In the crystal structure of the title compound, a dispiro[indoline-3,2′-pyrrolidine-3′,6′′-isoquinoline]-2,5′′-dione, C—H⋯O hydrogen bonding predominates, linking molecules to form chains propagating along [100].
Keywords: crystal structure, dispiro, indoline, pyrrolidine, isoquinoline, hydrogen bonding, Hirshfeld surface analysis
Abstract
In the title dispiro compound, C32H26ClN3O2, the cyclohexanone ring of the isoquinoline unit has a distorted envelope conformation, with the methylene C atom adjacent to the spiro C atom as the flap. The central 1-methylpyrrolidine ring has an envelope conformation with the N atom as the flap. The mean planes of the indolin-2-one ring system, the chlorobenzene ring and the isoquinoline ring system are inclined to the mean plane of the central 1-methylpyrrolidine ring by 87.95 (11), 71.01 (12) and 88.81 (10)°, respectively. There are two short C—H⋯O intramolecular contacts present. In the crystal, molecules are linked via C—H⋯ O hydrogen bonds, forming chains along the a-axis direction. The NH H atom is involved in a weak N—H⋯O hydrogen bond with the same carbonyl O atom. There are no further significant intermolecular contacts present. The largest contribution to the overall Hirshfeld surface of 52.3% is due to H—H contacts.
Chemical context
Spiro scaffolds are being used more and more in drug discovery because of their built-in three-dimensionality and structural variations, resulting in new synthetic routes to introduce spiro building blocks into more pharmaceutically active molecules (Kobayashi et al., 1991 ▸; James et al., 1991 ▸). The spiro-pyrrolidine ring system is a structural motif present in many biologically important and pharmacologically relevant alkaloids. Spiro-pyrrolidine-indolin-2-one ring systems are also found in a number of alkaloids of biological importance (Hilton et al., 2000 ▸). 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, the primary goal for the X-ray analyses of the title compound is to obtain detailed information on the structural conformation that may be useful in understanding the chemical reactivity of such compounds.
Structural commentary
The molecular structure of the title molecule is shown in Fig. 1 ▸. There are two short C—H⋯O intramolecular contacts present (Table 1 ▸). In the isoquinoline ring system (N3/C3/C31–C38) the cyclohexanone ring (C3/C31–C38) adopts a distorted envelope conformation [puckering parameters: Q = 0.500 (2) Å, θ = 63.7 (2)°, φ = 308.9 (3)°], with atom C38 as the flap. The pyridine ring (N3/C32–C36) has a shallow twist-boat conformation [puckering parameters: Q = 0.094 (2) Å, θ = 92.3 (13)°, φ = 84.5 (13)°]. Their mean planes are inclined to each other by 14.06 (10)°, and the phenyl ring (C51–C56) is inclined to the pyridine ring mean plane by 22.35 (12)°.
Figure 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids and atom labelling. The intramolecular C—H⋯O contacts (see Table 1 ▸) are shown as dashed lines.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C22—H22⋯O2 | 0.93 | 2.57 | 3.227 (3) | 128 |
| C38—H38A⋯O1 | 0.97 | 2.46 | 3.135 (3) | 127 |
| C37—H37A⋯O2i | 0.97 | 2.38 | 3.159 (3) | 137 |
| N2—H2⋯O2i | 0.88 (3) | 2.50 (2) | 2.911 (3) | 109.0 (19) |
Symmetry code: (i) 
.
In the indolin-2-one ring system (N2/C2/C21–C27), the benzene (C21–C26) and pyrrolidine (N2/C2/C21/C26/C27) rings make a dihedral angle of 2.45 (12)°, while the keto atom O1 deviates from the attached pyrrolidine ring by 0.043 (1) Å. The 1-methylpyrrole ring (N1/C2–C5) has an envelope conformation with atom N1 as the flap [puckering parameters: Q = 0.094 (2) Å, θ = 92.3 (13)°, φ = 84.5 (13)°]. The mean planes of the indolin-2-one ring system, the chlorobenzene (C41–C46) ring and the isoquinoline (N3/C3/C31–C38) ring system are inclined to the mean plane of the central 1-methylpyrrolidine (N1/C2–C5) ring by 87.95 (11), 71.01 (12) and 88.81 (10)°, respectively. The sum of the bond angles around atoms N1 and N2 are 333.6 and 358.6°, respectively, indicating a pyramidal geometry and sp3 hybridization.
Supramolecular features
In the crystal, molecules are linked by C—H⋯O hydrogen bonds and a weak N—H⋯O hydrogen bond, forming chains propagating along the a-axis direction (Fig. 2 ▸ and Table 1 ▸). There are no further significant intermolecular interactions present.
Figure 2.
A view along the b axis of the crystal packing of the title compound, illustrating the formation of the hydrogen-bonded (dashed lines; Table 1 ▸) chains running along the a-axis direction. H atoms not involved in these interactions have been omitted for clarity.
Database survey
A search of the Cambridge Structural Database (Version 5.39, last update February 2018; Groom et al., 2016 ▸) for the central dispiro fragment, 1′-methyldispiro[cyclohexane-1,3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione (see Fig. 3 ▸), gave eight hits of which coordinates were available for six structures. Two compounds closely resemble the title compound, viz. 4′-(4-chlorophenyl)-1′-methyl-3,4-dihydro-1H-dispiro[acridine-2,3′- pyrrolidine-2′,3′′-indole]-1,2′′(1′′H)-dione methanol solvate (CSD refcode NAQCAL: Maheswari et al., 2012 ▸), and 4′-(2,4-dichlorophenyl)-1′,3′′-dimethyl-1′′-phenyl-7′′,8′′-dihydrodispiro[indole-3,2′-pyrrolidine-3′,6′′-pyrazolo[3,4-b]quinoline]-2,5′′(1H,1′′H)-dione chloroform solvate (UQIROD; Sumesh et al., 2016 ▸). In both compounds, the mean plane of the 1-methylpyrrolidine ring was found to be almost perpendicular to the mean plane of the indoline ring system and the mean plane of the cyclohexanone ring, similar to the situation in the title compound, see Section 2 Structural commentary.
Figure 3.
Structural fragment for the CSD search.
Hirshfeld Analysis
The program CrystalExplorer (Wolff et al., 2012 ▸) was used to generate the Hirshfeld surfaces mapped over d norm, and the electrostatic potential for the title compound. The contact distances, d i and d e, from the Hirshfeld surface to the nearest atom, inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of d norm. Two-dimensional fingerprint plots (Rohl et al., 2008 ▸) provide an indication of the intermolecular contacts in the crystal.
The hydrogen-bonding network generated in the crystal can be visualized using Hirshfeld surface analysis. The bright-red spots on the Hirshfeld surface mapped over d norm (Fig. 4 ▸), with labels H2 and H37A, on the surface represent donors for potential hydrogen bonds (see Table 1 ▸); the corresponding acceptor on the surface appears as a bright-red spot at atom O2.
Figure 4.
d norm mapped on the Hirshfeld surface for visualizing the contacts of the title compound. Dotted lines indicate hydrogen bonds.
The overall two-dimensional fingerprint plot is illustrated in Fig. 5 ▸ a, and those delineated into C⋯H/H⋯C, Cl⋯H/H⋯Cl, H⋯H, N⋯H/H⋯·N and O⋯H/H⋯O in Fig. 5 ▸ b–f, respectively. The greatest contribution to the overall Hirshfeld surface, i.e. 52.3%, is due to H⋯H contacts (Fig. 5 ▸ d; widely scattered points with a high concentration in the middle region, shown in green). The relative contributions of the other different intermolecular interactions to the Hirshfeld surface in descending order are: C⋯H/H⋯C (23.3%), O⋯H/H⋯O (8.5%), Cl⋯H/H⋯Cl (8.4%), N⋯H/H⋯N (4.1%) and there is only a very small contribution from other contacts, i.e. 3.1%, in the structure. This illustrates that the N—H⋯O and C—H⋯O interactions contribute significantly to the crystal packing of the title compound.
Figure 5.
Fingerprint plot of the title compound, (a) all, (b) H⋯H, (c) C⋯H/H⋯C, (d) O⋯H/H⋯O, (e) Cl⋯H/H⋯Cl and (f) N⋯H/H⋯N contacts. The outline of the full fingerprint plots is shown in grey. d i is the closet internal distance from a given point on the Hirshfeld surface and d e is the closest external contact.
Synthesis and crystallization
An equimolar mixture of 2-phenyl-5,6,7,8-tetrahydro-5-quinolinone and 2-chlorobenzaldehyde was dissolved in 10 ml of ethanol followed by the addition of 0.5 equiv. of potassium hydroxide. The mixture was stirred for 1 h at ambient temperature and the precipitate formed was filtered and dried to obtain pure (E)-6-(2-chlorobenzylidene)-2-phenyl-7,8-dihydroquinolin-5(6H)-one (L) in 94% yield (m.p. 323–324 K). A mixture of isatin (1.1 mmol) and sarcosine (1.1 mmol) was taken in 10 ml of acetonitrile in a 50 ml round-bottom flask and heated to reflux for 2 h. Then 1 mmol of L was added to the above reaction mixture and reflux was continued for a further 14 h. After completion of the reaction, as evident from TLC, the solvent was removed under reduced pressure and the residue washed with ice-cold water (50 ml). The crude product was purified by column chromatography using a 90:10 (v/v) petroleum ether–ethyl acetate mixture to obtain the pure product (yield 82%, m.p. 356 K). Colourless block-like crystals were obtained by slow evaporation of a solution in ethyl acetate.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The NH H atom was located in a difference-Fourier map and freely refined. The C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms: C—H = 0.93–0.98 Å with U iso = 1.5U eq(C-methyl) and 1.2U eq(C) for other H atoms.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C32H26ClN3O2 |
| M r | 520.01 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 293 |
| a, b, c (Å) | 6.7722 (4), 11.5017 (8), 16.6305 (11) |
| α, β, γ (°) | 80.224 (3), 84.618 (3), 81.077 (3) |
| V (Å3) | 1258.09 (14) |
| Z | 2 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.19 |
| Crystal size (mm) | 0.23 × 0.21 × 0.19 |
| Data collection | |
| Diffractometer | Bruker Kappa APEXII |
| Absorption correction | Multi-scan (SADABS; Bruker, 2004 ▸) |
| T min, T max | 0.967, 0.974 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 25368, 4659, 3577 |
| R int | 0.035 |
| (sin θ/λ)max (Å−1) | 0.606 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.047, 0.133, 1.05 |
| No. of reflections | 4659 |
| No. of parameters | 347 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.37, −0.46 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018005455/su5434sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018005455/su5434Isup2.hkl
CCDC reference: 1835595
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
JS and RV thank the management of Madurai College for their encouragement and support.
supplementary crystallographic information
Crystal data
| C32H26ClN3O2 | Z = 2 |
| Mr = 520.01 | F(000) = 544 |
| Triclinic, P1 | Dx = 1.373 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.7722 (4) Å | Cell parameters from 4659 reflections |
| b = 11.5017 (8) Å | θ = 2–26° |
| c = 16.6305 (11) Å | µ = 0.19 mm−1 |
| α = 80.224 (3)° | T = 293 K |
| β = 84.618 (3)° | Block, colourless |
| γ = 81.077 (3)° | 0.23 × 0.21 × 0.19 mm |
| V = 1258.09 (14) Å3 |
Data collection
| Bruker Kappa APEXII diffractometer | 4659 independent reflections |
| Radiation source: fine-focus sealed tube | 3577 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.035 |
| Detector resolution: 0 pixels mm-1 | θmax = 25.5°, θmin = 2.0° |
| ω and φ scans | h = −8→8 |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −13→13 |
| Tmin = 0.967, Tmax = 0.974 | l = −20→20 |
| 25368 measured reflections |
Refinement
| 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.057P)2 + 0.8008P] where P = (Fo2 + 2Fc2)/3 |
| 4659 reflections | (Δ/σ)max < 0.001 |
| 347 parameters | Δρmax = 0.37 e Å−3 |
| 0 restraints | Δρmin = −0.46 e Å−3 |
Special details
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| C2 | 0.2424 (3) | 0.02521 (19) | 0.28318 (12) | 0.0341 (5) | |
| C3 | 0.2874 (3) | 0.15629 (19) | 0.28084 (12) | 0.0308 (4) | |
| C4 | 0.4045 (3) | 0.1455 (2) | 0.36013 (12) | 0.0346 (5) | |
| H4 | 0.5413 | 0.1597 | 0.3411 | 0.041* | |
| C5 | 0.4193 (4) | 0.0154 (2) | 0.39905 (14) | 0.0439 (6) | |
| H5A | 0.5457 | −0.0115 | 0.4239 | 0.053* | |
| H5B | 0.3102 | 0.0026 | 0.4402 | 0.053* | |
| C21 | 0.2282 (3) | −0.01793 (19) | 0.20329 (13) | 0.0354 (5) | |
| C22 | 0.3670 (4) | −0.0337 (2) | 0.13896 (15) | 0.0456 (6) | |
| H22 | 0.4960 | −0.0160 | 0.1401 | 0.055* | |
| C23 | 0.3124 (4) | −0.0761 (2) | 0.07238 (16) | 0.0545 (7) | |
| H23 | 0.4052 | −0.0861 | 0.0283 | 0.065* | |
| C24 | 0.1226 (4) | −0.1037 (2) | 0.07072 (16) | 0.0544 (7) | |
| H24 | 0.0882 | −0.1317 | 0.0254 | 0.065* | |
| C25 | −0.0169 (4) | −0.0903 (2) | 0.13520 (16) | 0.0487 (6) | |
| H25 | −0.1452 | −0.1093 | 0.1343 | 0.058* | |
| C26 | 0.0384 (3) | −0.04795 (19) | 0.20120 (13) | 0.0364 (5) | |
| C27 | 0.0290 (3) | 0.01083 (19) | 0.32584 (13) | 0.0366 (5) | |
| C31 | 0.4322 (3) | 0.18485 (19) | 0.20612 (12) | 0.0321 (5) | |
| C6 | 0.3840 (4) | −0.1718 (2) | 0.35516 (18) | 0.0606 (7) | |
| H03A | 0.3757 | −0.2075 | 0.3077 | 0.091* | |
| H03B | 0.2642 | −0.1783 | 0.3904 | 0.091* | |
| H03C | 0.4979 | −0.2120 | 0.3840 | 0.091* | |
| C32 | 0.3517 (3) | 0.25452 (19) | 0.13036 (12) | 0.0317 (4) | |
| C33 | 0.4809 (3) | 0.2861 (2) | 0.06304 (13) | 0.0402 (5) | |
| H33 | 0.6185 | 0.2756 | 0.0679 | 0.048* | |
| C34 | 0.4035 (3) | 0.3327 (2) | −0.01031 (13) | 0.0438 (6) | |
| H34 | 0.4870 | 0.3581 | −0.0554 | 0.053* | |
| C35 | 0.1978 (3) | 0.34183 (19) | −0.01695 (12) | 0.0340 (5) | |
| C36 | 0.1461 (3) | 0.28141 (17) | 0.12155 (12) | 0.0292 (4) | |
| C37 | 0.0024 (3) | 0.26574 (19) | 0.19474 (12) | 0.0322 (5) | |
| H37A | −0.0604 | 0.1955 | 0.1945 | 0.039* | |
| H37B | −0.1020 | 0.3341 | 0.1916 | 0.039* | |
| C38 | 0.1032 (3) | 0.25252 (19) | 0.27456 (12) | 0.0316 (4) | |
| H38A | 0.0069 | 0.2330 | 0.3199 | 0.038* | |
| H38B | 0.1434 | 0.3283 | 0.2794 | 0.038* | |
| C41 | 0.3264 (3) | 0.2350 (2) | 0.41643 (12) | 0.0355 (5) | |
| C42 | 0.3936 (3) | 0.3452 (2) | 0.40547 (14) | 0.0418 (5) | |
| C43 | 0.3308 (4) | 0.4279 (2) | 0.45654 (16) | 0.0517 (6) | |
| H43 | 0.3777 | 0.5012 | 0.4465 | 0.062* | |
| C44 | 0.1979 (4) | 0.4016 (3) | 0.52262 (16) | 0.0548 (7) | |
| H44 | 0.1572 | 0.4560 | 0.5585 | 0.066* | |
| C45 | 0.1265 (4) | 0.2950 (3) | 0.53485 (15) | 0.0556 (7) | |
| H45 | 0.0353 | 0.2773 | 0.5790 | 0.067* | |
| C46 | 0.1880 (3) | 0.2129 (2) | 0.48247 (14) | 0.0444 (6) | |
| H46 | 0.1356 | 0.1413 | 0.4916 | 0.053* | |
| C51 | 0.1096 (3) | 0.37258 (19) | −0.09725 (13) | 0.0364 (5) | |
| C52 | 0.2260 (4) | 0.3562 (2) | −0.16886 (14) | 0.0507 (6) | |
| H52 | 0.3628 | 0.3303 | −0.1668 | 0.061* | |
| C53 | 0.1402 (5) | 0.3779 (3) | −0.24306 (15) | 0.0594 (7) | |
| H53 | 0.2192 | 0.3664 | −0.2907 | 0.071* | |
| C54 | −0.0620 (5) | 0.4166 (3) | −0.24678 (15) | 0.0588 (7) | |
| H54 | −0.1200 | 0.4305 | −0.2967 | 0.071* | |
| C55 | −0.1772 (4) | 0.4346 (2) | −0.17684 (15) | 0.0515 (6) | |
| H55 | −0.3135 | 0.4619 | −0.1795 | 0.062* | |
| C56 | −0.0939 (3) | 0.4129 (2) | −0.10239 (14) | 0.0413 (5) | |
| H56 | −0.1743 | 0.4253 | −0.0553 | 0.050* | |
| N1 | 0.4056 (3) | −0.04573 (17) | 0.32992 (11) | 0.0408 (4) | |
| N2 | −0.0728 (3) | −0.03406 (17) | 0.27448 (12) | 0.0399 (4) | |
| N3 | 0.0704 (2) | 0.32058 (15) | 0.04888 (10) | 0.0322 (4) | |
| O1 | −0.0328 (2) | 0.03246 (16) | 0.39312 (10) | 0.0503 (4) | |
| O2 | 0.6092 (2) | 0.14584 (15) | 0.20669 (10) | 0.0455 (4) | |
| Cl1 | 0.56220 (11) | 0.38517 (7) | 0.32331 (5) | 0.0654 (2) | |
| H2 | −0.202 (4) | −0.037 (2) | 0.2839 (16) | 0.059 (8)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C2 | 0.0293 (10) | 0.0390 (12) | 0.0336 (11) | −0.0051 (9) | −0.0064 (8) | −0.0024 (9) |
| C3 | 0.0238 (9) | 0.0399 (11) | 0.0288 (10) | −0.0040 (8) | −0.0060 (8) | −0.0039 (8) |
| C4 | 0.0265 (10) | 0.0461 (12) | 0.0321 (11) | −0.0048 (9) | −0.0062 (8) | −0.0068 (9) |
| C5 | 0.0437 (12) | 0.0480 (14) | 0.0381 (12) | 0.0033 (10) | −0.0142 (10) | −0.0041 (10) |
| C21 | 0.0349 (11) | 0.0349 (11) | 0.0365 (11) | −0.0025 (9) | −0.0064 (9) | −0.0058 (9) |
| C22 | 0.0405 (12) | 0.0499 (14) | 0.0487 (14) | −0.0068 (10) | −0.0001 (10) | −0.0158 (11) |
| C23 | 0.0680 (17) | 0.0517 (15) | 0.0463 (14) | −0.0080 (13) | 0.0043 (12) | −0.0201 (12) |
| C24 | 0.0723 (18) | 0.0476 (15) | 0.0484 (15) | −0.0105 (13) | −0.0138 (13) | −0.0154 (12) |
| C25 | 0.0502 (14) | 0.0431 (13) | 0.0579 (15) | −0.0120 (11) | −0.0174 (12) | −0.0097 (11) |
| C26 | 0.0371 (11) | 0.0313 (11) | 0.0407 (12) | −0.0042 (9) | −0.0087 (9) | −0.0029 (9) |
| C27 | 0.0366 (11) | 0.0351 (11) | 0.0351 (12) | −0.0064 (9) | −0.0044 (9) | 0.0050 (9) |
| C31 | 0.0233 (10) | 0.0418 (12) | 0.0334 (11) | −0.0073 (8) | −0.0033 (8) | −0.0094 (9) |
| C6 | 0.0669 (17) | 0.0406 (14) | 0.0716 (18) | 0.0026 (12) | −0.0241 (14) | 0.0002 (13) |
| C32 | 0.0255 (10) | 0.0400 (12) | 0.0311 (11) | −0.0075 (8) | 0.0002 (8) | −0.0085 (9) |
| C33 | 0.0277 (10) | 0.0571 (14) | 0.0371 (12) | −0.0108 (10) | 0.0009 (9) | −0.0083 (10) |
| C34 | 0.0382 (12) | 0.0615 (15) | 0.0319 (12) | −0.0167 (11) | 0.0049 (9) | −0.0030 (10) |
| C35 | 0.0378 (11) | 0.0358 (11) | 0.0299 (11) | −0.0081 (9) | −0.0009 (9) | −0.0070 (9) |
| C36 | 0.0273 (9) | 0.0314 (10) | 0.0295 (10) | −0.0062 (8) | −0.0032 (8) | −0.0044 (8) |
| C37 | 0.0225 (9) | 0.0412 (12) | 0.0313 (11) | −0.0030 (8) | −0.0028 (8) | −0.0022 (9) |
| C38 | 0.0259 (10) | 0.0391 (11) | 0.0289 (10) | −0.0036 (8) | −0.0008 (8) | −0.0042 (8) |
| C41 | 0.0297 (10) | 0.0457 (13) | 0.0319 (11) | −0.0033 (9) | −0.0105 (8) | −0.0056 (9) |
| C42 | 0.0379 (12) | 0.0531 (14) | 0.0371 (12) | −0.0082 (10) | −0.0098 (9) | −0.0089 (10) |
| C43 | 0.0530 (14) | 0.0519 (15) | 0.0537 (15) | −0.0054 (12) | −0.0185 (12) | −0.0122 (12) |
| C44 | 0.0598 (16) | 0.0609 (17) | 0.0444 (14) | 0.0075 (13) | −0.0139 (12) | −0.0198 (12) |
| C45 | 0.0507 (15) | 0.0758 (19) | 0.0382 (13) | −0.0021 (13) | 0.0010 (11) | −0.0114 (12) |
| C46 | 0.0414 (12) | 0.0531 (14) | 0.0386 (12) | −0.0078 (11) | −0.0024 (10) | −0.0060 (11) |
| C51 | 0.0463 (12) | 0.0335 (11) | 0.0308 (11) | −0.0118 (9) | −0.0039 (9) | −0.0030 (9) |
| C52 | 0.0576 (15) | 0.0596 (16) | 0.0351 (13) | −0.0106 (12) | −0.0014 (11) | −0.0071 (11) |
| C53 | 0.080 (2) | 0.0679 (18) | 0.0300 (13) | −0.0144 (15) | −0.0011 (12) | −0.0050 (12) |
| C54 | 0.080 (2) | 0.0622 (17) | 0.0358 (14) | −0.0165 (15) | −0.0193 (13) | 0.0025 (12) |
| C55 | 0.0562 (15) | 0.0499 (15) | 0.0478 (15) | −0.0106 (12) | −0.0181 (12) | 0.0047 (11) |
| C56 | 0.0492 (13) | 0.0392 (12) | 0.0362 (12) | −0.0093 (10) | −0.0062 (10) | −0.0035 (9) |
| N1 | 0.0401 (10) | 0.0395 (10) | 0.0421 (11) | 0.0021 (8) | −0.0145 (8) | −0.0053 (8) |
| N2 | 0.0318 (10) | 0.0430 (11) | 0.0457 (11) | −0.0109 (8) | −0.0048 (8) | −0.0027 (8) |
| N3 | 0.0324 (9) | 0.0357 (9) | 0.0295 (9) | −0.0060 (7) | −0.0039 (7) | −0.0060 (7) |
| O1 | 0.0482 (9) | 0.0646 (11) | 0.0376 (9) | −0.0161 (8) | 0.0046 (7) | −0.0035 (8) |
| O2 | 0.0219 (7) | 0.0657 (11) | 0.0470 (9) | −0.0041 (7) | −0.0028 (6) | −0.0048 (8) |
| Cl1 | 0.0626 (4) | 0.0716 (5) | 0.0654 (5) | −0.0297 (4) | 0.0096 (3) | −0.0096 (3) |
Geometric parameters (Å, º)
| C2—N1 | 1.469 (3) | C33—H33 | 0.9300 |
| C2—C21 | 1.511 (3) | C34—C35 | 1.394 (3) |
| C2—C27 | 1.569 (3) | C34—H34 | 0.9300 |
| C2—C3 | 1.577 (3) | C35—N3 | 1.342 (3) |
| C3—C31 | 1.532 (3) | C35—C51 | 1.479 (3) |
| C3—C38 | 1.532 (3) | C36—N3 | 1.337 (3) |
| C3—C4 | 1.579 (3) | C36—C37 | 1.490 (3) |
| C4—C41 | 1.510 (3) | C37—C38 | 1.523 (3) |
| C4—C5 | 1.518 (3) | C37—H37A | 0.9700 |
| C4—H4 | 0.9800 | C37—H37B | 0.9700 |
| C5—N1 | 1.463 (3) | C38—H38A | 0.9700 |
| C5—H5A | 0.9700 | C38—H38B | 0.9700 |
| C5—H5B | 0.9700 | C41—C42 | 1.389 (3) |
| C21—C22 | 1.373 (3) | C41—C46 | 1.391 (3) |
| C21—C26 | 1.387 (3) | C42—C43 | 1.375 (4) |
| C22—C23 | 1.385 (3) | C42—Cl1 | 1.743 (2) |
| C22—H22 | 0.9300 | C43—C44 | 1.377 (4) |
| C23—C24 | 1.375 (4) | C43—H43 | 0.9300 |
| C23—H23 | 0.9300 | C44—C45 | 1.364 (4) |
| C24—C25 | 1.374 (4) | C44—H44 | 0.9300 |
| C24—H24 | 0.9300 | C45—C46 | 1.384 (4) |
| C25—C26 | 1.378 (3) | C45—H45 | 0.9300 |
| C25—H25 | 0.9300 | C46—H46 | 0.9300 |
| C26—N2 | 1.391 (3) | C51—C52 | 1.389 (3) |
| C27—O1 | 1.210 (3) | C51—C56 | 1.390 (3) |
| C27—N2 | 1.358 (3) | C52—C53 | 1.381 (3) |
| C31—O2 | 1.213 (2) | C52—H52 | 0.9300 |
| C31—C32 | 1.475 (3) | C53—C54 | 1.376 (4) |
| C6—N1 | 1.465 (3) | C53—H53 | 0.9300 |
| C6—H03A | 0.9600 | C54—C55 | 1.366 (4) |
| C6—H03B | 0.9600 | C54—H54 | 0.9300 |
| C6—H03C | 0.9600 | C55—C56 | 1.377 (3) |
| C32—C33 | 1.389 (3) | C55—H55 | 0.9300 |
| C32—C36 | 1.394 (3) | C56—H56 | 0.9300 |
| C33—C34 | 1.364 (3) | N2—H2 | 0.88 (3) |
| N1—C2—C21 | 112.06 (17) | C35—C34—H34 | 120.4 |
| N1—C2—C27 | 113.20 (17) | N3—C35—C34 | 121.76 (19) |
| C21—C2—C27 | 101.09 (16) | N3—C35—C51 | 116.63 (18) |
| N1—C2—C3 | 102.01 (16) | C34—C35—C51 | 121.59 (19) |
| C21—C2—C3 | 118.75 (17) | N3—C36—C32 | 122.40 (18) |
| C27—C2—C3 | 110.19 (16) | N3—C36—C37 | 117.68 (17) |
| C31—C3—C38 | 108.09 (16) | C32—C36—C37 | 119.91 (17) |
| C31—C3—C2 | 107.53 (16) | C36—C37—C38 | 112.47 (16) |
| C38—C3—C2 | 115.01 (16) | C36—C37—H37A | 109.1 |
| C31—C3—C4 | 108.09 (15) | C38—C37—H37A | 109.1 |
| C38—C3—C4 | 114.82 (16) | C36—C37—H37B | 109.1 |
| C2—C3—C4 | 102.89 (15) | C38—C37—H37B | 109.1 |
| C41—C4—C5 | 115.76 (18) | H37A—C37—H37B | 107.8 |
| C41—C4—C3 | 115.84 (16) | C37—C38—C3 | 113.25 (17) |
| C5—C4—C3 | 105.59 (17) | C37—C38—H38A | 108.9 |
| C41—C4—H4 | 106.3 | C3—C38—H38A | 108.9 |
| C5—C4—H4 | 106.3 | C37—C38—H38B | 108.9 |
| C3—C4—H4 | 106.3 | C3—C38—H38B | 108.9 |
| N1—C5—C4 | 103.22 (17) | H38A—C38—H38B | 107.7 |
| N1—C5—H5A | 111.1 | C42—C41—C46 | 115.9 (2) |
| C4—C5—H5A | 111.1 | C42—C41—C4 | 120.99 (19) |
| N1—C5—H5B | 111.1 | C46—C41—C4 | 123.1 (2) |
| C4—C5—H5B | 111.1 | C43—C42—C41 | 122.9 (2) |
| H5A—C5—H5B | 109.1 | C43—C42—Cl1 | 116.8 (2) |
| C22—C21—C26 | 119.4 (2) | C41—C42—Cl1 | 120.30 (18) |
| C22—C21—C2 | 131.5 (2) | C42—C43—C44 | 119.6 (3) |
| C26—C21—C2 | 109.14 (18) | C42—C43—H43 | 120.2 |
| C21—C22—C23 | 119.2 (2) | C44—C43—H43 | 120.2 |
| C21—C22—H22 | 120.4 | C45—C44—C43 | 119.2 (2) |
| C23—C22—H22 | 120.4 | C45—C44—H44 | 120.4 |
| C24—C23—C22 | 120.7 (2) | C43—C44—H44 | 120.4 |
| C24—C23—H23 | 119.6 | C44—C45—C46 | 120.9 (2) |
| C22—C23—H23 | 119.6 | C44—C45—H45 | 119.6 |
| C25—C24—C23 | 120.8 (2) | C46—C45—H45 | 119.6 |
| C25—C24—H24 | 119.6 | C45—C46—C41 | 121.4 (2) |
| C23—C24—H24 | 119.6 | C45—C46—H46 | 119.3 |
| C24—C25—C26 | 118.2 (2) | C41—C46—H46 | 119.3 |
| C24—C25—H25 | 120.9 | C52—C51—C56 | 118.4 (2) |
| C26—C25—H25 | 120.9 | C52—C51—C35 | 120.8 (2) |
| C25—C26—C21 | 121.8 (2) | C56—C51—C35 | 120.7 (2) |
| C25—C26—N2 | 128.1 (2) | C53—C52—C51 | 120.6 (3) |
| C21—C26—N2 | 110.08 (19) | C53—C52—H52 | 119.7 |
| O1—C27—N2 | 125.8 (2) | C51—C52—H52 | 119.7 |
| O1—C27—C2 | 126.6 (2) | C54—C53—C52 | 120.2 (2) |
| N2—C27—C2 | 107.54 (18) | C54—C53—H53 | 119.9 |
| O2—C31—C32 | 119.56 (18) | C52—C53—H53 | 119.9 |
| O2—C31—C3 | 121.31 (18) | C55—C54—C53 | 119.7 (2) |
| C32—C31—C3 | 119.01 (16) | C55—C54—H54 | 120.2 |
| N1—C6—H03A | 109.5 | C53—C54—H54 | 120.2 |
| N1—C6—H03B | 109.5 | C54—C55—C56 | 120.8 (2) |
| H03A—C6—H03B | 109.5 | C54—C55—H55 | 119.6 |
| N1—C6—H03C | 109.5 | C56—C55—H55 | 119.6 |
| H03A—C6—H03C | 109.5 | C55—C56—C51 | 120.4 (2) |
| H03B—C6—H03C | 109.5 | C55—C56—H56 | 119.8 |
| C33—C32—C36 | 118.10 (19) | C51—C56—H56 | 119.8 |
| C33—C32—C31 | 120.06 (18) | C5—N1—C6 | 112.86 (19) |
| C36—C32—C31 | 121.61 (18) | C5—N1—C2 | 105.95 (17) |
| C34—C33—C32 | 119.1 (2) | C6—N1—C2 | 114.76 (18) |
| C34—C33—H33 | 120.4 | C27—N2—C26 | 112.06 (18) |
| C32—C33—H33 | 120.4 | C27—N2—H2 | 120.9 (18) |
| C33—C34—C35 | 119.3 (2) | C26—N2—H2 | 125.6 (18) |
| C33—C34—H34 | 120.4 | C36—N3—C35 | 118.38 (17) |
| N1—C2—C3—C31 | 87.78 (18) | C33—C34—C35—C51 | −169.7 (2) |
| C21—C2—C3—C31 | −35.9 (2) | C33—C32—C36—N3 | 9.5 (3) |
| C27—C2—C3—C31 | −151.73 (16) | C31—C32—C36—N3 | −164.92 (19) |
| N1—C2—C3—C38 | −151.78 (16) | C33—C32—C36—C37 | −170.98 (19) |
| C21—C2—C3—C38 | 84.5 (2) | C31—C32—C36—C37 | 14.6 (3) |
| C27—C2—C3—C38 | −31.3 (2) | N3—C36—C37—C38 | −165.11 (18) |
| N1—C2—C3—C4 | −26.19 (19) | C32—C36—C37—C38 | 15.4 (3) |
| C21—C2—C3—C4 | −149.88 (17) | C36—C37—C38—C3 | −51.8 (2) |
| C27—C2—C3—C4 | 94.30 (18) | C31—C3—C38—C37 | 55.5 (2) |
| C31—C3—C4—C41 | 117.6 (2) | C2—C3—C38—C37 | −64.7 (2) |
| C38—C3—C4—C41 | −3.1 (3) | C4—C3—C38—C37 | 176.20 (16) |
| C2—C3—C4—C41 | −128.80 (18) | C5—C4—C41—C42 | 147.3 (2) |
| C31—C3—C4—C5 | −112.83 (19) | C3—C4—C41—C42 | −88.3 (2) |
| C38—C3—C4—C5 | 126.44 (19) | C5—C4—C41—C46 | −31.5 (3) |
| C2—C3—C4—C5 | 0.7 (2) | C3—C4—C41—C46 | 93.0 (2) |
| C41—C4—C5—N1 | 154.80 (17) | C46—C41—C42—C43 | 0.7 (3) |
| C3—C4—C5—N1 | 25.2 (2) | C4—C41—C42—C43 | −178.2 (2) |
| N1—C2—C21—C22 | −55.7 (3) | C46—C41—C42—Cl1 | −178.29 (16) |
| C27—C2—C21—C22 | −176.6 (2) | C4—C41—C42—Cl1 | 2.8 (3) |
| C3—C2—C21—C22 | 62.8 (3) | C41—C42—C43—C44 | 1.1 (4) |
| N1—C2—C21—C26 | 122.16 (19) | Cl1—C42—C43—C44 | −179.90 (18) |
| C27—C2—C21—C26 | 1.3 (2) | C42—C43—C44—C45 | −1.9 (4) |
| C3—C2—C21—C26 | −119.2 (2) | C43—C44—C45—C46 | 0.9 (4) |
| C26—C21—C22—C23 | 1.7 (3) | C44—C45—C46—C41 | 1.0 (4) |
| C2—C21—C22—C23 | 179.5 (2) | C42—C41—C46—C45 | −1.7 (3) |
| C21—C22—C23—C24 | −0.7 (4) | C4—C41—C46—C45 | 177.1 (2) |
| C22—C23—C24—C25 | −0.3 (4) | N3—C35—C51—C52 | −157.6 (2) |
| C23—C24—C25—C26 | 0.4 (4) | C34—C35—C51—C52 | 21.0 (3) |
| C24—C25—C26—C21 | 0.7 (3) | N3—C35—C51—C56 | 19.1 (3) |
| C24—C25—C26—N2 | −175.9 (2) | C34—C35—C51—C56 | −162.3 (2) |
| C22—C21—C26—C25 | −1.8 (3) | C56—C51—C52—C53 | −0.9 (4) |
| C2—C21—C26—C25 | −180.0 (2) | C35—C51—C52—C53 | 175.9 (2) |
| C22—C21—C26—N2 | 175.4 (2) | C51—C52—C53—C54 | 0.2 (4) |
| C2—C21—C26—N2 | −2.8 (2) | C52—C53—C54—C55 | 0.7 (4) |
| N1—C2—C27—O1 | 58.7 (3) | C53—C54—C55—C56 | −0.9 (4) |
| C21—C2—C27—O1 | 178.8 (2) | C54—C55—C56—C51 | 0.2 (4) |
| C3—C2—C27—O1 | −54.8 (3) | C52—C51—C56—C55 | 0.7 (3) |
| N1—C2—C27—N2 | −119.41 (19) | C35—C51—C56—C55 | −176.1 (2) |
| C21—C2—C27—N2 | 0.6 (2) | C4—C5—N1—C6 | −170.69 (19) |
| C3—C2—C27—N2 | 127.08 (18) | C4—C5—N1—C2 | −44.3 (2) |
| C38—C3—C31—O2 | 158.3 (2) | C21—C2—N1—C5 | 172.38 (18) |
| C2—C3—C31—O2 | −77.0 (2) | C27—C2—N1—C5 | −74.1 (2) |
| C4—C3—C31—O2 | 33.5 (3) | C3—C2—N1—C5 | 44.3 (2) |
| C38—C3—C31—C32 | −25.8 (2) | C21—C2—N1—C6 | −62.4 (3) |
| C2—C3—C31—C32 | 98.9 (2) | C27—C2—N1—C6 | 51.1 (3) |
| C4—C3—C31—C32 | −150.66 (18) | C3—C2—N1—C6 | 169.51 (19) |
| O2—C31—C32—C33 | −6.9 (3) | O1—C27—N2—C26 | 179.5 (2) |
| C3—C31—C32—C33 | 177.10 (19) | C2—C27—N2—C26 | −2.4 (2) |
| O2—C31—C32—C36 | 167.4 (2) | C25—C26—N2—C27 | −179.7 (2) |
| C3—C31—C32—C36 | −8.6 (3) | C21—C26—N2—C27 | 3.4 (3) |
| C36—C32—C33—C34 | −5.4 (3) | C32—C36—N3—C35 | −4.4 (3) |
| C31—C32—C33—C34 | 169.2 (2) | C37—C36—N3—C35 | 176.14 (18) |
| C32—C33—C34—C35 | −3.3 (4) | C34—C35—N3—C36 | −4.9 (3) |
| C33—C34—C35—N3 | 8.8 (4) | C51—C35—N3—C36 | 173.66 (18) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C22—H22···O2 | 0.93 | 2.57 | 3.227 (3) | 128 |
| C38—H38A···O1 | 0.97 | 2.46 | 3.135 (3) | 127 |
| C37—H37A···O2i | 0.97 | 2.38 | 3.159 (3) | 137 |
| N2—H2···O2i | 0.88 (3) | 2.50 (2) | 2.911 (3) | 109.0 (19) |
Symmetry code: (i) x−1, y, z.
Funding Statement
This work was funded by University Grants Commission grant F MRP-7018/16(SERO/UGC) to J. Suresh.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018005455/su5434sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018005455/su5434Isup2.hkl
CCDC reference: 1835595
Additional supporting information: crystallographic information; 3D view; checkCIF report