The title Schiff base compound was synthesized and its crystal structure characterized by X-ray diffraction. The molecular structure, frontier orbitals and molecular electrostatic potential map were also investigated by DFT methods.
Keywords: Schiff base, rotational disorder, enol–imine, tert-butyl, DFT, crystal structure
Abstract
The title compound, C23H28F3NO, is an ortho-hydroxy Schiff base compound, which adopts the enol–imine tautomeric form in the solid state. The molecular structure is not planar and the dihedral angle between the planes of the aromatic rings is 85.52 (10)°. The trifluoromethyl group shows rotational disorder over two sites, with occupancies of 0.798 (6) and 0.202 (6). An intramolecular O—H⋯N hydrogen bonding generates an S(6) ring motif. The crystal structure is consolidated by C—H⋯π interactions. The molecular structure was optimized via density functional theory (DFT) methods with the B3LYP functional and LanL2DZ basis set. The theoretical structure is in good agreement with the experimental data. The frontier orbitals and molecular electrostatic potential map were also examined by DFT computations.
Chemical context
Schiff base ligands have played an important role in the development of coordination chemistry, specifically in relation to magnetism, enzymatic reactions (Moutet & Ourari, 1997 ▸) and molecular architectures (Kaynar et al., 2018 ▸). Schiff bases and their metal complexes have been used in antibacterial, anticancer, antifungal, antitubercular and hypothermic reagents (Marchant et al., 1981 ▸; Turwatker & Mahta, 2007 ▸). Generally, ortho-hydroxy Schiff base compounds display two tautomeric, enol–imine (OH) and keto–amine (NH), forms. Depending on the tautomers, two types of intramolecular hydrogen bonds are observed in ortho-hydroxy Schiff bases, namely, O—H⋯N in enol–imine and N—H⋯O in keto–amine tautomers (Tanak et al., 2009 ▸, 2010 ▸). In this study, we report the synthesis, crystal structure and density functional theory (DFT) calculations of the title Schiff base compound.
Structural commentary
The molecular structure of the title compound is shown in Fig. 1 ▸(a). The crystal structure is monoclinic and has the space-group type P21/c. The CF3 group exhibits rotational disorder [Fig. 1 ▸(a)]. The site-occupancy factors are 0.798 (6) and 0.202 (6) for F1A/F2A/F3A and F1B/F2B/F3B, respectively. The DFT computations of the title compound were performed with the Gaussian 09W program package (Frisch et al., 2009 ▸) using the B3LYP functional and the LanL2DZ basis set. The optimized molecular structure is illustrated in Fig. 1 ▸(b). Some selected theoretical bond lengths, bond angles and torsion angles are given in Table 1 ▸ along with the experimental values. The molecular structure of the title compound is not planar: the dihedral angle between the 2,4-di-tert-butylphenol and the trifluoromethyl rings is 85.52 (10)°. This dihedral angle was calculated to be 65.73° for the B3LYP computationally derived structure. The imino group is nearly coplanar with the 2,4-di-tert-butylphenol ring, as indicated by the C1—C14—C15—N1 torsion angle [−3.9 (3)° for X-ray and −0.14° for B3LYP]. There is an intramolecular O1—H1⋯N1 hydrogen bond present (Fig. 1 ▸ and Table 2 ▸), generating an S(6) ring motif. The C1—O1 bond length [1.353 (2) Å for X-ray and 1.376 Å for B3LYP] indicates single-bond character. The imine C15=N1 bond length [1.273 (2) Å for X-ray and 1.308 Å for B3LYP] indicates double-bond character. In the title compound, the bond lengths and bond angles are within normal ranges and they are comparable with those in related Schiff base structures (Li et al., 2007 ▸; Sun et al., 2007 ▸; Çelik et al., 2009 ▸; Şahin et al., 2009 ▸; Kansiz et al., 2018 ▸). The C1—O1 and C15=N1 bond lengths confirm the enol–imine form of the title compound (Tanak, 2011 ▸; Kaynar et al., 2018 ▸).
Figure 1.
(a) The molecular structure of the title compound, showing the atom-numbering scheme and 20% probability displacement ellipsoids and (b) the optimized molecular structure of the title compound generated at the DFT/B3LYP/LanL2DZ level.
Table 1. Some selected bond lengths, bond angles and torsion angles (Å, °) in the experimentally determined and computed molecular structures.
| Parameters | X-ray | DFT |
|---|---|---|
| O1—C1 | 1.353 (2) | 1.376 |
| N1—C15 | 1.273 (2) | 1.308 |
| N1—C16 | 1.457 (3) | 1.467 |
| C14—C15 | 1.456 (3) | 1.457 |
| C15—N1—C16 | 118.68 (18) | 120.83 |
| O1—C1—C2 | 119.87 (16) | 120.63 |
| O1—C1—C14 | 119.60 (17) | 119.16 |
| N1—C15—C14 | 122.99 (18) | 121.96 |
| N1—C16—C17 | 113.09 (16) | 112.67 |
| O1—C1—C14—C15 | 2.2 (3) | 0.28 |
| C16—N1—C15—C14 | 178.67 (18) | 178.34 |
| C13—C14—C15—N1 | 175.7 (2) | 179.87 |
| C15—N1—C16—C17 | 107.5 (2) | 130.42 |
Table 2. Hydrogen-bond geometry (Å, °).
Cg1 and Cg2 are the centroids of the C1/C2/C7/C8/C13/C14 and C17–C23 rings, respectively.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H1⋯N1 | 0.92 (3) | 1.73 (3) | 2.587 (2) | 154 (3) |
| C16—H16B⋯Cg2i | 0.97 | 2.77 | 3.705 (3) | 162 |
| C21—H21⋯Cg1ii | 0.93 | 2.85 | 3.631 (3) | 143 |
Symmetry codes: (i) 
; (ii) 
.
Supramolecular features
The crystal structure of the title compound is consolidated by C—H⋯π interactions (Fig. 2 ▸), details of which are summarized in Table 2 ▸. A packing diagram is shown in Fig. 3 ▸. The only other interactions are van der Waals contacts.
Figure 2.
A partial packing plot of the title crystal. Dashed lines indicate the O—H⋯N intramolecular hydrogen bonding and C—H⋯π interactions.
Figure 3.
The crystal packing of the title compound, viewed along the a axis.
Molecular electrostatic potential (MEP)
The molecular electrostatic potential (MEP) is a very useful descriptor for classifying and understanding regions that are susceptible to electrophilic versus nucleophilic attack. In order to analyse reactive regions for electrophilic and nucleophilic reactions for the investigated Schiff base molecule, the MEP surface was computed using the B3LYP/LanL2DZ basis set for the optimized geometry. In the MEP surface, the negative potential regions (red areas) are associated with electrophilic reactivity, while the positive potential regions (blue areas) are related to nucleophilic reactivity. The MEP surface of the compound is shown in Fig. 4 ▸. The negative MEP regions are mainly over the O1, F1, F2, and F3 atoms and have values of −0.049 a.u., −0.031 a.u., −0.032 a.u. and −0.035 a.u., respectively. The largest maximum positive MEP region is localized on atom H15, and has a value of +0.048 a.u. According to these results, the preferred sites for electrophilic attack are around the oxygen and fluorine atoms, while the preferred region for nucleophilic attack is the imine group C—H atom, H15.
Figure 4.
The molecular electrostatic potential map of the title compound.
Frontier molecular orbitals
The highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) are known as frontier molecular orbitals. The electronic, optical and chemical reactivity properties of compounds are predicted by their frontier molecular orbitals (Tanak, 2019 ▸). The frontier molecular orbitals of the title compound were obtained using the DFT/B3LYP method with the LanL2DZ basis set. The energy levels and distributions of the frontier molecular orbitals are shown in Fig. 5 ▸. The HOMO–LUMO gap is used to analyse the chemical reactivity and stability of a molecule. If the molecule has a large HOMO–LUMO gap, the molecule is more stable and less chemically reactive. The term ‘hard molecule’ is used to describe such cases. The electron affinity (A = -E HOMO), the ionization potential (I = -E LUMO), HOMO–LUMO energy gap (ΔE), the chemical hardness (η) and softness (S) of the title compound were predicted based on the E HOMO and E LUMO energies (Tanak, 2019 ▸). For the title compound, I = 5.912 eV, A= 1.807 eV, ΔE = 4.105 eV, η = 2.052 eV and S = 0.243 eV. As a result of the large ΔE and η values, the title compound can be classified as a hard molecule.
Figure 5.
The frontier molecular orbitals.
Synthesis and crystallization
(E)-2,4-Di-tert-butyl-6-((3-(trifluoromethyl)benzylimino)methyl)phenol was prepared by refluxing a mixture of a solution containing 3,5-di-tert-butyl-2-hydroxybenzaldehyde (46.8 mg, 0.2 mmol) in ethanol (30 ml) and a solution containing 3-(trifluoromethyl)benzylamine (35.03 mg, 0.2 mmol) in ethanol (20 ml). The reaction mixture was stirred for 4 h under reflux. The title compound was obtained by slow evaporation of an ethanol solution (m.p. 401–403 K; yield 78%)
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and U iso(H) = 1.2–1.5U eq(C). The position of the H1 atom was obtained from a difference map of the electron density in the unit cell and was refined freely.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | C23H28F3NO |
| M r | 391.46 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 296 |
| a, b, c (Å) | 15.6783 (10), 15.7880 (14), 8.7054 (5) |
| β (°) | 91.217 (5) |
| V (Å3) | 2154.4 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.09 |
| Crystal size (mm) | 0.72 × 0.56 × 0.09 |
| Data collection | |
| Diffractometer | STOE IPDS 2 |
| Absorption correction | Integration (X-RED32; Stoe & Cie, 2002 ▸) |
| T min, T max | 0.938, 0.992 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 24168, 4981, 2875 |
| R int | 0.062 |
| (sin θ/λ)max (Å−1) | 0.652 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.059, 0.149, 1.01 |
| No. of reflections | 4981 |
| No. of parameters | 291 |
| No. of restraints | 67 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.17, −0.14 |
Supplementary Material
Crystal structure: contains datablock(s) I, namiko43. DOI: 10.1107/S205698902000537X/pk2624sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698902000537X/pk2624Isup2.hkl
Supporting information file. DOI: 10.1107/S205698902000537X/pk2624Isup3.cml
CCDC reference: 1997654
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).
supplementary crystallographic information
Crystal data
| C23H28F3NO | F(000) = 832 |
| Mr = 391.46 | Dx = 1.207 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 15.6783 (10) Å | Cell parameters from 19720 reflections |
| b = 15.7880 (14) Å | θ = 1.8–28.0° |
| c = 8.7054 (5) Å | µ = 0.09 mm−1 |
| β = 91.217 (5)° | T = 296 K |
| V = 2154.4 (3) Å3 | Plate, orange |
| Z = 4 | 0.72 × 0.56 × 0.09 mm |
Data collection
| STOE IPDS 2 diffractometer | 4981 independent reflections |
| Radiation source: fine-focus sealed tube | 2875 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.062 |
| Detector resolution: 6.67 pixels mm-1 | θmax = 27.6°, θmin = 2.6° |
| rotation method scans | h = −20→20 |
| Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −20→20 |
| Tmin = 0.938, Tmax = 0.992 | l = −10→11 |
| 24168 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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.149 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.072P)2] where P = (Fo2 + 2Fc2)/3 |
| 4981 reflections | (Δ/σ)max < 0.001 |
| 291 parameters | Δρmax = 0.17 e Å−3 |
| 67 restraints | Δρmin = −0.14 e Å−3 |
Special details
| Experimental. 248 frames, detector distance = 80 mm |
| 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 | Occ. (<1) | |
| F1A | 0.82817 (19) | 0.75361 (18) | 1.1564 (8) | 0.1412 (18) | 0.798 (6) |
| F2A | 0.8487 (2) | 0.6371 (4) | 1.2628 (5) | 0.1492 (18) | 0.798 (6) |
| F3A | 0.86847 (16) | 0.6497 (4) | 1.0276 (5) | 0.1431 (18) | 0.798 (6) |
| F1B | 0.8509 (6) | 0.7243 (11) | 1.0355 (15) | 0.108 (4) | 0.202 (6) |
| F2B | 0.8298 (5) | 0.7109 (13) | 1.2651 (14) | 0.112 (4) | 0.202 (6) |
| F3B | 0.8690 (5) | 0.6084 (6) | 1.140 (2) | 0.119 (4) | 0.202 (6) |
| O1 | 0.42489 (9) | 0.60037 (10) | 0.54544 (18) | 0.0583 (4) | |
| N1 | 0.47793 (10) | 0.69181 (11) | 0.77476 (19) | 0.0517 (4) | |
| C1 | 0.34413 (11) | 0.61230 (12) | 0.5935 (2) | 0.0442 (4) | |
| C2 | 0.27563 (12) | 0.57558 (12) | 0.5121 (2) | 0.0474 (5) | |
| C3 | 0.28920 (14) | 0.52313 (15) | 0.3652 (2) | 0.0604 (6) | |
| C4 | 0.3291 (2) | 0.57867 (19) | 0.2417 (3) | 0.0900 (9) | |
| H4A | 0.3843 | 0.5977 | 0.2770 | 0.135* | |
| H4B | 0.2931 | 0.6268 | 0.2216 | 0.135* | |
| H4C | 0.3350 | 0.5464 | 0.1490 | 0.135* | |
| C5 | 0.34662 (19) | 0.44671 (17) | 0.4018 (3) | 0.0866 (8) | |
| H5A | 0.4010 | 0.4662 | 0.4405 | 0.130* | |
| H5B | 0.3546 | 0.4142 | 0.3101 | 0.130* | |
| H5C | 0.3202 | 0.4120 | 0.4779 | 0.130* | |
| C6 | 0.20508 (18) | 0.4890 (2) | 0.2985 (3) | 0.0923 (9) | |
| H6A | 0.2160 | 0.4565 | 0.2078 | 0.138* | |
| H6B | 0.1680 | 0.5354 | 0.2728 | 0.138* | |
| H6C | 0.1784 | 0.4535 | 0.3732 | 0.138* | |
| C7 | 0.19492 (12) | 0.58784 (13) | 0.5719 (2) | 0.0520 (5) | |
| H7 | 0.1487 | 0.5639 | 0.5192 | 0.062* | |
| C8 | 0.17838 (12) | 0.63327 (13) | 0.7047 (2) | 0.0539 (5) | |
| C9 | 0.08888 (13) | 0.64131 (16) | 0.7727 (3) | 0.0680 (6) | |
| C10 | 0.02115 (17) | 0.5997 (3) | 0.6718 (5) | 0.1314 (15) | |
| H10A | −0.0338 | 0.6080 | 0.7159 | 0.197* | |
| H10B | 0.0327 | 0.5402 | 0.6642 | 0.197* | |
| H10C | 0.0216 | 0.6246 | 0.5712 | 0.197* | |
| C11 | 0.0905 (2) | 0.5998 (3) | 0.9306 (4) | 0.1116 (12) | |
| H11A | 0.1338 | 0.6261 | 0.9942 | 0.167* | |
| H11B | 0.1028 | 0.5406 | 0.9202 | 0.167* | |
| H11C | 0.0359 | 0.6067 | 0.9770 | 0.167* | |
| C12 | 0.06544 (18) | 0.7341 (2) | 0.7915 (4) | 0.1009 (10) | |
| H12A | 0.0639 | 0.7611 | 0.6926 | 0.151* | |
| H12B | 0.1073 | 0.7615 | 0.8565 | 0.151* | |
| H12C | 0.0104 | 0.7384 | 0.8371 | 0.151* | |
| C13 | 0.24757 (12) | 0.67031 (14) | 0.7790 (2) | 0.0550 (5) | |
| H13 | 0.2388 | 0.7024 | 0.8668 | 0.066* | |
| C14 | 0.32996 (11) | 0.66083 (12) | 0.7260 (2) | 0.0463 (5) | |
| C15 | 0.40013 (12) | 0.70132 (13) | 0.8100 (2) | 0.0512 (5) | |
| H15 | 0.3875 | 0.7357 | 0.8932 | 0.061* | |
| C16 | 0.54326 (13) | 0.73660 (13) | 0.8642 (3) | 0.0547 (5) | |
| H16A | 0.5162 | 0.7797 | 0.9258 | 0.066* | |
| H16B | 0.5814 | 0.7650 | 0.7945 | 0.066* | |
| C17 | 0.59483 (12) | 0.67922 (12) | 0.9685 (2) | 0.0456 (4) | |
| C18 | 0.67935 (12) | 0.69802 (13) | 1.0007 (2) | 0.0509 (5) | |
| H18 | 0.7044 | 0.7446 | 0.9543 | 0.061* | |
| C19 | 0.72737 (13) | 0.64835 (15) | 1.1014 (2) | 0.0581 (5) | |
| C20 | 0.81794 (16) | 0.6718 (2) | 1.1355 (4) | 0.0818 (7) | |
| C21 | 0.69155 (16) | 0.57852 (15) | 1.1692 (3) | 0.0685 (6) | |
| H21 | 0.7239 | 0.5445 | 1.2353 | 0.082* | |
| C22 | 0.60725 (16) | 0.55961 (15) | 1.1381 (3) | 0.0706 (7) | |
| H22 | 0.5824 | 0.5129 | 1.1845 | 0.085* | |
| C23 | 0.55955 (14) | 0.60916 (14) | 1.0392 (2) | 0.0571 (5) | |
| H23 | 0.5027 | 0.5955 | 1.0192 | 0.069* | |
| H1 | 0.4592 (18) | 0.6288 (18) | 0.616 (3) | 0.088 (9)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1A | 0.0791 (18) | 0.100 (2) | 0.242 (5) | −0.0161 (14) | −0.055 (3) | −0.027 (2) |
| F2A | 0.099 (2) | 0.203 (4) | 0.143 (3) | −0.021 (2) | −0.066 (2) | 0.050 (3) |
| F3A | 0.0563 (14) | 0.225 (5) | 0.149 (3) | −0.002 (2) | 0.0203 (16) | −0.047 (3) |
| F1B | 0.060 (5) | 0.146 (9) | 0.116 (7) | −0.030 (6) | −0.012 (5) | 0.022 (7) |
| F2B | 0.073 (5) | 0.162 (10) | 0.102 (6) | −0.002 (7) | −0.011 (5) | −0.046 (6) |
| F3B | 0.075 (5) | 0.130 (7) | 0.151 (10) | 0.046 (5) | −0.023 (7) | −0.009 (6) |
| O1 | 0.0422 (8) | 0.0723 (10) | 0.0606 (9) | −0.0033 (7) | 0.0091 (7) | −0.0136 (8) |
| N1 | 0.0455 (9) | 0.0569 (10) | 0.0526 (9) | −0.0018 (7) | −0.0032 (7) | −0.0023 (8) |
| C1 | 0.0407 (10) | 0.0457 (10) | 0.0465 (10) | 0.0016 (8) | 0.0054 (8) | 0.0020 (9) |
| C2 | 0.0491 (11) | 0.0469 (11) | 0.0462 (11) | −0.0004 (8) | 0.0016 (9) | −0.0005 (9) |
| C3 | 0.0616 (13) | 0.0663 (14) | 0.0532 (12) | −0.0070 (10) | 0.0051 (10) | −0.0139 (11) |
| C4 | 0.115 (2) | 0.105 (2) | 0.0502 (14) | −0.0252 (17) | 0.0177 (14) | −0.0142 (14) |
| C5 | 0.0966 (19) | 0.0724 (17) | 0.0909 (19) | 0.0110 (14) | 0.0060 (15) | −0.0301 (15) |
| C6 | 0.0825 (18) | 0.114 (2) | 0.0805 (17) | −0.0190 (16) | −0.0042 (14) | −0.0440 (17) |
| C7 | 0.0446 (11) | 0.0576 (12) | 0.0536 (11) | −0.0041 (9) | −0.0025 (9) | −0.0021 (10) |
| C8 | 0.0420 (10) | 0.0612 (13) | 0.0586 (12) | 0.0046 (9) | 0.0044 (9) | −0.0025 (10) |
| C9 | 0.0438 (11) | 0.0861 (17) | 0.0744 (15) | 0.0031 (11) | 0.0112 (10) | −0.0033 (13) |
| C10 | 0.0439 (14) | 0.200 (4) | 0.151 (3) | −0.0211 (19) | 0.0191 (17) | −0.066 (3) |
| C11 | 0.0784 (19) | 0.144 (3) | 0.114 (3) | 0.0155 (19) | 0.0436 (18) | 0.036 (2) |
| C12 | 0.0669 (17) | 0.107 (2) | 0.130 (3) | 0.0267 (16) | 0.0250 (17) | −0.003 (2) |
| C13 | 0.0492 (11) | 0.0631 (13) | 0.0528 (11) | 0.0048 (9) | 0.0041 (9) | −0.0113 (10) |
| C14 | 0.0426 (10) | 0.0490 (11) | 0.0473 (10) | 0.0027 (8) | 0.0008 (8) | −0.0026 (9) |
| C15 | 0.0521 (12) | 0.0519 (11) | 0.0494 (11) | 0.0026 (9) | 0.0001 (9) | −0.0063 (9) |
| C16 | 0.0508 (11) | 0.0525 (12) | 0.0607 (12) | −0.0066 (9) | −0.0058 (9) | 0.0001 (10) |
| C17 | 0.0476 (10) | 0.0460 (11) | 0.0433 (10) | −0.0035 (8) | 0.0035 (8) | −0.0069 (8) |
| C18 | 0.0475 (11) | 0.0524 (12) | 0.0530 (11) | −0.0068 (9) | 0.0040 (9) | −0.0036 (9) |
| C19 | 0.0515 (11) | 0.0658 (14) | 0.0569 (12) | 0.0044 (10) | −0.0030 (9) | −0.0076 (11) |
| C20 | 0.0551 (13) | 0.0978 (19) | 0.0921 (18) | 0.0080 (13) | −0.0109 (13) | −0.0007 (15) |
| C21 | 0.0743 (16) | 0.0650 (15) | 0.0655 (15) | 0.0072 (12) | −0.0106 (12) | 0.0095 (12) |
| C22 | 0.0817 (17) | 0.0594 (14) | 0.0706 (15) | −0.0142 (12) | −0.0044 (13) | 0.0155 (12) |
| C23 | 0.0558 (12) | 0.0585 (13) | 0.0570 (12) | −0.0127 (10) | −0.0018 (10) | 0.0007 (11) |
Geometric parameters (Å, º)
| F1A—C20 | 1.313 (4) | C7—C8 | 1.390 (3) |
| F2A—C20 | 1.318 (4) | C8—C13 | 1.381 (3) |
| F3A—C20 | 1.290 (4) | C8—C9 | 1.540 (3) |
| F1B—C20 | 1.315 (6) | C9—C10 | 1.514 (4) |
| F2B—C20 | 1.296 (6) | C9—C12 | 1.521 (4) |
| F3B—C20 | 1.282 (6) | C9—C11 | 1.522 (4) |
| O1—C1 | 1.355 (2) | C13—C14 | 1.389 (3) |
| N1—C15 | 1.273 (2) | C14—C15 | 1.456 (3) |
| N1—C16 | 1.457 (3) | C16—C17 | 1.506 (3) |
| C1—C2 | 1.400 (3) | C17—C18 | 1.381 (3) |
| C1—C14 | 1.406 (3) | C17—C23 | 1.387 (3) |
| C2—C7 | 1.392 (3) | C18—C19 | 1.386 (3) |
| C2—C3 | 1.542 (3) | C19—C21 | 1.376 (3) |
| C3—C6 | 1.528 (3) | C19—C20 | 1.491 (3) |
| C3—C4 | 1.531 (3) | C21—C22 | 1.376 (3) |
| C3—C5 | 1.535 (4) | C22—C23 | 1.373 (3) |
| C15—N1—C16 | 118.71 (18) | C18—C17—C16 | 119.59 (17) |
| O1—C1—C2 | 119.84 (17) | C23—C17—C16 | 122.23 (17) |
| O1—C1—C14 | 119.60 (17) | C17—C18—C19 | 120.85 (19) |
| C2—C1—C14 | 120.55 (16) | C21—C19—C18 | 120.2 (2) |
| C7—C2—C1 | 116.51 (17) | C21—C19—C20 | 120.6 (2) |
| C7—C2—C3 | 121.84 (18) | C18—C19—C20 | 119.2 (2) |
| C1—C2—C3 | 121.64 (17) | F3B—C20—F3A | 54.5 (8) |
| C6—C3—C4 | 107.3 (2) | F3B—C20—F2B | 105.4 (10) |
| C6—C3—C5 | 107.4 (2) | F3A—C20—F2B | 133.2 (5) |
| C4—C3—C5 | 110.5 (2) | F3B—C20—F1A | 133.6 (5) |
| C6—C3—C2 | 111.79 (18) | F3A—C20—F1A | 107.0 (4) |
| C4—C3—C2 | 109.91 (19) | F2B—C20—F1A | 52.9 (9) |
| C5—C3—C2 | 109.89 (19) | F3B—C20—F1B | 105.1 (10) |
| C8—C7—C2 | 124.77 (19) | F3A—C20—F1B | 55.4 (8) |
| C13—C8—C7 | 116.71 (17) | F2B—C20—F1B | 103.0 (10) |
| C13—C8—C9 | 119.89 (19) | F1A—C20—F1B | 54.8 (7) |
| C7—C8—C9 | 123.37 (19) | F3B—C20—F2A | 55.3 (8) |
| C10—C9—C12 | 108.2 (3) | F3A—C20—F2A | 106.3 (3) |
| C10—C9—C11 | 109.6 (3) | F2B—C20—F2A | 54.8 (8) |
| C12—C9—C11 | 108.5 (3) | F1A—C20—F2A | 104.5 (4) |
| C10—C9—C8 | 112.0 (2) | F1B—C20—F2A | 132.6 (4) |
| C12—C9—C8 | 110.2 (2) | F3B—C20—C19 | 113.8 (5) |
| C11—C9—C8 | 108.3 (2) | F3A—C20—C19 | 112.6 (3) |
| C8—C13—C14 | 121.71 (19) | F2B—C20—C19 | 114.2 (4) |
| C13—C14—C1 | 119.70 (18) | F1A—C20—C19 | 112.7 (2) |
| C13—C14—C15 | 118.93 (17) | F1B—C20—C19 | 114.2 (4) |
| C1—C14—C15 | 121.36 (16) | F2A—C20—C19 | 113.2 (3) |
| N1—C15—C14 | 123.01 (18) | C19—C21—C22 | 119.2 (2) |
| N1—C16—C17 | 113.12 (16) | C23—C22—C21 | 120.5 (2) |
| C18—C17—C23 | 118.13 (19) | C22—C23—C17 | 121.1 (2) |
| O1—C1—C2—C7 | 177.52 (18) | C16—N1—C15—C14 | 178.69 (18) |
| C14—C1—C2—C7 | −1.8 (3) | C13—C14—C15—N1 | 175.7 (2) |
| O1—C1—C2—C3 | −1.6 (3) | C1—C14—C15—N1 | −3.9 (3) |
| C14—C1—C2—C3 | 179.11 (19) | C15—N1—C16—C17 | 107.5 (2) |
| C7—C2—C3—C6 | 0.3 (3) | N1—C16—C17—C18 | 148.23 (18) |
| C1—C2—C3—C6 | 179.3 (2) | N1—C16—C17—C23 | −34.4 (3) |
| C7—C2—C3—C4 | 119.4 (2) | C23—C17—C18—C19 | −0.2 (3) |
| C1—C2—C3—C4 | −61.6 (3) | C16—C17—C18—C19 | 177.26 (19) |
| C7—C2—C3—C5 | −118.9 (2) | C17—C18—C19—C21 | 0.9 (3) |
| C1—C2—C3—C5 | 60.2 (3) | C17—C18—C19—C20 | −178.8 (2) |
| C1—C2—C7—C8 | 0.0 (3) | C21—C19—C20—F3B | 42.0 (11) |
| C3—C2—C7—C8 | 179.0 (2) | C18—C19—C20—F3B | −138.3 (10) |
| C2—C7—C8—C13 | 1.8 (3) | C21—C19—C20—F3A | 101.8 (4) |
| C2—C7—C8—C9 | −176.4 (2) | C18—C19—C20—F3A | −78.5 (4) |
| C13—C8—C9—C10 | 177.7 (3) | C21—C19—C20—F2B | −79.1 (12) |
| C7—C8—C9—C10 | −4.3 (4) | C18—C19—C20—F2B | 100.6 (12) |
| C13—C8—C9—C12 | 57.2 (3) | C21—C19—C20—F1A | −137.1 (4) |
| C7—C8—C9—C12 | −124.7 (3) | C18—C19—C20—F1A | 42.6 (5) |
| C13—C8—C9—C11 | −61.3 (3) | C21—C19—C20—F1B | 162.7 (10) |
| C7—C8—C9—C11 | 116.7 (3) | C18—C19—C20—F1B | −17.6 (11) |
| C7—C8—C13—C14 | −1.6 (3) | C21—C19—C20—F2A | −18.8 (5) |
| C9—C8—C13—C14 | 176.5 (2) | C18—C19—C20—F2A | 160.9 (4) |
| C8—C13—C14—C1 | −0.1 (3) | C18—C19—C21—C22 | −1.2 (4) |
| C8—C13—C14—C15 | −179.8 (2) | C20—C19—C21—C22 | 178.5 (2) |
| O1—C1—C14—C13 | −177.42 (18) | C19—C21—C22—C23 | 0.8 (4) |
| C2—C1—C14—C13 | 1.9 (3) | C21—C22—C23—C17 | −0.1 (4) |
| O1—C1—C14—C15 | 2.3 (3) | C18—C17—C23—C22 | −0.2 (3) |
| C2—C1—C14—C15 | −178.41 (18) | C16—C17—C23—C22 | −177.6 (2) |
Hydrogen-bond geometry (Å, º)
Cg1 and Cg2 are the centroids of the C1/C2/C7/C8/C13/C14 and C17–C23 rings, respectively.
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.92 (3) | 1.73 (3) | 2.587 (2) | 154 (3) |
| C16—H16B···Cg2i | 0.97 | 2.77 | 3.705 (3) | 162 |
| C21—H21···Cg1ii | 0.93 | 2.85 | 3.631 (3) | 143 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+2.
References
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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) I, namiko43. DOI: 10.1107/S205698902000537X/pk2624sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698902000537X/pk2624Isup2.hkl
Supporting information file. DOI: 10.1107/S205698902000537X/pk2624Isup3.cml
CCDC reference: 1997654
Additional supporting information: crystallographic information; 3D view; checkCIF report