organic compounds
Methyl (3S,3′R)-1-methyl-2,2′′-dioxo-1′,2′,3′,5′,6′,7′,8′,8a′-octahydrodispiro[indoline-3,2′-indolizine-3′,3′′-indoline]-1′-carboxylate
aDepartment of Physics, S.M.K. Fomra Institute of Technology, Thaiyur, Chennai 603 103, India, bIndustrial Chemistry Laboratory, Central Leather Research Institute, Adyar, Chennai 600 020, India, and cDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
*Correspondence e-mail: a_sp59@yahoo.in
In the title compound, C25H25N3O4, the central pyrrolidine ring and the two pyrrolidine rings adopt twisted conformations, whereas the piperidine ring in the octahydroindolizine fused ring system adopts a chair conformation. The indoline ring systems are almost perpendicular with respect to the mean plane of the octahydroindolizine ring system, making dihedral angles of 84.4 (5) and 79.4 (5)°. The acetate group attached to the octahydroindolizine ring system assumes an extended conformation. In the crystal, N—H⋯O hydrogen bonds result in the formation of a helical C(7) chain running parallel to [101]. The crystal packing features C—H⋯O hydrogen bonds and C—H⋯π interactions.
Related literature
For the biological activity of compounds with spiro-pyrrolidine ring systems, see: Sundar et al. (2011); Crooks & Sommerville (1982); Stylianakis et al. (2003). For a related structure, see: Selvanayagam et al. (2012). For puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Nardelli et al. (1983).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812037531/zl2499sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037531/zl2499Isup2.hkl
A mixture of 1eq of (E)-methyl 2-(1-methyl-2-oxoindolin-3-ylidene) acetate, 1eq of isatin and 1.5eq of pipecolinic acid were dissolved in acetonitrile. This reaction mixture was refluxed at 80°C for 8 h. Completion of the reaction was monitored by thin layer
The reaction mixture was taken up in water, extracted with ethyl acetate and washed with water. The product was dried and purified by using ethyl acetate and hexanes (1:9) as the elutent to afford pure dispiro oxindole (yield: 78%, M.p.: 541 K). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in ethyl acetate at room temperature.All H atoms were fixed geometrically and allowed to ride on their parent atoms, with C—H distances fixed in the range 0.93–0.97 Å and N—H distances of 0.86 ° with Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq(C/N) for all other H atoms.
The spiro-pyrrolidine ring system is a structural motif present in many biologically important and pharmacologically relevant
Some derivatives are used as antimicrobial and antitumour agents (Sundar et al., 2011), or possess analgesic (Crooks & Sommerville, 1982) and anti-influenza virus (Stylianakis et al., 2003) activities. In view of this importance and in continuation of our work on the analyis of spiro-pyrrolidine derivatives, the of the title compound has been determined and the results are presented here.X-Ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The geometry of the pyrrolidine and indoline group systems are comparable with those of related structures (Selvanayagam et al., 2012). The sum of the angles at N1 [336.3 (1)°], N2[360.0 (1)°] and N3 [359.8 (1)°] of the pyrrolidine rings are in accordance with sp3 hybridizations for N1 and sp2 hybridizations for N2 and N3. The indoline ring systems [N2/C6/C11—C17 and N3/C7/C18—C24] make dihedral angles of 84.4 (5)° and 79.4 (5)° with respect to the mean plane of the octahydroindolizine ring system, which clearly shows the indoline rings attached to the octahydroindolizine ring system are almost perpendicular to each other. The acetate group assumes an extended conformation as can be seen from the torsion angle C8—C9—O1—C10 = -177.9 (2)°.
The pyrrolidine rings [N1/C5—C8, N2/C6/C15—C17 and N3/C7/C22—C24] adopt twisted conformations, with puckering parameters q2 and φ (Cremer & Pople, 1975) and the smallest displacement asymmetric parameters, Δ, (Nardelli et al., 1983) as follows: q2 = 0.4349 (1) Å; 0.1063 (1) Å & 0.1221 (1) Å, φ = 194.8 (2)°; 123.4 (8)° & 127.6 (7)°, Δ2[(C7) = 4.86 (12)°]; [(C15) = 0.51 (15)] & [(C22) = 1.72 (14)]. The piperidine ring adopts a chair conformation, with the puckering parameters q2 = 0.0284 (2) Å; q3 = -0.5721 (2) Å & φ = 118 (3) ° and the smallest displacement asymmetric parameter, Δs (C2 & C5) = 2.32 (13)°.
Two intermolecular N2—H2C···O4 (-1/2 + x,1/2 - y,-1/2 + z) and C2—H2A···O3 (1/2 + x,1/2 - y,1/2 + z) hydrogen bonds both result in the formation of helicsu2496al C11(7) chains running running parallel to [1 0 1]. The crystal packing is stabilized by C—H···O, N—H···O and C–H···π interactions (Table. 1).
For the biological activity of compounds with spiro-pyrrolidine ring systems, see: Sundar et al. (2011); Crooks & Sommerville (1982); Stylianakis et al. (2003). For a related structure, see: Selvanayagam et al. (2012). For puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Nardelli et al. (1983).
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C25H25N3O4 | F(000) = 912 |
Mr = 431.48 | Dx = 1.323 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6752 reflections |
a = 10.0516 (3) Å | θ = 2.0–31.0° |
b = 17.9539 (6) Å | µ = 0.09 mm−1 |
c = 12.4471 (4) Å | T = 293 K |
β = 105.347 (2)° | Block, white crystalline |
V = 2166.17 (12) Å3 | 0.25 × 0.22 × 0.19 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 6752 independent reflections |
Radiation source: fine-focus sealed tube | 4374 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω and φ scans | θmax = 31.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.978, Tmax = 0.983 | k = −25→25 |
27282 measured reflections | l = −17→17 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0675P)2 + 0.2828P] where P = (Fo2 + 2Fc2)/3 |
6752 reflections | (Δ/σ)max < 0.001 |
291 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C25H25N3O4 | V = 2166.17 (12) Å3 |
Mr = 431.48 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.0516 (3) Å | µ = 0.09 mm−1 |
b = 17.9539 (6) Å | T = 293 K |
c = 12.4471 (4) Å | 0.25 × 0.22 × 0.19 mm |
β = 105.347 (2)° |
Bruker APEXII CCD area-detector diffractometer | 6752 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4374 reflections with I > 2σ(I) |
Tmin = 0.978, Tmax = 0.983 | Rint = 0.033 |
27282 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.23 e Å−3 |
6752 reflections | Δρmin = −0.24 e Å−3 |
291 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 | ||
C1 | 0.39509 (15) | 0.18055 (7) | 0.38847 (13) | 0.0389 (3) | |
H1A | 0.3661 | 0.1786 | 0.3077 | 0.047* | |
H1B | 0.3520 | 0.1394 | 0.4172 | 0.047* | |
C2 | 0.55128 (16) | 0.17364 (9) | 0.42873 (14) | 0.0475 (4) | |
H2A | 0.5783 | 0.1691 | 0.5092 | 0.057* | |
H2B | 0.5803 | 0.1288 | 0.3979 | 0.057* | |
C3 | 0.62352 (16) | 0.24026 (9) | 0.39500 (16) | 0.0528 (4) | |
H3A | 0.6072 | 0.2411 | 0.3146 | 0.063* | |
H3B | 0.7222 | 0.2362 | 0.4279 | 0.063* | |
C4 | 0.57047 (14) | 0.31205 (8) | 0.43361 (14) | 0.0421 (3) | |
H4A | 0.5954 | 0.3137 | 0.5144 | 0.051* | |
H4B | 0.6125 | 0.3545 | 0.4071 | 0.051* | |
C5 | 0.41569 (13) | 0.31611 (7) | 0.38920 (11) | 0.0312 (3) | |
H5 | 0.3898 | 0.3183 | 0.3076 | 0.037* | |
C6 | 0.20445 (12) | 0.26486 (7) | 0.39870 (10) | 0.0296 (3) | |
C7 | 0.19738 (12) | 0.35157 (7) | 0.42780 (10) | 0.0287 (3) | |
C8 | 0.34676 (13) | 0.37893 (7) | 0.43616 (11) | 0.0314 (3) | |
H8 | 0.3936 | 0.3815 | 0.5159 | 0.038* | |
C9 | 0.35351 (14) | 0.45585 (7) | 0.39114 (14) | 0.0411 (3) | |
C11 | 0.14592 (16) | 0.18861 (8) | 0.56175 (13) | 0.0434 (3) | |
H11 | 0.2242 | 0.2033 | 0.6161 | 0.052* | |
C12 | 0.04945 (18) | 0.14130 (9) | 0.58827 (16) | 0.0545 (4) | |
H12 | 0.0624 | 0.1252 | 0.6613 | 0.065* | |
C13 | −0.06500 (17) | 0.11821 (9) | 0.50720 (17) | 0.0571 (5) | |
H13 | −0.1290 | 0.0872 | 0.5268 | 0.068* | |
C14 | −0.08675 (15) | 0.14005 (8) | 0.39767 (15) | 0.0475 (4) | |
H14 | −0.1628 | 0.1233 | 0.3428 | 0.057* | |
C15 | 0.00836 (13) | 0.18761 (7) | 0.37260 (12) | 0.0357 (3) | |
C16 | 0.12326 (13) | 0.21318 (7) | 0.45356 (11) | 0.0332 (3) | |
C17 | 0.12949 (14) | 0.25295 (7) | 0.27335 (11) | 0.0349 (3) | |
C18 | 0.04727 (17) | 0.41569 (8) | 0.24454 (12) | 0.0447 (3) | |
H18 | 0.1102 | 0.4081 | 0.2027 | 0.054* | |
C19 | −0.07771 (19) | 0.45125 (9) | 0.19857 (15) | 0.0575 (5) | |
H19 | −0.0988 | 0.4670 | 0.1248 | 0.069* | |
C20 | −0.17011 (18) | 0.46340 (10) | 0.25991 (16) | 0.0591 (5) | |
H20 | −0.2529 | 0.4873 | 0.2269 | 0.071* | |
C21 | −0.14357 (15) | 0.44103 (8) | 0.36957 (15) | 0.0485 (4) | |
H21 | −0.2065 | 0.4495 | 0.4112 | 0.058* | |
C22 | −0.01959 (13) | 0.40548 (7) | 0.41489 (12) | 0.0344 (3) | |
C23 | 0.07557 (13) | 0.39205 (7) | 0.35351 (11) | 0.0325 (3) | |
C24 | 0.16580 (13) | 0.35799 (7) | 0.54149 (11) | 0.0315 (3) | |
N1 | 0.35207 (10) | 0.25114 (6) | 0.42717 (9) | 0.0302 (2) | |
N2 | 0.01226 (12) | 0.21398 (7) | 0.26806 (10) | 0.0399 (3) | |
H2C | −0.0517 | 0.2065 | 0.2077 | 0.048* | |
N3 | 0.03374 (11) | 0.38133 (6) | 0.52466 (10) | 0.0349 (3) | |
O1 | 0.38982 (14) | 0.45660 (6) | 0.29638 (11) | 0.0609 (3) | |
O2 | 0.33032 (14) | 0.51090 (6) | 0.43692 (13) | 0.0672 (4) | |
O3 | 0.16969 (12) | 0.27330 (6) | 0.19483 (8) | 0.0488 (3) | |
O4 | 0.24468 (10) | 0.34408 (6) | 0.63171 (8) | 0.0432 (2) | |
C25 | −0.03937 (16) | 0.38432 (10) | 0.61061 (14) | 0.0509 (4) | |
H25A | 0.0221 | 0.3706 | 0.6809 | 0.076* | |
H25B | −0.1159 | 0.3504 | 0.5924 | 0.076* | |
H25C | −0.0727 | 0.4340 | 0.6154 | 0.076* | |
C10 | 0.4028 (3) | 0.52914 (11) | 0.2504 (2) | 0.0971 (8) | |
H10A | 0.3167 | 0.5553 | 0.2378 | 0.146* | |
H10B | 0.4268 | 0.5236 | 0.1811 | 0.146* | |
H10C | 0.4737 | 0.5569 | 0.3017 | 0.146* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0442 (8) | 0.0309 (6) | 0.0414 (8) | 0.0046 (6) | 0.0107 (6) | −0.0048 (6) |
C2 | 0.0450 (8) | 0.0427 (8) | 0.0523 (9) | 0.0141 (6) | 0.0088 (7) | −0.0067 (7) |
C3 | 0.0377 (8) | 0.0529 (9) | 0.0708 (11) | 0.0085 (7) | 0.0194 (8) | −0.0090 (8) |
C4 | 0.0315 (7) | 0.0413 (7) | 0.0546 (9) | 0.0007 (6) | 0.0134 (6) | −0.0045 (7) |
C5 | 0.0314 (6) | 0.0300 (6) | 0.0329 (7) | 0.0007 (5) | 0.0099 (5) | −0.0019 (5) |
C6 | 0.0296 (6) | 0.0300 (6) | 0.0278 (6) | −0.0002 (5) | 0.0050 (5) | −0.0023 (5) |
C7 | 0.0267 (6) | 0.0308 (6) | 0.0269 (6) | 0.0012 (5) | 0.0042 (5) | −0.0024 (5) |
C8 | 0.0281 (6) | 0.0311 (6) | 0.0345 (7) | −0.0006 (5) | 0.0072 (5) | −0.0050 (5) |
C9 | 0.0332 (7) | 0.0304 (7) | 0.0605 (10) | −0.0013 (5) | 0.0137 (7) | −0.0040 (6) |
C11 | 0.0428 (8) | 0.0429 (8) | 0.0431 (8) | −0.0014 (6) | 0.0086 (6) | 0.0068 (6) |
C12 | 0.0558 (10) | 0.0529 (9) | 0.0585 (11) | 0.0014 (8) | 0.0218 (8) | 0.0191 (8) |
C13 | 0.0422 (9) | 0.0482 (9) | 0.0847 (14) | −0.0038 (7) | 0.0235 (9) | 0.0130 (9) |
C14 | 0.0323 (7) | 0.0394 (8) | 0.0696 (11) | −0.0032 (6) | 0.0114 (7) | −0.0023 (7) |
C15 | 0.0296 (6) | 0.0304 (6) | 0.0457 (8) | 0.0032 (5) | 0.0073 (6) | −0.0040 (6) |
C16 | 0.0320 (6) | 0.0295 (6) | 0.0371 (7) | −0.0001 (5) | 0.0077 (5) | −0.0007 (5) |
C17 | 0.0362 (7) | 0.0333 (6) | 0.0312 (7) | 0.0025 (5) | 0.0021 (5) | −0.0042 (5) |
C18 | 0.0539 (9) | 0.0390 (8) | 0.0361 (8) | 0.0001 (6) | 0.0031 (7) | 0.0017 (6) |
C19 | 0.0641 (11) | 0.0469 (9) | 0.0455 (9) | 0.0034 (8) | −0.0136 (8) | 0.0082 (7) |
C20 | 0.0417 (9) | 0.0468 (9) | 0.0727 (13) | 0.0083 (7) | −0.0129 (8) | 0.0059 (8) |
C21 | 0.0304 (7) | 0.0407 (8) | 0.0698 (11) | 0.0028 (6) | 0.0053 (7) | 0.0004 (8) |
C22 | 0.0288 (6) | 0.0293 (6) | 0.0423 (8) | −0.0009 (5) | 0.0046 (6) | −0.0011 (5) |
C23 | 0.0308 (6) | 0.0299 (6) | 0.0333 (7) | 0.0006 (5) | 0.0020 (5) | −0.0005 (5) |
C24 | 0.0306 (6) | 0.0311 (6) | 0.0319 (7) | 0.0016 (5) | 0.0067 (5) | −0.0028 (5) |
N1 | 0.0283 (5) | 0.0279 (5) | 0.0333 (6) | 0.0015 (4) | 0.0061 (4) | −0.0021 (4) |
N2 | 0.0341 (6) | 0.0414 (6) | 0.0375 (6) | −0.0029 (5) | −0.0020 (5) | −0.0079 (5) |
N3 | 0.0319 (6) | 0.0375 (6) | 0.0366 (6) | 0.0026 (5) | 0.0115 (5) | −0.0006 (5) |
O1 | 0.0904 (9) | 0.0347 (6) | 0.0664 (8) | −0.0031 (6) | 0.0362 (7) | 0.0076 (5) |
O2 | 0.0742 (8) | 0.0343 (6) | 0.1035 (11) | 0.0019 (5) | 0.0418 (8) | −0.0131 (6) |
O3 | 0.0554 (6) | 0.0600 (7) | 0.0290 (5) | −0.0038 (5) | 0.0078 (5) | −0.0021 (5) |
O4 | 0.0426 (6) | 0.0548 (6) | 0.0282 (5) | 0.0092 (5) | 0.0024 (4) | −0.0019 (4) |
C25 | 0.0466 (9) | 0.0592 (10) | 0.0551 (10) | 0.0026 (7) | 0.0280 (8) | −0.0015 (8) |
C10 | 0.149 (2) | 0.0460 (11) | 0.110 (2) | −0.0063 (13) | 0.0586 (18) | 0.0246 (12) |
C1—N1 | 1.4613 (16) | C12—H12 | 0.9300 |
C1—C2 | 1.521 (2) | C13—C14 | 1.379 (3) |
C1—H1A | 0.9700 | C13—H13 | 0.9300 |
C1—H1B | 0.9700 | C14—C15 | 1.3778 (19) |
C2—C3 | 1.515 (2) | C14—H14 | 0.9300 |
C2—H2A | 0.9700 | C15—C16 | 1.394 (2) |
C2—H2B | 0.9700 | C15—N2 | 1.3949 (19) |
C3—C4 | 1.521 (2) | C17—O3 | 1.2087 (17) |
C3—H3A | 0.9700 | C17—N2 | 1.3570 (18) |
C3—H3B | 0.9700 | C18—C23 | 1.3772 (19) |
C4—C5 | 1.5087 (19) | C18—C19 | 1.390 (2) |
C4—H4A | 0.9700 | C18—H18 | 0.9300 |
C4—H4B | 0.9700 | C19—C20 | 1.367 (3) |
C5—N1 | 1.4672 (15) | C19—H19 | 0.9300 |
C5—C8 | 1.5193 (16) | C20—C21 | 1.380 (3) |
C5—H5 | 0.9800 | C20—H20 | 0.9300 |
C6—N1 | 1.4525 (15) | C21—C22 | 1.3807 (19) |
C6—C16 | 1.5126 (17) | C21—H21 | 0.9300 |
C6—C17 | 1.5574 (19) | C22—C23 | 1.3942 (18) |
C6—C7 | 1.6041 (17) | C22—N3 | 1.3980 (18) |
C7—C23 | 1.5109 (18) | C24—O4 | 1.2169 (16) |
C7—C24 | 1.5344 (17) | C24—N3 | 1.3543 (16) |
C7—C8 | 1.5569 (17) | N2—H2C | 0.8600 |
C8—C9 | 1.4987 (18) | N3—C25 | 1.4503 (17) |
C8—H8 | 0.9800 | O1—C10 | 1.442 (2) |
C9—O2 | 1.1942 (17) | C25—H25A | 0.9600 |
C9—O1 | 1.3237 (19) | C25—H25B | 0.9600 |
C11—C16 | 1.378 (2) | C25—H25C | 0.9600 |
C11—C12 | 1.393 (2) | C10—H10A | 0.9600 |
C11—H11 | 0.9300 | C10—H10B | 0.9600 |
C12—C13 | 1.378 (3) | C10—H10C | 0.9600 |
N1—C1—C2 | 109.38 (11) | C12—C13—H13 | 119.3 |
N1—C1—H1A | 109.8 | C14—C13—H13 | 119.3 |
C2—C1—H1A | 109.8 | C15—C14—C13 | 117.52 (15) |
N1—C1—H1B | 109.8 | C15—C14—H14 | 121.2 |
C2—C1—H1B | 109.8 | C13—C14—H14 | 121.2 |
H1A—C1—H1B | 108.2 | C14—C15—C16 | 122.15 (14) |
C3—C2—C1 | 111.89 (13) | C14—C15—N2 | 127.88 (14) |
C3—C2—H2A | 109.2 | C16—C15—N2 | 109.88 (12) |
C1—C2—H2A | 109.2 | C11—C16—C15 | 119.47 (13) |
C3—C2—H2B | 109.2 | C11—C16—C6 | 131.94 (12) |
C1—C2—H2B | 109.2 | C15—C16—C6 | 108.57 (12) |
H2A—C2—H2B | 107.9 | O3—C17—N2 | 126.05 (13) |
C2—C3—C4 | 110.35 (12) | O3—C17—C6 | 126.30 (12) |
C2—C3—H3A | 109.6 | N2—C17—C6 | 107.64 (11) |
C4—C3—H3A | 109.6 | C23—C18—C19 | 118.39 (15) |
C2—C3—H3B | 109.6 | C23—C18—H18 | 120.8 |
C4—C3—H3B | 109.6 | C19—C18—H18 | 120.8 |
H3A—C3—H3B | 108.1 | C20—C19—C18 | 121.13 (16) |
C5—C4—C3 | 109.82 (12) | C20—C19—H19 | 119.4 |
C5—C4—H4A | 109.7 | C18—C19—H19 | 119.4 |
C3—C4—H4A | 109.7 | C19—C20—C21 | 121.61 (15) |
C5—C4—H4B | 109.7 | C19—C20—H20 | 119.2 |
C3—C4—H4B | 109.7 | C21—C20—H20 | 119.2 |
H4A—C4—H4B | 108.2 | C20—C21—C22 | 117.14 (15) |
N1—C5—C4 | 109.79 (11) | C20—C21—H21 | 121.4 |
N1—C5—C8 | 100.62 (9) | C22—C21—H21 | 121.4 |
C4—C5—C8 | 115.22 (11) | C21—C22—C23 | 122.14 (14) |
N1—C5—H5 | 110.3 | C21—C22—N3 | 127.87 (13) |
C4—C5—H5 | 110.3 | C23—C22—N3 | 109.91 (11) |
C8—C5—H5 | 110.3 | C18—C23—C22 | 119.57 (13) |
N1—C6—C16 | 115.10 (10) | C18—C23—C7 | 132.35 (12) |
N1—C6—C17 | 114.40 (10) | C22—C23—C7 | 108.08 (11) |
C16—C6—C17 | 101.08 (10) | O4—C24—N3 | 125.36 (12) |
N1—C6—C7 | 102.30 (9) | O4—C24—C7 | 126.32 (11) |
C16—C6—C7 | 115.59 (10) | N3—C24—C7 | 108.31 (11) |
C17—C6—C7 | 108.71 (10) | C6—N1—C1 | 116.04 (10) |
C23—C7—C24 | 101.32 (10) | C6—N1—C5 | 106.90 (10) |
C23—C7—C8 | 120.00 (11) | C1—N1—C5 | 113.03 (10) |
C24—C7—C8 | 110.24 (10) | C17—N2—C15 | 111.60 (11) |
C23—C7—C6 | 113.94 (10) | C17—N2—H2C | 124.2 |
C24—C7—C6 | 108.26 (10) | C15—N2—H2C | 124.2 |
C8—C7—C6 | 102.82 (9) | C24—N3—C22 | 110.72 (11) |
C9—C8—C5 | 118.03 (11) | C24—N3—C25 | 124.37 (13) |
C9—C8—C7 | 113.84 (10) | C22—N3—C25 | 124.84 (12) |
C5—C8—C7 | 105.66 (10) | C9—O1—C10 | 115.98 (15) |
C9—C8—H8 | 106.2 | N3—C25—H25A | 109.5 |
C5—C8—H8 | 106.2 | N3—C25—H25B | 109.5 |
C7—C8—H8 | 106.2 | H25A—C25—H25B | 109.5 |
O2—C9—O1 | 123.47 (14) | N3—C25—H25C | 109.5 |
O2—C9—C8 | 123.39 (15) | H25A—C25—H25C | 109.5 |
O1—C9—C8 | 113.14 (12) | H25B—C25—H25C | 109.5 |
C16—C11—C12 | 118.79 (15) | O1—C10—H10A | 109.5 |
C16—C11—H11 | 120.6 | O1—C10—H10B | 109.5 |
C12—C11—H11 | 120.6 | H10A—C10—H10B | 109.5 |
C13—C12—C11 | 120.57 (16) | O1—C10—H10C | 109.5 |
C13—C12—H12 | 119.7 | H10A—C10—H10C | 109.5 |
C11—C12—H12 | 119.7 | H10B—C10—H10C | 109.5 |
C12—C13—C14 | 121.43 (15) | ||
N1—C1—C2—C3 | −54.22 (17) | C7—C6—C17—N2 | −111.06 (11) |
C1—C2—C3—C4 | 53.92 (19) | C23—C18—C19—C20 | 0.7 (2) |
C2—C3—C4—C5 | −55.34 (18) | C18—C19—C20—C21 | 0.0 (3) |
C3—C4—C5—N1 | 58.10 (15) | C19—C20—C21—C22 | −0.2 (2) |
C3—C4—C5—C8 | 170.81 (12) | C20—C21—C22—C23 | −0.3 (2) |
N1—C6—C7—C23 | 147.66 (10) | C20—C21—C22—N3 | 176.32 (14) |
C16—C6—C7—C23 | −86.48 (13) | C19—C18—C23—C22 | −1.2 (2) |
C17—C6—C7—C23 | 26.31 (14) | C19—C18—C23—C7 | 179.05 (14) |
N1—C6—C7—C24 | −100.46 (11) | C21—C22—C23—C18 | 1.0 (2) |
C16—C6—C7—C24 | 25.40 (14) | N3—C22—C23—C18 | −176.14 (12) |
C17—C6—C7—C24 | 138.19 (10) | C21—C22—C23—C7 | −179.20 (12) |
N1—C6—C7—C8 | 16.20 (11) | N3—C22—C23—C7 | 3.66 (15) |
C16—C6—C7—C8 | 142.06 (11) | C24—C7—C23—C18 | 170.03 (14) |
C17—C6—C7—C8 | −105.16 (11) | C8—C7—C23—C18 | 48.5 (2) |
N1—C5—C8—C9 | −163.80 (11) | C6—C7—C23—C18 | −73.96 (18) |
C4—C5—C8—C9 | 78.22 (16) | C24—C7—C23—C22 | −9.74 (13) |
N1—C5—C8—C7 | −35.14 (12) | C8—C7—C23—C22 | −131.27 (12) |
C4—C5—C8—C7 | −153.12 (11) | C6—C7—C23—C22 | 106.27 (12) |
C23—C7—C8—C9 | 15.14 (16) | C23—C7—C24—O4 | −167.64 (13) |
C24—C7—C8—C9 | −101.89 (13) | C8—C7—C24—O4 | −39.52 (17) |
C6—C7—C8—C9 | 142.87 (11) | C6—C7—C24—O4 | 72.24 (16) |
C23—C7—C8—C5 | −115.95 (12) | C23—C7—C24—N3 | 12.89 (13) |
C24—C7—C8—C5 | 127.02 (11) | C8—C7—C24—N3 | 141.01 (11) |
C6—C7—C8—C5 | 11.78 (12) | C6—C7—C24—N3 | −107.23 (11) |
C5—C8—C9—O2 | −163.28 (14) | C16—C6—N1—C1 | 66.27 (14) |
C7—C8—C9—O2 | 72.00 (19) | C17—C6—N1—C1 | −50.20 (15) |
C5—C8—C9—O1 | 15.76 (18) | C7—C6—N1—C1 | −167.55 (10) |
C7—C8—C9—O1 | −108.95 (14) | C16—C6—N1—C5 | −166.61 (10) |
C16—C11—C12—C13 | 1.4 (2) | C17—C6—N1—C5 | 76.93 (12) |
C11—C12—C13—C14 | 1.0 (3) | C7—C6—N1—C5 | −40.43 (11) |
C12—C13—C14—C15 | −1.8 (2) | C2—C1—N1—C6 | −177.87 (11) |
C13—C14—C15—C16 | 0.2 (2) | C2—C1—N1—C5 | 58.12 (15) |
C13—C14—C15—N2 | 176.36 (14) | C4—C5—N1—C6 | 170.13 (10) |
C12—C11—C16—C15 | −2.9 (2) | C8—C5—N1—C6 | 48.25 (12) |
C12—C11—C16—C6 | 178.76 (14) | C4—C5—N1—C1 | −60.98 (14) |
C14—C15—C16—C11 | 2.1 (2) | C8—C5—N1—C1 | 177.14 (10) |
N2—C15—C16—C11 | −174.62 (12) | O3—C17—N2—C15 | 169.09 (14) |
C14—C15—C16—C6 | −179.17 (12) | C6—C17—N2—C15 | −9.49 (14) |
N2—C15—C16—C6 | 4.08 (14) | C14—C15—N2—C17 | −172.88 (13) |
N1—C6—C16—C11 | 45.73 (19) | C16—C15—N2—C17 | 3.64 (15) |
C17—C6—C16—C11 | 169.56 (14) | O4—C24—N3—C22 | 168.88 (13) |
C7—C6—C16—C11 | −73.29 (18) | C7—C24—N3—C22 | −11.64 (14) |
N1—C6—C16—C15 | −132.75 (11) | O4—C24—N3—C25 | −8.2 (2) |
C17—C6—C16—C15 | −8.92 (13) | C7—C24—N3—C25 | 171.31 (12) |
C7—C6—C16—C15 | 108.23 (12) | C21—C22—N3—C24 | −171.74 (14) |
N1—C6—C17—O3 | −43.25 (18) | C23—C22—N3—C24 | 5.19 (15) |
C16—C6—C17—O3 | −167.55 (14) | C21—C22—N3—C25 | 5.3 (2) |
C7—C6—C17—O3 | 70.37 (16) | C23—C22—N3—C25 | −177.78 (13) |
N1—C6—C17—N2 | 135.32 (11) | O2—C9—O1—C10 | 1.1 (3) |
C16—C6—C17—N2 | 11.02 (13) | C8—C9—O1—C10 | −177.99 (17) |
Cg6 is the centroid of the C18–C23 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O4i | 0.86 | 2.21 | 2.9639 (15) | 146 |
C2—H2A···O3ii | 0.97 | 2.48 | 3.348 (2) | 150 |
C25—H25C···Cg6iii | 0.96 | 2.81 | 3.5617 (19) | 135 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C25H25N3O4 |
Mr | 431.48 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.0516 (3), 17.9539 (6), 12.4471 (4) |
β (°) | 105.347 (2) |
V (Å3) | 2166.17 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.25 × 0.22 × 0.19 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.978, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27282, 6752, 4374 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.724 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.143, 1.03 |
No. of reflections | 6752 |
No. of parameters | 291 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.24 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Cg6 is the centroid of the C18–C23 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O4i | 0.86 | 2.21 | 2.9639 (15) | 146.3 |
C2—H2A···O3ii | 0.97 | 2.48 | 3.348 (2) | 149.5 |
C25—H25C···Cg6iii | 0.96 | 2.81 | 3.5617 (19) | 135 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1. |
Acknowledgements
The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection. ASP thanks the University Grants Commission, India, for a Minor Research Project.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The spiro-pyrrolidine ring system is a structural motif present in many biologically important and pharmacologically relevant alkaloids. Some derivatives are used as antimicrobial and antitumour agents (Sundar et al., 2011), or possess analgesic (Crooks & Sommerville, 1982) and anti-influenza virus (Stylianakis et al., 2003) activities. In view of this importance and in continuation of our work on the crystal structure analyis of spiro-pyrrolidine derivatives, the crystal structure of the title compound has been determined and the results are presented here.
X-Ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The geometry of the pyrrolidine and indoline group systems are comparable with those of related structures (Selvanayagam et al., 2012). The sum of the angles at N1 [336.3 (1)°], N2[360.0 (1)°] and N3 [359.8 (1)°] of the pyrrolidine rings are in accordance with sp3 hybridizations for N1 and sp2 hybridizations for N2 and N3. The indoline ring systems [N2/C6/C11—C17 and N3/C7/C18—C24] make dihedral angles of 84.4 (5)° and 79.4 (5)° with respect to the mean plane of the octahydroindolizine ring system, which clearly shows the indoline rings attached to the octahydroindolizine ring system are almost perpendicular to each other. The acetate group assumes an extended conformation as can be seen from the torsion angle C8—C9—O1—C10 = -177.9 (2)°.
The pyrrolidine rings [N1/C5—C8, N2/C6/C15—C17 and N3/C7/C22—C24] adopt twisted conformations, with puckering parameters q2 and φ (Cremer & Pople, 1975) and the smallest displacement asymmetric parameters, Δ, (Nardelli et al., 1983) as follows: q2 = 0.4349 (1) Å; 0.1063 (1) Å & 0.1221 (1) Å, φ = 194.8 (2)°; 123.4 (8)° & 127.6 (7)°, Δ2[(C7) = 4.86 (12)°]; [(C15) = 0.51 (15)] & [(C22) = 1.72 (14)]. The piperidine ring adopts a chair conformation, with the puckering parameters q2 = 0.0284 (2) Å; q3 = -0.5721 (2) Å & φ = 118 (3) ° and the smallest displacement asymmetric parameter, Δs (C2 & C5) = 2.32 (13)°.
Two intermolecular N2—H2C···O4 (-1/2 + x,1/2 - y,-1/2 + z) and C2—H2A···O3 (1/2 + x,1/2 - y,1/2 + z) hydrogen bonds both result in the formation of helicsu2496al C11(7) chains running running parallel to [1 0 1]. The crystal packing is stabilized by C—H···O, N—H···O and C–H···π interactions (Table. 1).