34 | 118.8 (3) | C36—C37—C63—C64 | 55.4 (3) |
C34—C29—C30—C31 | 0.4 (4) | C68—C63—C64—C65 | −1.2 (4) |
C3—C29—C30—C31 | −179.7 (3) | C37—C63—C64—C65 | 176.6 (3) |
C29—C30—C31—C32 | −0.5 (5) | C63—C64—C65—C66 | 0.4 (5) |
C30—C31—C32—C33 | 0.0 (5) | C64—C65—C66—C67 | 0.5 (6) |
C31—C32—C33—C34 | 0.6 (6) | C65—C66—C67—C68 | −0.4 (6) |
C30—C29—C34—C33 | 0.2 (5) | C64—C63—C68—C67 | 1.2 (4) |
C3—C29—C34—C33 | −179.6 (3) | C37—C63—C68—C67 | −176.6 (3) |
C32—C33—C34—C29 | −0.8 (6) | C66—C67—C68—C63 | −0.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O4i | 0.86 | 2.19 | 3.023 (3) | 164 |
N4—H4A···O2ii | 0.86 | 2.23 | 3.047 (3) | 159 |
C2—H2A···O1 | 0.98 | 2.57 | 3.034 (3) | 109 |
C12—H12A···O1 | 0.97 | 2.54 | 3.201 (3) | 125 |
C37—H37···O4 | 0.98 | 2.44 | 2.784 (3) | 100 |
C56—H56···O4 | 0.93 | 2.51 | 2.830 (4) | 101 |
Symmetry codes: (i) x+1/2, −y+1, z; (ii) x−1/2, −y, z. |
Experimental details
Crystal data | |
Chemical formula | C34H28N2O2 |
Mr | 496.58 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 293 |
a, b, c (Å) | 19.301 (4), 14.725 (3), 18.583 (4) |
V (Å3) | 5281 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.28 × 0.24 × 0.23 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 44375, 6482, 5365 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.122, 1.12 |
No. of reflections | 6482 |
No. of parameters | 685 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.13 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PARST (Nardelli, 1995).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O4i | 0.86 | 2.19 | 3.023 (3) | 164.2 |
N4—H4A···O2ii | 0.86 | 2.23 | 3.047 (3) | 159.3 |
C2—H2A···O1 | 0.98 | 2.57 | 3.034 (3) | 108.8 |
C12—H12A···O1 | 0.97 | 2.54 | 3.201 (3) | 125.4 |
C37—H37···O4 | 0.98 | 2.44 | 2.784 (3) | 100.2 |
C56—H56···O4 | 0.93 | 2.51 | 2.830 (4) | 100.7 |
Symmetry codes: (i) x+1/2, −y+1, z; (ii) x−1/2, −y, z. |
Pyrrolidine occurs widely in nature and is a structural part of porphyrin heme, chlorophyll and vitamin B12. Pyrrolidine compounds have antifungal and antimicrobial activity (Amal Raj et al., 2003). The spiro ring system is a frequently encountered structural motif in many pharmacologically relevant alkaloids. Synthetic spiro-pyrrolidine derivatives have activity against the aldose reductase enzyme which controls influenza (Stylianakis et al., 2003). As spiropyrrolidine compounds are of great pharmaceutical importance, we have undertaken the three dimensional crystal structure determination of the title compound, C34 H28 N2 O2, by X-ray diffraction (Fig.1).
The bond lengths and angles are comparable with the literature values (Allen et al., 1987). The sum of the bond angles around N1 (339.5 (6)°) and N3 (336.0 (6)°) indicates the sp3 hybridization. The pyrrolidine ring in molecule A adopts a twisted conformation with a pseudo twofold axis passing through atom C1 and C3—C4 bond. In molecule B, it adopts an envelope conformation with atom C38 deviating by -0.608 (2)Å from the plane of rest of the atoms in the ring. The six membered rings N1/C4—C6/C11/C12 and N3/C38—C40/C45/C46 in molecules A and B, respectively, are non-planar. The oxindole ring in molecules A and B is planar with the dihedral angle between five and six membered rings being 2.3 (1) and 1.8 (1)°, respectively. Oxygen atoms O1 and O3 lie below the plane of the five membered rings in the oxindole moiety in molecule A and B by 0.021 (2) and 0.049 (2) Å, respectively.
The puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) for pyrrolidine ring N1/C1—C4 in the molecule A are q2 = 0.392 (3) Å, φ = 310.6 (4)° and Δ 2(C1) = 7.5 (2), for pyrrolidine ring N3/C35—C38 in the molecule B are q2 = 0.400 (3) Å, φ = 152.0 (4)° and Δ s(C38) = 9.7 (2), for six memebered rings (N1/C4—C6/C11/C12 and N3/C38—C40/C45/C46) in molecule A and B are q2 = 0.394 (3) Å; 0.369 (3) Å, q3 = 0.328 (3) Å; -0.314 (3) Å, QT = 0.513 (3) Å; 0.485 (3)Å and θ = 50.2 (3)°; s130.4(3)°, respectively.
The molecule is stabilized by weak C—H···O intramolecular interactions. The crystal packing is stabilized by two N—H···O intermolecular interactions. Atoms N2 and N4 act as donors to O4 (1/2 + x,1 - y,z) and O2 (-1/2 + x,-y,z), generating a chain running along b axis.