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

Merabet, L.; Tassé, M.; Mallet-Ladeira, S.; Kaboub, L.; Malfant, I.

doi:10.1107/S205698902101183X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 12| December 2021| Pages 1296-1298

https://doi.org/10.1107/S205698902101183X

Open

access

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 Kaboub ^b and Isabelle Malfant ^a

^aLaboratoire de Chimie de Coordination, UPR-CNRS 8241, 205 route de Narbonne, 31077 Toulouse cedex, France, ^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

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 22 October 2021; accepted 8 November 2021; online 16 November 2021)

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.

Keywords: crystal structure; hydrogen bonding; π–π interactions.

CCDC reference: 2120892

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 $[\overline{1}]$ with one cationic molecule, two chloride anions, and two water 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 ).

Figure 1
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; (iii) x − 1, y + 1, z; (iv) −x + 1, −y + 1, −z + 2; (v) x, y − 1, z.]

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.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H201⋯Cl2	0.85 (3)	2.41 (3)	3.1844 (15)	152 (2)
O2—H202⋯N5	0.91 (3)	2.10 (3)	2.947 (2)	155 (2)
N2—H21⋯O2	0.94 (2)	1.89 (2)	2.804 (2)	165 (2)
N2—H22⋯Cl1ⁱ	0.86 (2)	2.31 (2)	3.1446 (17)	162.5 (17)
N4—H41⋯Cl2	0.91 (2)	2.25 (2)	3.1319 (17)	164.1 (19)
N4—H42⋯O1ⁱ	0.97 (2)	1.90 (2)	2.825 (2)	158 (2)
O1—H101⋯Cl1	0.93 (3)	2.43 (3)	3.2611 (15)	149 (2)
O1—H102⋯N3ⁱⁱ	1.00 (4)	1.93 (4)	2.920 (2)	172 (3)
C3—H3⋯Cl1ⁱⁱⁱ	0.95	2.73	3.5702 (19)	148
C6—H6A⋯Cl1	0.99	2.8	3.751 (2)	161
C7—H7A⋯Cl1^iv	0.99	2.78	3.7351 (18)	162
C10—H10⋯Cl1^v	0.95	2.71	3.6469 (18)	168
C17—H17⋯O1^vi	0.95	2.57	3.437 (2)	151
Symmetry codes: (i) ; (ii) x+1, y, z; (iii) ; (iv) ; (v) ; (vi) .

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).

Figure 2
Views of the stacking along the a axis. Orange lines indicate π–π interactions. Displacement ellipsoids are drawn at the 50% probability level.

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-pyridylmethyl)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., 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 U_iso(H) = 1.2U_eq(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.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₂₃N₅²⁺·2Cl⁻·2H₂O
M_r	428.36
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	110
a, b, c (Å)	7.1579 (6), 8.8119 (7), 17.4150 (13)
α, β, γ (°)	80.357 (3), 80.805 (3), 68.919 (3)
V (Å³)	1004.52 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.35
Crystal size (mm)	0.2 × 0.08 × 0.04

Data collection
Diffractometer	Bruker Kappa APEXII Quazar
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.660, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	29584, 6970, 4632
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.05, 0.123, 1.03
No. of reflections	6970
No. of parameters	283
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.38
Computer programs: APEX3 and SAINT (Bruker, 2012 ), SHELXT (Sheldrick 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2120892

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902101183X/tx2045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902101183X/tx2045Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902101183X/tx2045Isup3.cml

checkCIF report

Computing details top

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 top

Crystal data top

C₁₉H₂₃N₅²⁺·2Cl⁻·2H₂O	Z = 2
M_r = 428.36	F(000) = 452
Triclinic, P1	D_x = 1.416 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1579 (6) Å	Cell parameters from 4444 reflections
b = 8.8119 (7) Å	θ = 3.2–31.4°
c = 17.4150 (13) Å	µ = 0.35 mm⁻¹
α = 80.357 (3)°	T = 110 K
β = 80.805 (3)°	Needle, colourless
γ = 68.919 (3)°	0.2 × 0.08 × 0.04 mm
V = 1004.52 (14) Å³

Data collection top

Bruker Kappa APEXII Quazar diffractometer	6970 independent reflections
Radiation source: microfocus sealed tube	4632 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.097
phi and ω scans	θ_max = 32.0°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −10→10
T_min = 0.660, T_max = 0.746	k = −13→13
29584 measured reflections	l = −25→25

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.05	Hydrogen site location: mixed
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0518P)²] where P = (F_o² + 2F_c²)/3
6970 reflections	(Δ/σ)_max = 0.002
283 parameters	Δρ_max = 0.45 e Å⁻³
1 restraint	Δρ_min = −0.38 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
C1	−0.0133 (3)	1.1436 (2)	0.77592 (11)	0.0187 (4)
H1	−0.057178	1.157686	0.725689	0.022*
C2	−0.0514 (3)	1.2816 (2)	0.81173 (12)	0.0209 (4)
H2	−0.118646	1.387618	0.786614	0.025*
C3	0.0110 (3)	1.2617 (2)	0.88529 (12)	0.0209 (4)
H3	−0.013857	1.353959	0.91186	0.025*
C4	0.1098 (3)	1.1057 (2)	0.91921 (11)	0.0177 (4)
H4	0.15363	1.089007	0.969628	0.021*
C5	0.1446 (3)	0.9729 (2)	0.87872 (10)	0.0141 (3)
C6	0.2661 (3)	0.8058 (2)	0.91424 (10)	0.0154 (3)
H6A	0.405015	0.802589	0.916169	0.018*
H6B	0.20699	0.78592	0.968744	0.018*
C7	0.3958 (3)	0.5088 (2)	0.90648 (10)	0.0152 (3)
H7A	0.32656	0.482715	0.958206	0.018*
H7B	0.528732	0.510415	0.914788	0.018*
C8	0.4252 (3)	0.3788 (2)	0.85503 (10)	0.0123 (3)
C9	0.5158 (3)	0.2141 (2)	0.88081 (10)	0.0159 (4)
H9	0.555649	0.180246	0.93221	0.019*
C10	0.5467 (3)	0.1000 (2)	0.82986 (11)	0.0169 (4)
H10	0.610739	−0.013533	0.84539	0.02*
C11	0.4830 (3)	0.1539 (2)	0.75619 (10)	0.0153 (3)
H11	0.502104	0.078354	0.720177	0.018*
C12	0.3904 (3)	0.3211 (2)	0.73580 (10)	0.0126 (3)
C13	0.3100 (3)	0.3899 (2)	0.65770 (10)	0.0143 (3)
H13A	0.397572	0.323319	0.616689	0.017*
H13B	0.172891	0.385542	0.659994	0.017*
C14	0.2369 (3)	0.6343 (2)	0.55940 (10)	0.0155 (3)
H14A	0.096005	0.640498	0.55942	0.019*
H14B	0.321889	0.562201	0.519947	0.019*
C15	0.2502 (3)	0.8035 (2)	0.53686 (10)	0.0134 (3)
C16	0.2354 (3)	0.8748 (2)	0.45938 (10)	0.0161 (4)
H16	0.225967	0.815293	0.420322	0.019*
C17	0.2348 (3)	1.0342 (2)	0.44024 (11)	0.0186 (4)
H17	0.225559	1.085635	0.387808	0.022*
C18	0.2479 (3)	1.1176 (2)	0.49930 (11)	0.0197 (4)
H18	0.245914	1.227408	0.488339	0.024*
C19	0.2640 (3)	1.0358 (2)	0.57442 (11)	0.0169 (4)
H19	0.273735	1.092671	0.614568	0.02*
N1	0.3620 (2)	0.43202 (17)	0.78433 (8)	0.0120 (3)
N2	0.2743 (2)	0.67297 (17)	0.87003 (9)	0.0127 (3)
N3	0.0822 (2)	0.99031 (18)	0.80798 (9)	0.0160 (3)
N4	0.3036 (2)	0.56233 (17)	0.63771 (8)	0.0129 (3)
N5	0.2668 (2)	0.88122 (17)	0.59397 (8)	0.0146 (3)
Cl1	0.82559 (7)	0.68542 (5)	0.91223 (3)	0.01828 (11)
Cl2	0.76725 (7)	0.49614 (5)	0.62355 (3)	0.01743 (11)
O1	0.9786 (2)	0.76904 (17)	0.72866 (8)	0.0210 (3)
O2	0.4905 (2)	0.76661 (17)	0.73277 (8)	0.0205 (3)
H201	0.592 (4)	0.689 (3)	0.7158 (14)	0.038*
H202	0.389 (4)	0.807 (3)	0.7017 (16)	0.05*
H21	0.345 (3)	0.689 (2)	0.8209 (11)	0.018 (5)*
H22	0.152 (3)	0.676 (2)	0.8706 (11)	0.013 (5)*
H41	0.431 (4)	0.562 (3)	0.6375 (13)	0.026 (6)*
H42	0.216 (4)	0.622 (3)	0.6789 (12)	0.037 (7)*
H101	0.917 (4)	0.721 (3)	0.7716 (15)	0.040 (7)*
H102	1.026 (5)	0.841 (4)	0.7531 (19)	0.084 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0158 (9)	0.0187 (9)	0.0217 (9)	−0.0080 (7)	−0.0011 (7)	0.0014 (7)
C2	0.0147 (9)	0.0153 (8)	0.0302 (10)	−0.0057 (7)	0.0053 (8)	−0.0016 (7)
C3	0.0187 (10)	0.0150 (8)	0.0291 (10)	−0.0080 (7)	0.0087 (8)	−0.0084 (7)
C4	0.0159 (9)	0.0194 (9)	0.0187 (9)	−0.0077 (7)	0.0042 (7)	−0.0068 (7)
C5	0.0121 (9)	0.0145 (8)	0.0164 (8)	−0.0062 (7)	0.0024 (7)	−0.0031 (6)
C6	0.0184 (9)	0.0148 (8)	0.0142 (8)	−0.0053 (7)	−0.0028 (7)	−0.0047 (6)
C7	0.0179 (9)	0.0132 (8)	0.0133 (8)	−0.0039 (7)	−0.0046 (7)	0.0012 (6)
C8	0.0109 (8)	0.0136 (7)	0.0136 (8)	−0.0062 (6)	−0.0010 (6)	−0.0002 (6)
C9	0.0164 (9)	0.0144 (8)	0.0173 (8)	−0.0061 (7)	−0.0060 (7)	0.0032 (6)
C10	0.0135 (9)	0.0112 (8)	0.0240 (9)	−0.0035 (7)	−0.0021 (7)	0.0016 (7)
C11	0.0147 (9)	0.0122 (8)	0.0202 (9)	−0.0061 (7)	0.0005 (7)	−0.0038 (6)
C12	0.0099 (8)	0.0121 (7)	0.0160 (8)	−0.0043 (6)	−0.0005 (6)	−0.0015 (6)
C13	0.0180 (9)	0.0109 (7)	0.0156 (8)	−0.0059 (7)	−0.0022 (7)	−0.0030 (6)
C14	0.0199 (9)	0.0153 (8)	0.0120 (8)	−0.0060 (7)	−0.0053 (7)	−0.0003 (6)
C15	0.0100 (8)	0.0148 (8)	0.0138 (8)	−0.0028 (6)	−0.0017 (6)	−0.0007 (6)
C16	0.0129 (9)	0.0186 (8)	0.0145 (8)	−0.0030 (7)	−0.0016 (7)	−0.0012 (7)
C17	0.0116 (9)	0.0227 (9)	0.0174 (9)	−0.0045 (7)	−0.0013 (7)	0.0052 (7)
C18	0.0141 (9)	0.0163 (8)	0.0270 (10)	−0.0057 (7)	−0.0035 (8)	0.0038 (7)
C19	0.0147 (9)	0.0151 (8)	0.0219 (9)	−0.0062 (7)	−0.0029 (7)	−0.0014 (7)
N1	0.0113 (7)	0.0118 (6)	0.0129 (7)	−0.0042 (5)	−0.0020 (5)	−0.0004 (5)
N2	0.0147 (8)	0.0116 (7)	0.0125 (7)	−0.0044 (6)	−0.0030 (6)	−0.0018 (5)
N3	0.0153 (8)	0.0146 (7)	0.0187 (7)	−0.0069 (6)	0.0005 (6)	−0.0023 (6)
N4	0.0155 (8)	0.0111 (6)	0.0124 (7)	−0.0049 (6)	−0.0030 (6)	−0.0001 (5)
N5	0.0146 (8)	0.0142 (7)	0.0160 (7)	−0.0065 (6)	−0.0029 (6)	0.0004 (5)
Cl1	0.0158 (2)	0.01449 (19)	0.0216 (2)	−0.00422 (16)	−0.00132 (17)	0.00282 (16)
Cl2	0.0160 (2)	0.0182 (2)	0.0178 (2)	−0.00561 (17)	−0.00165 (16)	−0.00182 (16)
O1	0.0217 (8)	0.0225 (7)	0.0175 (7)	−0.0062 (6)	−0.0017 (6)	−0.0028 (5)
O2	0.0234 (8)	0.0193 (7)	0.0194 (7)	−0.0083 (6)	−0.0002 (6)	−0.0040 (5)

Geometric parameters (Å, º) top

C1—N3	1.345 (2)	C12—C13	1.507 (2)
C1—C2	1.380 (3)	C13—N4	1.487 (2)
C1—H1	0.95	C13—H13A	0.99
C2—C3	1.387 (3)	C13—H13B	0.99
C2—H2	0.95	C14—N4	1.480 (2)
C3—C4	1.379 (3)	C14—C15	1.511 (2)
C3—H3	0.95	C14—H14A	0.99
C4—C5	1.393 (2)	C14—H14B	0.99
C4—H4	0.95	C15—N5	1.340 (2)
C5—N3	1.343 (2)	C15—C16	1.393 (2)
C5—C6	1.501 (2)	C16—C17	1.387 (3)
C6—N2	1.485 (2)	C16—H16	0.95
C6—H6A	0.99	C17—C18	1.393 (3)
C6—H6B	0.99	C17—H17	0.95
C7—N2	1.488 (2)	C18—C19	1.384 (2)
C7—C8	1.507 (2)	C18—H18	0.95
C7—H7A	0.99	C19—N5	1.342 (2)
C7—H7B	0.99	C19—H19	0.95
C8—N1	1.331 (2)	N2—H21	0.937 (18)
C8—C9	1.388 (2)	N2—H22	0.86 (2)
C9—C10	1.387 (2)	N4—H41	0.91 (2)
C9—H9	0.95	N4—H42	0.967 (19)
C10—C11	1.381 (2)	O1—H101	0.93 (3)
C10—H10	0.95	O1—H102	1.00 (4)
C11—C12	1.390 (2)	O2—H201	0.85 (3)
C11—H11	0.95	O2—H202	0.91 (3)
C12—N1	1.338 (2)

N3—C1—C2	123.83 (18)	N4—C13—H13A	109.7
N3—C1—H1	118.1	C12—C13—H13A	109.7
C2—C1—H1	118.1	N4—C13—H13B	109.7
C1—C2—C3	118.32 (17)	C12—C13—H13B	109.7
C1—C2—H2	120.8	H13A—C13—H13B	108.2
C3—C2—H2	120.8	N4—C14—C15	111.73 (14)
C4—C3—C2	118.88 (17)	N4—C14—H14A	109.3
C4—C3—H3	120.6	C15—C14—H14A	109.3
C2—C3—H3	120.6	N4—C14—H14B	109.3
C3—C4—C5	119.23 (17)	C15—C14—H14B	109.3
C3—C4—H4	120.4	H14A—C14—H14B	107.9
C5—C4—H4	120.4	N5—C15—C16	122.97 (16)
N3—C5—C4	122.47 (16)	N5—C15—C14	117.68 (14)
N3—C5—C6	119.35 (15)	C16—C15—C14	119.28 (15)
C4—C5—C6	118.09 (16)	C17—C16—C15	118.87 (16)
N2—C6—C5	112.92 (14)	C17—C16—H16	120.6
N2—C6—H6A	109	C15—C16—H16	120.6
C5—C6—H6A	109	C16—C17—C18	118.78 (17)
N2—C6—H6B	109	C16—C17—H17	120.6
C5—C6—H6B	109	C18—C17—H17	120.6
H6A—C6—H6B	107.8	C19—C18—C17	118.13 (17)
N2—C7—C8	110.77 (13)	C19—C18—H18	120.9
N2—C7—H7A	109.5	C17—C18—H18	120.9
C8—C7—H7A	109.5	N5—C19—C18	123.98 (17)
N2—C7—H7B	109.5	N5—C19—H19	118
C8—C7—H7B	109.5	C18—C19—H19	118
H7A—C7—H7B	108.1	C8—N1—C12	118.13 (14)
N1—C8—C9	123.01 (15)	C6—N2—C7	111.76 (13)
N1—C8—C7	116.08 (14)	C6—N2—H21	106.6 (12)
C9—C8—C7	120.90 (15)	C7—N2—H21	105.3 (13)
C10—C9—C8	118.50 (16)	C6—N2—H22	107.3 (13)
C10—C9—H9	120.7	C7—N2—H22	108.9 (13)
C8—C9—H9	120.7	H21—N2—H22	117.1 (18)
C11—C10—C9	118.94 (16)	C5—N3—C1	117.25 (15)
C11—C10—H10	120.5	C14—N4—C13	112.47 (13)
C9—C10—H10	120.5	C14—N4—H41	108.2 (14)
C10—C11—C12	118.65 (16)	C13—N4—H41	107.4 (14)
C10—C11—H11	120.7	C14—N4—H42	112.1 (14)
C12—C11—H11	120.7	C13—N4—H42	106.6 (15)
N1—C12—C11	122.75 (16)	H41—N4—H42	110 (2)
N1—C12—C13	115.14 (14)	C15—N5—C19	117.26 (15)
C11—C12—C13	122.10 (15)	H101—O1—H102	102 (2)
N4—C13—C12	109.75 (13)	H201—O2—H202	115 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H201···Cl2	0.85 (3)	2.41 (3)	3.1844 (15)	152 (2)
O2—H202···N5	0.91 (3)	2.10 (3)	2.947 (2)	155 (2)
N2—H21···O2	0.94 (2)	1.89 (2)	2.804 (2)	165 (2)
N2—H22···Cl1ⁱ	0.86 (2)	2.31 (2)	3.1446 (17)	162.5 (17)
N4—H41···Cl2	0.91 (2)	2.25 (2)	3.1319 (17)	164.1 (19)
N4—H42···O1ⁱ	0.97 (2)	1.90 (2)	2.825 (2)	158 (2)
O1—H101···Cl1	0.93 (3)	2.43 (3)	3.2611 (15)	149 (2)
O1—H102···N3ⁱⁱ	1.00 (4)	1.93 (4)	2.920 (2)	172 (3)
C3—H3···Cl1ⁱⁱⁱ	0.95	2.73	3.5702 (19)	148
C6—H6A···Cl1	0.99	2.8	3.751 (2)	161
C7—H7A···Cl1^iv	0.99	2.78	3.7351 (18)	162
C10—H10···Cl1^v	0.95	2.71	3.6469 (18)	168
C17—H17···O1^vi	0.95	2.57	3.437 (2)	151

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.

References

Afshar, R. K., Patra, A. K., Olmstead, M. M. & Mascharak, P. K. (2004). Inorg. Chem. 43, 5736–5743. CSD CrossRef PubMed CAS Google Scholar
Bruker (2012). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Darbre, T., Dubs, C., Rusanov, E. & Stoeckli-Evans, H. (2002). Eur. J. Inorg. Chem. pp. 3284–3291. CrossRef Google Scholar
Eroy-Reveles, A. A., Hoffman-Luca, C. G. & Mascharak, P. K. (2007). Dalton Trans. pp. 5268–5274. Google Scholar
Fry, N. L. & Mascharak, P. K. (2011). Acc. Chem. Res. 44, 289–298. Web of Science CrossRef CAS PubMed Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gruenwedel, D. W. (1968). Inorg. Chem. 7, 495–501. CrossRef CAS Web of Science Google Scholar
Halpenny, G. M., Olmstead, M. M. & Mascharak, P. K. (2007). Inorg. Chem. 46, 6601–6606. CSD CrossRef PubMed CAS Google Scholar
Harrop, T. C., Olmstead, M. M. & Mascharak, P. K. (2005). Inorg. Chem. 44, 6918–6920. CSD CrossRef PubMed CAS Google Scholar
Heilman, B. J., St John, J., Oliver, S. R. J. & Mascharak, P. K. (2012). J. Am. Chem. Soc. 134, 11573–11582. CrossRef CAS PubMed Google Scholar
Hoffman-Luca, C. G., Eroy-Reveles, A. A., Alvarenga, J. & Mascharak, P. K. (2009). Inorg. Chem. 48, 9104–9111. Web of Science PubMed CAS Google Scholar
Jain, S. L., Bhattacharyya, P., Milton, H. L., Slawin, A. M. Z., Crayston, J. A. & Woollins, J. D. (2004). Dalton Trans. pp. 862–871. Web of Science CSD CrossRef PubMed Google Scholar
Kobayashi, T., Yaita, T., Sugo, Y., Suda, H., Suzuki, S., Fujii, Y. & Nakano, Y. (2006). J. Heterocycl. Chem. 43, 549–557. CSD CrossRef CAS 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
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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Martell, A. E. (1967). Editor. Advances in Chemistry, pp. 272–294. Washington: American Chemical Society. Google Scholar
Newkome, G. R., Gupta, V. K., Fronczek, F. R. & Pappalardo, S. (1984). Inorg. Chem. 23, 2400–2408. CSD CrossRef CAS Web of Science Google Scholar
Patra, A. K. & Mascharak, P. K. (2003). Inorg. Chem. 42, 7363–7365. CSD CrossRef PubMed CAS Google Scholar
Qi, J. Y., Chen, J., Yang, Q. Y., Zhou, Z. Y. & Chan, A. S. C. (2002). Acta Cryst. E58, o1232–o1233. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rose, M. J. & Mascharak, P. K. (2008a). Coord. Chem. Rev. 252, 2093–2114. CrossRef CAS PubMed Google Scholar
Rose, M. J. & Mascharak, P. K. (2008b). Curr. Opin. Chem. Biol. 12, 238–244. CrossRef PubMed CAS Google Scholar
Schaniel, D., Imlau, M., Weisemoeller, T., Woike, T., Krämer, K. W. & Güdel, H. U. (2007). Adv. Mater. 19, 723–726. CrossRef CAS 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals 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.