2-[4-(2-Chloro­benz­yl)-3-methyl-6-oxo-1,6-di­hydro­pyridazin-1-yl]-N-(4-fluoro­phen­yl)acetamide

Assila, H.; Ameziane El Hassani, I.; El Moutaouakil Ala Allah, A.; Alsubari, A.; Mague, J.T.; Ramli, Y.; Ansar, M.H.

doi:10.1107/S241431462300901X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 10| October 2023| x230901

https://doi.org/10.1107/S241431462300901X

Open

access

2-[4-(2-Chlorobenzyl)-3-methyl-6-oxo-1,6-dihydropyridazin-1-yl]-N-(4-fluorophenyl)acetamide

Hamza Assila,^a Issam Ameziane El Hassani,^a Abderrazzak El Moutaouakil Ala Allah,^a Abdulsalam Alsubari,^b ^* Joel T Mague,^c Youssef Ramli ^a,^d ^* and MHammed Ansar ^a

^aLaboratory of Medicinal Chemistry, Drug Sciences Research Center, Faculty of Medicine and Pharmacy, Mohammed V University in Rabat, Morocco, ^bLaboratory of Medicinal Chemistry, Faculty of Clinical Pharmacy, 21 September University, Yemen, ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and ^dMohammed VI Center for Research and Innovation (CM6), Rabat 10000, Morocco
^*Correspondence e-mail: alsubaripharmaco@21umas.edu.ye, y.ramli@um5r.ac.ma

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 12 October 2023; accepted 14 October 2023; online 19 October 2023)

The conformation of the title molecule, C₂₀H₁₇ClFN₃O₂, is partly determined by an intramolecular C—H⋯O hydrogen bond, which leads to a dihedral angle of 14.7 (4)° between the fluorobenzene ring and the acetamide group. The 2-chlorobenzyl group is rotationally disordered over two orientations in a 0.656 (2): 0.344 (2) ratio. In the crystal, a layered structure is formed by N—H⋯O, C—H⋯O and C—H⋯F hydrogen bonds plus slipped π–π stacking interactions.

Keywords: crystal structure; pyridazine; hydrogen bond; π-stacking; arylacetamide; crystal structure.

CCDC reference: 2301289

Structure description

Pyridazinone derivatives possess a number of biological activities including anti-oxidant (Khokra et al., 2016 ), anti-bacterial and antifungal (Abiha et al. 2018 ), anti-cancer (Kamble et al. 2017 ), analgesic and anti-inflammatory (Ibrahim et al. 2017 ), anti-depressant (Boukharsa et al. 2016 ) and anti-ulcer properties (Yamada et al., 1981 ). In addition, N-arylacetamide derivatives with their wide spectrum of activities (e.g., Missioui et al., 2022 ) have significant importance as intermediates in organic chemistry. As a continuation of a our work in synthesizing new N-arylacetamide derivatives (e.g., Mortada et al., 2023 ), and developing new pyridazine-3(2H)-one compounds (e.g., Zaoui et al., 2022 ), the title compound C₂₀H₁₇ClFN₃O₂ was synthesized and its crystal structure is reported here.

The title molecule adopts an `extended' conformation with a dihedral angle between the mean plane of the C15–C20 fluorobenzene ring and that defined by N2, C14, C13 and O2 of 14.7 (4)°. This is likely due in part to the intramolecular C16—H16⋯O2 hydrogen bond (Table 1 and Fig. 1). The dihedral angle between this latter plane and the mean plane of the C8–C11/N1/N2 ring is 72.07 (16)° while that between the mean planes of the C8–C11/N1/N2 and the C1–C6 rings is 80.38 (16)°. The disorder in this part of the molecule features a 177.2 (5)° rotation of the 2-chlorophenyl between the two components of the disorder in a 0.656 (2): 0.344 (2) ratio.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.88	1.95	2.815 (5)	168
C7—H7A⋯O2ⁱⁱ	0.99	2.32	3.282 (15)	164
C16—H16⋯O2	0.95	2.29	2.900 (6)	121
C19—H19⋯F1ⁱⁱⁱ	0.95	2.42	3.336 (7)	162
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z]$ .

Figure 1
The title molecule with labeling scheme and 50% probability ellipsoids. The intramolecular C—H⋯O hydrogen bond is depicted by a dashed line and only the major component of the disorder is shown.

In the crystal, N3—H3⋯O1 hydrogen bonds form chains of molecules extending along the b-axis direction. These are reinforced by slipped π-stacking interactions between a pyridazine and a 4-fluorophenyl ring at –x + 2, y + $[{1\over 2}]$ , –z + 1 [centroid–centroid separation = 3.706 (3) Å, dihedral angle = 8.7 (2)°, slippage = 1.18 Å] (Fig. 2). These chains are connected into layers by C19—H19⋯F1 hydrogen bonds with the layers further connected by C7—H7A⋯O2 hydrogen bonds (Fig. 3).

Figure 2
A portion of one chain of molecules viewed along the a-axis direction with N—H⋯O hydrogen bonds and slipped, π-stacking interactions depicted, respectively, by violet and orange dashed lines. Non-interacting hydrogen atoms are omitted for clarity.

Figure 3
Packing viewed along the a-axis direction with N—H⋯O, C—H⋯O and C—H⋯F hydrogen bonds depicted, respectively, by violet, black and light blue dashed lines. Slipped π-stacking interactions are depicted by orange dashed lines and non-interacting hydrogen atoms are omitted for clarity.

Synthesis and crystallization

A mixture of 3-benzylidene-4-oxopentanoic acid derivative (0.010 mol) and hydrazine hydrate (0.020 mol) in ethanol was refluxed to obtain the 5-(2-chlorobenzyl)-6-methylpyridazin-3(2H)-one precursor. To this pyridazine-3(2H)-one (0.010 mol) was added 0.010 mol of 2-chloro-N-(4-fluorophenyl)acetamide, followed by 0.020 mol of potassium bicarbonate and a spatula tip of BTBA (benzyltributylammonium bromide). The mixture was kept stirring at room temperature for 24 h and the progress of the reaction was monitored by TLC. Then, 200 ml of distilled water were added to the reaction mixture, the precipitated product was filtered off, dried and recrystallized from acetone solution to yield colorless crystals of the title compound.

Yield 82%; m.p: 477–479 K. ¹H NMR [300 MHz DMSO-d₆, δ(p.p.m.)]: 2.25 (s, 3H, CH₃); 3.96 (s, 2H, phenyl-CH₂-pyridazinone); 4,78 (s, 2H, N—CH₂—CO); 6.06 (s, 1H, pyridazinone); 7.07–7.58 (m, 8H, two phenyl); 10.32 (s, 1H, NH). ¹³C NMR [126 MHz DMSO-d₆, δ(p.p.m.)]: 19.06 (CH₃); 35.32 (phenyle-CH₂-pyridazinone); 54.61 (pyridazinone-CH₂—CO); 115.84 (d, J = 22.5 Hz) (C aromatic acetamide); 121.32 (d, J = 7.7 Hz) (C aromatic acetamide); 126.55 (CH pyridazinone); 128.32 (C aromatic); 129.73 (C aromatic); 130.17 (C aromatic); 132.08 (C aromatic); 134.02 (C aromatic); 134.87 (C aromatic-CH₂); 135.67 (d, J = 2,5 Hz) (C aromatic-NH); 144.88 (CH₂—C pyridazinone); 145.96 (C pyridazinone–CH₃); 157.63 (d, J = 293,9 Hz) (C aromatic-F); 159.83 (C pyridazinone=O); 165.68 (NH—C=O). MS (ESI+): m/z = 386.10.

Refinement

Crystal data, data collection and refinement details are presented in Table 2. The o-chlorobenzyl group is rotationally disordered over two orientations in a 0.656 (2): 0.344 (2) ratio with the components refined with restraints to make their geometries comparable. One reflection affected by the beamstop was omitted from the final refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₁₇ClFN₃O₂
M_r	385.82
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	150
a, b, c (Å)	10.0602 (13), 6.7704 (9), 14.524 (2)
β (°)	110.168 (2)
V (Å³)	928.6 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.19 × 0.14 × 0.08

Data collection
Diffractometer	Bruker D8 QUEST PHOTON 3 diffractometer
Absorption correction	Numerical (SADABS; Krause et al., 2015 )
T_min, T_max	0.80, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	6266, 2856, 2376
R_int	0.039
θ_max (°)	23.9
(sin θ/λ)_max (Å⁻¹)	0.570

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.131, 1.03
No. of reflections	2856
No. of parameters	240
No. of restraints	17
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.28
Absolute structure	Flack x determined using 904 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.01 (7)
Computer programs: APEX4 and SAINT (Bruker, 2021 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/1 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 2301289

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431462300901X/hb4454sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462300901X/hb4454Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431462300901X/hb4454Isup3.cml

checkCIF report

Computing details top

Data collection: APEX4 (Bruker, 2021); cell refinement: SAINT (Bruker, 2021); data reduction: SAINT (Bruker, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-[4-(2-Chlorobenzyl)-3-methyl-6-oxo-1,6-dihydropyridazin-1-yl]-N-(4-fluorophenyl)acetamide top

Crystal data top

C₂₀H₁₇ClFN₃O₂	F(000) = 400
M_r = 385.82	D_x = 1.380 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 10.0602 (13) Å	Cell parameters from 3275 reflections
b = 6.7704 (9) Å	θ = 3.0–23.6°
c = 14.524 (2) Å	µ = 0.24 mm⁻¹
β = 110.168 (2)°	T = 150 K
V = 928.6 (2) Å³	Plate, colourless
Z = 2	0.19 × 0.14 × 0.08 mm

Data collection top

Bruker D8 QUEST PHOTON 3 diffractometer	2856 independent reflections
Radiation source: fine-focus sealed tube	2376 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 7.3910 pixels mm^-1	θ_max = 23.9°, θ_min = 3.0°
φ and ω scans	h = −11→11
Absorption correction: numerical (SADABS; Krause et al., 2015)	k = −7→7
T_min = 0.80, T_max = 0.98	l = −16→16
6266 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.0712P)² + 0.1965P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2856 reflections	Δρ_max = 0.27 e Å⁻³
240 parameters	Δρ_min = −0.28 e Å⁻³
17 restraints	Absolute structure: Flack x determined using 904 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: −0.01 (7)

Special details top

Experimental. The diffraction data were collected in three sets of 363 frames (0.5° width in ω) at φ = 0, 120 and 240°. A scan time of 40 sec/frame was used.

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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) and were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. That attached to nitrogen was located in a difference map and refined with a DFIX 0.91 0.01 instruction. The o-chlorobenzyl group is rotationally disoordered over two sites 177.2 (5)° apart in a 0.656 (2)/0.344 (2) ratio. The two components were refined as rigid hexagons with additional restraints to make their geometries comparable. One reflection affected by the beam stop was omitted from the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.7132 (2)	0.6802 (4)	0.94862 (15)	0.0618 (6)	0.656 (2)
Cl1A	0.3896 (4)	0.3635 (7)	0.6576 (3)	0.0618 (6)	0.344 (2)
F1	0.9061 (5)	0.0075 (7)	0.0379 (3)	0.1107 (17)
O1	0.9168 (3)	0.3291 (5)	0.6332 (3)	0.0492 (9)
O2	0.7561 (3)	0.3559 (5)	0.4072 (2)	0.0485 (9)
N1	0.8281 (4)	0.6205 (5)	0.5611 (3)	0.0390 (9)
N2	0.7474 (4)	0.7866 (6)	0.5485 (3)	0.0400 (9)
N3	0.9225 (4)	0.4816 (6)	0.3484 (3)	0.0391 (9)
H3	0.983416	0.579248	0.357540	0.047*
C7	0.5560 (15)	0.6816 (12)	0.7246 (10)	0.046 (3)	0.656 (2)
H7A	0.463053	0.714697	0.674956	0.055*	0.656 (2)
H7B	0.585469	0.795035	0.770111	0.055*	0.656 (2)
C1	0.5373 (5)	0.5015 (6)	0.7825 (3)	0.041 (2)	0.656 (2)
C2	0.6067 (5)	0.4920 (7)	0.8834 (3)	0.0432 (13)	0.656 (2)
C3	0.5904 (6)	0.3270 (8)	0.9354 (3)	0.052 (2)	0.656 (2)
H3A	0.637871	0.320515	1.004371	0.063*	0.656 (2)
C4	0.5046 (6)	0.1717 (7)	0.8867 (4)	0.059 (2)	0.656 (2)
H4	0.493389	0.058937	0.922286	0.071*	0.656 (2)
C5	0.4351 (5)	0.1812 (7)	0.7858 (4)	0.056 (2)	0.656 (2)
H5	0.376434	0.075013	0.752518	0.067*	0.656 (2)
C6	0.4514 (5)	0.3461 (8)	0.7338 (3)	0.0432 (13)	0.656 (2)
H6	0.403960	0.352669	0.664833	0.052*	0.656 (2)
C7A	0.583 (4)	0.712 (2)	0.741 (2)	0.046 (3)	0.344 (2)
H7C	0.484915	0.750414	0.700522	0.055*	0.344 (2)
H7D	0.628844	0.828556	0.780181	0.055*	0.344 (2)
C1A	0.5776 (10)	0.5441 (14)	0.8094 (7)	0.041 (2)	0.344 (2)
C2A	0.6600 (10)	0.5581 (14)	0.9082 (7)	0.0432 (13)	0.344 (2)
H2A	0.718157	0.670747	0.931670	0.052*	0.344 (2)
C3A	0.6572 (11)	0.4075 (16)	0.9725 (6)	0.052 (2)	0.344 (2)
H3B	0.713505	0.417063	1.039937	0.063*	0.344 (2)
C4A	0.5721 (13)	0.2427 (14)	0.9381 (8)	0.059 (2)	0.344 (2)
H4A	0.570209	0.139715	0.982019	0.071*	0.344 (2)
C5A	0.4897 (12)	0.2286 (14)	0.8393 (9)	0.056 (2)	0.344 (2)
H5A	0.431564	0.116050	0.815834	0.067*	0.344 (2)
C6A	0.4925 (10)	0.3793 (18)	0.7750 (6)	0.0432 (13)	0.344 (2)
C8	0.6632 (4)	0.6569 (7)	0.6726 (3)	0.0385 (11)
C9	0.7456 (5)	0.4970 (7)	0.6832 (4)	0.0393 (10)
H9	0.743747	0.398076	0.729138	0.047*
C10	0.8370 (4)	0.4717 (7)	0.6265 (3)	0.0374 (10)
C11	0.6674 (4)	0.8051 (7)	0.6030 (3)	0.0381 (11)
C12	0.5826 (5)	0.9905 (8)	0.5867 (4)	0.0513 (13)
H12A	0.606286	1.063382	0.648541	0.077*
H12B	0.481472	0.957689	0.562809	0.077*
H12C	0.604076	1.072240	0.537915	0.077*
C13	0.9116 (5)	0.6132 (7)	0.4974 (4)	0.0429 (12)
H13A	1.009880	0.574945	0.536509	0.052*
H13B	0.914605	0.746647	0.470293	0.052*
C14	0.8535 (5)	0.4690 (7)	0.4135 (3)	0.0393 (11)
C15	0.9084 (4)	0.3573 (7)	0.2676 (3)	0.0410 (11)
C16	0.8316 (5)	0.1846 (8)	0.2489 (3)	0.0450 (11)
H16	0.778599	0.147835	0.289062	0.054*
C17	0.8311 (6)	0.0641 (9)	0.1718 (4)	0.0572 (14)
H17	0.779684	−0.056479	0.159180	0.069*
C18	0.9065 (6)	0.1228 (10)	0.1143 (4)	0.0662 (17)
C19	0.9804 (7)	0.2951 (11)	0.1287 (4)	0.0687 (17)
H19	1.029488	0.333303	0.086165	0.082*
C20	0.9824 (5)	0.4130 (9)	0.2065 (4)	0.0526 (14)
H20	1.034536	0.532974	0.218520	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0550 (10)	0.0672 (12)	0.0641 (11)	−0.0116 (9)	0.0217 (8)	−0.0154 (10)
Cl1A	0.0550 (10)	0.0672 (12)	0.0641 (11)	−0.0116 (9)	0.0217 (8)	−0.0154 (10)
F1	0.134 (4)	0.130 (4)	0.094 (3)	−0.030 (3)	0.072 (3)	−0.054 (3)
O1	0.0436 (18)	0.038 (2)	0.074 (2)	0.0100 (16)	0.0311 (17)	−0.0024 (17)
O2	0.0387 (17)	0.052 (2)	0.063 (2)	−0.0123 (17)	0.0283 (16)	−0.0098 (18)
N1	0.035 (2)	0.034 (2)	0.054 (2)	0.0004 (17)	0.0227 (18)	−0.0041 (18)
N2	0.037 (2)	0.032 (2)	0.054 (2)	−0.0014 (17)	0.0195 (19)	−0.0036 (18)
N3	0.034 (2)	0.039 (2)	0.050 (2)	−0.0057 (18)	0.0216 (17)	−0.0019 (19)
C7	0.043 (6)	0.044 (4)	0.060 (5)	0.008 (5)	0.029 (6)	0.002 (5)
C1	0.026 (4)	0.049 (5)	0.050 (4)	0.007 (4)	0.017 (3)	−0.012 (4)
C2	0.037 (3)	0.043 (3)	0.051 (4)	−0.005 (2)	0.017 (3)	−0.021 (3)
C3	0.054 (5)	0.043 (5)	0.067 (6)	0.001 (4)	0.030 (5)	0.001 (4)
C4	0.055 (5)	0.060 (5)	0.074 (5)	0.007 (4)	0.036 (4)	0.009 (4)
C5	0.048 (5)	0.033 (4)	0.100 (8)	−0.008 (4)	0.041 (5)	−0.021 (5)
C6	0.037 (3)	0.043 (3)	0.051 (4)	−0.005 (2)	0.017 (3)	−0.021 (3)
C7A	0.043 (6)	0.044 (4)	0.060 (5)	0.008 (5)	0.029 (6)	0.002 (5)
C1A	0.026 (4)	0.049 (5)	0.050 (4)	0.007 (4)	0.017 (3)	−0.012 (4)
C2A	0.037 (3)	0.043 (3)	0.051 (4)	−0.005 (2)	0.017 (3)	−0.021 (3)
C3A	0.054 (5)	0.043 (5)	0.067 (6)	0.001 (4)	0.030 (5)	0.001 (4)
C4A	0.055 (5)	0.060 (5)	0.074 (5)	0.007 (4)	0.036 (4)	0.009 (4)
C5A	0.048 (5)	0.033 (4)	0.100 (8)	−0.008 (4)	0.041 (5)	−0.021 (5)
C6A	0.037 (3)	0.043 (3)	0.051 (4)	−0.005 (2)	0.017 (3)	−0.021 (3)
C8	0.035 (2)	0.037 (3)	0.045 (3)	0.001 (2)	0.016 (2)	−0.003 (2)
C9	0.036 (2)	0.037 (3)	0.051 (3)	0.003 (2)	0.022 (2)	−0.001 (2)
C10	0.035 (2)	0.033 (2)	0.046 (3)	0.002 (2)	0.017 (2)	−0.002 (2)
C11	0.033 (2)	0.035 (3)	0.048 (3)	0.000 (2)	0.015 (2)	−0.006 (2)
C12	0.050 (3)	0.043 (3)	0.067 (3)	0.006 (2)	0.028 (3)	−0.002 (3)
C13	0.037 (2)	0.041 (3)	0.059 (3)	−0.007 (2)	0.028 (2)	−0.009 (2)
C14	0.031 (2)	0.040 (3)	0.052 (3)	0.000 (2)	0.020 (2)	0.001 (2)
C15	0.033 (2)	0.048 (3)	0.045 (3)	0.000 (2)	0.017 (2)	0.001 (2)
C16	0.043 (3)	0.047 (3)	0.047 (3)	−0.003 (2)	0.018 (2)	−0.006 (3)
C17	0.058 (3)	0.058 (3)	0.059 (3)	−0.007 (3)	0.025 (3)	−0.013 (3)
C18	0.070 (4)	0.079 (4)	0.057 (3)	−0.007 (3)	0.031 (3)	−0.024 (3)
C19	0.068 (4)	0.096 (5)	0.057 (3)	−0.012 (4)	0.041 (3)	−0.010 (3)
C20	0.044 (3)	0.065 (4)	0.055 (3)	−0.003 (3)	0.026 (3)	0.003 (3)

Geometric parameters (Å, º) top

Cl1—C2	1.723 (4)	C1A—C6A	1.3900
Cl1A—C6A	1.666 (9)	C2A—C3A	1.3900
F1—C18	1.355 (7)	C2A—H2A	0.9500
O1—C10	1.237 (5)	C3A—C4A	1.3900
O2—C14	1.222 (5)	C3A—H3B	0.9500
N1—N2	1.362 (5)	C4A—C5A	1.3900
N1—C10	1.366 (6)	C4A—H4A	0.9500
N1—C13	1.450 (6)	C5A—C6A	1.3900
N2—C11	1.314 (6)	C5A—H5A	0.9500
N3—C14	1.356 (5)	C8—C9	1.340 (6)
N3—C15	1.410 (6)	C8—C11	1.435 (7)
N3—H3	0.8800	C9—C10	1.441 (6)
C7—C8	1.525 (6)	C9—H9	0.9500
C7—C1	1.529 (6)	C11—C12	1.490 (6)
C7—H7A	0.9900	C12—H12A	0.9800
C7—H7B	0.9900	C12—H12B	0.9800
C1—C2	1.3900	C12—H12C	0.9800
C1—C6	1.3900	C13—C14	1.512 (7)
C2—C3	1.3900	C13—H13A	0.9900
C3—C4	1.3900	C13—H13B	0.9900
C3—H3A	0.9500	C15—C16	1.376 (7)
C4—C5	1.3900	C15—C20	1.393 (6)
C4—H4	0.9500	C16—C17	1.384 (7)
C5—C6	1.3900	C16—H16	0.9500
C5—H5	0.9500	C17—C18	1.367 (8)
C6—H6	0.9500	C17—H17	0.9500
C7A—C8	1.524 (7)	C18—C19	1.360 (9)
C7A—C1A	1.529 (6)	C19—C20	1.378 (8)
C7A—H7C	0.9900	C19—H19	0.9500
C7A—H7D	0.9900	C20—H20	0.9500
C1A—C2A	1.3900

N2—N1—C10	126.5 (4)	C6A—C5A—H5A	120.0
N2—N1—C13	113.1 (4)	C5A—C6A—C1A	120.0
C10—N1—C13	120.3 (4)	C5A—C6A—Cl1A	119.4 (7)
C11—N2—N1	117.3 (4)	C1A—C6A—Cl1A	120.5 (8)
C14—N3—C15	127.9 (4)	C9—C8—C11	118.6 (4)
C14—N3—H3	116.0	C9—C8—C7A	124.8 (6)
C15—N3—H3	116.0	C11—C8—C7A	115.8 (5)
C8—C7—C1	115.3 (4)	C9—C8—C7	123.1 (5)
C8—C7—H7A	108.4	C11—C8—C7	118.0 (4)
C1—C7—H7A	108.4	C8—C9—C10	121.4 (4)
C8—C7—H7B	108.4	C8—C9—H9	119.3
C1—C7—H7B	108.4	C10—C9—H9	119.3
H7A—C7—H7B	107.5	O1—C10—N1	121.0 (4)
C2—C1—C6	120.0	O1—C10—C9	124.9 (4)
C2—C1—C7	120.3 (7)	N1—C10—C9	114.1 (4)
C6—C1—C7	119.7 (7)	N2—C11—C8	122.0 (4)
C1—C2—C3	120.0	N2—C11—C12	114.9 (4)
C1—C2—Cl1	122.4 (3)	C8—C11—C12	123.1 (4)
C3—C2—Cl1	117.6 (3)	C11—C12—H12A	109.5
C4—C3—C2	120.0	C11—C12—H12B	109.5
C4—C3—H3A	120.0	H12A—C12—H12B	109.5
C2—C3—H3A	120.0	C11—C12—H12C	109.5
C3—C4—C5	120.0	H12A—C12—H12C	109.5
C3—C4—H4	120.0	H12B—C12—H12C	109.5
C5—C4—H4	120.0	N1—C13—C14	112.8 (4)
C6—C5—C4	120.0	N1—C13—H13A	109.0
C6—C5—H5	120.0	C14—C13—H13A	109.0
C4—C5—H5	120.0	N1—C13—H13B	109.0
C5—C6—C1	120.0	C14—C13—H13B	109.0
C5—C6—H6	120.0	H13A—C13—H13B	107.8
C1—C6—H6	120.0	O2—C14—N3	125.2 (4)
C8—C7A—C1A	112.7 (6)	O2—C14—C13	122.9 (4)
C8—C7A—H7C	109.1	N3—C14—C13	111.9 (4)
C1A—C7A—H7C	109.1	C16—C15—C20	119.4 (4)
C8—C7A—H7D	109.1	C16—C15—N3	124.1 (4)
C1A—C7A—H7D	109.1	C20—C15—N3	116.5 (4)
H7C—C7A—H7D	107.8	C15—C16—C17	120.4 (5)
C2A—C1A—C6A	120.0	C15—C16—H16	119.8
C2A—C1A—C7A	118.8 (17)	C17—C16—H16	119.8
C6A—C1A—C7A	121.2 (17)	C18—C17—C16	118.4 (5)
C1A—C2A—C3A	120.0	C18—C17—H17	120.8
C1A—C2A—H2A	120.0	C16—C17—H17	120.8
C3A—C2A—H2A	120.0	F1—C18—C19	117.9 (5)
C4A—C3A—C2A	120.0	F1—C18—C17	119.1 (5)
C4A—C3A—H3B	120.0	C19—C18—C17	123.0 (5)
C2A—C3A—H3B	120.0	C18—C19—C20	118.4 (5)
C5A—C4A—C3A	120.0	C18—C19—H19	120.8
C5A—C4A—H4A	120.0	C20—C19—H19	120.8
C3A—C4A—H4A	120.0	C19—C20—C15	120.4 (5)
C4A—C5A—C6A	120.0	C19—C20—H20	119.8
C4A—C5A—H5A	120.0	C15—C20—H20	119.8

C10—N1—N2—C11	−1.5 (6)	C7—C8—C9—C10	174.7 (9)
C13—N1—N2—C11	179.6 (4)	N2—N1—C10—O1	−178.3 (4)
C8—C7—C1—C2	98.6 (11)	C13—N1—C10—O1	0.6 (6)
C8—C7—C1—C6	−80.7 (11)	N2—N1—C10—C9	2.5 (6)
C6—C1—C2—C3	0.0	C13—N1—C10—C9	−178.7 (4)
C7—C1—C2—C3	−179.3 (3)	C8—C9—C10—O1	179.2 (5)
C6—C1—C2—Cl1	−179.3 (4)	C8—C9—C10—N1	−1.6 (6)
C7—C1—C2—Cl1	1.4 (4)	N1—N2—C11—C8	−0.5 (6)
C1—C2—C3—C4	0.0	N1—N2—C11—C12	179.5 (4)
Cl1—C2—C3—C4	179.3 (4)	C9—C8—C11—N2	1.2 (7)
C2—C3—C4—C5	0.0	C7A—C8—C11—N2	171.4 (18)
C3—C4—C5—C6	0.0	C7—C8—C11—N2	−173.8 (8)
C4—C5—C6—C1	0.0	C9—C8—C11—C12	−178.7 (4)
C2—C1—C6—C5	0.0	C7A—C8—C11—C12	−8.6 (18)
C7—C1—C6—C5	179.3 (3)	C7—C8—C11—C12	6.2 (10)
C8—C7A—C1A—C2A	107 (2)	N2—N1—C13—C14	−105.4 (4)
C8—C7A—C1A—C6A	−73 (2)	C10—N1—C13—C14	75.6 (5)
C6A—C1A—C2A—C3A	0.0	C15—N3—C14—O2	−7.4 (7)
C7A—C1A—C2A—C3A	179.9 (4)	C15—N3—C14—C13	172.5 (4)
C1A—C2A—C3A—C4A	0.0	N1—C13—C14—O2	−7.6 (7)
C2A—C3A—C4A—C5A	0.0	N1—C13—C14—N3	172.5 (4)
C3A—C4A—C5A—C6A	0.0	C14—N3—C15—C16	−8.1 (7)
C4A—C5A—C6A—C1A	0.0	C14—N3—C15—C20	174.3 (4)
C4A—C5A—C6A—Cl1A	−178.2 (7)	C20—C15—C16—C17	1.9 (7)
C2A—C1A—C6A—C5A	0.0	N3—C15—C16—C17	−175.5 (5)
C7A—C1A—C6A—C5A	−179.9 (4)	C15—C16—C17—C18	−1.1 (8)
C2A—C1A—C6A—Cl1A	178.2 (7)	C16—C17—C18—F1	−179.4 (5)
C7A—C1A—C6A—Cl1A	−1.8 (8)	C16—C17—C18—C19	−0.8 (9)
C1A—C7A—C8—C9	−13 (3)	F1—C18—C19—C20	−179.6 (6)
C1A—C7A—C8—C11	177.5 (16)	C17—C18—C19—C20	1.8 (10)
C1—C7—C8—C9	−5.9 (15)	C18—C19—C20—C15	−1.0 (9)
C1—C7—C8—C11	168.9 (8)	C16—C15—C20—C19	−0.9 (8)
C11—C8—C9—C10	−0.1 (7)	N3—C15—C20—C19	176.8 (5)
C7A—C8—C9—C10	−169.2 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.88	1.95	2.815 (5)	168
C7—H7A···O2ⁱⁱ	0.99	2.32	3.282 (15)	164
C16—H16···O2	0.95	2.29	2.900 (6)	121
C19—H19···F1ⁱⁱⁱ	0.95	2.42	3.336 (7)	162

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

Acknowledgements

Author contributions are as follows. Conceptualization, MA and IAE; methodology, YR; investigation, HA and AEAA; writing (original draft), JMT and YR; writing (review and editing of the manuscript), YR; formal analysis, AS and YR; supervision, MA and YR; crystal structure determination and validation, JTM.

Funding information

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

References

Abiha, G. B., Bahar, L. & Utku, S. (2018). Rev. Rom. Med. Lab. 26, 231–241. Google Scholar
Boukharsa, Y., Meddah, B., Tiendrebeogo, R. Y., Ibrahimi, A., Taoufik, J., Cherrah, Y., Benomar, A., Faouzi, M. E. A. & Ansar, M. (2016). Med. Chem. Res. 25, 494–500. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2012). DIAMOND, Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2021). APEX4 and SAINT . Bruker AXS LLC, Madison, Wisconsin, USA. Google Scholar
Ibrahim, T. H., Loksha, Y. M., Elshihawy, H. A., Khodeer, D. M. & Said, M. M. (2017). Arch. Pharm. Chem. Life Sci. 350, e1700093. Web of Science CrossRef Google Scholar
Kamble, V. T., Sawant, A.-S., Sawant, S. S., Pisal, P. M., Gacche, R. N., Kamble, S. S., Shegokar, H. D. & Kamble, V. A. (2017). J. Basic Appl. Res. Int. 21, 10–39. Google Scholar
Khokra, S. L., Khan, S. A., Thakur, P., Chowdhary, D., Ahmad, A. & Husain, A. (2016). J. Chin. Chem. Soc. 63, 739–750. Web of Science CrossRef 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
Missioui, M., Said, M. A., Demirtaş, G., Mague, J. T. & Ramli, Y. (2022). J. Mol. Struct. 1247, 131420. Web of Science CSD CrossRef Google Scholar
Mortada, S., Guerrab, W., Missioui, M., Salhi, N., Naceiri Mrabti, H., Rouass, L., Benkirane, S., Hassane, M., Masrar, A., Mezzour, H., Faouzi, M. E. A. & Ramli, Y. (2023). J. Biomol. Struct. Dyn. pp. 1–15. CrossRef Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals 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
Yamada, T., Nobuhara, Y., Shimamura, H., Yoshihara, K., Yamaguchi, A. & Ohki, M. (1981). Chem. Pharm. Bull. 29, 3433–3439. CrossRef CAS PubMed Google Scholar
Zaoui, Y., Assila, H., Mague, J. T., Alsubari, A., Taoufik, J., Ramli, Y. & Ansar, M. (2022). IUCrData, 7, x220582. 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.