Crystal structure and DFT computational studies of (E)-2,4-di-tert-butyl-6-{[3-(tri­fluoro­meth­yl)benz­yl]imino­meth­yl}phenol

Kan Kaynar, N.; Tanak, H.; Macit, M.; Özdemir, N.

doi:10.1107/S205698902000537X

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ISSN: 2056-9890

Volume 76| Part 5| May 2020| Pages 732-735

https://doi.org/10.1107/S205698902000537X

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Crystal structure and DFT computational studies of (E)-2,4-di-tert-butyl-6-{[3-(trifluoromethyl)benzyl]iminomethyl}phenol

Nihal Kan Kaynar,^a ^* Hasan Tanak,^a Mustafa Macit ^b and Namık Özdemir ^c

^aDepartment of Physics, Faculty of Arts & Science, Amasya University, TR-05100, Amasya, Turkey, ^bDepartment of Chemistry, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Samsun, Turkey, and ^cFaculty of Education, Department of Mathematics and, Science Education, Division of Physics Education, Ondokuz Mayıs University, TR-55139 Samsun, Turkey
^*Correspondence e-mail: nihal_kan84@windowslive.com

Edited by S. Parkin, University of Kentucky, USA (Received 7 April 2020; accepted 16 April 2020; online 24 April 2020)

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.

Keywords: Schiff base; rotational disorder; enol–imine; tert-butyl; DFT; crystal structure.

CCDC reference: 1997654

1. 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.

2. 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).

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) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, 2-z.

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.

3. 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.

4. 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.

5. 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.

6. 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%)

7. 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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.14
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1997654

Crystal structure: contains datablocks I, namiko43. DOI: https://doi.org/10.1107/S205698902000537X/pk2624sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902000537X/pk2624Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902000537X/pk2624Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

(E)-2,4-Di-tert-butyl-6-{[3-(trifluoromethyl)benzyl]iminomethyl}phenol top

Crystal data top

C₂₃H₂₈F₃NO	F(000) = 832
M_r = 391.46	D_x = 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 top

STOE IPDS 2 diffractometer	4981 independent reflections
Radiation source: fine-focus sealed tube	2875 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.6°, θ_min = 2.6°
rotation method scans	h = −20→20
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −20→20
T_min = 0.938, T_max = 0.992	l = −10→11
24168 measured reflections

Refinement top

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(F_o²) + (0.072P)²] where P = (F_o² + 2F_c²)/3
4981 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.17 e Å⁻³
67 restraints	Δρ_min = −0.14 e Å⁻³

Special details top

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) top

	x	y	z	U_iso*/U_eq	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) top

	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) top

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) top

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.

Some selected bond lengths, bond angles and torsion angles (Å , °) in the experimentally determined and computed molecular structures top

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	119.88 (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

Acknowledgements

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).

References

Çelik, Ö., Kasumov, V. T. & Şahin, E. (2009). Acta Cryst. E65, o2786. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A. Jr, Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, J. M., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, Ö., Foresman, J. B., Ortiz, J. V., Cioslowski, J. & Fox, D. J. (2009). GAUSSIAN09. Gaussian Inc., Wallingford, CT, USA. Google Scholar
Kansiz, S., Macit, M., Dege, N. & Pavlenko, V. A. (2018). Acta Cryst. E74, 1887–1890. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kaynar, N. K., Ağar, E., Tanak, H., Şahin, S., Büyükgüngör, O. & Yavuz, M. (2018). Crystallogr. Rep. 63, 372–374. CSD CrossRef CAS Google Scholar
Li, J., Zhao, R. & Ma, C. (2007). Acta Cryst. E63, o4923. Web of Science CSD CrossRef IUCr Journals Google Scholar
Marchant, J. R., Martysen, G. & Venkatesh, N. S. (1981). Indian J. Chem. 20B, 493–495. Google Scholar
Moutet, J. C. & Ourari, A. (1997). Electrochim. Acta, 42, 2525–2531. CrossRef CAS Web of Science Google Scholar
Şahin, Z. S., Gümüş, S., Macit, M. & Işık, Ş. (2009). Acta Cryst. E65, o2754. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Sun, Y.-F., Wang, X.-L., Ma, S.-Y. & Chen, H.-J. (2007). Acta Cryst. E63, o3746. CSD CrossRef IUCr Journals Google Scholar
Tanak, H. (2011). J. Phys. Chem. A, 115, 13865–13876. Web of Science CSD CrossRef CAS PubMed Google Scholar
Tanak, H. (2019). ChemistrySelect 4, 10876–10883. CrossRef CAS Google Scholar
Tanak, H., Ağar, A. & Yavuz, M. (2010). J. Mol. Model. 16, 577–587. Web of Science CSD CrossRef PubMed CAS Google Scholar
Tanak, H., Erşahin, F., Ağar, E., Yavuz, M. & Büyükgüngör, O. (2009). Acta Cryst. E65, o2291. Web of Science CSD CrossRef IUCr Journals Google Scholar
Turwatker, S. L. & Mahta, B. H. (2007). Asian J. Chem. 19, 3671–3676. Google Scholar

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