Crystal structure of 1-[(4-chloro­phen­yl)di­phenylyl­meth­yl]-3-(tri­fluoro­meth­yl)-1H-pyrazole

Guseinov, F.I.; Afanaseva, K.A.; A.Vil, V.; Ugrak, B.I.; Samigullina, A.I.; Zangrando, E.; Belay, A.N.

doi:10.1107/S2056989025001185

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 81| Part 3| March 2025|

https://doi.org/10.1107/S2056989025001185

Open

access

Crystal structure of 1-[(4-chlorophenyl)diphenylylmethyl]-3-(trifluoromethyl)-1H-pyrazole

Firudin I. Guseinov,^a,^b Ksenia A. Afanaseva,^a,^b Vera A.Vil,^b Bogdan I. Ugrak,^b Aida I. Samigullina,^b Ennio Zangrando ^c and Alebel N. Belay ^d ^*

^aKosygin State University of Russia, 117997 Moscow, Russian Federation, ^bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation, ^cDepartment of Chemical and Pharmaceutical Sciences, University of Trieste, 34127, Trieste, Italy, and ^dDepartment of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia
^*Correspondence e-mail: alebel.nibret@bdu.edu.et

Edited by A. S. Batsanov, University of Durham, United Kingdom (Received 11 November 2024; accepted 10 February 2025; online 18 February 2025)

The title compound, C₂₃H₁₆ClF₃N₂, was synthesized from 3-(trifluoromethyl)-1H-pyrazole and chloro(4-chlorophenyl)methylene)dibenzene. The structure features intramolecular (Ph)C—H⋯N and intermolecular (Ph)C—H⋯F hydrogen bonds, as well as C—H⋯π-ring interactions between the phenyl and pyrazole rings.

Keywords: crystal structure; trifluoromethylpyrazole; trifluoromethyl; non-covalent interactions.

CCDC reference: 2422692

1. Chemical context

Pyrazoles and their derivatives are found in natural compounds and drugs, and are widely used in organic synthesis (Guseinov et al., 2006 , 2024 ; Küçükgüzel et al., 2015 ; Pizzuti et al., 2014 ). Similarly to hydrazones (Mahmudov et al., 2011 ), new pyrazole derivatives can also be used in crystal engineering as well as in the synthesis of coordination compounds for catalysis (Jlassi et al., 2014 ; Ma et al., 2021 ; Mac Leod et al., 2012 ) and biological studies (Martins et al., 2017 ). The hydrogen-bond acceptor ability of the pyrazole motif can be employed as a tool for crystal growth and design (Guseinov et al., 2017 , 2022 ; Abdelhamid et al., 2011 ; Afkhami et al., 2017 ). We believe that the attachment of a trifluoromethyl group to the pyrazole ring can improve the functional properties of new derivative ligands or supramolecular synthons. In fact, trifluoromethylated pyrazoles are indispensable heterocyclic motifs that constitute the core of a variety of bioactive substrates and pharmaceuticals (Kumar et al., 2023 ; Westphal et al., 2015 ; Zhu et al., 2014 ). Among them, the 3-trifluoromethylpyrazole scaffold is of great medicinal significance and is present in several drugs and bioactive molecules including celecoxib, mavacoxib (anti-inflammatory), razaxaban (anticoagulant), SC-560 (antitumor) and penthiopyrad (antifungal) (Davis et al., 2013 ; Fang et al., 2020 ; Liu et al., 2023 ).

2. Structural commentary

The title molecule, 1, is shown in Fig. 1. The central carbon atom C5 exhibits a geometry close to ideal tetrahedral and with similar C5—C(Ph) bond lengths (Table 1). The pyrazole ring geometry is unexceptional (Secrieru et al., 2020 ). The phenyl rings show an irregular propeller conformation about the C5—N2 bond: the ring planes A, B and C are inclined to the C6/C12/C18 plane in the same sense by 43.15 (5), 70.58 (6) and 22.62 (6)°, respectively. These angles (φ) vary much more widely than in 1,1,1-triphenylethane or triphenylchloromethane (see Section 4), partly as a result of the presence of the pyrazole ring, which assumes a nearly eclipsed orientation with a C1—N2—C5—C18 torsion angle of 16.58 (18)°, and partly because of the intramolecular C17—H17⋯N1 hydrogen bond (Table 2). It is noteworthy that the observed orientation of ring B (which shows the largest φ angle) is close to the simulated orientation (with φ = 64°) that would give the shortest H17⋯N1 distance. This can be seen as the proof that this contact is a stabilizing hydrogen bond, rather than an incidental effect of crystal packing.

Table 1
Selected geometric parameters (Å, °)

N1—N2	1.3517 (16)	C1—C2	1.373 (2)
N1—C3	1.3328 (19)	C5—C6	1.5400 (18)
N2—C1	1.3575 (19)	C5—C12	1.5431 (18)
N2—C5	1.4981 (17)	C5—C18	1.5511 (17)

N2—C5—C6	106.37 (10)	C6—C5—C12	110.99 (11)
N2—C5—C12	110.49 (10)	C6—C5—C18	112.58 (10)
N2—C5—C18	107.06 (10)	C12—C5—C18	109.24 (10)

Table 2
Hydrogen-bond geometry and C—H⋯π interaction parameters (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯N1	0.98 (2)	2.382 (19)	3.0541 (19)	125.1 (14)
C22—H22⋯F2ⁱ	0.96 (2)	2.48 (2)	3.3596 (18)	151.6 (16)
C2—H2⋯Cg1ⁱ	0.95	2.96	3.6237 (17)	128
C7—H7⋯Cg1	0.95	2.98	3.6784 (15)	132
C8—H8⋯Cg2ⁱⁱ	0.95	2.80	3.4721 (15)	129
C13—H13⋯Cg3ⁱⁱ	0.95	2.98	3.7873 (15)	144
C21—H21⋯Cg3ⁱⁱⁱ	0.95	2.71	3.4928 (15)	140
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 1
Molecular structure of 1. Displacement ellipsoids are drawn at the 50% probability level. The dotted line indicates the intramolecular hydrogen bond.

3. Supramolecular features

The crystal packing is shown in Fig. 2. Molecules are linked into centrosymmetric dimers by pairs of C22—H⋯F2 hydrogen bonds (Table 2, Fig. 3). Neither the phenyl nor the pyrazole rings are involved in π–π stacking interactions; however, there are C—H⋯π-type interactions between rings contacting edge-to-face, at interplanar angles of 69.62 (6) to 78.68 (5)° and H⋯ring distances of 2.71–2.98 Å. Numerical details of hydoren bonds and C—H⋯π interactions are given in Table 2.

Figure 2
Crystal packing of 1 (H atoms are omitted for clarity).

Figure 3
Intermolecular hydrogen bonds in the structure of 1. Symmetry code: (i) −x + 2, −y + 1, −z + 1.

4. Database survey

The propeller conformation of the CPh₃ moiety in 1 can be compared with those in 1,1,1-triphenylethane (2) and triphenylchloromethane (3). In 2, the φ angles range from 41.3 to 55.3° at room temperature (TRPETN; Destro et al., 1980 ) and from 42.0 to 53.9° at 100 K (TRPETN01; Fronczek, 2014 ). Three polymorphs of compound 3 have been reported: trigonal phase I and monoclinic phases II and III. Phase I (ZZZVTY12; Dunand & Gerdil, 1982 ) contains three crystallographically non-equivalent molecules, each lying on a threefold axis and thus having a regular propeller conformation, with φ = 43.4, 47.0 and 51.0°. Phase II (ZZZVTY03; Kahr & Carter, 1992 ) has three molecules per asymmetric unit, with φ varying from 38.2 to 59.0°, whereas phase III has five, with φ = 36.9–57.5° at 248 K (ZZZVTY04; Kahr & Carter, 1992) and φ = 34.6–58.2° at 100 K (ZZZVTY13; Wang et al., 2013 ).

5. Synthesis and crystallization

A mixture of 435 mg (3.2 mmol) of 3-(trifluoromethyl)-1H-pyrazole and 485 mg (3.5 mmol) of K₂CO₃ was dissolved in 20 mL of tetrahydrofuran and stirred at reflux for 10–15 minutes. Then 1.00 g (3.2 mmol) of chloro(4-chlorophenyl)methylene)dibenzene was added to the reaction mixture and continued to boil for 5 h. After completion of the reaction, tetrahydrofuran was removed under vacuum and 10 mL of diethyl ether were added to the obtained oily residue, which formed compound 1 as a solid product. Colourless prismatic crystals suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution.

Yield: 936 mg (71%); m.p. 355–360 K. Analysis calculated (%) for C₂₃H₁₆ClF₃N₂: C 66.92, H 3.91, N 6.79; found C 66.90, H 3.90, N 6.77. ¹H NMR (300 MHz, CDCl₃): 6.52–6.53 (1H, CF₃CCH), 7.07–7.37 (10H, 2Ph, 4H, 4-ClPh, 1H, NCH). ¹³C NMR (75 MHz, CDCl₃): 79.24, 103.19, 111.07, 127.93, 128.04, 128.30, 130.01, 131.65, 133.79, 134.05, 139.12, 141.17, 142.18. ESI-MS: 413.8 (M + H⁺).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were placed geometrically with C—H = 0.95 Å and included in the refinement in the riding-motion model with U_iso(H) = 1.2U_eq(C), except H17 and H22 which were refined in an isotropic approximation. About 50 hkl data were missed due to collection via the spindle axis only.

Table 3
Experimental details

Crystal data
Chemical formula	C₂₃H₁₆ClF₃N₂
M_r	412.83
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.12054 (10), 8.93314 (6), 17.75198 (15)
β (°)	90.4278 (8)
V (Å³)	1922.03 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.11
Crystal size (mm)	0.18 × 0.11 × 0.06

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.688, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25542, 4102, 3917
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.108, 1.07
No. of reflections	4102
No. of parameters	270
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.46
Computer programs: CrysAlis PRO (Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 1999 and Crystal Explorer 17.5 (Spackman et al., 2021 ).

Supporting information

CCDC reference: 2422692

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025001185/zv2037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025001185/zv2037Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025001185/zv2037Isup3.cml

checkCIF report

Computing details top

1-[(4-Chlorophenyl)diphenylmethyl]-3-(trifluoromethyl)-1H-pyrazole top

Crystal data top

C₂₃H₁₆ClF₃N₂	F(000) = 848
M_r = 412.83	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 12.12054 (10) Å	Cell parameters from 19127 reflections
b = 8.93314 (6) Å	θ = 2.5–79.5°
c = 17.75198 (15) Å	µ = 2.11 mm⁻¹
β = 90.4278 (8)°	T = 100 K
V = 1922.03 (3) Å³	Prism, colorless
Z = 4	0.18 × 0.11 × 0.06 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3917 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.026
ω scans	θ_max = 79.8°, θ_min = 3.7°
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2024)	h = −14→15
T_min = 0.688, T_max = 1.000	k = −10→11
25542 measured reflections	l = −22→22
4102 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.056P)² + 0.9694P] where P = (F_o² + 2F_c²)/3
4102 reflections	(Δ/σ)_max = 0.001
270 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.36774 (3)	0.04033 (5)	0.33222 (2)	0.03673 (13)
F1	0.93996 (8)	−0.01654 (11)	0.32090 (6)	0.0377 (2)
F2	1.04152 (11)	0.00747 (12)	0.41780 (6)	0.0499 (3)
F3	1.09493 (10)	0.09519 (13)	0.31067 (8)	0.0583 (4)
N1	0.86043 (10)	0.23237 (13)	0.40816 (7)	0.0227 (2)
N2	0.83992 (9)	0.38039 (12)	0.41539 (6)	0.0201 (2)
C1	0.92135 (13)	0.46447 (17)	0.38471 (9)	0.0290 (3)
H1	0.924180	0.570700	0.383099	0.035*
C2	0.99888 (13)	0.36792 (18)	0.35644 (9)	0.0320 (3)
H2	1.065849	0.391975	0.331748	0.038*
C3	0.95659 (12)	0.22665 (17)	0.37235 (8)	0.0244 (3)
C4	1.00804 (12)	0.07923 (18)	0.35536 (9)	0.0280 (3)
C5	0.73785 (11)	0.42950 (14)	0.45553 (7)	0.0190 (3)
C6	0.64342 (11)	0.32991 (14)	0.42577 (8)	0.0192 (3)
C7	0.56995 (11)	0.25784 (15)	0.47346 (8)	0.0213 (3)
H7	0.577978	0.269227	0.526420	0.026*
C8	0.48472 (12)	0.16921 (16)	0.44485 (8)	0.0239 (3)
H8	0.434854	0.120859	0.477957	0.029*
C9	0.47364 (12)	0.15249 (16)	0.36766 (8)	0.0245 (3)
C10	0.54608 (12)	0.22183 (15)	0.31846 (8)	0.0239 (3)
H10	0.537938	0.209519	0.265557	0.029*
C11	0.63059 (11)	0.30946 (14)	0.34793 (8)	0.0210 (3)
H11	0.680799	0.356557	0.314612	0.025*
C12	0.75251 (11)	0.41134 (14)	0.54147 (7)	0.0198 (3)
C13	0.68273 (12)	0.49156 (16)	0.58885 (8)	0.0242 (3)
H13	0.629103	0.556908	0.567554	0.029*
C14	0.69039 (13)	0.47746 (17)	0.66662 (8)	0.0267 (3)
H14	0.642528	0.533415	0.698044	0.032*
C15	0.76794 (13)	0.38167 (16)	0.69848 (8)	0.0261 (3)
H15	0.773672	0.371902	0.751657	0.031*
C16	0.83678 (13)	0.30059 (16)	0.65192 (8)	0.0268 (3)
H16	0.889550	0.234290	0.673460	0.032*
C17	0.82977 (12)	0.31486 (16)	0.57365 (8)	0.0239 (3)
H17	0.8794 (16)	0.257 (2)	0.5412 (11)	0.028 (4)*
C18	0.72023 (11)	0.59740 (14)	0.43669 (7)	0.0197 (3)
C19	0.64102 (12)	0.64777 (15)	0.38557 (8)	0.0225 (3)
H19	0.591919	0.578336	0.362534	0.027*
C20	0.63317 (12)	0.80002 (16)	0.36787 (8)	0.0248 (3)
H20	0.578844	0.833085	0.332791	0.030*
C21	0.70372 (13)	0.90285 (15)	0.40092 (8)	0.0247 (3)
H21	0.699169	1.005792	0.387826	0.030*
C22	0.78131 (12)	0.85427 (16)	0.45345 (8)	0.0256 (3)
H22	0.8306 (17)	0.924 (2)	0.4781 (11)	0.031 (5)*
C23	0.78900 (12)	0.70327 (16)	0.47162 (8)	0.0237 (3)
H23	0.841568	0.671365	0.508187	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0276 (2)	0.0408 (2)	0.0417 (2)	−0.00851 (14)	−0.00535 (16)	−0.01070 (16)
F1	0.0353 (5)	0.0348 (5)	0.0429 (5)	0.0067 (4)	−0.0064 (4)	−0.0102 (4)
F2	0.0671 (8)	0.0418 (6)	0.0404 (6)	0.0279 (5)	−0.0212 (5)	−0.0061 (5)
F3	0.0413 (6)	0.0447 (6)	0.0894 (9)	0.0068 (5)	0.0370 (6)	−0.0065 (6)
N1	0.0209 (6)	0.0201 (5)	0.0270 (6)	0.0029 (4)	0.0014 (4)	−0.0007 (4)
N2	0.0195 (5)	0.0188 (5)	0.0219 (5)	0.0014 (4)	0.0009 (4)	0.0017 (4)
C1	0.0264 (7)	0.0245 (7)	0.0363 (8)	−0.0001 (5)	0.0081 (6)	0.0066 (6)
C2	0.0256 (7)	0.0317 (8)	0.0390 (8)	0.0017 (6)	0.0107 (6)	0.0070 (6)
C3	0.0210 (6)	0.0297 (7)	0.0224 (6)	0.0037 (5)	−0.0006 (5)	0.0011 (5)
C4	0.0227 (7)	0.0322 (8)	0.0290 (7)	0.0053 (6)	0.0007 (6)	−0.0013 (6)
C5	0.0184 (6)	0.0176 (6)	0.0211 (6)	0.0013 (5)	0.0012 (5)	0.0011 (5)
C6	0.0185 (6)	0.0149 (5)	0.0241 (6)	0.0029 (4)	−0.0003 (5)	0.0009 (5)
C7	0.0210 (6)	0.0203 (6)	0.0228 (6)	0.0017 (5)	0.0010 (5)	0.0006 (5)
C8	0.0205 (6)	0.0219 (6)	0.0294 (7)	0.0004 (5)	0.0035 (5)	0.0011 (5)
C9	0.0198 (6)	0.0213 (6)	0.0322 (7)	0.0024 (5)	−0.0031 (5)	−0.0035 (5)
C10	0.0256 (7)	0.0229 (6)	0.0230 (6)	0.0053 (5)	−0.0030 (5)	−0.0018 (5)
C11	0.0225 (6)	0.0179 (6)	0.0225 (6)	0.0033 (5)	0.0006 (5)	0.0020 (5)
C12	0.0197 (6)	0.0180 (6)	0.0217 (6)	−0.0022 (5)	−0.0006 (5)	0.0020 (5)
C13	0.0246 (7)	0.0238 (6)	0.0242 (7)	0.0026 (5)	0.0003 (5)	0.0022 (5)
C14	0.0278 (7)	0.0278 (7)	0.0246 (7)	0.0011 (6)	0.0030 (6)	−0.0007 (5)
C15	0.0295 (7)	0.0272 (7)	0.0216 (6)	−0.0058 (6)	−0.0016 (5)	0.0034 (5)
C16	0.0286 (7)	0.0247 (7)	0.0270 (7)	0.0017 (5)	−0.0044 (6)	0.0055 (5)
C17	0.0250 (7)	0.0218 (6)	0.0249 (7)	0.0019 (5)	−0.0012 (5)	0.0013 (5)
C18	0.0207 (6)	0.0174 (6)	0.0210 (6)	0.0010 (5)	0.0017 (5)	0.0014 (5)
C19	0.0245 (6)	0.0197 (6)	0.0231 (6)	0.0012 (5)	−0.0013 (5)	−0.0004 (5)
C20	0.0288 (7)	0.0211 (6)	0.0245 (6)	0.0037 (5)	−0.0024 (5)	0.0027 (5)
C21	0.0296 (7)	0.0177 (6)	0.0269 (7)	0.0012 (5)	0.0038 (6)	0.0030 (5)
C22	0.0272 (7)	0.0211 (6)	0.0284 (7)	−0.0042 (5)	0.0005 (6)	−0.0006 (5)
C23	0.0237 (7)	0.0218 (6)	0.0255 (6)	−0.0013 (5)	−0.0019 (5)	0.0021 (5)

Geometric parameters (Å, º) top

Cl1—C9	1.7422 (14)	C10—C11	1.388 (2)
F1—C4	1.3340 (18)	C11—H11	0.9500
F2—C4	1.3408 (18)	C12—C13	1.395 (2)
F3—C4	1.3308 (19)	C12—C17	1.3920 (19)
N1—N2	1.3517 (16)	C13—H13	0.9500
N1—C3	1.3328 (19)	C13—C14	1.389 (2)
N2—C1	1.3575 (19)	C14—H14	0.9500
N2—C5	1.4981 (17)	C14—C15	1.388 (2)
C1—H1	0.9500	C15—H15	0.9500
C1—C2	1.373 (2)	C15—C16	1.384 (2)
C2—H2	0.9500	C16—H16	0.9500
C2—C3	1.392 (2)	C16—C17	1.397 (2)
C3—C4	1.489 (2)	C17—H17	0.98 (2)
C5—C6	1.5400 (18)	C18—C19	1.3910 (19)
C5—C12	1.5431 (18)	C18—C23	1.4021 (19)
C5—C18	1.5511 (17)	C19—H19	0.9500
C6—C7	1.3911 (19)	C19—C20	1.3990 (19)
C6—C11	1.4013 (18)	C20—H20	0.9500
C7—H7	0.9500	C20—C21	1.383 (2)
C7—C8	1.394 (2)	C21—H21	0.9500
C8—H8	0.9500	C21—C22	1.389 (2)
C8—C9	1.384 (2)	C22—H22	0.96 (2)
C9—C10	1.389 (2)	C22—C23	1.390 (2)
C10—H10	0.9500	C23—H23	0.9500

C3—N1—N2	104.17 (11)	C6—C11—H11	119.3
N1—N2—C1	111.62 (12)	C10—C11—C6	121.41 (13)
N1—N2—C5	118.99 (11)	C10—C11—H11	119.3
C1—N2—C5	129.37 (12)	C13—C12—C5	118.43 (12)
N2—C1—H1	126.3	C17—C12—C5	122.88 (12)
N2—C1—C2	107.50 (13)	C17—C12—C13	118.66 (12)
C2—C1—H1	126.3	C12—C13—H13	119.5
C1—C2—H2	128.0	C14—C13—C12	121.08 (13)
C1—C2—C3	103.96 (13)	C14—C13—H13	119.5
C3—C2—H2	128.0	C13—C14—H14	120.0
N1—C3—C2	112.75 (13)	C15—C14—C13	120.06 (14)
N1—C3—C4	119.98 (13)	C15—C14—H14	120.0
C2—C3—C4	127.26 (14)	C14—C15—H15	120.4
F1—C4—F2	104.77 (13)	C16—C15—C14	119.25 (13)
F1—C4—C3	113.68 (12)	C16—C15—H15	120.4
F2—C4—C3	112.33 (12)	C15—C16—H16	119.5
F3—C4—F1	106.56 (13)	C15—C16—C17	120.92 (13)
F3—C4—F2	107.94 (13)	C17—C16—H16	119.5
F3—C4—C3	111.13 (13)	C12—C17—C16	120.02 (14)
N2—C5—C6	106.37 (10)	C12—C17—H17	119.9 (11)
N2—C5—C12	110.49 (10)	C16—C17—H17	120.1 (11)
N2—C5—C18	107.06 (10)	C19—C18—C5	123.14 (12)
C6—C5—C12	110.99 (11)	C19—C18—C23	118.39 (12)
C6—C5—C18	112.58 (10)	C23—C18—C5	118.46 (11)
C12—C5—C18	109.24 (10)	C18—C19—H19	119.8
C7—C6—C5	122.41 (12)	C18—C19—C20	120.43 (13)
C7—C6—C11	118.22 (12)	C20—C19—H19	119.8
C11—C6—C5	119.36 (12)	C19—C20—H20	119.7
C6—C7—H7	119.4	C21—C20—C19	120.65 (13)
C6—C7—C8	121.14 (13)	C21—C20—H20	119.7
C8—C7—H7	119.4	C20—C21—H21	120.3
C7—C8—H8	120.4	C20—C21—C22	119.39 (13)
C9—C8—C7	119.21 (13)	C22—C21—H21	120.3
C9—C8—H8	120.4	C21—C22—H22	121.3 (12)
C8—C9—Cl1	119.04 (12)	C21—C22—C23	120.19 (13)
C8—C9—C10	121.16 (13)	C23—C22—H22	118.6 (12)
C10—C9—Cl1	119.80 (11)	C18—C23—H23	119.6
C9—C10—H10	120.6	C22—C23—C18	120.90 (13)
C11—C10—C9	118.86 (13)	C22—C23—H23	119.6
C11—C10—H10	120.6

Cl1—C9—C10—C11	−179.33 (10)	C5—C18—C23—C22	176.11 (13)
N1—N2—C1—C2	−0.28 (18)	C6—C5—C12—C13	−81.65 (15)
N1—N2—C5—C6	−44.59 (14)	C6—C5—C12—C17	96.19 (15)
N1—N2—C5—C12	75.97 (14)	C6—C5—C18—C19	−12.64 (18)
N1—N2—C5—C18	−165.17 (11)	C6—C5—C18—C23	168.79 (12)
N1—C3—C4—F1	51.16 (19)	C6—C7—C8—C9	0.3 (2)
N1—C3—C4—F2	−67.59 (18)	C7—C6—C11—C10	1.02 (19)
N1—C3—C4—F3	171.36 (14)	C7—C8—C9—Cl1	179.45 (10)
N2—N1—C3—C2	0.17 (16)	C7—C8—C9—C10	0.3 (2)
N2—N1—C3—C4	178.79 (12)	C8—C9—C10—C11	−0.2 (2)
N2—C1—C2—C3	0.35 (18)	C9—C10—C11—C6	−0.5 (2)
N2—C5—C6—C7	131.58 (12)	C11—C6—C7—C8	−0.89 (19)
N2—C5—C6—C11	−48.00 (15)	C12—C5—C6—C7	11.35 (17)
N2—C5—C12—C13	160.59 (12)	C12—C5—C6—C11	−168.23 (11)
N2—C5—C12—C17	−21.57 (17)	C12—C5—C18—C19	−136.42 (13)
N2—C5—C18—C19	103.91 (14)	C12—C5—C18—C23	45.01 (16)
N2—C5—C18—C23	−74.66 (14)	C12—C13—C14—C15	−0.4 (2)
C1—N2—C5—C6	137.16 (14)	C13—C12—C17—C16	−0.4 (2)
C1—N2—C5—C12	−102.28 (16)	C13—C14—C15—C16	−0.2 (2)
C1—N2—C5—C18	16.58 (18)	C14—C15—C16—C17	0.5 (2)
C1—C2—C3—N1	−0.33 (18)	C15—C16—C17—C12	−0.2 (2)
C1—C2—C3—C4	−178.83 (14)	C17—C12—C13—C14	0.7 (2)
C2—C3—C4—F1	−130.44 (16)	C18—C5—C6—C7	−111.46 (14)
C2—C3—C4—F2	110.81 (18)	C18—C5—C6—C11	68.96 (15)
C2—C3—C4—F3	−10.2 (2)	C18—C5—C12—C13	43.06 (16)
C3—N1—N2—C1	0.07 (15)	C18—C5—C12—C17	−139.10 (13)
C3—N1—N2—C5	−178.47 (11)	C18—C19—C20—C21	−0.1 (2)
C5—N2—C1—C2	178.07 (13)	C19—C18—C23—C22	−2.5 (2)
C5—C6—C7—C8	179.53 (12)	C19—C20—C21—C22	−1.5 (2)
C5—C6—C11—C10	−179.39 (12)	C20—C21—C22—C23	1.0 (2)
C5—C12—C13—C14	178.64 (13)	C21—C22—C23—C18	1.0 (2)
C5—C12—C17—C16	−178.24 (13)	C23—C18—C19—C20	2.1 (2)
C5—C18—C19—C20	−176.47 (13)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the C12–17, C18–23 and C6–11 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N1	0.98 (2)	2.382 (19)	3.0541 (19)	125.1 (14)
C22—H22···F2ⁱ	0.96 (2)	2.48 (2)	3.3596 (18)	151.6 (16)
C2—H2···Cg1ⁱ	0.95	2.96	3.6237 (17)	128
C7—H7···Cg1	0.95	2.98	3.6784 (15)	132
C8—H8···Cg2ⁱⁱ	0.95	2.80	3.4721 (15)	129
C13—H13···Cg3ⁱⁱ	0.95	2.98	3.7873 (15)	144
C21—H21···Cg3ⁱⁱⁱ	0.95	2.71	3.4928 (15)	140

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z.

References

Abdelhamid, A. A., Mohamed, S. K., Khalilov, A. N., Gurbanov, A. V. & Ng, S. W. (2011). Acta Cryst. E67, o744. Web of Science CSD CrossRef IUCr Journals Google Scholar
Afkhami, F. A., Mahmoudi, G., Gurbanov, A. V., Zubkov, F. I., Qu, F., Gupta, A. & Safin, D. A. (2017). Dalton Trans. 46, 14888–14896. Web of Science PubMed Google Scholar
Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Davis, L. O. (2013). Org. Prep. Proced. Int. 45, 437–464. CrossRef CAS Google Scholar
Destro, R., Pilati, T. & Simonetta, M. (1980). Acta Cryst. B36, 2495–2497. CrossRef CAS IUCr Journals Google Scholar
Dunand, A. & Gerdil, R. (1982). Acta Cryst. B38, 570–575. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Fang, Z., Yin, H., Lin, L., Wen, S., Xie, L., Huang, Y. & Weng, Z. (2020). J. Org. Chem. 85, 8714–8722. CrossRef CAS PubMed Google Scholar
Fronczek, F. R. (2014). Private Communication (refcode TRPETN01) CCDC, Cambridge, England. https://doi.org/10.5517/cc11k9d9 Google Scholar
Guseinov, F. I., Çelikesir, S. T., Akkurt, M., Ovsyannikov, V. O., Ugrak, B. I., Lavrova, O. M., Samigullina, A. I. & Bhattarai, A. (2024). Acta Cryst. E80, 582–585. CrossRef IUCr Journals Google Scholar
Guseinov, F. I., Malinnikov, V. M., Lialin, K. N., Kobrakov, K. I., Shuvalova, E. V., Nelyubina, Y. V., Ugrak, B. I., Kustov, L. M. & Mahmudov, K. T. (2022). Dyes Pigments, 197, 109898. Web of Science CSD CrossRef Google Scholar
Guseinov, F. I., Pistsov, M. F., Movsumzade, E. M., Kustov, L. M., Tafeenko, V. A., Chernyshev, V. V., Gurbanov, A. V., Mahmudov, K. T. & Pombeiro, A. J. L. (2017). Crystals, 7, 327. Web of Science CSD CrossRef Google Scholar
Guseinov, F. N., Burangulova, R. N., Mukhamedzyanova, E. F., Strunin, B. P., Sinyashin, O. G., Litvinov, I. A. & Gubaidullin, A. T. (2006). Chem. Heterocycl. Compd. 42, 943–947. CrossRef CAS Google Scholar
Jlassi, R., Ribeiro, A. P. C., Guedes da Silva, M. F. C., Mahmudov, K. T., Kopylovich, M. N., Anisimova, T. B., Naïli, H., Tiago, G. A. O. & Pombeiro, A. J. L. (2014). Eur. J. Inorg. Chem. pp. 4541–4550. Web of Science CSD CrossRef Google Scholar
Kahr, B. & Carter, R. L. (1992). Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. A. 219, 79–100. CrossRef CAS Google Scholar
Küçükgüzel, Ş. G., ŞG, & Şenkardeş, S. (2015). Eur. J. Med. Chem. 97, 786–815. Google Scholar
Kumar, A., Mathew, S., Jamali, M. F., Ahamad, S., Kant, R. & Mohanan, K. (2023). Adv. Synth. Catal. 365, 2218–2224. CrossRef CAS Google Scholar
Liu, R. H., Chai, G. L., Wang, X., Deng, H. Y. & Chang, J. (2023). J. Org. Chem. 88, 16566–16580. CrossRef CAS PubMed Google Scholar
Ma, Z., Mahmudov, K. T., Aliyeva, V. A., Gurbanov, A. V., Guedes da Silva, M. F. C. & Pombeiro, A. J. L. (2021). Coord. Chem. Rev. 437, 213859. Web of Science CrossRef Google Scholar
Mac Leod, T. C., Kopylovich, M. N., Guedes da Silva, M. F. C., Mahmudov, K. T. & Pombeiro, A. J. L. (2012). Appl. Catal. Gen. 439–440, 15–23. Web of Science CrossRef CAS Google Scholar
Mahmudov, K. T., Maharramov, A. M., Aliyeva, R. A., Aliyev, I. A., Askerov, R. K., Batmaz, R., Kopylovich, M. N. & Pombeiro, A. J. L. (2011). J. Photochem. Photobiol. Chem. 219, 159–165. Web of Science CSD CrossRef CAS Google Scholar
Martins, N. M. R., Anbu, S., Mahmudov, K. T., Ravishankaran, R., Guedes da Silva, M. F. C., Martins, L. M. D. R. S., Karande, A. A. & Pombeiro, A. J. L. (2017). New J. Chem. 41, 4076–4086. Web of Science CrossRef CAS Google Scholar
Pizzuti, L. G., Barschak, A. M., Stefanello, F. D., Farias, M., Lencina, C., Roesch-Ely, M., Cunico, W., Moura, S. & Pereira, C. (2014). Curr. Org. Chem. 18, 115–126. CrossRef CAS Google Scholar
Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Secrieru, A., O'Neill, P. M. & Cristiano, M. L. S. (2020). Molecules, 25, 42. CrossRef Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, R., Dols, T., Lehmann, C. & Englert, U. (2013). Z. Anorg. Allg. Chem. 639, 1933–1939. CrossRef CAS Google Scholar
Westphal, M. V., Wolfstädter, B. T., Plancher, J. M., Gatfield, J. & Carreira, E. M. (2015). ChemMedChem, 10, 461–469. CrossRef CAS PubMed Google Scholar
Zhu, W., Wang, J., Wang, S., Gu, Z., Aceña, J. L., Izawa, K., Liu, H. & Soloshonok, V. A. (2014). J. Fluor. Chem. 167, 37–54. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.