Crystal structure and Hirshfeld surface analysis of isopropyl 4-[2-fluoro-5-(tri­fluoro­meth­yl)phen­yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate

Yıldırım, S. Ö.; Akkurt, M.; Çetin, G.; Şimşek, R.; Butcher, R.J.; Bhattarai, A.

doi:10.1107/S205698902300141X

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ISSN: 2056-9890

Volume 79| Part 3| March 2023| Pages 187-191

https://doi.org/10.1107/S205698902300141X

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Crystal structure and Hirshfeld surface analysis of isopropyl 4-[2-fluoro-5-(trifluoromethyl)phenyl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate

Sema Öztürk Yıldırım,^a,^b Mehmet Akkurt,^b Gökalp Çetin,^c,^d Rahime Şimşek,^d Ray J. Butcher ^e and Ajaya Bhattarai ^f ^*

^aDepartment of Physics, Faculty of Science, Eskisehir Technical University, Yunus Emre Campus 26470 Eskisehir, Türkiye, ^bDepartment of Physics, Faculty of Science, Erciyes University, 38039 Kayseri, Türkiye, ^cDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Erzincan Binali Yıldırım University, 24100 Erzincan, Türkiye, ^dDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Hacettepe University, 06100 Sıhhiye-Ankara, Türkiye, ^eDepartment of Chemistry, Howard University, Washington DC 20059, USA, and ^fDepartment of Chemistry, M.M.A.M.C (Tribhuvan University), Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 25 January 2023; accepted 16 February 2023; online 21 February 2023)

In the title compound, C₂₃H₂₅F₄NO₃, the 1,4-dihydropyridine ring adopts a distorted boat conformation, while the cyclohexene ring is almost showing a half-chair conformation. In the crystal, intermolecular N—H⋯O hydrogen bonds connect the molecules into chains with graph-set motif C(6) parallel to the a-axis. These chains are linked together by C—H⋯O and C—H⋯F interactions, forming a three-dimensional network. In addition, C—H⋯π interactions link the molecules into layers parallel to the (100) plane. A Hirshfeld surface analysis was performed to further investigate the intermolecular interactions.

Keywords: crystal structure; 1,4-dihydropyridine ring; cyclohexene ring; quinoline ring system; van der Waals interactions; Hirshfeld surface analysis.

CCDC reference: 2242647

1. Chemical context

5-Oxo-1,4,5,6,7,8-hexahydroquinoline (5-oxo-HHQ) is a condensed heterocycle, which is formed with dihydropyridine (DHP) and cyclohexanone. In recent years, compounds containing the 5-oxo-HHQ scaffold have been widely studied because of their diverse pharmacological and biological attributes (Ranjbar et al., 2019 ).

In this study, isopropyl 4-[2-fluoro-5-(trifluoromethyl)phenyl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate was synthesized and its molecular structure was confirmed by IR, ¹H NMR, ¹³C NMR, HRMS and X-ray crystallography. The intermolecular interactions observed in the crystal packing were investigated by Hirshfeld surface analysis.

2. Structural commentary

As shown in Fig. 1, the 1,4-dihydropyridine ring (N1/C1/C6-C9) adopts a distorted boat conformation [puckering parameters (Cremer & Pople, 1975 ): Q_T = 0.3164 (16) Å, θ = 75.3 (3)°, φ = 180.0 (3)°], while the cyclohexene ring (C1–C6) shows a twisted boat conformation [puckering parameters: Q_T = 0.4602 (18) Å, θ = 122.0 (2)°, φ = 312.6 (3)°]. The 1-fluoro-4-(trifluoromethyl)benzene ring (C17–C22) makes a dihedral angle of 87.91 (8)° with the mean plane of the quinoline ring system [N1/C1–C9; maximum deviation = 0.975 (2) Å for C4]. The geometrical parameter values of the the title compound are in agreement with those reported for similar compounds in the Database survey section.

Figure 1
View of the title molecule. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only the major disorder components are included.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, N—H⋯O hydrogen bonds link the molecules into infinite chains with a a C(6) chain motif (Bernstein et al., 1995 ) along the a-axis direction (Table 1 and Fig. 2). These chains are linked together by C—H⋯O and C—H⋯F interactions (Table 1 and Fig. 3), forming a three-dimensional network. C—H⋯π interactions link the molecules into layers parallel to the (100) plane (Table 1 and Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C17–C22 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.88 (2)	2.12 (2)	2.9798 (19)	165 (2)
C2—H2A⋯F3ⁱⁱ	0.99	2.59	3.187 (4)	119
C12—H12B⋯F1ⁱ	0.98	2.64	3.206 (2)	117
C12—H12B⋯O1ⁱ	0.98	2.65	3.505 (2)	145
C12—H12C⋯F3Aⁱⁱⁱ	0.98	2.43	3.243 (15)	141
C16—H16A⋯O2	0.98	2.59	3.106 (2)	113
C16—H16C⋯F4A^iv	0.98	2.43	3.409 (6)	174
C19—H19A⋯F2^v	0.95	2.52	3.117 (3)	121
C10—H10C⋯Cg3ⁱⁱ	0.98	2.93	3.631 (2)	130
C14—H14A⋯Cg3^iv	1.00	2.91	3.7707 (18)	145
Symmetry codes: (i) ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y, z+1; (iv) ; (v) x+1, y, z.

Figure 2
A view of the molecular packing of the title compound, showing the N—H⋯O hydrogen bonds. Only the major components of the disordered atoms are shown.

Figure 3
A view of the molecular packing of the title compound, showing the N—H⋯O, C—H⋯O and C—H⋯F hydrogen bonds.

Figure 4
A view of the molecular packing of the title compound, showing the C—H⋯π interactions. Only the major components of the disordered atoms are shown.

The Hirshfeld surface analysis of molecular crystal structures is an attempt to go beyond crystal packing diagrams with molecules represented by different patterns and internuclear distances and angles. Crystal Explorer 17.5 (Turner et al., 2017 ) was used to construct Hirshfeld surfaces for the title compound. The d_norm mappings for the title compound were performed in the range of −0.4718 to +1.7749 a.u. On the d_norm surfaces, bright red spots show the locations of the N—H⋯O, C—H⋯O and C—H⋯F interactions (Tables 1 and 2; Fig. 5a,b).

Table 2
Summary of short interatomic contacts (Å)

O1⋯H1N	2.12 (2)	1 + x, y, z
F3A⋯H12C	2.43	x, y, −1 + z
F3⋯H2A	2.59	x, $[{1\over 2}]$ − y, − $[{3\over 2}]$ + z
F4A⋯H16C	2.58	−1 + x, y, −1 + z
H16C⋯F4A	2.43	1 − x, 1 − y, 1 − z
F2A⋯H10A	2.81	−1 + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z
H15C⋯H15C	2.41	2 − x, 1 − y, 1 − z
H20A⋯H20A	2.52	1 − x, 1 − y, −z

Figure 5
(a) Front and (b) back views of the three-dimensional Hirshfeld surface for the title compound. Some N—H⋯O, C—H⋯O and C—H⋯F interactions are shown as dashed lines.

The overall two-dimensional fingerprint plot for the title compound and those delineated into H⋯H (Fig. 6b; 42.3), F⋯H/H⋯F (Fig. 6c; 28.5%), C⋯H/H⋯C (Fig. 6d; 14.6%) and O⋯H/H⋯O (Fig. 6e; 10.8%) contacts are shown in Fig. 6. F⋯O/O⋯F (1.8%), F⋯F (1.3%), N⋯H/H⋯N (0.5%) and F⋯C/C⋯F (0.2%) contacts have little directional influence on the molecular packing.

Figure 6
The two-dimensional fingerprint plots for the title compound showing (a) all interactions, and delineated into (b) H⋯H, (c) F⋯H/H⋯F, (d) C⋯H/H⋯C and (e) O⋯H/H⋯O interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ) for similar structures with the 1,4,5,6,7,8-hexahydroquinoline group showed that the eight most closely related to the title compound are refcodes ECUCUE [(I); Yıldırım et al., 2022 ], LOQCAX [(II); Steiger et al., 2014 ), NEQMON [(III); Öztürk Yıldırım et al., 2013 ], PECPUK [(IV); Gündüz et al., 2012 ] IMEJOA [(V); Linden et al., 2011 ], PUGCIE [(VI); Mookiah et al., 2009 ], UCOLOO [(VII); Linden et al., 2006 ] and DAYJET [(VIII); Linden et al., 2005 ]. Molecules of all these compounds are linked by N—H⋯O hydrogen bonds. Additionally, C—H⋯O hydrogen bonds in (I), (III), (V) and (VI) and C—H⋯π interactions in (I) were also observed.

5. Synthesis and crystallization

The compound was obtained by a modified one-pot Hantzsch synthesis, which consists of refluxing 4,4-dimethyl-1,3-cyclohexanedione (1 mmol), isopropyl acetoacetate (1 mmol) and 2-fluoro-5-(trifluoromethyl)benzaldehyde (1 mmol) in methanol in the presence of ammonium acetate (5 mmol). The reaction was monitored by TLC using ethyl acetate–n-hexane (1:1). The reaction mixture was cooled down to room temperature and then poured into ice–water. The precipitated solid was filtered and crystallized from methanol (Çetin et al., 2022 ).

Isopropyl 2,6,6-trimethyl-4-(3-fluoro-5-trifluoromethylphenyl)-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate. Yellowish solid, m.p: 469–471 K, yield: 60%. IR (cm⁻¹) 3299 (N—H), 1697 (C=O, ester), 1646 (C=O, ketone), ¹H NMR (400 MHz, DMSO-d₆): δ 0.82 (3H, s, 6-CH₃), 0.91 [3H, d, J = 6.4 Hz, CH(CH₃)_2a], 0.97 (3H, s, 6-CH₃), 1.16 [3H, d, J = 6.4, CH(CH₃)_2b], 1.64–1.76 (2H, m, quinoline H7), 2.26 (3H, s, 2-CH₃), 2.48–2.51 (2H, m, quinoline H8), 4.75–4.81 [H, m, CH(CH₃)₂], 5.02 (H, s, quinoline H4), 7.24 (H, dd, J = 9.2, 6.8 Hz, Ar-H3), 7.50–7.54 (2H, m, Ar-H), 9.21 (H, s, NH). ¹³C NMR (100 MHz, DMSO-d₆): δ 18.2 (2-CH₃), 21.2 [COOCH(CH₃)_2a], 21.7 [COOCH(CH₃)_2b], 22.9 (C-8), 24.2 (6-CH₃), 24.7 (6-CH₃), 33.1 (C-7), 34.0 (C-4), 39.4 (C-6), 66.0 [COOCH(CH₃)₂], 101.2 (C-3), 107.5 (C-4a), 116.4, 122.7, 125.4, 128.2, 135.5, 163.4 (phenyl carbons), 125.1 (CF₃), 146.1 (C-2), 150.4 (C-8a), 165.9 [COOCH(CH₃)₂], 199.3 (C-5). HRMS (ESI/Q-TOF) m/z: [M + H]⁺ calculated for C₂₃H₂₅F₄NO_3: 440.1804; found: 440.1975.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All C-bound H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) while the hydrogen atom attached to N1 was found in a difference map, and was subsequently refined freely [N1—H1N = 0.88 (2) Å]. All C-bound H atoms were included as riding contributions with isotropic displacement parameters 1.2 times those of the parent atoms (1.5 for methyl groups). All F atoms of the trifluoromethyl unit of the molecule are disordered over two sites [relative occupancies 0.763 (5):0.237 (5)]. DFIX, SIMU and DELU instructions were used to restrain the disordered F atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₂₃H₂₅F₄NO₃
M_r	439.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.4918 (3), 27.8140 (11), 10.2023 (4)
β (°)	97.053 (2)
V (Å³)	2109.84 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.23 × 0.17 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.663, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	21749, 5221, 3801
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.129, 1.08
No. of reflections	5221
No. of parameters	318
No. of restraints	48
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.37
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2242647

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902300141X/tx2062sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300141X/tx2062Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902300141X/tx2062Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2020).

Propan-2-yl 4-[2-fluoro-5-(trifluoromethyl)phenyl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate top

Crystal data top

C₂₃H₂₅F₄NO₃	F(000) = 920
M_r = 439.44	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4918 (3) Å	Cell parameters from 8405 reflections
b = 27.8140 (11) Å	θ = 2.5–28.2°
c = 10.2023 (4) Å	µ = 0.11 mm⁻¹
β = 97.053 (2)°	T = 100 K
V = 2109.84 (14) Å³	Prism, yellowish
Z = 4	0.23 × 0.17 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	3801 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.056
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 28.3°, θ_min = 2.5°
T_min = 0.663, T_max = 0.746	h = −9→9
21749 measured reflections	k = −36→36
5221 independent reflections	l = −13→13

Refinement top

Refinement on F²	48 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.044P)² + 1.2617P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
5221 reflections	Δρ_max = 0.35 e Å⁻³
318 parameters	Δρ_min = −0.37 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	Occ. (<1)
F1	0.83123 (14)	0.59076 (4)	0.35900 (11)	0.0285 (3)
F2	0.0433 (2)	0.58544 (9)	0.09930 (16)	0.0425 (7)	0.763 (5)
F3	0.1611 (9)	0.62597 (14)	−0.0465 (4)	0.0398 (9)	0.763 (5)
F4	0.1702 (3)	0.54913 (6)	−0.04875 (18)	0.0370 (5)	0.763 (5)
F2A	0.0323 (7)	0.6241 (3)	0.0914 (6)	0.056 (2)	0.237 (5)
F3A	0.167 (3)	0.6171 (5)	−0.0756 (14)	0.049 (4)	0.237 (5)
F4A	0.0756 (10)	0.5551 (2)	0.0171 (8)	0.059 (3)	0.237 (5)
O1	0.81859 (16)	0.71304 (4)	0.41408 (13)	0.0227 (3)
O2	0.38263 (18)	0.57179 (5)	0.71526 (13)	0.0288 (3)
O3	0.60880 (16)	0.56439 (4)	0.58997 (12)	0.0199 (3)
N1	0.20965 (19)	0.69030 (5)	0.46495 (15)	0.0207 (3)
H1N	0.099 (3)	0.7016 (8)	0.459 (2)	0.031 (6)*
C1	0.3454 (2)	0.71772 (6)	0.42567 (16)	0.0190 (3)
C2	0.2984 (2)	0.76895 (6)	0.3917 (2)	0.0255 (4)
H2A	0.285175	0.786980	0.473603	0.031*
H2B	0.181746	0.770062	0.334509	0.031*
C3	0.4424 (2)	0.79280 (6)	0.32062 (18)	0.0232 (4)
H3A	0.419816	0.827862	0.315943	0.028*
H3B	0.432982	0.780416	0.229056	0.028*
C4	0.6335 (2)	0.78392 (6)	0.38858 (17)	0.0190 (3)
C5	0.6655 (2)	0.72984 (6)	0.40730 (16)	0.0175 (3)
C6	0.5124 (2)	0.69908 (5)	0.42489 (15)	0.0170 (3)
C7	0.5444 (2)	0.64570 (5)	0.45008 (16)	0.0164 (3)
H7A	0.668292	0.641386	0.497582	0.020*
C8	0.4092 (2)	0.62727 (5)	0.53860 (16)	0.0170 (3)
C9	0.2458 (2)	0.64791 (6)	0.53611 (16)	0.0185 (3)
C10	0.6615 (3)	0.80687 (7)	0.52669 (19)	0.0293 (4)
H10A	0.783401	0.799820	0.568766	0.044*
H10B	0.573604	0.793666	0.580624	0.044*
H10C	0.645383	0.841759	0.518702	0.044*
C11	0.7685 (2)	0.80522 (6)	0.30387 (19)	0.0261 (4)
H11A	0.756447	0.789038	0.217908	0.039*
H11B	0.890814	0.800633	0.348417	0.039*
H11C	0.744789	0.839655	0.290953	0.039*
C12	0.0930 (2)	0.63118 (6)	0.60675 (18)	0.0223 (3)
H12A	0.092211	0.595962	0.609755	0.033*
H12B	−0.020875	0.642682	0.559688	0.033*
H12C	0.107879	0.643951	0.696950	0.033*
C13	0.4600 (2)	0.58570 (6)	0.62451 (17)	0.0197 (3)
C14	0.6800 (2)	0.52376 (6)	0.67080 (18)	0.0233 (4)
H14A	0.579391	0.502405	0.690737	0.028*
C15	0.8005 (3)	0.49721 (7)	0.5873 (2)	0.0320 (4)
H15A	0.732182	0.488837	0.502190	0.048*
H15B	0.845165	0.467797	0.632940	0.048*
H15C	0.902333	0.517761	0.572403	0.048*
C16	0.7809 (3)	0.54265 (7)	0.79772 (19)	0.0321 (4)
H16A	0.698202	0.560747	0.846536	0.048*
H16B	0.878266	0.563824	0.777245	0.048*
H16C	0.831503	0.515642	0.851701	0.048*
C17	0.5305 (2)	0.61730 (5)	0.32111 (16)	0.0180 (3)
C18	0.6711 (2)	0.59070 (6)	0.28216 (17)	0.0221 (3)
C19	0.6575 (3)	0.56336 (6)	0.16787 (19)	0.0297 (4)
H19A	0.757188	0.545153	0.146365	0.036*
C20	0.4966 (3)	0.56302 (7)	0.08575 (18)	0.0310 (4)
H20A	0.484741	0.545016	0.006024	0.037*
C21	0.3531 (3)	0.58922 (7)	0.12102 (17)	0.0261 (4)
C22	0.3689 (2)	0.61593 (6)	0.23693 (17)	0.0216 (3)
H22A	0.268204	0.633535	0.259244	0.026*
C23	0.1789 (3)	0.58922 (8)	0.03321 (19)	0.0355 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0201 (5)	0.0332 (6)	0.0326 (6)	0.0071 (4)	0.0043 (4)	−0.0038 (5)
F2	0.0219 (8)	0.0783 (19)	0.0270 (8)	−0.0104 (9)	0.0018 (6)	−0.0014 (9)
F3	0.0451 (19)	0.0281 (10)	0.0418 (19)	−0.0055 (10)	−0.0127 (16)	0.0106 (11)
F4	0.0431 (12)	0.0323 (8)	0.0324 (9)	−0.0078 (7)	−0.0088 (8)	−0.0090 (7)
F2A	0.025 (3)	0.098 (6)	0.041 (3)	0.019 (3)	−0.011 (2)	−0.028 (4)
F3A	0.037 (5)	0.073 (8)	0.037 (6)	0.002 (6)	0.012 (5)	0.026 (5)
F4A	0.051 (4)	0.042 (3)	0.073 (6)	−0.023 (3)	−0.033 (4)	0.020 (4)
O1	0.0149 (6)	0.0213 (6)	0.0324 (7)	0.0021 (5)	0.0044 (5)	0.0027 (5)
O2	0.0299 (7)	0.0294 (6)	0.0297 (7)	0.0054 (5)	0.0138 (6)	0.0089 (5)
O3	0.0180 (6)	0.0186 (5)	0.0236 (6)	0.0031 (4)	0.0045 (5)	0.0039 (5)
N1	0.0119 (7)	0.0219 (7)	0.0285 (8)	0.0021 (5)	0.0039 (6)	0.0045 (6)
C1	0.0152 (8)	0.0202 (8)	0.0216 (8)	0.0017 (6)	0.0031 (6)	0.0013 (6)
C2	0.0171 (8)	0.0226 (8)	0.0372 (10)	0.0054 (6)	0.0055 (7)	0.0084 (7)
C3	0.0187 (9)	0.0198 (8)	0.0312 (9)	0.0051 (6)	0.0041 (7)	0.0068 (7)
C4	0.0168 (8)	0.0164 (7)	0.0238 (8)	0.0016 (6)	0.0029 (6)	0.0021 (6)
C5	0.0167 (8)	0.0187 (7)	0.0172 (7)	0.0013 (6)	0.0023 (6)	0.0000 (6)
C6	0.0161 (8)	0.0176 (7)	0.0171 (7)	0.0005 (6)	0.0016 (6)	0.0013 (6)
C7	0.0135 (7)	0.0177 (7)	0.0179 (7)	0.0012 (6)	0.0014 (6)	−0.0006 (6)
C8	0.0166 (8)	0.0172 (7)	0.0172 (7)	−0.0010 (6)	0.0019 (6)	−0.0013 (6)
C9	0.0182 (8)	0.0191 (7)	0.0181 (7)	−0.0018 (6)	0.0015 (6)	−0.0015 (6)
C10	0.0331 (11)	0.0224 (8)	0.0322 (10)	0.0024 (7)	0.0035 (8)	−0.0053 (7)
C11	0.0208 (9)	0.0215 (8)	0.0369 (10)	−0.0006 (7)	0.0071 (8)	0.0058 (7)
C12	0.0167 (8)	0.0245 (8)	0.0266 (9)	−0.0009 (6)	0.0068 (7)	0.0013 (7)
C13	0.0177 (8)	0.0198 (7)	0.0217 (8)	0.0008 (6)	0.0029 (6)	−0.0015 (6)
C14	0.0201 (9)	0.0186 (8)	0.0314 (9)	0.0017 (6)	0.0036 (7)	0.0077 (7)
C15	0.0261 (10)	0.0225 (9)	0.0485 (12)	0.0055 (7)	0.0082 (9)	0.0031 (8)
C16	0.0314 (11)	0.0334 (10)	0.0298 (10)	−0.0021 (8)	−0.0026 (8)	0.0104 (8)
C17	0.0205 (8)	0.0161 (7)	0.0178 (7)	−0.0029 (6)	0.0044 (6)	0.0013 (6)
C18	0.0220 (9)	0.0213 (8)	0.0237 (8)	−0.0006 (6)	0.0055 (7)	0.0002 (6)
C19	0.0375 (11)	0.0234 (9)	0.0311 (10)	−0.0030 (8)	0.0157 (9)	−0.0056 (7)
C20	0.0448 (12)	0.0281 (9)	0.0220 (9)	−0.0142 (8)	0.0109 (8)	−0.0067 (7)
C21	0.0305 (10)	0.0294 (9)	0.0181 (8)	−0.0139 (7)	0.0012 (7)	0.0030 (7)
C22	0.0221 (9)	0.0240 (8)	0.0190 (8)	−0.0048 (7)	0.0034 (7)	0.0032 (6)
C23	0.0409 (12)	0.0448 (11)	0.0196 (9)	−0.0198 (9)	−0.0006 (8)	0.0048 (8)

Geometric parameters (Å, º) top

F1—C18	1.350 (2)	C8—C13	1.472 (2)
F2—C23	1.291 (3)	C9—C12	1.500 (2)
F3—C23	1.303 (4)	C10—H10A	0.9800
F4—C23	1.390 (3)	C10—H10B	0.9800
F2A—C23	1.632 (6)	C10—H10C	0.9800
F3A—C23	1.348 (13)	C11—H11A	0.9800
F4A—C23	1.223 (6)	C11—H11B	0.9800
O1—C5	1.233 (2)	C11—H11C	0.9800
O2—C13	1.215 (2)	C12—H12A	0.9800
O3—C13	1.3470 (19)	C12—H12B	0.9800
O3—C14	1.4607 (19)	C12—H12C	0.9800
N1—C1	1.370 (2)	C14—C15	1.508 (3)
N1—C9	1.394 (2)	C14—C16	1.511 (3)
N1—H1N	0.88 (2)	C14—H14A	1.0000
C1—C6	1.355 (2)	C15—H15A	0.9800
C1—C2	1.498 (2)	C15—H15B	0.9800
C2—C3	1.523 (2)	C15—H15C	0.9800
C2—H2A	0.9900	C16—H16A	0.9800
C2—H2B	0.9900	C16—H16B	0.9800
C3—C4	1.532 (2)	C16—H16C	0.9800
C3—H3A	0.9900	C17—C18	1.385 (2)
C3—H3B	0.9900	C17—C22	1.396 (2)
C4—C11	1.528 (2)	C18—C19	1.385 (2)
C4—C5	1.531 (2)	C19—C20	1.381 (3)
C4—C10	1.538 (2)	C19—H19A	0.9500
C5—C6	1.459 (2)	C20—C21	1.383 (3)
C6—C7	1.521 (2)	C20—H20A	0.9500
C7—C8	1.526 (2)	C21—C22	1.389 (2)
C7—C17	1.527 (2)	C21—C23	1.489 (3)
C7—H7A	1.0000	C22—H22A	0.9500
C8—C9	1.350 (2)

C13—O3—C14	116.69 (13)	C9—C12—H12B	109.5
C1—N1—C9	121.29 (14)	H12A—C12—H12B	109.5
C1—N1—H1N	120.3 (14)	C9—C12—H12C	109.5
C9—N1—H1N	117.5 (14)	H12A—C12—H12C	109.5
C6—C1—N1	120.53 (15)	H12B—C12—H12C	109.5
C6—C1—C2	123.60 (15)	O2—C13—O3	123.17 (15)
N1—C1—C2	115.80 (14)	O2—C13—C8	126.25 (15)
C1—C2—C3	111.35 (14)	O3—C13—C8	110.58 (13)
C1—C2—H2A	109.4	O3—C14—C15	105.20 (14)
C3—C2—H2A	109.4	O3—C14—C16	108.92 (14)
C1—C2—H2B	109.4	C15—C14—C16	112.55 (16)
C3—C2—H2B	109.4	O3—C14—H14A	110.0
H2A—C2—H2B	108.0	C15—C14—H14A	110.0
C2—C3—C4	113.03 (14)	C16—C14—H14A	110.0
C2—C3—H3A	109.0	C14—C15—H15A	109.5
C4—C3—H3A	109.0	C14—C15—H15B	109.5
C2—C3—H3B	109.0	H15A—C15—H15B	109.5
C4—C3—H3B	109.0	C14—C15—H15C	109.5
H3A—C3—H3B	107.8	H15A—C15—H15C	109.5
C11—C4—C5	110.31 (13)	H15B—C15—H15C	109.5
C11—C4—C3	109.16 (14)	C14—C16—H16A	109.5
C5—C4—C3	109.75 (13)	C14—C16—H16B	109.5
C11—C4—C10	109.38 (15)	H16A—C16—H16B	109.5
C5—C4—C10	106.97 (14)	C14—C16—H16C	109.5
C3—C4—C10	111.26 (14)	H16A—C16—H16C	109.5
O1—C5—C6	120.70 (14)	H16B—C16—H16C	109.5
O1—C5—C4	120.64 (14)	C18—C17—C22	116.21 (15)
C6—C5—C4	118.56 (14)	C18—C17—C7	123.34 (15)
C1—C6—C5	121.08 (14)	C22—C17—C7	120.43 (15)
C1—C6—C7	119.93 (14)	F1—C18—C17	119.05 (15)
C5—C6—C7	118.91 (14)	F1—C18—C19	117.23 (16)
C6—C7—C8	109.00 (13)	C17—C18—C19	123.71 (18)
C6—C7—C17	111.51 (13)	C20—C19—C18	118.87 (18)
C8—C7—C17	110.85 (13)	C20—C19—H19A	120.6
C6—C7—H7A	108.5	C18—C19—H19A	120.6
C8—C7—H7A	108.5	C19—C20—C21	119.17 (17)
C17—C7—H7A	108.5	C19—C20—H20A	120.4
C9—C8—C13	120.85 (15)	C21—C20—H20A	120.4
C9—C8—C7	120.83 (14)	C20—C21—C22	121.04 (18)
C13—C8—C7	118.31 (14)	C20—C21—C23	119.70 (17)
C8—C9—N1	119.18 (14)	C22—C21—C23	119.26 (18)
C8—C9—C12	127.09 (15)	C21—C22—C17	120.99 (17)
N1—C9—C12	113.69 (14)	C21—C22—H22A	119.5
C4—C10—H10A	109.5	C17—C22—H22A	119.5
C4—C10—H10B	109.5	F2—C23—F3	111.3 (3)
H10A—C10—H10B	109.5	F4A—C23—F3A	111.0 (8)
C4—C10—H10C	109.5	F2—C23—F4	105.48 (18)
H10A—C10—H10C	109.5	F3—C23—F4	105.1 (2)
H10B—C10—H10C	109.5	F4A—C23—C21	125.0 (3)
C4—C11—H11A	109.5	F2—C23—C21	111.93 (16)
C4—C11—H11B	109.5	F3—C23—C21	113.0 (3)
H11A—C11—H11B	109.5	F3A—C23—C21	117.5 (9)
C4—C11—H11C	109.5	F4—C23—C21	109.55 (19)
H11A—C11—H11C	109.5	F4A—C23—F2A	93.9 (5)
H11B—C11—H11C	109.5	F3A—C23—F2A	88.7 (8)
C9—C12—H12A	109.5	C21—C23—F2A	111.1 (2)

C9—N1—C1—C6	16.7 (2)	C14—O3—C13—C8	177.28 (13)
C9—N1—C1—C2	−160.28 (16)	C9—C8—C13—O2	−14.5 (3)
C6—C1—C2—C3	16.0 (3)	C7—C8—C13—O2	166.88 (17)
N1—C1—C2—C3	−167.16 (16)	C9—C8—C13—O3	166.01 (15)
C1—C2—C3—C4	−47.4 (2)	C7—C8—C13—O3	−12.6 (2)
C2—C3—C4—C11	174.92 (14)	C13—O3—C14—C15	161.43 (15)
C2—C3—C4—C5	53.91 (19)	C13—O3—C14—C16	−77.70 (18)
C2—C3—C4—C10	−64.28 (19)	C6—C7—C17—C18	119.37 (17)
C11—C4—C5—O1	33.3 (2)	C8—C7—C17—C18	−118.98 (17)
C3—C4—C5—O1	153.65 (15)	C6—C7—C17—C22	−62.54 (19)
C10—C4—C5—O1	−85.53 (19)	C8—C7—C17—C22	59.10 (19)
C11—C4—C5—C6	−150.30 (15)	C22—C17—C18—F1	179.63 (14)
C3—C4—C5—C6	−30.0 (2)	C7—C17—C18—F1	−2.2 (2)
C10—C4—C5—C6	90.83 (18)	C22—C17—C18—C19	−0.7 (2)
N1—C1—C6—C5	−168.50 (15)	C7—C17—C18—C19	177.43 (16)
C2—C1—C6—C5	8.2 (3)	F1—C18—C19—C20	−178.98 (15)
N1—C1—C6—C7	8.1 (2)	C17—C18—C19—C20	1.4 (3)
C2—C1—C6—C7	−175.12 (16)	C18—C19—C20—C21	−1.2 (3)
O1—C5—C6—C1	175.91 (16)	C19—C20—C21—C22	0.4 (3)
C4—C5—C6—C1	−0.4 (2)	C19—C20—C21—C23	179.90 (17)
O1—C5—C6—C7	−0.8 (2)	C20—C21—C22—C17	0.3 (3)
C4—C5—C6—C7	−177.12 (14)	C23—C21—C22—C17	−179.26 (15)
C1—C6—C7—C8	−28.8 (2)	C18—C17—C22—C21	−0.1 (2)
C5—C6—C7—C8	147.86 (14)	C7—C17—C22—C21	−178.31 (15)
C1—C6—C7—C17	93.87 (18)	C20—C21—C23—F4A	71.2 (7)
C5—C6—C7—C17	−89.42 (17)	C22—C21—C23—F4A	−109.2 (7)
C6—C7—C8—C9	29.1 (2)	C20—C21—C23—F2	137.6 (2)
C17—C7—C8—C9	−93.96 (18)	C22—C21—C23—F2	−42.9 (3)
C6—C7—C8—C13	−152.26 (14)	C20—C21—C23—F3	−95.8 (3)
C17—C7—C8—C13	84.64 (18)	C22—C21—C23—F3	83.7 (3)
C13—C8—C9—N1	172.97 (15)	C20—C21—C23—F3A	−77.8 (8)
C7—C8—C9—N1	−8.5 (2)	C22—C21—C23—F3A	101.8 (8)
C13—C8—C9—C12	−4.9 (3)	C20—C21—C23—F4	21.0 (2)
C7—C8—C9—C12	173.69 (15)	C22—C21—C23—F4	−159.50 (17)
C1—N1—C9—C8	−16.5 (2)	C20—C21—C23—F2A	−177.7 (4)
C1—N1—C9—C12	161.63 (15)	C22—C21—C23—F2A	1.8 (4)
C14—O3—C13—O2	−2.2 (2)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C17–C22 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.88 (2)	2.12 (2)	2.9798 (19)	165 (2)
C2—H2A···F3ⁱⁱ	0.99	2.59	3.187 (4)	119
C12—H12B···F1ⁱ	0.98	2.64	3.206 (2)	117
C12—H12B···O1ⁱ	0.98	2.65	3.505 (2)	145
C12—H12C···F3Aⁱⁱⁱ	0.98	2.43	3.243 (15)	141
C16—H16A···O2	0.98	2.59	3.106 (2)	113
C16—H16C···F4A^iv	0.98	2.43	3.409 (6)	174
C19—H19A···F2^v	0.95	2.52	3.117 (3)	121
C10—H10C···Cg3ⁱⁱ	0.98	2.93	3.631 (2)	130
C14—H14A···Cg3^iv	1.00	2.91	3.7707 (18)	145

Symmetry codes: (i) x−1, y, z; (ii) x, −y+3/2, z+1/2; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z.

Summary of short interatomic contacts (Å) top

O1···H1N	2.12 (2)	1 + x, y, z
F3A···H12C	2.43	x, y, -1 + z
F3···H2A	2.59	x, 1/2 - y, -3/2 + z
F4A···H16C	2.58	-1 + x, y, -1 + z
H16C···F4A	2.43	1 - x, 1 - y, 1 - z
F2A···H10A	2.81	-1 + x, 3/2 - y, -1/2 + z
H15C···H15C	2.41	2 - x, 1 - y, 1 - z
H20A···H20A	2.52	1 - x, 1 - y, -z

Acknowledgements

Authors' contributions are as follows. Conceptualization, RS and SOY; methodology, RS and GC; investigation, RS and SOY; writing (original draft), GC and MA writing (review and editing of the manuscript), RS and SOY; crystal data production and validation, RJB and SOY; visualization, MA; funding acquisition, RJB; resources, AB, RJB and RS.

Funding information

RJB is grateful for funding from NSF (award 1205608) and to the Partnership for Reduced Dimensional Materials for partial funding of this research, to Howard University Nanoscience Facility for access to liquid nitrogen, and the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer. This study was supported by the Hacettepe University Scientific Research Unit (project No. THD-2020–18806).

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2018). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Çetin, G., Çetin, B., Çolak, B., Aşan, M., Birlik Demirel, G., Cansaran-Duman, D., Akçelik, N. & Şimşek, R. (2022). J. Res. Pharm. 26, 219–230. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gündüz, M. G., Butcher, R. J., Öztürk Yildirim, S., El-Khouly, A., Şafak, C. & Şimşek, R. (2012). Acta Cryst. E68, o3404–o3405. CSD CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Linden, A., Gündüz, M. G., Şimşek, R. & Şafak, C. (2006). Acta Cryst. C62, o227–o230. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Linden, A., Şafak, C., Şimşek, R. & Gündüz, M. G. (2011). Acta Cryst. C67, o80–o84. Web of Science CSD CrossRef IUCr Journals Google Scholar
Linden, A., Şimşek, R., Gündüz, M. & Şafak, C. (2005). Acta Cryst. C61, o731–o734. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mookiah, P., Rajesh, K., Narasimhamurthy, T., Vijayakumar, V. & Srinivasan, N. (2009). Acta Cryst. E65, o2664. Web of Science CSD CrossRef IUCr Journals Google Scholar
Öztürk Yildirim, S., Butcher, R. J., Gündüz, M. G., El-Khouly, A., Şimşek, R. & Şafak, C. (2013). Acta Cryst. E69, o40–o41. CSD CrossRef IUCr Journals Google Scholar
Ranjbar, S., Edraki, N., Firuzi, O., Khoshneviszadeh, M. & Miri, R. (2019). Mol. Divers. 23, 471–508. CrossRef CAS PubMed 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
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Steiger, S. A., Monacelli, A. J., Li, C., Hunting, J. L. & Natale, N. R. (2014). Acta Cryst. C70, 790–795. Web of Science CSD CrossRef IUCr Journals Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://Hirshfeldsurface.net. Google Scholar
Yıldırım, S. Ö., Akkurt, M., Çetin, G., Şimşek, R., Butcher, R. J. & Bhattarai, A. (2022). Acta Cryst. E78, 798–803. CSD CrossRef IUCr Journals Google Scholar

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