Crystal structure of (E)-3-({6-[2-(4-chloro­phen­yl)ethen­yl]-3-oxo-2,3-di­hydro­pyridazin-4-yl}meth­yl)pyridin-1-ium chloride dihydrate

Daoui, S.; Çınar, E.B.; Dege, N.; Benchat, N.; Saif, E.; Karrouchi, K.

doi:10.1107/S2056989022003346

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ISSN: 2056-9890

Volume 78| Part 4| April 2022| Pages 458-462

https://doi.org/10.1107/S2056989022003346

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Crystal structure of (E)-3-({6-[2-(4-chlorophenyl)ethenyl]-3-oxo-2,3-dihydropyridazin-4-yl}methyl)pyridin-1-ium chloride dihydrate

Said Daoui,^a Emine Berrin Çınar,^b ^* Necmi Dege,^b Noureddine Benchat,^a Eiad Saif ^c ^* and Khalid Karrouchi ^d

^aLaboratory of Applied Chemistry and Environment (LCAE), Faculty of Sciences, Mohamed I University, 60000 Oujda, Morocco, ^bDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun, 55200, Turkey, ^cDepartment of Computer and Electronic Engineering, Sana'a Community College, Sana'a, Yemen, and ^dLaboratory of Analytical Chemistry and Bromatology, Faculty of Medicine and Pharmacy, Mohammed V University in Rabat, Morocco
^*Correspondence e-mail: emineberrin.cinar@omu.edu.tr, eiad.saif@scc.edu.ye

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 4 January 2022; accepted 24 March 2022; online 31 March 2022)

In the title compound, C₁₈H₁₅ClN₃O⁺·Cl⁻·2H₂O, three intramolecular hydrogen bonds are observed, N—H⋯O, O—H⋯Cl and O—H⋯O. In the crystal, molecules are connected by C—H⋯Cl and N—H⋯O hydrogen bonds. Strong C—H⋯Cl, N—H⋯O, O—H⋯Cl and O—H⋯O hydrogen-bonding interactions are implied by the Hirshfeld surface analysis, which indicate that H⋯H contacts make the largest contribution to the overall crystal packing at 33.0%.

Keywords: crystal structure; pyridazine; pyridazinone derivative; hydrogen bonding; Hirshfeld surfaces.

CCDC reference: 2161716

1. Chemical context

Pyridazine derivatives are an important class of heterocyclic chemicals that exhibit a wide range of biological actions. For example, their biological activity and antimicrobial properties have been researched extensively (Neumann et al., 2018 ). As a result, the pyridazine ring can be found in a range of commercial medicinal compounds, including Cadralazine and Hydralazine, Minaprine, Pipofezine and others (Abu-Hashem et al., 2020 ). Pyridazine derivatives can be found also in the backbones of several organic light-emitting diodes (OLEDs) (Liu et al., 2017 ), organic solar cells (OSCs) (Knall et al., 2021 ), chemosensors (Peng et al., 2020 ), trifluoroacetic acid (TFA) sensors (Li et al., 2018 ), bioconjugates (Bahou et al., 2021 ), low carbon steel corrosion inhibitors (Khadiria et al., 2016 ), and several other materials. They have also been used as starting materials in organic synthesis (Llona-Minguez et al., 2017 ), acylating agents (Kung et al., 2002 ), precursors for N-heterocyclic carbenes (NHCs) (Liu et al., 2012 ) and metallocarbene precursors. An overview of arylglyoxal monohydrates-based one-pot multi-component synthesis of potentially biologically active pyridazines is given by Mousavi (2022 ).

2. Structural commentary

A perspective view of the title molecule is shown in Fig. 1. The pyridazine and pyridine rings subtend a dihedral angle of 57.27 (5)°. The other two rings, pyridazine and chlorobenzene, are almost planar, making an angle of 8.54 (11)°. The lengths of the C=C [1.349 (3) Å], C=N [1.313 (2) Å], N—N [1.351 (2) Å] and C=O [1.237 (2) Å] bonds are comparable with values published for other pyridazinones (see the Database survey section). Three intramolecular hydrogen bonds are observed, N2—H2C⋯O2, O2—H2A⋯Cl2 and O2—H2B⋯O3 (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Cl2ⁱ	0.93	2.72	3.6387 (19)	168
C18—H18⋯Cl2ⁱⁱ	0.93	2.94	3.622 (2)	132
N3—H3⋯O2ⁱⁱⁱ	0.80 (3)	2.35 (3)	2.965 (2)	135 (2)
N3—H3⋯O1ⁱⁱⁱ	0.80 (3)	2.25 (3)	2.855 (2)	133 (3)
N2—H2C⋯O2	0.86 (2)	1.97 (2)	2.801 (2)	161 (2)
O2—H2A⋯Cl2	0.83 (2)	2.35 (2)	3.170 (2)	175 (3)
O2—H2B⋯O3	0.84 (2)	1.92 (2)	2.739 (3)	167 (3)
Symmetry codes: (i) ; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y, -z+1]$ .

Figure 1
Perspective view and atom labelling of the molecule. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

The water molecules and chloride anions are located in channels between the organic cations and are connected by O—H⋯O and O—H⋯Cl hydrogen bonds (Table 1) into chains, which are further connected via N—H⋯O and C—H⋯Cl hydrogen bonds into a three-dimensional supramolecular architecture. Fig. 2a shows a view of the hydrogen bonds along the b-axis direction. π–π interactions are present (Fig. 2b) between the pyridazine rings [centroid–centroid distance = 3.4902 (12) Å], and also between the pyridine and benzene rings [3.7293 (13) and 3.8488 (13) Å], forming sheets.

Figure 2
(a)View along the b axis of the unit cell showing the molecular sheets. (b) π–π interactions.

4. Database survey

There are no direct precedents for the structure of the title compound in the crystallographic literature. A search of the Cambridge Structural Database (ConQuest version 2021.3.0; Groom et al., 2016 ) for the 2,3-dihydropyridazin-4-yl moiety gave various hits, four of them for similar pyridazine compounds but with different substituents on the pyridazine ring: 5-(2-chlorobenzyl)-6-methyl-3(2H)pyridazinone (ZAYJIS; Moreau et al., 1995 ), 2-{4-[(5-chloro- 1-benzofuran-2-yl)methyl]-3-methyl-6- oxo-1,6-dihydropyridazin-1-yl}acetate (XULSEE; Boukharsa et al., 2015 ) , 4-[3-(trifluoromethyl)phenyl]-5,6,7,8-tetrahydrocinnolin-3(2H)-one (GISZAK; Wang et al., 2008 ) and 5-(2-Chlorobenzyl)-2-(2-hydroxyethyl)-6-methylpyridazin-3(2H)-one (IJEMOZ; Abourichaa et al., 2003 ). In ZAYJIS, the lengths of the C=C [1.343 (3) Å], C=N [1.301 (4) Å], N—N [1.357 (3) Å] and C=O [1.255 (3) Å] bonds in the pyridazinone ring are very similar to those in the title compound. In XULSEE, te Cl—C1 bond length is 1.742 (2) Å while in the pyridazine ring, the N1—N2 bond length is 1.365 (2) Å and O2=C2 is 1.228 (2) Å. In GISZAK, the N1—N2 bond is 1.343 (5) Å whereas the C8=O1 bond is 1.246 (5) Å. In IJEMOZ, the pyridazinone ring has a similar value for the N4—N5 bond of 1.367 (2) Å.

5. Hirshfeld surface analysis

To investigate the effect of the molecular interactions on the crystal packing, the Hirshfeld surface (Fig. 3) and fingerprint plots of the organic cation were analysed (Turner et al., 2017 ). In Fig. 4a, the circular depressions (deep red) on the Hirshfeld surface imply strong hydrogen-bonding interactions of types C—H⋯Cl, N—H⋯O, O—H⋯Cl and O—H⋯O. In the shape-index map (Fig. 4b), the π–π interactions are indicated by the red and blue triangles. Fig. 4c and Fig. 4d show d_i and d_e surfaces and Fig. 4e and 4f the curvedness and fragment path surfaces. Fig. 5a shows the overall two-dimensional fingerprint plot. The fingerprint plot delineated into H⋯H contacts (33.0% contribution, Fig. 5b) has a point with the tip at d_e + d_i = 2.05 Å. The pair of wings in the fingerprint plot defined into H⋯C/C⋯H contacts (19.3 percent contribution to the HS), Fig.5c, has a pair of thin edges at d_e + d_i ∼2.99 Å while the pair of wings for the H⋯Cl/Cl⋯H contacts (15.9% contribution, Fig. 5d) are seen as two spikes with the points at d_e + d_i = 2.97 Å and d_e + d_i = 2.41 Å. The fingerprint plot for H⋯O/O⋯H contacts (11.5% contribution, Fig. 5e) has two spikes with the tips at d_e + d_i = 2.11 Å and d_e + d_i = 1.83 Å. As seen in Fig. 5f the C⋯C contacts (7.4%) have an arrow-shaped distribution of points with tips at d_e + d_i = 3.37 Å. The contributions of the N⋯H/H⋯N contacts to the Hirshfeld surface (5.8%) are less important (Fig. 5g). Fig. 6 shows a pie chart of all interactions with their percentage contributions.

Figure 3
Intermolecular interactions with d_norm surface.

Figure 4
Graphical depictions of the molecular Hirshfeld surfaces; (a) d_norm, (b)shape-index, (c) d_i, (d) d_e,(e) curvedness and (f) fragment-path.

Figure 5
Fingerprint plots of the interactions involving the organic cation. (a) All contributions and decomposed into the main contributions: (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯Cl/Cl⋯H, (e) H⋯O/O⋯H, (f) C⋯C and (g) N⋯H/H⋯N interactions

Figure 6
All interactions with percentage contributions.

6. Synthesis and crystallization

The title compound was synthesized according to a previously published procedure (Daoui et al., 2019 , 2021 ). To a solution of (E)-6-(4-chlorostyryl)-4,5-dihydropyridazin-3(2H)-one (0.23 g, 1 mmol) and nicotinaldehyde (0.107 g, 1 mmol) in 30 ml of ethanol, sodium ethanoate (0.23 g, 2.8 mmol) was added. The mixture was refluxed for 3 h. The reaction mixture was cooled, diluted with cold water and acidified with concentrated hydrochloric acid. The precipitate was filtered, washed with water, dried and recrystallized from ethanol. White single crystals were obtained by slow evaporation at room temperature, yield 86%; m.p. 453 K; FT–IR (KBr): ν 3322 (NH), 1651 (C=O), 1584 cm⁻¹ (C=N); ¹H NMR (300 MHz, DMSO-d₆) δ 13.20 (s, 1H, H-pyridyl) , 8.98 (d, J = 1.8 Hz, 1H, H-pyridyl), 8.83 (d, J = 5.6 Hz, 1H, H-pyridyl), 8.57 (dt, J = 8.1, 1.8 Hz, 1H, H-pyridyl), 8.05 (s, 1H, H-pyridazinone) 8.02 (dd, J = 8.1, 5.6 Hz, 1H, H-pyridyl), 7.65 (d, J = 8.4 Hz, 2H, H1, H-Ar), 7.45 (d, J = 8.4 Hz, 2H, H 4, H-Ar), 7.36 (d, J = 16.7 Hz, 1H, CH=CH), 7.08 (,d J = 16.7 Hz, 1H, CH=CH), 4.09 ppm (s, 2H, CH₂); ¹³C NMR (75 MHz, DMSO-d₆) δ 160.43, 145.98, 143.89, 141.87, 140.05, 139.25, 137.97, 134.90, 132.84,130.85, 128.82, 128.62, 128.54, 126.80, 125.08, 32.33 ppm. ESI-MS: m/z = 324.08 [M+H]⁺.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound H atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and thereafter treated as riding. A torsional parameter was refined for the methyl group. The positions of N- and O-bound H atoms were refined freely (distances are in Table 1). For all H atoms, U_iso(H) = 1.2 U_eq(C,N,O).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₁₅ClN₃O⁺·Cl⁻·2H₂O
M_r	396.26
Crystal system, space group	Monoclinic, I2/a
Temperature (K)	296
a, b, c (Å)	19.6562 (14), 7.5587 (3), 26.4903 (16)
β (°)	109.762 (5)
V (Å³)	3704.0 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.37
Crystal size (mm)	0.68 × 0.41 × 0.16

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Numerical (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.818, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	13762, 5273, 3083
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.702

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.142, 0.98
No. of reflections	5273
No. of parameters	265
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.43
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002), SHELXT2018/3 (Sheldrick, 2015a ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2020 ), WinGX (Farrugia, 2012 ), SHELXL2018/3 (Sheldrick, 2015b ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2161716

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022003346/jq2014sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022003346/jq2014Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022003346/jq2014Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2018/3 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX (Farrugia, 2012), SHELXL2018/3 (Sheldrick, 2015b), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

(E)-3-({6-[2-(4-Chlorophenyl)ethenyl]-3-oxo-2,3-dihydropyridazin-4-yl}methyl)pyridin-1-ium chloride dihydrate top

Crystal data top

C₁₈H₁₅ClN₃O⁺·Cl⁻·2H₂O	F(000) = 1648
M_r = 396.26	D_x = 1.421 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 19.6562 (14) Å	Cell parameters from 18653 reflections
b = 7.5587 (3) Å	θ = 1.6–30.3°
c = 26.4903 (16) Å	µ = 0.37 mm⁻¹
β = 109.762 (5)°	T = 296 K
V = 3704.0 (4) Å³	Prism, colorless
Z = 8	0.68 × 0.41 × 0.16 mm

Data collection top

Stoe IPDS 2 diffractometer	5273 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	3083 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.064
Detector resolution: 6.67 pixels mm^-1	θ_max = 29.9°, θ_min = 1.6°
rotation method scans	h = −21→27
Absorption correction: numerical (X-RED32; Stoe & Cie, 2002)	k = −8→10
T_min = 0.818, T_max = 0.961	l = −36→36
13762 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)] = 0.050	Hydrogen site location: mixed
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0709P)²] where P = (F_o² + 2F_c²)/3
5273 reflections	(Δ/σ)_max < 0.001
265 parameters	Δρ_max = 0.26 e Å⁻³
2 restraints	Δρ_min = −0.43 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
Cl2	0.43892 (4)	0.44826 (8)	0.29544 (2)	0.06204 (18)
Cl1	0.16095 (4)	0.93975 (11)	0.67565 (3)	0.0831 (2)
O2	0.51631 (9)	0.7860 (3)	0.36086 (6)	0.0569 (4)
O1	0.63332 (8)	0.6580 (2)	0.47656 (6)	0.0603 (4)
N2	0.52423 (9)	0.7727 (2)	0.46837 (7)	0.0440 (4)
N1	0.46811 (9)	0.8166 (2)	0.48443 (6)	0.0437 (4)
O3	0.47043 (12)	1.0366 (3)	0.28189 (9)	0.0724 (5)
N3	0.83161 (10)	0.6802 (3)	0.61940 (8)	0.0521 (4)
C11	0.58620 (10)	0.6148 (3)	0.54755 (7)	0.0414 (4)
C9	0.47235 (10)	0.7645 (3)	0.53269 (7)	0.0427 (4)
C12	0.58492 (10)	0.6822 (3)	0.49587 (7)	0.0434 (4)
C15	0.71539 (10)	0.5767 (3)	0.61025 (7)	0.0420 (4)
C6	0.34431 (11)	0.8182 (3)	0.61458 (8)	0.0470 (5)
C10	0.53148 (11)	0.6600 (3)	0.56490 (7)	0.0441 (4)
H10	0.5323	0.6223	0.5985	0.053*
C8	0.41189 (11)	0.8140 (3)	0.54971 (8)	0.0477 (5)
H8	0.3747	0.8785	0.5256	0.057*
C7	0.40518 (11)	0.7752 (3)	0.59642 (8)	0.0481 (5)
H7	0.4434	0.7136	0.6206	0.058*
C14	0.76951 (11)	0.6075 (3)	0.58944 (8)	0.0479 (5)
H14	0.7626	0.5772	0.5540	0.057*
C13	0.64570 (11)	0.4898 (3)	0.57732 (8)	0.0496 (5)
H13A	0.6554	0.4116	0.5515	0.060*
H13B	0.6288	0.4173	0.6009	0.060*
C5	0.34973 (12)	0.7804 (3)	0.66698 (9)	0.0540 (5)
H5	0.3919	0.7288	0.6898	0.065*
C16	0.72876 (12)	0.6223 (3)	0.66349 (8)	0.0514 (5)
H16	0.6936	0.6025	0.6792	0.062*
C18	0.84516 (12)	0.7257 (3)	0.67006 (9)	0.0577 (5)
H18	0.8892	0.7768	0.6897	0.069*
C3	0.23208 (13)	0.8927 (3)	0.65221 (9)	0.0566 (6)
C2	0.22442 (12)	0.9330 (3)	0.60014 (9)	0.0583 (6)
H2	0.1820	0.9840	0.5776	0.070*
C1	0.28082 (12)	0.8966 (3)	0.58179 (9)	0.0561 (5)
H1	0.2762	0.9252	0.5466	0.067*
C17	0.79392 (13)	0.6969 (3)	0.69313 (9)	0.0593 (6)
H17	0.8029	0.7274	0.7288	0.071*
C4	0.29405 (13)	0.8174 (3)	0.68616 (9)	0.0600 (6)
H4	0.2986	0.7917	0.7215	0.072*
H3	0.8616 (16)	0.701 (4)	0.6061 (11)	0.070 (8)*
H2C	0.5201 (13)	0.802 (3)	0.4362 (10)	0.053 (6)*
H2A	0.4937 (17)	0.700 (3)	0.3444 (12)	0.094 (11)*
H2B	0.5030 (16)	0.874 (3)	0.3409 (10)	0.079 (9)*
H3A	0.495 (3)	1.018 (6)	0.2630 (17)	0.127 (16)*
H3B	0.466 (2)	1.141 (6)	0.2847 (14)	0.095 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.0694 (4)	0.0648 (4)	0.0496 (3)	0.0006 (3)	0.0170 (2)	0.0021 (2)
Cl1	0.0642 (4)	0.1042 (6)	0.0982 (5)	−0.0103 (4)	0.0502 (4)	−0.0206 (4)
O2	0.0539 (9)	0.0660 (12)	0.0463 (8)	0.0028 (9)	0.0111 (7)	0.0035 (8)
O1	0.0471 (8)	0.0848 (12)	0.0534 (8)	0.0146 (8)	0.0229 (7)	0.0071 (8)
N2	0.0415 (8)	0.0494 (10)	0.0429 (8)	0.0012 (8)	0.0168 (7)	0.0023 (7)
N1	0.0375 (8)	0.0469 (10)	0.0463 (8)	0.0001 (7)	0.0138 (7)	0.0001 (7)
O3	0.0801 (14)	0.0676 (14)	0.0748 (12)	0.0046 (11)	0.0331 (10)	0.0102 (10)
N3	0.0397 (9)	0.0596 (12)	0.0591 (10)	0.0003 (9)	0.0195 (8)	0.0078 (8)
C11	0.0363 (9)	0.0416 (10)	0.0427 (9)	−0.0032 (8)	0.0089 (7)	−0.0017 (7)
C9	0.0394 (9)	0.0448 (11)	0.0431 (9)	−0.0026 (9)	0.0128 (7)	−0.0010 (8)
C12	0.0385 (9)	0.0455 (11)	0.0454 (9)	−0.0018 (8)	0.0130 (8)	−0.0034 (8)
C15	0.0373 (9)	0.0417 (11)	0.0445 (9)	0.0049 (8)	0.0107 (7)	0.0040 (7)
C6	0.0431 (10)	0.0513 (12)	0.0468 (10)	−0.0051 (9)	0.0153 (8)	−0.0065 (8)
C10	0.0424 (10)	0.0486 (12)	0.0396 (9)	−0.0033 (9)	0.0116 (8)	0.0009 (8)
C8	0.0402 (10)	0.0529 (12)	0.0479 (10)	0.0024 (9)	0.0123 (8)	−0.0003 (8)
C7	0.0390 (10)	0.0570 (13)	0.0463 (10)	0.0018 (9)	0.0119 (8)	−0.0015 (8)
C14	0.0458 (11)	0.0560 (12)	0.0423 (9)	0.0039 (10)	0.0154 (8)	0.0037 (8)
C13	0.0397 (10)	0.0481 (12)	0.0552 (10)	0.0008 (9)	0.0085 (9)	0.0019 (9)
C5	0.0495 (11)	0.0632 (14)	0.0496 (11)	−0.0041 (11)	0.0171 (9)	−0.0003 (9)
C16	0.0483 (11)	0.0615 (13)	0.0473 (10)	0.0002 (10)	0.0200 (9)	0.0003 (9)
C18	0.0437 (11)	0.0615 (14)	0.0594 (12)	−0.0045 (10)	0.0062 (9)	0.0012 (10)
C3	0.0494 (11)	0.0620 (14)	0.0662 (13)	−0.0148 (11)	0.0297 (10)	−0.0187 (10)
C2	0.0414 (11)	0.0720 (16)	0.0589 (12)	−0.0006 (11)	0.0133 (9)	−0.0128 (11)
C1	0.0500 (11)	0.0731 (15)	0.0453 (10)	0.0025 (11)	0.0163 (9)	−0.0048 (10)
C17	0.0588 (13)	0.0703 (16)	0.0449 (10)	−0.0028 (12)	0.0125 (10)	−0.0049 (10)
C4	0.0611 (14)	0.0736 (16)	0.0527 (12)	−0.0123 (12)	0.0290 (11)	−0.0046 (10)

Geometric parameters (Å, º) top

Cl1—C3	1.748 (2)	C6—C1	1.389 (3)
O2—H2A	0.825 (18)	C6—C7	1.469 (3)
O2—H2B	0.837 (18)	C10—H10	0.9300
O1—C12	1.237 (2)	C8—C7	1.321 (3)
N2—N1	1.351 (2)	C8—H8	0.9300
N2—C12	1.354 (3)	C7—H7	0.9300
N2—H2C	0.86 (2)	C14—H14	0.9300
N1—C9	1.313 (2)	C13—H13A	0.9700
O3—H3A	0.81 (5)	C13—H13B	0.9700
O3—H3B	0.80 (4)	C5—C4	1.382 (3)
N3—C18	1.322 (3)	C5—H5	0.9300
N3—C14	1.329 (3)	C16—C17	1.376 (3)
N3—H3	0.80 (3)	C16—H16	0.9300
C11—C10	1.349 (3)	C18—C17	1.361 (3)
C11—C12	1.453 (3)	C18—H18	0.9300
C11—C13	1.503 (3)	C3—C4	1.369 (4)
C9—C10	1.426 (3)	C3—C2	1.370 (3)
C9—C8	1.455 (3)	C2—C1	1.380 (3)
C15—C14	1.373 (3)	C2—H2	0.9300
C15—C16	1.388 (3)	C1—H1	0.9300
C15—C13	1.504 (3)	C17—H17	0.9300
C6—C5	1.386 (3)	C4—H4	0.9300

H2A—O2—H2B	107 (3)	N3—C14—C15	120.65 (18)
N1—N2—C12	128.25 (16)	N3—C14—H14	119.7
N1—N2—H2C	116.0 (16)	C15—C14—H14	119.7
C12—N2—H2C	115.7 (16)	C11—C13—C15	115.12 (17)
C9—N1—N2	116.31 (16)	C11—C13—H13A	108.5
H3A—O3—H3B	109 (4)	C15—C13—H13A	108.5
C18—N3—C14	122.87 (19)	C11—C13—H13B	108.5
C18—N3—H3	118 (2)	C15—C13—H13B	108.5
C14—N3—H3	119 (2)	H13A—C13—H13B	107.5
C10—C11—C12	118.06 (18)	C4—C5—C6	121.6 (2)
C10—C11—C13	123.32 (18)	C4—C5—H5	119.2
C12—C11—C13	118.51 (17)	C6—C5—H5	119.2
N1—C9—C10	121.28 (17)	C17—C16—C15	120.08 (19)
N1—C9—C8	115.79 (17)	C17—C16—H16	120.0
C10—C9—C8	122.88 (17)	C15—C16—H16	120.0
O1—C12—N2	120.86 (17)	N3—C18—C17	119.2 (2)
O1—C12—C11	124.57 (18)	N3—C18—H18	120.4
N2—C12—C11	114.55 (16)	C17—C18—H18	120.4
C14—C15—C16	117.37 (19)	C4—C3—C2	121.6 (2)
C14—C15—C13	121.23 (17)	C4—C3—Cl1	119.49 (17)
C16—C15—C13	121.36 (18)	C2—C3—Cl1	118.91 (19)
C5—C6—C1	117.58 (18)	C3—C2—C1	118.8 (2)
C5—C6—C7	119.16 (19)	C3—C2—H2	120.6
C1—C6—C7	123.26 (18)	C1—C2—H2	120.6
C11—C10—C9	121.28 (17)	C2—C1—C6	121.6 (2)
C11—C10—H10	119.4	C2—C1—H1	119.2
C9—C10—H10	119.4	C6—C1—H1	119.2
C7—C8—C9	125.74 (19)	C18—C17—C16	119.8 (2)
C7—C8—H8	117.1	C18—C17—H17	120.1
C9—C8—H8	117.1	C16—C17—H17	120.1
C8—C7—C6	127.5 (2)	C3—C4—C5	118.8 (2)
C8—C7—H7	116.3	C3—C4—H4	120.6
C6—C7—H7	116.3	C5—C4—H4	120.6

C12—N2—N1—C9	−0.4 (3)	C13—C15—C14—N3	−178.22 (19)
N2—N1—C9—C10	−3.0 (3)	C10—C11—C13—C15	−100.2 (2)
N2—N1—C9—C8	179.47 (17)	C12—C11—C13—C15	83.7 (2)
N1—N2—C12—O1	−177.03 (19)	C14—C15—C13—C11	−92.5 (2)
N1—N2—C12—C11	4.6 (3)	C16—C15—C13—C11	90.2 (2)
C10—C11—C12—O1	176.3 (2)	C1—C6—C5—C4	0.5 (3)
C13—C11—C12—O1	−7.4 (3)	C7—C6—C5—C4	−179.8 (2)
C10—C11—C12—N2	−5.4 (3)	C14—C15—C16—C17	0.6 (3)
C13—C11—C12—N2	170.88 (18)	C13—C15—C16—C17	178.0 (2)
C12—C11—C10—C9	2.6 (3)	C14—N3—C18—C17	0.3 (4)
C13—C11—C10—C9	−173.49 (19)	C4—C3—C2—C1	0.0 (4)
N1—C9—C10—C11	1.8 (3)	Cl1—C3—C2—C1	179.66 (18)
C8—C9—C10—C11	179.15 (19)	C3—C2—C1—C6	0.9 (4)
N1—C9—C8—C7	179.9 (2)	C5—C6—C1—C2	−1.1 (3)
C10—C9—C8—C7	2.5 (3)	C7—C6—C1—C2	179.2 (2)
C9—C8—C7—C6	−178.2 (2)	N3—C18—C17—C16	−0.5 (4)
C5—C6—C7—C8	−174.2 (2)	C15—C16—C17—C18	0.0 (4)
C1—C6—C7—C8	5.4 (4)	C2—C3—C4—C5	−0.5 (4)
C18—N3—C14—C15	0.3 (3)	Cl1—C3—C4—C5	179.77 (19)
C16—C15—C14—N3	−0.8 (3)	C6—C5—C4—C3	0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cl2ⁱ	0.93	2.72	3.6387 (19)	168
C18—H18···Cl2ⁱⁱ	0.93	2.94	3.622 (2)	132
N3—H3···O2ⁱⁱⁱ	0.80 (3)	2.35 (3)	2.965 (2)	135 (2)
N3—H3···O1ⁱⁱⁱ	0.80 (3)	2.25 (3)	2.855 (2)	133 (3)
N2—H2C···O2	0.86 (2)	1.97 (2)	2.801 (2)	161 (2)
O2—H2A···Cl2	0.83 (2)	2.35 (2)	3.170 (2)	175 (3)
O2—H2B···O3	0.84 (2)	1.92 (2)	2.739 (3)	167 (3)

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

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer. The authors' contributions are as follows. Conceptualization, SD, EBÇ, ND, and ES; methodology, KK, EBÇ, and ND; investigation, NB and ND; writing (original draft), EBÇ and SD; writing (review and editing of the manuscript), SD, NB, ES, KK and EBÇ; visualization, EBÇ, and KK; funding acquisition, ND; resources, ND and KK; supervision, SD and NB.

Funding information

Funding for this research was provided by: Ondokuz Mayıs University under Project No. PYO.FEN.1906.19.001 .

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