Crystal structure of (E)-3-({6-[2-(4-chloro-phen-yl)ethen-yl]-3-oxo-2,3-di-hydro-pyridazin-4-yl}meth-yl)pyridin-1-ium chloride dihydrate.

In the title compound, C18H15ClN3O+·Cl-·2H2O, three intra-mol-ecular hydrogen bonds are observed, N-H⋯O, O-H⋯Cl and O-H⋯O. In the crystal, mol-ecules 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 inter-actions 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%. © Daoui et al. 2022.

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 ▸).

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 ▸).

Figure 1

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

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) ; (iii) .

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. 2 ▸ a shows a view of the hydrogen bonds along the b-axis direction. π–π inter­actions are present (Fig. 2 ▸ b) 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.

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.

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. 4 ▸ a, 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. 4 ▸ b), the π–π inter­actions are indicated by the red and blue triangles. Fig. 4 ▸ c and Fig. 4 ▸ d show d i and d e surfaces and Fig. 4 ▸ e and 4f the curvedness and fragment path surfaces. Fig. 5 ▸ a shows the overall two-dimensional fingerprint plot. The fingerprint plot delineated into H⋯H contacts (33.0% contribution, Fig. 5 ▸ b) 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. 5 ▸ d) 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. 5 ▸ e) 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. 5 ▸ f 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. 5 ▸ g). 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.

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-d 6) 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-d 6) 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]+.

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[F 2 > 2σ(F 2)], wR(F 2), 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
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022003346/jq2014sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022003346/jq2014Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989022003346/jq2014Isup3.cml

CCDC reference: 2161716

Additional supporting information: crystallographic information; 3D view; checkCIF report

C18H15ClN3O+·Cl−·2H2O	F(000) = 1648
Mr = 396.26	Dx = 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

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	Rint = 0.064
Detector resolution: 6.67 pixels mm-1	θmax = 29.9°, θmin = 1.6°
rotation method scans	h = −21→27
Absorption correction: numerical (X-RED32; Stoe & Cie, 2002)	k = −8→10
Tmin = 0.818, Tmax = 0.961	l = −36→36
13762 measured reflections

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(Fo2) + (0.0709P)2] where P = (Fo2 + 2Fc2)/3
5273 reflections	(Δ/σ)max < 0.001
265 parameters	Δρmax = 0.26 e Å−3
2 restraints	Δρmin = −0.43 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)