The dihedral angles between the mean plane of the piperidine ring, which adopts a chair conformation, and the phenyl rings are 89.72 (8) and 48.32 (8)°. In the crystal, molecules are linked into chains along the b-axis direction by C—H⋯O hydrogen bonds.
Keywords: crystal structure, piperidine derivative, Hirshfeld surface, DFT
Abstract
In the title compound, C22H27NO, the piperidine ring adopts a chair conformation. The dihedral angles between the mean plane of the piperidine ring and the phenyl rings are 89.78 (7) and 48.30 (8)°. In the crystal, molecules are linked into chains along the b-axis direction by C—H⋯O hydrogen bonds. The DFT/B3LYP/6–311 G(d,p) method was used to determine the HOMO–LUMO energy levels. The molecular electrostatic potential surfaces were investigated by Hirshfeld surface analysis and two-dimensional fingerprint plots were used to analyse the intermolecular interactions in the molecule.
Chemical context
Piperidine is a heterocyclic six-membered ring containing nitrogen as a hetero atom and is an essential structural part of many important drugs including paroxetine, raloxifene, haloperidol, droperidol and minoxidiln (Wagstaff et al., 2002 ▸). Piperidine derivatives exhibit a wide range of biological activities, such as antimicrobial, anti-inflammatory, antiviral, antimalarial and general anesthetic (Aridoss et al., 2009 ▸). The biological properties of piperidines are highly dependent on the type and position of substituents on the heterocyclic ring. 2,6-Disubstituted piperidine derivatives have been found to possess fungicidal, bactericidal and herbicidal activities (Mobio et al., 1989 ▸). Piperidine derivatives are the intermediate products in agrochemicals, pharmaceuticals, rubber vulcanization accelerators and are widely used as building block molecules in many industries. Various piperidine derivatives are present in numerous alkaloids (Badorrey et al., 1999 ▸).
This wide range of biological activities prompted us to synthesize novel 2,6-diphenyl piperdine derivatives. Against this background, the structure of the title compound has been determined.
Structural commentary
The molecular structure of the title compound is shown in Fig. 1 ▸. The diphenyl-substituted piperidine compound crystallizes in the monoclinic space group P21/n. The bond lengths and angles are well within the expected limits and comparable with literature values (Allen et al., 1998 ▸).
Figure 1.
The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at the 30% probability level.
The piperidine ring adopts a chair conformation with the puckering parameters Q 2 = 0.6191 (15) Å and ϕ2 = 335.12 (14) Å. The piperidine ring (N1/C2–C6) makes dihedral angles of 89.78 (7) and 48.30 (8)°, respectively, with the C7–12 and C13–C18 phenyl rings, and confirms the fact that the moieties are in an axial orientations.
The keto and methyl groups substituted at atom C19 are equatorially orientated as confirmed from the torsion angle values O1—C19—N1—C2 = 177.54 (12)° and C20—C19—N1—C6 = 172.81 (11)°. In the molecule, the isopropyl group substituted at the 5-position of the piperidine ring is equatorially oriented, as confirmed by the torsion angles of C4—C5—C21—C22 = −172.13 (14)° and C6—C5—C21—C23 = −174.73 (14)°. The sum of the bond angles (359.87°) around atom N1 of the piperidine ring is in accordance with the sp 2-hybridization state (Beddoes et al., 1986 ▸).
Supramolecular features
In the crystal, molecules are linked into C(8) chains along the b-axis direction by C—H⋯O hydrogen bonds (Table 1 ▸, Fig. 2 ▸). The overall crystal packing of the title compound is shown in Fig. 3 ▸.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C9—H9⋯O1i | 0.93 | 2.54 | 3.4378 (19) | 163 |
Symmetry code: (i) 
.
Figure 2.
A partial view along the b axis of the crystal packing of the title compound, showing the formation of a molecular chain by C—H⋯O interactions (dotted lines).
Figure 3.
The overall crystal packing of the title compound, viewed along the b-axis direction. Hydrogen bonds are shown as dashed lines, and only the H atoms involved in hydrogen bonding have been included.
DFT study
The optimized structure of the molecule in the gas phase was generated theoretically via density functional theory (DFT) using standard B3LYP functional and 6-311G(d,p) basis-set calculations (Becke et al., 1993 ▸), as implemented in GAUSSIAN09 (Frisch et al., 2009 ▸).
The overlay diagram for the optimized structure (purple) and the structure in solid state (green) with respect to the piperidine ring is shown in Fig. 4 ▸. The piperidine rings in the two phases have an r.m.s deviation of 0.434 Å for the non-hydrogen atoms. The conformation of the molecules in the two phases differs with respect to the central piperidine ring, as seen in the disparity of about 38.5° in the N1—C6—C5—C4 torsion angles (39.88/1.38°) and 2.25° in the N1—C2—C3—C4 torsion angles (44.41/39.81°) for the optimized and solid-state molecules, respectively.
Figure 4.
A structural overlay diagram (Mercury; Macrae et al., 2020 ▸) for the optimized structure (purple) and the solid-state structure (green) of the title compound.
The highest-occupied molecular orbital (HOMO), acting as an electron donor, and the lowest-unoccupied molecular orbital (LUMO), acting as an electron acceptor, are known as frontier molecular orbitals (FMOs). The FMOs play an important role in the optical and electric properties, as well as in quantum chemistry (Fleming, 1976 ▸). When the energy gap is small, the molecule is highly polarizable and has high chemical reactivity. The electron distribution of the HOMO−1, HOMO, LUMO and LUMO+1 energy levels and the energy values are shown in Fig. 5 ▸. The positive and negative phases are shown in green and red, respectively.
Figure 5.
The frontier molecular orbitals (FMOs) of the title compound.
The HOMO of the title molecule is localized on the C=O group, one aromatic ring and the piperidine ring, while the LUMO is located over the whole molecule expect for the isopropyl group. The DFT study shows that the FMO energies E HOMO and E LUMO are −4.804 and −1.694 eV, respectively, and the HOMO–LUMO energy gap is 3.110 eV. The title compound has a small frontier orbital gap, hence the molecule has high chemical reactivity and low kinetic stability.
The electron affinity (I) and ionization potential (A) of the molecule were calculated using the DFT/B3LYP/6-311++G(d,p) basis set. A high value of the electrophilicity index describes a good electrophile, while a small value of electrophilicity index describes a good nucleophile. The values of the hardness (η), softness (σ), electronegativity (χ) and electrophilicity index (ω) for the title compound are given in Table 2 ▸.
Table 2. Calculated frontier molecular orbital analysis of the title compound.
| Parameter | Value |
|---|---|
| EHOMO (eV) | −4.804 |
| ELUMO (eV) | −1.694 |
| Energy gap, ΔE (eV) | 3.110 |
| HOMO−1 (eV) | −5.478 |
| LUMO+1 (eV) | −1.113 |
| Ionization potential, I (eV) | 4.804 |
| Electron affinity, A | 1.694 |
| Electrophilicity Index, ω | 3.394 |
| Hardness, η | 1.555 |
| Electro negativity, χ | 3.249 |
| Softness, σ | 0.322 |
Hirshfeld surface analysis
CrystalExplorer17 (Turner et al., 2017 ▸) was used for the Hirshfeld surface (HS) analysis (Spackman & Jayatilaka, 2009 ▸) and to generate the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ▸) to quantify the various intermolecular interactions in the structure of the title compound. In the HS plotted over d norm (Fig. 6 ▸), the white surface indicates contacts with distances equal to the sum of the van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ▸).
Figure 6.
Hirshfeld surfaces mapped over (a) d norm, (b) shape-index, (c) curvedness and (d) fragment patches.
The HS mapped over curvedness and shape-index, introduced by Koendrink (Koenderink, 1990 ▸; Koenderink & van Doorn, 1992 ▸), give further chemical insight into molecular packing. A surface with low curvedness designates a flat region and may be indicative of π–π stacking in the crystal. A Hirshfeld surface with high curvedness is highlighted as dark-blue edges, and is indicative of the absence of π–π stacking (Fig. 6 ▸). The nearest neighbour coordination environment of a molecule is identified from the colour patches on the Hirshfeld surface, depending on their closeness to adjacent molecules (Mohamooda Sumaya et al., 2018 ▸).
The 2D fingerprint plots of the d i and d e points for the contacts contributing to the Hirshfeld surface are shown in Fig. 7 ▸. They indicate that intermolecular H⋯H contacts provide the largest contribution (74.2%) to the Hirshfeld surface. The percentage contributions of the other interactions are C⋯H/H⋯C = 18.7%, O⋯H/H⋯O = 7.0% and N⋯H/H⋯N = 0.1%. The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions suggest that hydrogen bonding and van der Waals interactions play the major roles in the crystal packing (Hathwar et al., 2015 ▸).
Figure 7.
Two-dimensional fingerprint plot for the title compound showing the contributions of individual types of interactions: (a) all intermolecular contacts, (b) H⋯H contacts, (c) C⋯H/H⋯C contacts, (d) O⋯H/H⋯O contacts, (e) N⋯H/H⋯N contacts.
Database survey
A search of the Cambridge Structural Database (CSD, version 5.39; Groom et al., 2016 ▸) using piperidine as the main skeleton revealed the presence of more than 30 records with different substituents on the piperidine ring. However, there are only two compounds with the same skeleton as the title compound, viz. r-2,c-6-diphenylpiperidine (NIKYEN; Maheshwaran et al., 2013 ▸) and methyl 4-oxo-r-2,c-6-diphenylpiperidine-3-carboxylate (BIHZEY; Sampath et al., 2004 ▸). In these compounds, the piperidine ring adopts a chair conformation as the title compound. The phenyl rings substituted at the 2- and 6-positions of the piperidine ring subtend dihedral angles of 89.78 (7) and 48.30 (8)°, respectively, with the best plane of the piperidine ring in the title compound and 81.04 (7) and 81.10 (7)°, respectively, in NIKYEN, whereas in BIHZEY they are equatorially oriented. The C—H⋯O interaction leads to the formation of a C(8) chain in the title compound, while it forms dimers in the other two structures.
Synthesis and crystallization
t-3-Isopropyl-r-2,c-6-diphenylpiperidin-4-one was reduced to the corresponding piperidine using the Wolf–Kishner reduction (Ravindran & Jeyaraman, 1992 ▸). Piperidine-4-one (10 mmol) was treated with diethylene glycol (40 ml), hydrazine hydrate (10 mmol) and KOH pellets (10 mmol) to give t-3-isopropyl-r-2,c-6-diphenylpiperidine. N-Acetyl piperidine was synthesized by the acetylation of the above piperidine. To t-3-isopropyl-r-2,c-6-diphenylpiperidine (5 mmol) dissolved in benzene (50 ml) were added triethylamine (20 mmol) and acetyl chloride (20 mmol) to give the title compound, which was crystallized by slow evaporation from a benzene/petroleum ether ( v : v = ?:?) solution.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. H atoms were positioned geometrically (N—H = 0.88–0.90 Å and C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms,with U iso(H) = 1.5Ueq(C) for methyl H 1.2Ueq(C) for other H atoms.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | C22H27NO |
| M r | 321.44 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 296 |
| a, b, c (Å) | 13.3077 (5), 10.3009 (4), 13.9338 (5) |
| β (°) | 104.657 (1) |
| V (Å3) | 1847.91 (12) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.07 |
| Crystal size (mm) | 0.30 × 0.25 × 0.20 |
| Data collection | |
| Diffractometer | Bruker SMART APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2008 ▸) |
| T min, T max | 0.979, 0.986 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 43393, 5246, 3546 |
| R int | 0.028 |
| (sin θ/λ)max (Å−1) | 0.707 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.053, 0.169, 1.02 |
| No. of reflections | 5246 |
| No. of parameters | 221 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.45, −0.22 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020002042/dx2023sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989020002042/dx2023Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989020002042/dx2023Isup3.cml
CCDC reference: 1814839
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the SAIF, IIT Madras, India, for the data collection.
supplementary crystallographic information
Crystal data
| C22H27NO | F(000) = 696 |
| Mr = 321.44 | Dx = 1.155 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 13.3077 (5) Å | Cell parameters from 3546 reflections |
| b = 10.3009 (4) Å | θ = 1.9–30.2° |
| c = 13.9338 (5) Å | µ = 0.07 mm−1 |
| β = 104.657 (1)° | T = 296 K |
| V = 1847.91 (12) Å3 | Block, white crystalline |
| Z = 4 | 0.30 × 0.25 × 0.20 mm |
Data collection
| Bruker SMART APEXII CCD diffractometer | 3546 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.028 |
| ω and φ scans | θmax = 30.2°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −18→18 |
| Tmin = 0.979, Tmax = 0.986 | k = −14→14 |
| 43393 measured reflections | l = −19→19 |
| 5246 independent reflections |
Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.0897P)2 + 0.2822P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.169 | (Δ/σ)max = 0.001 |
| S = 1.02 | Δρmax = 0.45 e Å−3 |
| 5246 reflections | Δρmin = −0.22 e Å−3 |
| 221 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.028 (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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| C2 | 0.65890 (11) | −0.04974 (12) | 0.67960 (9) | 0.0430 (3) | |
| H2 | 0.710803 | −0.117590 | 0.703575 | 0.052* | |
| C3 | 0.55791 (12) | −0.11907 (14) | 0.63075 (11) | 0.0535 (4) | |
| H3A | 0.509789 | −0.058442 | 0.589793 | 0.064* | |
| H3B | 0.571443 | −0.188289 | 0.588507 | 0.064* | |
| C4 | 0.51045 (13) | −0.17493 (14) | 0.70987 (12) | 0.0553 (4) | |
| H4A | 0.562934 | −0.221549 | 0.758707 | 0.066* | |
| H4B | 0.455515 | −0.235360 | 0.680048 | 0.066* | |
| C5 | 0.46657 (10) | −0.06466 (13) | 0.75983 (10) | 0.0434 (3) | |
| H5 | 0.406942 | −0.029180 | 0.710452 | 0.052* | |
| C6 | 0.54640 (9) | 0.04763 (12) | 0.79099 (9) | 0.0386 (3) | |
| H6 | 0.561919 | 0.050544 | 0.863560 | 0.046* | |
| C7 | 0.50324 (9) | 0.18152 (12) | 0.75655 (9) | 0.0401 (3) | |
| C8 | 0.44865 (11) | 0.20754 (15) | 0.65996 (11) | 0.0509 (3) | |
| H8 | 0.438587 | 0.141664 | 0.612841 | 0.061* | |
| C9 | 0.40861 (12) | 0.33048 (16) | 0.63217 (13) | 0.0608 (4) | |
| H9 | 0.372408 | 0.346381 | 0.566876 | 0.073* | |
| C10 | 0.42249 (12) | 0.42814 (15) | 0.70093 (15) | 0.0649 (5) | |
| H10 | 0.395238 | 0.510190 | 0.682456 | 0.078* | |
| C11 | 0.47650 (13) | 0.40503 (15) | 0.79693 (15) | 0.0639 (4) | |
| H11 | 0.486050 | 0.471484 | 0.843544 | 0.077* | |
| C12 | 0.51698 (11) | 0.28257 (14) | 0.82473 (11) | 0.0508 (3) | |
| H12 | 0.553878 | 0.267904 | 0.889987 | 0.061* | |
| C13 | 0.69896 (10) | 0.03120 (13) | 0.60592 (9) | 0.0435 (3) | |
| C14 | 0.68956 (14) | 0.16488 (15) | 0.59909 (12) | 0.0593 (4) | |
| H14 | 0.656620 | 0.209142 | 0.640704 | 0.071* | |
| C15 | 0.72856 (16) | 0.23353 (17) | 0.53114 (13) | 0.0693 (5) | |
| H15 | 0.722127 | 0.323421 | 0.527699 | 0.083* | |
| C16 | 0.77685 (15) | 0.16916 (19) | 0.46859 (13) | 0.0695 (5) | |
| H16 | 0.803555 | 0.215281 | 0.423235 | 0.083* | |
| C17 | 0.78528 (15) | 0.03651 (18) | 0.47370 (13) | 0.0664 (5) | |
| H17 | 0.816965 | −0.007417 | 0.430922 | 0.080* | |
| C18 | 0.74709 (12) | −0.03242 (15) | 0.54185 (11) | 0.0528 (4) | |
| H18 | 0.753688 | −0.122304 | 0.544822 | 0.063* | |
| C19 | 0.73417 (10) | 0.06355 (13) | 0.83744 (10) | 0.0443 (3) | |
| C20 | 0.83981 (11) | 0.02750 (16) | 0.82495 (13) | 0.0565 (4) | |
| H20A | 0.851320 | 0.070404 | 0.767506 | 0.085* | |
| H20B | 0.843344 | −0.064779 | 0.816729 | 0.085* | |
| H20C | 0.892096 | 0.053889 | 0.882667 | 0.085* | |
| C21 | 0.42650 (12) | −0.10889 (15) | 0.84920 (12) | 0.0546 (4) | |
| H21 | 0.486985 | −0.132684 | 0.902717 | 0.065* | |
| C22 | 0.37021 (14) | 0.00100 (17) | 0.88713 (14) | 0.0665 (5) | |
| H22A | 0.313140 | 0.030351 | 0.834665 | 0.100* | |
| H22B | 0.417520 | 0.071598 | 0.909149 | 0.100* | |
| H22C | 0.344502 | −0.029708 | 0.941477 | 0.100* | |
| C23 | 0.35598 (17) | −0.22597 (19) | 0.82723 (17) | 0.0826 (6) | |
| H23A | 0.299342 | −0.208302 | 0.770673 | 0.124* | |
| H23B | 0.329279 | −0.244610 | 0.883608 | 0.124* | |
| H23C | 0.394522 | −0.299376 | 0.813439 | 0.124* | |
| N1 | 0.64819 (8) | 0.02265 (10) | 0.76798 (7) | 0.0396 (2) | |
| O1 | 0.72737 (8) | 0.12759 (12) | 0.90987 (7) | 0.0591 (3) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C2 | 0.0512 (7) | 0.0375 (6) | 0.0451 (7) | 0.0024 (5) | 0.0209 (6) | −0.0028 (5) |
| C3 | 0.0679 (9) | 0.0462 (7) | 0.0528 (8) | −0.0114 (7) | 0.0272 (7) | −0.0134 (6) |
| C4 | 0.0683 (9) | 0.0406 (7) | 0.0652 (9) | −0.0110 (6) | 0.0322 (7) | −0.0093 (6) |
| C5 | 0.0452 (7) | 0.0406 (6) | 0.0475 (7) | −0.0036 (5) | 0.0172 (5) | −0.0013 (5) |
| C6 | 0.0403 (6) | 0.0406 (6) | 0.0370 (6) | −0.0001 (5) | 0.0135 (5) | −0.0022 (5) |
| C7 | 0.0361 (6) | 0.0390 (6) | 0.0482 (7) | −0.0005 (5) | 0.0159 (5) | −0.0026 (5) |
| C8 | 0.0510 (8) | 0.0485 (7) | 0.0519 (8) | 0.0004 (6) | 0.0102 (6) | 0.0004 (6) |
| C9 | 0.0479 (8) | 0.0585 (9) | 0.0731 (10) | 0.0054 (7) | 0.0097 (7) | 0.0153 (8) |
| C10 | 0.0458 (8) | 0.0446 (8) | 0.1057 (14) | 0.0073 (6) | 0.0220 (9) | 0.0102 (8) |
| C11 | 0.0551 (9) | 0.0444 (8) | 0.0961 (13) | 0.0018 (6) | 0.0264 (8) | −0.0164 (8) |
| C12 | 0.0490 (8) | 0.0469 (7) | 0.0585 (8) | −0.0001 (6) | 0.0171 (6) | −0.0094 (6) |
| C13 | 0.0444 (7) | 0.0455 (7) | 0.0436 (7) | −0.0016 (5) | 0.0166 (5) | −0.0024 (5) |
| C14 | 0.0767 (10) | 0.0461 (8) | 0.0656 (9) | 0.0005 (7) | 0.0375 (8) | 0.0000 (7) |
| C15 | 0.0948 (13) | 0.0505 (9) | 0.0723 (10) | −0.0069 (8) | 0.0390 (9) | 0.0065 (8) |
| C16 | 0.0826 (12) | 0.0743 (11) | 0.0609 (9) | −0.0179 (9) | 0.0357 (9) | 0.0030 (8) |
| C17 | 0.0757 (11) | 0.0735 (11) | 0.0628 (9) | −0.0068 (9) | 0.0411 (8) | −0.0087 (8) |
| C18 | 0.0575 (8) | 0.0527 (8) | 0.0548 (8) | 0.0004 (6) | 0.0264 (7) | −0.0062 (6) |
| C19 | 0.0435 (7) | 0.0426 (7) | 0.0472 (7) | 0.0009 (5) | 0.0122 (5) | 0.0026 (5) |
| C20 | 0.0419 (7) | 0.0572 (9) | 0.0714 (10) | 0.0005 (6) | 0.0162 (7) | 0.0017 (7) |
| C21 | 0.0575 (8) | 0.0525 (8) | 0.0612 (8) | −0.0021 (6) | 0.0287 (7) | 0.0055 (6) |
| C22 | 0.0701 (10) | 0.0686 (10) | 0.0743 (10) | −0.0087 (8) | 0.0433 (9) | −0.0094 (8) |
| C23 | 0.0985 (15) | 0.0604 (11) | 0.1080 (15) | −0.0175 (10) | 0.0617 (12) | −0.0009 (10) |
| N1 | 0.0411 (5) | 0.0404 (5) | 0.0398 (5) | 0.0016 (4) | 0.0149 (4) | −0.0026 (4) |
| O1 | 0.0509 (6) | 0.0719 (7) | 0.0518 (6) | −0.0013 (5) | 0.0080 (4) | −0.0156 (5) |
Geometric parameters (Å, º)
| C2—N1 | 1.4770 (15) | C13—C14 | 1.384 (2) |
| C2—C13 | 1.5199 (18) | C13—C18 | 1.3878 (18) |
| C2—C3 | 1.522 (2) | C14—C15 | 1.384 (2) |
| C2—H2 | 0.9800 | C14—H14 | 0.9300 |
| C3—C4 | 1.516 (2) | C15—C16 | 1.377 (3) |
| C3—H3A | 0.9700 | C15—H15 | 0.9300 |
| C3—H3B | 0.9700 | C16—C17 | 1.371 (3) |
| C4—C5 | 1.5238 (19) | C16—H16 | 0.9300 |
| C4—H4A | 0.9700 | C17—C18 | 1.381 (2) |
| C4—H4B | 0.9700 | C17—H17 | 0.9300 |
| C5—C21 | 1.5422 (19) | C18—H18 | 0.9300 |
| C5—C6 | 1.5561 (18) | C19—O1 | 1.2280 (16) |
| C5—H5 | 0.9800 | C19—N1 | 1.3648 (17) |
| C6—N1 | 1.4913 (15) | C19—C20 | 1.5061 (19) |
| C6—C7 | 1.5241 (17) | C20—H20A | 0.9600 |
| C6—H6 | 0.9800 | C20—H20B | 0.9600 |
| C7—C8 | 1.3843 (19) | C20—H20C | 0.9600 |
| C7—C12 | 1.3897 (18) | C21—C23 | 1.511 (2) |
| C8—C9 | 1.390 (2) | C21—C22 | 1.524 (2) |
| C8—H8 | 0.9300 | C21—H21 | 0.9800 |
| C9—C10 | 1.369 (2) | C22—H22A | 0.9600 |
| C9—H9 | 0.9300 | C22—H22B | 0.9600 |
| C10—C11 | 1.370 (3) | C22—H22C | 0.9600 |
| C10—H10 | 0.9300 | C23—H23A | 0.9600 |
| C11—C12 | 1.388 (2) | C23—H23B | 0.9600 |
| C11—H11 | 0.9300 | C23—H23C | 0.9600 |
| C12—H12 | 0.9300 | ||
| N1—C2—C13 | 114.24 (10) | C14—C13—C18 | 118.30 (13) |
| N1—C2—C3 | 110.44 (10) | C14—C13—C2 | 123.46 (12) |
| C13—C2—C3 | 112.10 (11) | C18—C13—C2 | 118.25 (12) |
| N1—C2—H2 | 106.5 | C15—C14—C13 | 120.84 (15) |
| C13—C2—H2 | 106.5 | C15—C14—H14 | 119.6 |
| C3—C2—H2 | 106.5 | C13—C14—H14 | 119.6 |
| C4—C3—C2 | 109.64 (12) | C16—C15—C14 | 120.20 (16) |
| C4—C3—H3A | 109.7 | C16—C15—H15 | 119.9 |
| C2—C3—H3A | 109.7 | C14—C15—H15 | 119.9 |
| C4—C3—H3B | 109.7 | C17—C16—C15 | 119.48 (15) |
| C2—C3—H3B | 109.7 | C17—C16—H16 | 120.3 |
| H3A—C3—H3B | 108.2 | C15—C16—H16 | 120.3 |
| C3—C4—C5 | 109.13 (11) | C16—C17—C18 | 120.55 (15) |
| C3—C4—H4A | 109.9 | C16—C17—H17 | 119.7 |
| C5—C4—H4A | 109.9 | C18—C17—H17 | 119.7 |
| C3—C4—H4B | 109.9 | C17—C18—C13 | 120.63 (15) |
| C5—C4—H4B | 109.9 | C17—C18—H18 | 119.7 |
| H4A—C4—H4B | 108.3 | C13—C18—H18 | 119.7 |
| C4—C5—C21 | 113.54 (11) | O1—C19—N1 | 121.72 (12) |
| C4—C5—C6 | 111.60 (11) | O1—C19—C20 | 119.50 (13) |
| C21—C5—C6 | 110.21 (11) | N1—C19—C20 | 118.78 (12) |
| C4—C5—H5 | 107.0 | C19—C20—H20A | 109.5 |
| C21—C5—H5 | 107.0 | C19—C20—H20B | 109.5 |
| C6—C5—H5 | 107.0 | H20A—C20—H20B | 109.5 |
| N1—C6—C7 | 112.27 (10) | C19—C20—H20C | 109.5 |
| N1—C6—C5 | 113.89 (10) | H20A—C20—H20C | 109.5 |
| C7—C6—C5 | 114.11 (10) | H20B—C20—H20C | 109.5 |
| N1—C6—H6 | 105.2 | C23—C21—C22 | 109.18 (14) |
| C7—C6—H6 | 105.2 | C23—C21—C5 | 113.34 (13) |
| C5—C6—H6 | 105.2 | C22—C21—C5 | 111.18 (13) |
| C8—C7—C12 | 117.74 (13) | C23—C21—H21 | 107.6 |
| C8—C7—C6 | 122.99 (12) | C22—C21—H21 | 107.6 |
| C12—C7—C6 | 119.25 (12) | C5—C21—H21 | 107.6 |
| C7—C8—C9 | 121.13 (14) | C21—C22—H22A | 109.5 |
| C7—C8—H8 | 119.4 | C21—C22—H22B | 109.5 |
| C9—C8—H8 | 119.4 | H22A—C22—H22B | 109.5 |
| C10—C9—C8 | 120.00 (15) | C21—C22—H22C | 109.5 |
| C10—C9—H9 | 120.0 | H22A—C22—H22C | 109.5 |
| C8—C9—H9 | 120.0 | H22B—C22—H22C | 109.5 |
| C9—C10—C11 | 120.01 (15) | C21—C23—H23A | 109.5 |
| C9—C10—H10 | 120.0 | C21—C23—H23B | 109.5 |
| C11—C10—H10 | 120.0 | H23A—C23—H23B | 109.5 |
| C10—C11—C12 | 120.09 (15) | C21—C23—H23C | 109.5 |
| C10—C11—H11 | 120.0 | H23A—C23—H23C | 109.5 |
| C12—C11—H11 | 120.0 | H23B—C23—H23C | 109.5 |
| C11—C12—C7 | 121.02 (15) | C19—N1—C2 | 120.44 (11) |
| C11—C12—H12 | 119.5 | C19—N1—C6 | 116.00 (10) |
| C7—C12—H12 | 119.5 | C2—N1—C6 | 123.43 (10) |
| N1—C2—C3—C4 | −39.81 (16) | C18—C13—C14—C15 | −1.0 (3) |
| C13—C2—C3—C4 | −168.43 (12) | C2—C13—C14—C15 | 179.32 (15) |
| C2—C3—C4—C5 | 72.53 (16) | C13—C14—C15—C16 | 0.5 (3) |
| C3—C4—C5—C21 | −173.93 (13) | C14—C15—C16—C17 | 0.5 (3) |
| C3—C4—C5—C6 | −48.63 (16) | C15—C16—C17—C18 | −0.9 (3) |
| C4—C5—C6—N1 | −1.38 (15) | C16—C17—C18—C13 | 0.4 (3) |
| C21—C5—C6—N1 | 125.74 (12) | C14—C13—C18—C17 | 0.5 (2) |
| C4—C5—C6—C7 | 129.33 (12) | C2—C13—C18—C17 | −179.74 (14) |
| C21—C5—C6—C7 | −103.55 (13) | C4—C5—C21—C23 | −48.70 (19) |
| N1—C6—C7—C8 | 82.58 (15) | C6—C5—C21—C23 | −174.73 (14) |
| C5—C6—C7—C8 | −48.92 (16) | C4—C5—C21—C22 | −172.13 (14) |
| N1—C6—C7—C12 | −98.65 (13) | C6—C5—C21—C22 | 61.84 (16) |
| C5—C6—C7—C12 | 129.85 (12) | O1—C19—N1—C2 | 177.54 (12) |
| C12—C7—C8—C9 | −0.2 (2) | C20—C19—N1—C2 | −3.16 (18) |
| C6—C7—C8—C9 | 178.56 (13) | O1—C19—N1—C6 | −6.49 (18) |
| C7—C8—C9—C10 | −0.3 (2) | C20—C19—N1—C6 | 172.81 (11) |
| C8—C9—C10—C11 | 0.5 (3) | C13—C2—N1—C19 | −69.70 (15) |
| C9—C10—C11—C12 | −0.2 (2) | C3—C2—N1—C19 | 162.84 (12) |
| C10—C11—C12—C7 | −0.4 (2) | C13—C2—N1—C6 | 114.64 (13) |
| C8—C7—C12—C11 | 0.6 (2) | C3—C2—N1—C6 | −12.81 (17) |
| C6—C7—C12—C11 | −178.28 (13) | C7—C6—N1—C19 | 87.19 (13) |
| N1—C2—C13—C14 | −23.54 (19) | C5—C6—N1—C19 | −141.19 (11) |
| C3—C2—C13—C14 | 103.05 (16) | C7—C6—N1—C2 | −96.97 (13) |
| N1—C2—C13—C18 | 156.75 (12) | C5—C6—N1—C2 | 34.64 (15) |
| C3—C2—C13—C18 | −76.66 (16) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C9—H9···O1i | 0.93 | 2.54 | 3.4378 (19) | 163 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2.
Funding Statement
This work was funded by University Grants Commission grant .
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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/S2056989020002042/dx2023sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989020002042/dx2023Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989020002042/dx2023Isup3.cml
CCDC reference: 1814839
Additional supporting information: crystallographic information; 3D view; checkCIF report