# Crystal structure of 1,1'-(pyridine-2,6-diyl)bis[N-(pyridin-2-ylmethyl)methanaminium] dichloride dihydrate

Layachi Merabet, Marine Tassé, Sonia Mallet-Ladeira, Lakhemici Kaboub, Isabelle Malfant

► To cite this version:

Layachi Merabet, Marine Tassé, Sonia Mallet-Ladeira, Lakhemici Kaboub, Isabelle Malfant. Crystal structure of 1,1'-(pyridine-2,6-diyl)bis[N-(pyridin-2-ylmethyl)methanaminium] dichloride dihydrate. Acta crystallographica Section E: Crystallographic communications [2015-..], 2021, 77 (12), pp.1296-1298. 10.1107/S205698902101183X. hal-03600453

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Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 22 October 2021
Accepted 8 November 2021

Edited by B. Therrien, University of Neuchâtel,
Switzerland

**Keywords:** crystal structure; hydrogen bonding; π-π interactions.

CCDC reference: 2120892

**Supporting information:** this article has
supporting information at journals.iucr.org/e

# Crystal structure of 1,1'-(pyridine-2,6-diyl)bis[N- (pyridin-2-ylmethyl)methanaminium] dichloride dihydrate

Layachi Merabet,ª,ᵇ Marine Tassé,ª Sonia Mallet-Ladeira,ᶜ,ª* Lakhemici Kaboubᵇ and Isabelle Malfantª

In the title compound, C₁₉H₂₃N₅²⁺·2Cl⁻·2H₂O, the two pyridine side arms are not coplanar, with the terminal pyridine rings subtending a dihedral angle of 26.45 (6)°. In the crystal, hydrogen bonds, intermolecular C-H···Cl contacts and a weak C-H···O interaction connect the molecule with neighbouring chloride counter-anions and lattice water molecules. The crystal packing also features by π-π interactions with centroid-centroid distances of 3.4864 (12) and 3.5129 (13) Å.

## 1. Chemical context

In recent years, ruthenium nitrosyl complexes have attracted considerable attention, essentially because of their interesting photoreactivity properties such as photochromism (Schaniel *et al.*, 2007) and nitric oxide photorelease (Rose & Mascharak, 2008a). Ruthenium nitrosyl complexes could have desirable photoreactivity properties relying on the nature of the ligands. The utilization of polydentate ligands in coordination chemistry gives a few benefits over monodentate ligands, in particular because of the chelate effect (Martell, 1967). Multidentate pyridylamine derivative ligands can better control the stability (Afshar *et al.*, 2004; Eroy-Reveles *et al.*, 2007), solubility (Harrop *et al.*, 2005) and structural characteristics of the resulting complex. More particularly, ruthenium complexes derived from pentadentate ligands are generally stable in physiological media (Halpenny *et al.*, 2007; Rose & Mascharak, 2008b). This stability is necessary for (i) maintaining pharmacological activity, (ii) reducing the toxicity of free metal ions, and (iii) avoiding non-specific binding of partially connected metal ions with other biomolecules (Fry & Mascharak, 2011; Hoffman-Luca *et al.*, 2009; Patra & Mascharak, 2003; Heilman *et al.*, 2012). In the search for new systems, we report here the synthesis and crystal structure of 1,1'-(pyridine-2,6-diyl)bis[N-(pyridin-2-ylmethyl)methanaminium] dichloride dihydrate, which contains multiple coordination sites, and is thus an excellent candidate for forming stable ruthenium nitrosyl complexes.

## 2. Structural commentary

The title compound crystallizes in the triclinic space group P\bar{1} with one cationic molecule, two chloride anions, and two water

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OPEN

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ACCESS

<footnote>ªLaboratoire de Chimie de Coordination, UPR-CNRS 8241, 205 route de Narbonne, 31077 Toulouse cedex, France,</footnote>

<footnote>ᵇLaboratory of Chemistry, Molecular Engineering and Nanostructures, Department of Chemistry, Faculty of Sciences, University of Ferhat Abbas-Sétif -1, 19000 Sétif, Algeria, and ᶜInstitut de Chimie de Toulouse UAR-CNRS 2599, 118 route de Narbonne, 31062 Toulouse Cedex 09, France. *Correspondence e-mail: sonia.ladeira@lcc-toulouse.fr</footnote>
molecules per asymmetric unit. In the organic molecule, one terminal pyridine ring is almost co-planar with the central pyridine ring, making a dihedral angle of 4.56 (8)°, while the second terminal pyridine ring is out of the plane with a dihedral angle between the two terminal pyridine rings of 26.45 (6)° (Fig. 1). Bond lengths are within normal ranges and comparable with values found for a similar compound, N,N'-dialkyl-2,6-pyridinedimethanaminium (Kobayashi *et al.*, 2006).

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### 3. Supramolecular features

In the crystal, there are intermolecular hydrogen bonds (Table 1) and C-H···Cl and C-H···O interactions between the molecules, the chloride anions and the lattice water molecules. The molecular structure of the compound is illustrated in Fig. 1 with hydrogen bonding indicated.

<figure><img src="image_7.png" /><figcaption>**Figure 1**</figcaption></figure>

Molecular structure showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as small spheres of an arbitrary radius. The orange dashed lines represent hydrogen bonds, C-H···Cl interactions and the weak C-H···O interaction. [Symmetry codes: (i) x − 1, y, z; (ii) x − 1, y + 1, z; (iii) x − 1, y + 1, z; (iv) x + 1, − y + 1, − z + 2; (v) x, y − 1, z.]

<caption>**Table 1**</caption>

Hydrogen-bond geometry (Å, °).

<table><thead><tr><th>D-H···A</th><th>D-H</th><th>H···A</th><th>D···A</th><th>D-H···A</th></tr></thead><tbody><tr><td>O2-H201···Cl2</td><td>0.85 (3)</td><td>2.41 (3)</td><td>3.1844 (15)</td><td>152 (2)</td></tr><tr><td>O2-H202···N5</td><td>0.91 (3)</td><td>2.10 (3)</td><td>2.947 (2)</td><td>155 (2)</td></tr><tr><td>N2-H21···O2</td><td>0.94 (2)</td><td>1.89 (2)</td><td>2.804 (2)</td><td>165 (2)</td></tr><tr><td>N2-H22···Cl1<sup>i</sup></td><td>0.86 (2)</td><td>2.31 (2)</td><td>3.1446 (17)</td><td>162.5 (17)</td></tr><tr><td>N4-H41···Cl2</td><td>0.91 (2)</td><td>2.25 (2)</td><td>3.1319 (17)</td><td>164.1 (19)</td></tr><tr><td>N4-H42···O1<sup>i</sup></td><td>0.97 (2)</td><td>1.90 (2)</td><td>2.825 (2)</td><td>158 (2)</td></tr><tr><td>O1-H101···Cl1</td><td>0.93 (3)</td><td>2.43 (3)</td><td>3.2611 (15)</td><td>149 (2)</td></tr><tr><td>O1-H102···N3<sup>ii</sup></td><td>1.00 (4)</td><td>1.93 (4)</td><td>2.920 (2)</td><td>172 (3)</td></tr><tr><td>C3-H3···Cl1<sup>iii</sup></td><td>0.95</td><td>2.73</td><td>3.5702 (19)</td><td>148</td></tr><tr><td>C6-H6A···Cl1</td><td>0.99</td><td>2.8</td><td>3.751 (2)</td><td>161</td></tr><tr><td>C7-H7A···Cl1<sup>iv</sup></td><td>0.99</td><td>2.78</td><td>3.7351 (18)</td><td>162</td></tr><tr><td>C10-H10···Cl1<sup>v</sup></td><td>0.95</td><td>2.71</td><td>3.6469 (18)</td><td>168</td></tr><tr><td>C17-H17···O1<sup>vi</sup></td><td>0.95</td><td>2.57</td><td>3.437 (2)</td><td>151</td></tr></tbody></table>

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

The crystal packing shows π-π interactions between two parallel neighbouring molecules along the a-axis direction with a Cg1···Cg2 (x, y − 1, z) centroid-centroid distance of 3.4864 (12) Å, a perpendicular distance from the centroid Cg1 to the plane of the other ring of 3.2472 (8) Å and a slippage between the centroids of 1.100 Å. Similarly, the second π-π stacking interaction has a Cg3···Cg3(−x, −y + 2, −z + 1) centroid-centroid distance of 3.5129 (13) Å, a perpendicular distance from the centroid Cg3 to the plane of the other ring of 3.2177 (8) Å and a slippage between the centroids of 1.410 Å. Cg1, Cg2 and Cg3 are the centroids of N1/C8–C12, N3/C1–C5 and N5/C15–C19 pyridine rings, respectively (Fig. 2).

### 4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.42, last updated May 2021; Groom *et al.*, 2016) for similar compounds gave three hits. They include N,N'-bis(2-pyridyl-methyl)pyridine-2,6-dicarboxamide (CSD refcode AVURAK; Jain *et al.*, 2004), N,N'-bis[2-(2-pyridyl)methyl]pyridine-2,6-dicarboxamide hemihydrate (HULKUU; Jian Ying Qi *et al.*,

<figure><img src="image_8.png" /><figcaption>**Figure 2**</figcaption></figure>

Views of the stacking along the a axis. Orange lines indicate π-π interactions. Displacement ellipsoids are drawn at the 50% probability level.
2002) and 2,6-bis[(2-pyridiniomethyl)ammoniomethyl]pyridine tetrachloride monohydrate (IRODAV; Kobayashi *et al.*, 2006). In those compounds, the two terminal pyridine rings are rotated out of the plane of the central pyridine ring with dihedral angles ranging from 63 to 89°.

## 5. Synthesis and crystallization

1,1'--(Pyridine-2,6-diyl)bis[N-(pyridin-2-ylmethyl)methanaminium] dichloride dihydrate compound was obtained following the procedure previously reported in the literature (Gruenwedel, 1968; Newkome *et al.*, 1984; Darbre *et al.*, 2002; Kobayashi *et al.*, 2006). The procedure used for the synthesis has three steps. Firstly, the synthesis of 2-[(tosylamino)methyl]pyridine was carried out by treatment of 2-(aminomethyl) pyridine with NaOH and tosyl chloride in a two-phase system (water/diethyl ether) (Newkome *et al.*, 1984). In the second step, the coupling of 2-[(tosylamino)methyl] pyridine with 2,6-bis(bromomethyl) pyridine, also in an two-phase system (dichloromethane/water) and nBu₄NBr as phase-transfer catalyst gave 2,6-bis[(pyrid-2-ylmethyl)(tosyl)amino]methyl]pyridine, which could be isolated after chromatography (Darbre *et al.*, 2002). Finally, the tosylate group of 2,6-bis[(pyrid-2-ylmethyl)(tosyl)amino]methyl]pyridine was removed using concentrated sulfuric acid for deprotection with heating at 393 K for 3 h to give an unstable brownish oil (Newkome *et al.*, 1984).

Slow diffusion between toluene and a wet dichloromethane solution of the brown oil set aside at room temperature gave colourless needles of the title compound suitable for X-ray diffraction within five days.

## 6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms of the water molecules and those bonded to nitrogen atoms were located in difference-Fourier maps and refined freely with isotropic displacement parameters. All C-bound H atoms were placed in calculated positions and refined using a riding model, with C–H = 0.95 (aromatic) or 0.99 Å (methylene) and with Uiso(H) = 1.2Ueq(C). For two similar N–H distances, a restraint was applied to make them approximately equal with an effective standard deviation of 0.02 Å.

## References

* Afshar, R. K., Patra, A. K., Olmstead, M. M. & Mascharak, P. K. (2004). *Inorg. Chem.* **43**, 5736–5743.

* Bruker (2012). *APEX3* and *SAINT*. Bruker AXS Inc., Madison, Wisconsin, USA.

* Darbre, T., Dubs, C., Rusanov, E. & Stoeckli-Evans, H. (2002). *Eur. J. Inorg. Chem.* pp. 3284–3291.

* Eroy-Reveles, A. A., Hoffman-Luca, C. G. & Mascharak, P. K. (2007). *Dalton Trans.* pp. 5268–5274.

* Fry, N. L. & Mascharak, P. K. (2011). *Acc. Chem. Res.* **44**, 289–298.

* Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). *Acta Cryst.* **B72**, 171–179.

* Gruenwedel, D. W. (1968). *Inorg. Chem.* **7**, 495–501.

* Halpenny, G. M., Olmstead, M. M. & Mascharak, P. K. (2007). *Inorg. Chem.* **46**, 6601–6606.

<caption>Table 2</caption>

Experimental details.

<table><tr><td colspan="2">Crystal data</td></tr><tr><td>Chemical formula</td><td>C<sub>19</sub>H<sub>23</sub>N<sub>5</sub><sup>2+</sup>.2Cl<sup>-</sup>.2H<sub>2</sub>O</td></tr><tr><td>M<sub>r</sub></td><td>428.36</td></tr><tr><td>Crystal system, space group</td><td>Triclinic, <i>P</i>1</td></tr><tr><td>Temperature (K)</td><td>110</td></tr><tr><td><i>a</i>, <i>b</i>, <i>c</i> (Å)</td><td>7.1579 (6), 8.8119 (7), 17.4150 (13)</td></tr><tr><td>α, β<sub>z</sub> γ (°)</td><td>80.357 (3), 80.805 (3), 68.919 (3)</td></tr><tr><td><i>V</i> (Å<sup>3</sup>)</td><td>1004.52 (14)</td></tr><tr><td><i>Z</i></td><td>2</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>0.35</td></tr><tr><td>Crystal size (mm)</td><td>0.2 × 0.08 × 0.04</td></tr><tr><td colspan="2">Data collection</td></tr><tr><td>Diffractometer</td><td>Bruker Kappa APEXII Quazar</td></tr><tr><td>Absorption correction</td><td>Multi-scan (SADABS; Krause *et al.*, 2015)</td></tr><tr><td><i>T</i><sub>min</sub>, <i>T</i><sub>max</sub></td><td>0.660, 0.746</td></tr><tr><td>No. of measured, independent and observed [<i>I</i> > 2σ(<i>I</i>)] reflections</td><td>29584, 6970, 4632</td></tr><tr><td><i>R</i><sub>int</sub></td><td>0.097</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.746</td></tr><tr><td colspan="2">Refinement</td></tr><tr><td><i>R</i>[<i>F</i><sup>2</sup> > 2σ(<i>F</i><sup>2</sup>)], <i>wR</i>(<i>F</i><sup>2</sup>), <i>S</i></td><td>0.05, 0.123, 1.03</td></tr><tr><td>No. of reflections</td><td>6970</td></tr><tr><td>No. of parameters</td><td>283</td></tr><tr><td>No. of restraints</td><td>1</td></tr><tr><td>H-atom treatment</td><td>H atoms treated by a mixture of independent and constrained refinement</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.45, -0.38</td></tr></table>

Computer programs: *APEX3* and *SAINT* (Bruker, 2012), *SHELXT* (Sheldrick 2015a), *SHELXL2018/3* (Sheldrick, 2015b), *Mercury* (Macrae *et al.*, 2020) and *publCIF* (Westrip, 2010).

* Harrop, T. C., Olmstead, M. M. & Mascharak, P. K. (2005). *Inorg. Chem.* **44**, 6918–6920.

* Heilman, B. J., St John, J., Oliver, S. R. J. & Mascharak, P. K. (2012). *J. Am. Chem. Soc.* **134**, 11573–11582.

* Hoffman-Luca, C. G., Eroy-Reveles, A. A., Alvarenga, J. & Mascharak, P. K. (2009). *Inorg. Chem.* **48**, 9104–9111.

* Jain, S. L., Bhattacharyya, P., Milton, H. L., Slawin, A. M. Z., Crayston, J. A. & Woollins, J. D. (2004). *Dalton Trans.* pp. 862–871.

* Kobayashi, T., Yaita, T., Sugo, Y., Suda, H., Suzuki, S., Fujii, Y. & Nakano, Y. (2006). *J. Heterocycl. Chem.* **43**, 549–557.

* Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). *J. Appl. Cryst.* **48**, 3–10.

* Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). *J. Appl. Cryst.* **53**, 226–235.

* Martell, A. E. (1967). Editor. *Advances in Chemistry*, pp. 272–294. Washington: American Chemical Society.

* Newkome, G. R., Gupta, V. K., Fronczek, F. R. & Pappalardo, S. (1984). *Inorg. Chem.* **23**, 2400–2408.

* Patra, A. K. & Mascharak, P. K. (2003). *Inorg. Chem.* **42**, 7363–7365.

* Qi, J. Y., Chen, J., Yang, Q. Y., Zhou, Z. Y. & Chan, A. S. C. (2002). *Acta Cryst.* **E58**, o1232–o1233.

* Rose, M. J. & Mascharak, P. K. (2008a). *Coord. Chem. Rev.* **252**, 2093–2114.

* Rose, M. J. & Mascharak, P. K. (2008b). *Curr. Opin. Chem. Biol.* **12**, 238–244.

* Schaniel, D., Imlau, M., Weisemoeller, T., Woike, T., Krämer, K. W. & Güdel, H. U. (2007). *Adv. Mater.* **19**, 723–726.

* Sheldrick, G. M. (2015a). *Acta Cryst.* **A71**, 3–8.

* Sheldrick, G. M. (2015b). *Acta Cryst.* **C71**, 3–8.

* Westrip, S. P. (2010). *J. Appl. Cryst.* **43**, 920–925.
supporting information

*Acta Cryst.* (2021). E77, 1296-1298 [https://doi.org/10.1107/S205698902101183X]

# Crystal structure of 1,1'-(pyridine-2,6-diyl)bis[N-(pyridin-2-ylmethyl)-methanaminium] dichloride dihydrate

Layachi Merabet, Marine Tassé, Sonia Mallet-Ladeira, Lakhemici Kaboub and Isabelle Malfant

## Computing details

Data collection: *APEX3* (Bruker, 2012); cell refinement: *APEX3* and *SAINT* (Bruker, 2012); data reduction: *SAINT* (Bruker, 2012); program(s) used to solve structure: *SHELXT* (Sheldrick 2015a); program(s) used to refine structure: *SHELXL2018/3* (Sheldrick, 2015b); molecular graphics: *Mercury* (Macrae *et al.*, 2020); software used to prepare material for publication: *publCIF* (Westrip, 2010).

## 1,1'-(Pyridine-2,6-diyl)bis[N-(pyridin-2-ylmethyl)methanaminium] dichloride dihydrate

### Crystal data

$C_{19}H_{23}N_{5}^{2+}·2Cl⁻·2H₂O$

$M_r = 428.36$

Triclinic, $P\overline{1}$

Hall symbol: -P 1

$a = 7.1579 (6) Å$

$b = 8.8119 (7) Å$

$c = 17.4150 (13) Å$

$α = 80.357 (3)°$

$β = 80.805 (3)°$

$γ = 68.919 (3)°$

$V = 1004.52 (14) Å³$

### Data collection

Bruker Kappa APEXII Quazar
diffractometer

Radiation source: microfocus sealed tube

Multilayer optics monochromator

phi and ω scans

Absorption correction: multi-scan
(SADABS; Krause *et al.*, 2015)

$T_{min} = 0.660, T_{max} = 0.746$

### Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2σ(F^2)] = 0.05$

$wR(F^2) = 0.123$

$S = 1.03$

6970 reflections

283 parameters

1 restraint

$Z = 2$

$F(000) = 452$

$D_x = 1.416 Mg m⁻³$

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 4444 reflections

$θ = 3.2–31.4°$

$μ = 0.35 mm⁻¹$

$T = 110 K$

Needle, colourless

0.2 × 0.08 × 0.04 mm

29584 measured reflections

6970 independent reflections

4632 reflections with $I > 2σ(I)$

$R_{int} = 0.097$

$θ_{max} = 32.0°, θ_{min} = 1.2°$

$h = -10→10$

$k = -13→13$

$l = -25→25$

Primary atom site location: dual

Secondary atom site location: difference Fourier map

Hydrogen site location: mixed

H atoms treated by a mixture of independent and constrained refinement

$w = 1/[σ²(F_o²) + (0.0518P)²]$

where $P = (F_o² + 2F_c²)/3$
$$ \begin{aligned} (\Delta/\sigma)_{\max} &= 0.002 \\ \Delta\rho_{\max} &= 0.45 \text{ e Å}^{-3} \end{aligned} $$

$$ \Delta\rho_{\min} = -0.38 \text{ e Å}^{-3} $$

Special details

**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)

<table><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th></tr></thead><tbody><tr><td>C1</td><td>-0.0133 (3)</td><td>1.1436 (2)</td><td>0.77592 (11)</td><td>0.0187 (4)</td></tr><tr><td>H1</td><td>-0.057178</td><td>1.157686</td><td>0.725689</td><td>0.022*</td></tr><tr><td>C2</td><td>-0.0514 (3)</td><td>1.2816 (2)</td><td>0.81173 (12)</td><td>0.0209 (4)</td></tr><tr><td>H2</td><td>-0.118646</td><td>1.387618</td><td>0.786614</td><td>0.025*</td></tr><tr><td>C3</td><td>0.0110 (3)</td><td>1.2617 (2)</td><td>0.88529 (12)</td><td>0.0209 (4)</td></tr><tr><td>H3</td><td>-0.013857</td><td>1.353959</td><td>0.91186</td><td>0.025*</td></tr><tr><td>C4</td><td>0.1098 (3)</td><td>1.1057 (2)</td><td>0.91921 (11)</td><td>0.0177 (4)</td></tr><tr><td>H4</td><td>0.15363</td><td>1.089007</td><td>0.969628</td><td>0.021*</td></tr><tr><td>C5</td><td>0.1446 (3)</td><td>0.9729 (2)</td><td>0.87872 (10)</td><td>0.0141 (3)</td></tr><tr><td>C6</td><td>0.2661 (3)</td><td>0.8058 (2)</td><td>0.91424 (10)</td><td>0.0154 (3)</td></tr><tr><td>H6A</td><td>0.405015</td><td>0.802589</td><td>0.916169</td><td>0.018*</td></tr><tr><td>H6B</td><td>0.20699</td><td>0.78592</td><td>0.968744</td><td>0.018*</td></tr><tr><td>C7</td><td>0.3958 (3)</td><td>0.5088 (2)</td><td>0.90648 (10)</td><td>0.0152 (3)</td></tr><tr><td>H7A</td><td>0.32656</td><td>0.482715</td><td>0.958206</td><td>0.018*</td></tr><tr><td>H7B</td><td>0.528732</td><td>0.510415</td><td>0.914788</td><td>0.018*</td></tr><tr><td>C8</td><td>0.4252 (3)</td><td>0.3788 (2)</td><td>0.85503 (10)</td><td>0.0123 (3)</td></tr><tr><td>C9</td><td>0.5158 (3)</td><td>0.2141 (2)</td><td>0.88081 (10)</td><td>0.0159 (4)</td></tr><tr><td>H9</td><td>0.555649</td><td>0.180246</td><td>0.93221</td><td>0.019*</td></tr><tr><td>C10</td><td>0.5467 (3)</td><td>0.1000 (2)</td><td>0.82986 (11)</td><td>0.0169 (4)</td></tr><tr><td>H10</td><td>0.610739</td><td>-0.013533</td><td>0.84539</td><td>0.02*</td></tr><tr><td>C11</td><td>0.4830 (3)</td><td>0.1539 (2)</td><td>0.75619 (10)</td><td>0.0153 (3)</td></tr><tr><td>H11</td><td>0.502104</td><td>0.078354</td><td>0.720177</td><td>0.018*</td></tr><tr><td>C12</td><td>0.3904 (3)</td><td>0.3211 (2)</td><td>0.73580 (10)</td><td>0.0126 (3)</td></tr><tr><td>C13</td><td>0.3100 (3)</td><td>0.3899 (2)</td><td>0.65770 (10)</td><td>0.0143 (3)</td></tr><tr><td>H13A</td><td>0.397572</td><td>0.323319</td><td>0.616689</td><td>0.017*</td></tr><tr><td>H13B</td><td>0.172891</td><td>0.385542</td><td>0.659994</td><td>0.017*</td></tr><tr><td>C14</td><td>0.2369 (3)</td><td>0.6343 (2)</td><td>0.55940 (10)</td><td>0.0155 (3)</td></tr><tr><td>H14A</td><td>0.096005</td><td>0.640498</td><td>0.55942</td><td>0.019*</td></tr><tr><td>H14B</td><td>0.321889</td><td>0.562201</td><td>0.519947</td><td>0.019*</td></tr><tr><td>C15</td><td>0.2502 (3)</td><td>0.8035 (2)</td><td>0.53686 (10)</td><td>0.0134 (3)</td></tr><tr><td>C16</td><td>0.2354 (3)</td><td>0.8748 (2)</td><td>0.45938 (10)</td><td>0.0161 (4)</td></tr><tr><td>H16</td><td>0.225967</td><td>0.815293</td><td>0.420322</td><td>0.019*</td></tr><tr><td>C17</td><td>0.2348 (3)</td><td>1.0342 (2)</td><td>0.44024 (11)</td><td>0.0186 (4)</td></tr><tr><td>H17</td><td>0.225559</td><td>1.085635</td><td>0.387808</td><td>0.022*</td></tr><tr><td>C18</td><td>0.2479 (3)</td><td>1.1176 (2)</td><td>0.49930 (11)</td><td>0.0197 (4)</td></tr><tr><td>H18</td><td>0.245914</td><td>1.227408</td><td>0.488339</td><td>0.024*</td></tr></tbody></table>
<table><tr><td>C19</td><td>0.2640 (3)</td><td>1.0358 (2)</td><td>0.57442 (11)</td><td>0.0169 (4)</td></tr><tr><td>H19</td><td>0.273735</td><td>1.092671</td><td>0.614568</td><td>0.02*</td></tr><tr><td>N1</td><td>0.3620 (2)</td><td>0.43202 (17)</td><td>0.78433 (8)</td><td>0.0120 (3)</td></tr><tr><td>N2</td><td>0.2743 (2)</td><td>0.67297 (17)</td><td>0.87003 (9)</td><td>0.0127 (3)</td></tr><tr><td>N3</td><td>0.0822 (2)</td><td>0.99031 (18)</td><td>0.80798 (9)</td><td>0.0160 (3)</td></tr><tr><td>N4</td><td>0.3036 (2)</td><td>0.56233 (17)</td><td>0.63771 (8)</td><td>0.0129 (3)</td></tr><tr><td>N5</td><td>0.2668 (2)</td><td>0.88122 (17)</td><td>0.59397 (8)</td><td>0.0146 (3)</td></tr><tr><td>Cl1</td><td>0.82559 (7)</td><td>0.68542 (5)</td><td>0.91223 (3)</td><td>0.01828 (11)</td></tr><tr><td>Cl2</td><td>0.76725 (7)</td><td>0.49614 (5)</td><td>0.62355 (3)</td><td>0.01743 (11)</td></tr><tr><td>O1</td><td>0.9786 (2)</td><td>0.76904 (17)</td><td>0.72866 (8)</td><td>0.0210 (3)</td></tr><tr><td>O2</td><td>0.4905 (2)</td><td>0.76661 (17)</td><td>0.73277 (8)</td><td>0.0205 (3)</td></tr><tr><td>H201</td><td>0.592 (4)</td><td>0.689 (3)</td><td>0.7158 (14)</td><td>0.038*</td></tr><tr><td>H202</td><td>0.389 (4)</td><td>0.807 (3)</td><td>0.7017 (16)</td><td>0.05*</td></tr><tr><td>H21</td><td>0.345 (3)</td><td>0.689 (2)</td><td>0.8209 (11)</td><td>0.018 (5)*</td></tr><tr><td>H22</td><td>0.152 (3)</td><td>0.676 (2)</td><td>0.8706 (11)</td><td>0.013 (5)*</td></tr><tr><td>H41</td><td>0.431 (4)</td><td>0.562 (3)</td><td>0.6375 (13)</td><td>0.026 (6)*</td></tr><tr><td>H42</td><td>0.216 (4)</td><td>0.622 (3)</td><td>0.6789 (12)</td><td>0.037 (7)*</td></tr><tr><td>H101</td><td>0.917 (4)</td><td>0.721 (3)</td><td>0.7716 (15)</td><td>0.040 (7)*</td></tr><tr><td>H102</td><td>1.026 (5)</td><td>0.841 (4)</td><td>0.7531 (19)</td><td>0.084 (11)*</td></tr></table>

Atomic displacement parameters (Å²)

<table><thead><tr><th></th><th>U<sup>11</sup></th><th>U<sup>22</sup></th><th>U<sup>33</sup></th><th>U<sup>12</sup></th><th>U<sup>13</sup></th><th>U<sup>23</sup></th></tr></thead><tbody><tr><td>C1</td><td>0.0158 (9)</td><td>0.0187 (9)</td><td>0.0217 (9)</td><td>-0.0080 (7)</td><td>-0.0011 (7)</td><td>0.0014 (7)</td></tr><tr><td>C2</td><td>0.0147 (9)</td><td>0.0153 (8)</td><td>0.0302 (10)</td><td>-0.0057 (7)</td><td>0.0053 (8)</td><td>-0.0016 (7)</td></tr><tr><td>C3</td><td>0.0187 (10)</td><td>0.0150 (8)</td><td>0.0291 (10)</td><td>-0.0080 (7)</td><td>0.0087 (8)</td><td>-0.0084 (7)</td></tr><tr><td>C4</td><td>0.0159 (9)</td><td>0.0194 (9)</td><td>0.0187 (9)</td><td>-0.0077 (7)</td><td>0.0042 (7)</td><td>-0.0068 (7)</td></tr><tr><td>C5</td><td>0.0121 (9)</td><td>0.0145 (8)</td><td>0.0164 (8)</td><td>-0.0062 (7)</td><td>0.0024 (7)</td><td>-0.0031 (6)</td></tr><tr><td>C6</td><td>0.0184 (9)</td><td>0.0148 (8)</td><td>0.0142 (8)</td><td>-0.0053 (7)</td><td>-0.0028 (7)</td><td>-0.0047 (6)</td></tr><tr><td>C7</td><td>0.0179 (9)</td><td>0.0132 (8)</td><td>0.0133 (8)</td><td>-0.0039 (7)</td><td>-0.0046 (7)</td><td>0.0012 (6)</td></tr><tr><td>C8</td><td>0.0109 (8)</td><td>0.0136 (7)</td><td>0.0136 (8)</td><td>-0.0062 (6)</td><td>-0.0010 (6)</td><td>-0.0002 (6)</td></tr><tr><td>C9</td><td>0.0164 (9)</td><td>0.0144 (8)</td><td>0.0173 (8)</td><td>-0.0061 (7)</td><td>-0.0060 (7)</td><td>0.0032 (6)</td></tr><tr><td>C10</td><td>0.0135 (9)</td><td>0.0112 (8)</td><td>0.0240 (9)</td><td>-0.0035 (7)</td><td>-0.0021 (7)</td><td>0.0016 (7)</td></tr><tr><td>C11</td><td>0.0147 (9)</td><td>0.0122 (8)</td><td>0.0202 (9)</td><td>-0.0061 (7)</td><td>0.0005 (7)</td><td>-0.0038 (6)</td></tr><tr><td>C12</td><td>0.0099 (8)</td><td>0.0121 (7)</td><td>0.0160 (8)</td><td>-0.0043 (6)</td><td>-0.0005 (6)</td><td>-0.0015 (6)</td></tr><tr><td>C13</td><td>0.0180 (9)</td><td>0.0109 (7)</td><td>0.0156 (8)</td><td>-0.0059 (7)</td><td>-0.0022 (7)</td><td>-0.0030 (6)</td></tr><tr><td>C14</td><td>0.0199 (9)</td><td>0.0153 (8)</td><td>0.0120 (8)</td><td>-0.0060 (7)</td><td>-0.0053 (7)</td><td>-0.0003 (6)</td></tr><tr><td>C15</td><td>0.0100 (8)</td><td>0.0148 (8)</td><td>0.0138 (8)</td><td>-0.0028 (6)</td><td>-0.0017 (6)</td><td>-0.0007 (6)</td></tr><tr><td>C16</td><td>0.0129 (9)</td><td>0.0186 (8)</td><td>0.0145 (8)</td><td>-0.0030 (7)</td><td>-0.0016 (7)</td><td>-0.0012 (7)</td></tr><tr><td>C17</td><td>0.0116 (9)</td><td>0.0227 (9)</td><td>0.0174 (9)</td><td>-0.0045 (7)</td><td>-0.0013 (7)</td><td>0.0052 (7)</td></tr><tr><td>C18</td><td>0.0141 (9)</td><td>0.0163 (8)</td><td>0.0270 (10)</td><td>-0.0057 (7)</td><td>-0.0035 (8)</td><td>0.0038 (7)</td></tr><tr><td>C19</td><td>0.0147 (9)</td><td>0.0151 (8)</td><td>0.0219 (9)</td><td>-0.0062 (7)</td><td>-0.0029 (7)</td><td>-0.0014 (7)</td></tr><tr><td>N1</td><td>0.0113 (7)</td><td>0.0118 (6)</td><td>0.0129 (7)</td><td>-0.0042 (5)</td><td>-0.0020 (5)</td><td>-0.0004 (5)</td></tr><tr><td>N2</td><td>0.0147 (8)</td><td>0.0116 (7)</td><td>0.0125 (7)</td><td>-0.0044 (6)</td><td>-0.0030 (6)</td><td>-0.0018 (5)</td></tr><tr><td>N3</td><td>0.0153 (8)</td><td>0.0146 (7)</td><td>0.0187 (7)</td><td>-0.0069 (6)</td><td>0.0005 (6)</td><td>-0.0023 (6)</td></tr><tr><td>N4</td><td>0.0155 (8)</td><td>0.0111 (6)</td><td>0.0124 (7)</td><td>-0.0049 (6)</td><td>-0.0030 (6)</td><td>-0.0001 (5)</td></tr><tr><td>N5</td><td>0.0146 (8)</td><td>0.0142 (7)</td><td>0.0160 (7)</td><td>-0.0065 (6)</td><td>-0.0029 (6)</td><td>0.0004 (5)</td></tr><tr><td>C11</td><td>0.0158 (2)</td><td>0.01449 (19)</td><td>0.0216 (2)</td><td>-0.00422 (16)</td><td>-0.00132 (17)</td><td>0.00282 (16)</td></tr></tbody></table>
<table><tr><td>C12</td><td>0.0160 (2)</td><td>0.0182 (2)</td><td>0.0178 (2)</td><td>-0.00561 (17)</td><td>-0.00165 (16)</td><td>-0.00182 (16)</td></tr><tr><td>O1</td><td>0.0217 (8)</td><td>0.0225 (7)</td><td>0.0175 (7)</td><td>-0.0062 (6)</td><td>-0.0017 (6)</td><td>-0.0028 (5)</td></tr><tr><td>O2</td><td>0.0234 (8)</td><td>0.0193 (7)</td><td>0.0194 (7)</td><td>-0.0083 (6)</td><td>-0.0002 (6)</td><td>-0.0040 (5)</td></tr></table>

Geometric parameters (Å, °)

<table><tr><td>C1—N3</td><td>1.345 (2)</td><td>C12—C13</td><td>1.507 (2)</td></tr><tr><td>C1—C2</td><td>1.380 (3)</td><td>C13—N4</td><td>1.487 (2)</td></tr><tr><td>C1—H1</td><td>0.95</td><td>C13—H13A</td><td>0.99</td></tr><tr><td>C2—C3</td><td>1.387 (3)</td><td>C13—H13B</td><td>0.99</td></tr><tr><td>C2—H2</td><td>0.95</td><td>C14—N4</td><td>1.480 (2)</td></tr><tr><td>C3—C4</td><td>1.379 (3)</td><td>C14—C15</td><td>1.511 (2)</td></tr><tr><td>C3—H3</td><td>0.95</td><td>C14—H14A</td><td>0.99</td></tr><tr><td>C4—C5</td><td>1.393 (2)</td><td>C14—H14B</td><td>0.99</td></tr><tr><td>C4—H4</td><td>0.95</td><td>C15—N5</td><td>1.340 (2)</td></tr><tr><td>C5—N3</td><td>1.343 (2)</td><td>C15—C16</td><td>1.393 (2)</td></tr><tr><td>C5—C6</td><td>1.501 (2)</td><td>C16—C17</td><td>1.387 (3)</td></tr><tr><td>C6—N2</td><td>1.485 (2)</td><td>C16—H16</td><td>0.95</td></tr><tr><td>C6—H6A</td><td>0.99</td><td>C17—C18</td><td>1.393 (3)</td></tr><tr><td>C6—H6B</td><td>0.99</td><td>C17—H17</td><td>0.95</td></tr><tr><td>C7—N2</td><td>1.488 (2)</td><td>C18—C19</td><td>1.384 (2)</td></tr><tr><td>C7—C8</td><td>1.507 (2)</td><td>C18—H18</td><td>0.95</td></tr><tr><td>C7—H7A</td><td>0.99</td><td>C19—N5</td><td>1.342 (2)</td></tr><tr><td>C7—H7B</td><td>0.99</td><td>C19—H19</td><td>0.95</td></tr><tr><td>C8—N1</td><td>1.331 (2)</td><td>N2—H21</td><td>0.937 (18)</td></tr><tr><td>C8—C9</td><td>1.388 (2)</td><td>N2—H22</td><td>0.86 (2)</td></tr><tr><td>C9—C10</td><td>1.387 (2)</td><td>N4—H41</td><td>0.91 (2)</td></tr><tr><td>C9—H9</td><td>0.95</td><td>N4—H42</td><td>0.967 (19)</td></tr><tr><td>C10—C11</td><td>1.381 (2)</td><td>O1—H101</td><td>0.93 (3)</td></tr><tr><td>C10—H10</td><td>0.95</td><td>O1—H102</td><td>1.00 (4)</td></tr><tr><td>C11—C12</td><td>1.390 (2)</td><td>O2—H201</td><td>0.85 (3)</td></tr><tr><td>C11—H11</td><td>0.95</td><td>O2—H202</td><td>0.91 (3)</td></tr><tr><td>C12—N1</td><td>1.338 (2)</td><td></td><td></td></tr><tr><td>N3—C1—C2</td><td>123.83 (18)</td><td>N4—C13—H13A</td><td>109.7</td></tr><tr><td>N3—C1—H1</td><td>118.1</td><td>C12—C13—H13A</td><td>109.7</td></tr><tr><td>C2—C1—H1</td><td>118.1</td><td>N4—C13—H13B</td><td>109.7</td></tr><tr><td>C1—C2—C3</td><td>118.32 (17)</td><td>C12—C13—H13B</td><td>109.7</td></tr><tr><td>C1—C2—H2</td><td>120.8</td><td>H13A—C13—H13B</td><td>108.2</td></tr><tr><td>C3—C2—H2</td><td>120.8</td><td>N4—C14—C15</td><td>111.73 (14)</td></tr><tr><td>C4—C3—C2</td><td>118.88 (17)</td><td>N4—C14—H14A</td><td>109.3</td></tr><tr><td>C4—C3—H3</td><td>120.6</td><td>C15—C14—H14A</td><td>109.3</td></tr><tr><td>C2—C3—H3</td><td>120.6</td><td>N4—C14—H14B</td><td>109.3</td></tr><tr><td>C3—C4—C5</td><td>119.23 (17)</td><td>C15—C14—H14B</td><td>109.3</td></tr><tr><td>C3—C4—H4</td><td>120.4</td><td>H14A—C14—H14B</td><td>107.9</td></tr><tr><td>C5—C4—H4</td><td>120.4</td><td>N5—C15—C16</td><td>122.97 (16)</td></tr><tr><td>N3—C5—C4</td><td>122.47 (16)</td><td>N5—C15—C14</td><td>117.68 (14)</td></tr><tr><td>N3—C5—C6</td><td>119.35 (15)</td><td>C16—C15—C14</td><td>119.28 (15)</td></tr></table>
<table><caption>Hydrogen-bond geometry (Å, °)</caption><tr><td>C4—C5—C6</td><td>118.09 (16)</td><td>C17—C16—C15</td><td>118.87 (16)</td></tr><tr><td>N2—C6—C5</td><td>112.92 (14)</td><td>C17—C16—H16</td><td>120.6</td></tr><tr><td>N2—C6—H6A</td><td>109</td><td>C15—C16—H16</td><td>120.6</td></tr><tr><td>C5—C6—H6A</td><td>109</td><td>C16—C17—C18</td><td>118.78 (17)</td></tr><tr><td>N2—C6—H6B</td><td>109</td><td>C16—C17—H17</td><td>120.6</td></tr><tr><td>C5—C6—H6B</td><td>109</td><td>C18—C17—H17</td><td>120.6</td></tr><tr><td>H6A—C6—H6B</td><td>107.8</td><td>C19—C18—C17</td><td>118.13 (17)</td></tr><tr><td>N2—C7—C8</td><td>110.77 (13)</td><td>C19—C18—H18</td><td>120.9</td></tr><tr><td>N2—C7—H7A</td><td>109.5</td><td>C17—C18—H18</td><td>120.9</td></tr><tr><td>C8—C7—H7A</td><td>109.5</td><td>N5—C19—C18</td><td>123.98 (17)</td></tr><tr><td>N2—C7—H7B</td><td>109.5</td><td>N5—C19—H19</td><td>118</td></tr><tr><td>C8—C7—H7B</td><td>109.5</td><td>C18—C19—H19</td><td>118</td></tr><tr><td>H7A—C7—H7B</td><td>108.1</td><td>C8—N1—C12</td><td>118.13 (14)</td></tr><tr><td>N1—C8—C9</td><td>123.01 (15)</td><td>C6—N2—C7</td><td>111.76 (13)</td></tr><tr><td>N1—C8—C7</td><td>116.08 (14)</td><td>C6—N2—H21</td><td>106.6 (12)</td></tr><tr><td>C9—C8—C7</td><td>120.90 (15)</td><td>C7—N2—H21</td><td>105.3 (13)</td></tr><tr><td>C10—C9—C8</td><td>118.50 (16)</td><td>C6—N2—H22</td><td>107.3 (13)</td></tr><tr><td>C10—C9—H9</td><td>120.7</td><td>C7—N2—H22</td><td>108.9 (13)</td></tr><tr><td>C8—C9—H9</td><td>120.7</td><td>H21—N2—H22</td><td>117.1 (18)</td></tr><tr><td>C11—C10—C9</td><td>118.94 (16)</td><td>C5—N3—C1</td><td>117.25 (15)</td></tr><tr><td>C11—C10—H10</td><td>120.5</td><td>C14—N4—C13</td><td>112.47 (13)</td></tr><tr><td>C9—C10—H10</td><td>120.5</td><td>C14—N4—H41</td><td>108.2 (14)</td></tr><tr><td>C10—C11—C12</td><td>118.65 (16)</td><td>C13—N4—H41</td><td>107.4 (14)</td></tr><tr><td>C10—C11—H11</td><td>120.7</td><td>C14—N4—H42</td><td>112.1 (14)</td></tr><tr><td>C12—C11—H11</td><td>120.7</td><td>C13—N4—H42</td><td>106.6 (15)</td></tr><tr><td>N1—C12—C11</td><td>122.75 (16)</td><td>H41—N4—H42</td><td>110 (2)</td></tr><tr><td>N1—C12—C13</td><td>115.14 (14)</td><td>C15—N5—C19</td><td>117.26 (15)</td></tr><tr><td>C11—C12—C13</td><td>122.10 (15)</td><td>H101—O1—H102</td><td>102 (2)</td></tr><tr><td>N4—C13—C12</td><td>109.75 (13)</td><td>H201—O2—H202</td><td>115 (2)</td></tr></table>

<table><thead><tr><th>D—H···A</th><th>D—H</th><th>H···A</th><th>D···A</th><th>D—H···A</th></tr></thead><tbody><tr><td>O2—H201···Cl2</td><td>0.85 (3)</td><td>2.41 (3)</td><td>3.1844 (15)</td><td>152 (2)</td></tr><tr><td>O2—H202···N5</td><td>0.91 (3)</td><td>2.10 (3)</td><td>2.947 (2)</td><td>155 (2)</td></tr><tr><td>N2—H21···O2</td><td>0.94 (2)</td><td>1.89 (2)</td><td>2.804 (2)</td><td>165 (2)</td></tr><tr><td>N2—H22···Cl1<sup>i</sup></td><td>0.86 (2)</td><td>2.31 (2)</td><td>3.1446 (17)</td><td>162.5 (17)</td></tr><tr><td>N4—H41···Cl2</td><td>0.91 (2)</td><td>2.25 (2)</td><td>3.1319 (17)</td><td>164.1 (19)</td></tr><tr><td>N4—H42···O1<sup>i</sup></td><td>0.97 (2)</td><td>1.90 (2)</td><td>2.825 (2)</td><td>158 (2)</td></tr><tr><td>O1—H101···Cl1</td><td>0.93 (3)</td><td>2.43 (3)</td><td>3.2611 (15)</td><td>149 (2)</td></tr><tr><td>O1—H102···N3<sup>ii</sup></td><td>1.00 (4)</td><td>1.93 (4)</td><td>2.920 (2)</td><td>172 (3)</td></tr><tr><td>C3—H3···Cl1<sup>iii</sup></td><td>0.95</td><td>2.73</td><td>3.5702 (19)</td><td>148</td></tr><tr><td>C6—H6A···Cl1</td><td>0.99</td><td>2.8</td><td>3.751 (2)</td><td>161</td></tr><tr><td>C7—H7A···Cl1<sup>iv</sup></td><td>0.99</td><td>2.78</td><td>3.7351 (18)</td><td>162</td></tr><tr><td>C10—H10···Cl1<sup>v</sup></td><td>0.95</td><td>2.71</td><td>3.6469 (18)</td><td>168</td></tr><tr><td>C17—H17···O1<sup>vi</sup></td><td>0.95</td><td>2.57</td><td>3.437 (2)</td><td>151</td></tr></tbody></table>

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