Triclinic polymorph of bis­[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] tetra­chloridocadmium(II)

Vassilyeva, O.Y.; Buvaylo, E.A.; Kokozay, V.N.; Goreshnik, E.A.

doi:10.1107/S2056989024009654

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ISSN: 2056-9890

Volume 80| Part 11| November 2024| Pages 1125-1129

https://doi.org/10.1107/S2056989024009654

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Triclinic polymorph of bis[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] tetrachloridocadmium(II)

Olga Yu. Vassilyeva,^a ^* Elena A. Buvaylo,^a Vladimir N. Kokozay ^a and Evgeny A. Goreshnik ^b

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, and ^bDepartment of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
^*Correspondence e-mail: vassilyeva@univ.kiev.ua

Edited by G. Ferrence, Illinois State University, USA (Received 11 July 2024; accepted 30 September 2024; online 4 October 2024)

The crystal structure of the title organic–inorganic hybrid salt, (C₁₃H₁₂N₃)₂[CdCl₄], (I), has been reported with four molecules in the asymmetric unit in a monoclinic cell [Vassilyeva et al. (2021 ). RSC Advances, 11, 7713–7722]. While using two different aldehydes in the oxidative cyclization–condensation involving CH₃NH₂·HCl to prepare a new monovalent cation with the imidazo[1,5-a]pyridinium skeleton, a new polymorph was obtained for (I) in space group P1 and a unit cell with approximately half the volume of the monoclinic form. The structural configurations of the two crystallographically non-equivalent organic cations as well as the geometry of the moderately distorted tetrahedral CdCl₄^2– dianion show minor changes. In the crystal, identically stacked cations and tetrachlorocadmate anions form separate columns parallel to the a axis. The loose packing of the anions leads to a minimal separation of approximately 9.53 Å between the metal atoms in the triclinic form versus 7.51 Å in the monoclinic one, indicating that the latter is packed slightly more densely. The two forms also differ by aromatic stacking motifs. Similar to the monoclinic polymorph, the triclinic one excited at 364 nm shows an intense unsymmetrical photoluminescent band with maximum at 403 nm and a full width at half maximum of 51 nm in the solid state.

Keywords: crystal structure; Cd^II; organic–inorganic hybrid; tetrahalometallate; π–π stacking; photoluminescence..

CCDC reference: 2388010

1. Chemical context

Polymorphism – the existence of more than one crystal structure for a given material – is of interest in many research areas and applications ranging from crystallography and solid-state chemistry, materials science, and pharmaceuticals, to agricultural chemistry and food industry. Understanding differences in polymorphs properties is essential for selecting the right form for specific applications, optimizing material performance, and providing better predictive models for crystal formation (Bergeron et al., 2021 ; Cai et al., 2023 ; Cruz-Cabeza et al., 2020 ). The control of the molecular assemblies during the crystallization process of a polymorphic cyclometalated Ir^III ethylenediamine complex was demonstrated as an efficient tool to modulate emission and limit the aggregation-quenching phenomenum in the solid crystalline state (Talarico et al., 2010 ). The intermolecular interactions in two polymorphic modifications of a platinum emitter with 3-(benzen-2-idyl)-1-methyl-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-ylidene ligand have been shown to strongly affect its photophysical properties and even make the polymorphs separable (Pinter et al., 2021 ).

In a previous study, we used organic–inorganic hybrid salts made of imidazo[1,5-a]pyridinium-based cations and tetrachlorocadmate anions as fluorescent agents to modify cross-linked polyurethane (CPU; Vassilyeva et al., 2021). The use of ionic compounds immobilized in situ in the CPU in low content (1 wt%) ensured excellent dispersion of components in the polymer matrix so that uniformly luminescent films were fabricated. In [L]₂[CdCl₄], 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium cations (L⁺) resulted from the oxidative cyclization–condensation involving CH₃NH₂·HCl and 2-pyridinecarbaldehyde (2-PCA) in methanol. The developed synthetic approach enables the systematic modification of the photoluminescent properties of imidazo[1,5-a]pyridine species through varying substituents on the polyheterocyclic core as well as through introduction of different metal ions (Vassilyeva et al., 2020 ). In the present work, an attempt to prepare another electron-deficient monovalent cation with the imidazo[1,5-a]pyridinium skeleton by replacing half the amount of 2-PCA with 2-hydroxy-3-methoxybenzaldehyde in the reaction with CH₃NH₂·HCl appeared unsuccessful due to presumably insufficient reaction time. The isolated compound was crystallographically identified as a new triclinic polymorph of [L]₂[CdCl₄], (I), which was reported previously in space group P2₁/c [Cambridge Structural Database (CSD) refcode GOSYUL; Vassilyeva et al., 2021]. The photoluminescent properties of the monoclinic and triclinic polymorphs in the solid state were found to be very similar, suggesting that structural differences of the two modifications of the organic–inorganic hybrid material are not significant enough to affect their photophysical properties.

2. Structural commentary

Triclinic crystals of [L]₂[CdCl₄], which crystallize in the space group P $[\overline{1}]$ , contain discrete organic cations and tetrachlorocadmate anions (Fig. 1). The structural configurations of two crystallographically non-equivalent L1(N1, N2) and L2(N4, N5) cations are similar with small differences in bond distances and angles. The pyridinium rings in the flattened fused cores have expected bond lengths; the bond distances in the imidazolium entities are in the range 1.341 (3)–1.399 (3) Å. The five- and six-membered rings in the cores are almost coplanar showing dihedral angles between them of approximately 2.46 (L1) and 2.08° (L2). The geometric parameters of the cations are highly comparable to those found in monoclinic GOSYUL except for the dihedral angles between the pendant pyridyl rings and the planes of the remainder of the cation. The dihedral angles are about 43.35 and 40.04° for L1 and L2, respectively, in (I) and 36.4 (2), and 35.9 (2)° for the two crystallographically non-equivalent cations in GOSYUL. The tetrahedral CdCl₄^2– anion is more distorted compared with the anion geometry in the monoclinic polymorph. The Cd—Cl distances vary from 2.4436 (7) to 2.4895 (6) Å and the Cl—Cd—Cl angles fall in the range 100.36 (2)–115.56 (2)° (Table 1). The maximum differences in the lengths and angles are 0.0459 (7) Å and 15.2 (2)°, respectively, while those in GOSYUL amount to 0.048 Å and 4.94°.

Table 1
Selected geometric parameters (Å, °)

Cd1—Cl1	2.4436 (7)	Cd1—Cl3	2.4496 (7)
Cd1—Cl2	2.4448 (6)	Cd1—Cl4	2.4895 (6)

Cl1—Cd1—Cl2	108.30 (2)	Cl2—Cd1—Cl3	110.40 (2)
Cl1—Cd1—Cl3	113.98 (2)	Cl2—Cd1—Cl4	115.56 (2)
Cl1—Cd1—Cl4	108.24 (2)	Cl3—Cd1—Cl4	100.36 (2)

Figure 1
Molecular structure and labelling of the triclinic polymorph of [L]₂[CdCl₄] with ellipsoids at the 50% probability level.

3. Supramolecular features

In the crystal, identically stacked L1, L2 cations and CdCl₄^2– anions form separate columns parallel to the a axis (Fig. 2). The cations from neighbouring columns are involved in aromatic stacking between the offset pyridinium and imidazolium entities of the fused cores with ring–centroid distances of 3.607 (1) and 3.683 (1) Å. The π–π stacking between the adjacent pendant pyridyl rings of L1 and L2, which are twisted to each other by approximately 43.81°, is negligible [the ring-centroid separation is 4.344 (1) Å]. The loose packing of the tetrachlorocadmate anions leads to a closest separation of approximately 9.53 Å between the metal atoms in the crystal. This separation in GOSYUL is equal to 7.51 Å, indicating that the latter is packed slightly more densely, while the spatial organization of both polymorphs remains rather similar (Figs. 2, 3). The title compound lacks classical hydrogen-bonding interactions. Additional structure consolidation is provided by several C—H⋯Cl—Cd hydrogen bonds between organic and inorganic counterparts (Table 2) at H⋯Cl distances below the van der Waals contact limit of 2.85 Å (Mantina et al., 2009 ). The longer contacts are considered a result of the crystal packing.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4C⋯Cl3ⁱ	0.98	2.72	3.664 (3)	162
C5—H5⋯Cl3	0.95	2.71	3.446 (2)	135
C7—H7⋯Cl4ⁱⁱ	0.95	2.72	3.651 (3)	166
C8—H8⋯Cl2ⁱⁱ	0.95	2.75	3.518 (3)	138
C12—H12⋯Cl4ⁱⁱⁱ	0.95	2.70	3.644 (2)	171
C17—H17A⋯Cl4^iv	0.98	2.79	3.695 (3)	155
C17—H17C⋯Cl1^v	0.98	2.80	3.721 (3)	158
C23—H23⋯Cl4^iv	0.95	2.69	3.576 (3)	156
C26—H26⋯Cl2ⁱⁱ	0.95	2.84	3.689 (3)	149
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 2
Fragment of the crystal packing of the triclinic polymorph of [L]₂[CdCl₄] viewed along the a axis and showing the L1 and L2 independent cations (green and blue) joined by aromatic stacking and the intermolecular C—H⋯Cl contacts given as blue dashed lines.

Figure 3
Fragment of the crystal packing of the monoclinic polymorph of [L]₂[CdCl₄], GOSYUL, viewed along the a axis with the independent cations shown in green and blue.

4. Database survey

More than 50 structures of salts with imidazo[1,5-a]pyridinium-based cations have been deposited in the CSD (Version 5.45, update March 2024; Groom et al., 2016 ) with above half of them being a contribution from our research group. These span Mn, Co, Fe, Ni, Cu, Zn, Cd, Pb and Sn halometalates (Cl, Br, I) with 2-methylimidazo[1,5-a]pyridin-2-ium, 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium (L⁺), 2-hydroxyethylimidazo[1,5-a]pyridin-2-ium and 2,2′-(ethane-1,2-diyl)bis(imidazo[1,5-a]pyridin-2-ium) cations. Most of them either are built of cations and anions arranged in separate columns similar to (I) or show pseudo-layered structures with alternating sheets of organic cations and of halometalate anions (Buvaylo et al., 2015 ; Vassilyeva et al., 2019 , 2021). Lead halide hybrid perovskites from the series are distinguished by their one-dimensional architecture (Vassilyeva et al., 2020, 2023 ).

Organic salts with imidazo[1,5-a]pyridinium cations having varying substituents on the imidazolium ring and inorganic anions such as hexafluorophosphate or perchlorate constitute another large group. The structures similar to (I) are 2-(2-pyridyl)-N³-(4-chlorophenyl)imidazo[1,5-a]pyridinium perchlorate (YIHFEB; Mitra et al., 2007 ) and 2-(2-(1H-imidazol-3-ium-5-yl)ethyl)-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium diperchlorate (UREYIA; Türkyılmaz et al., 2011 ) with chlorophenyl and ethylimidazolium substituents in place of the methyl group in L⁺, respectively. 3-(Pyridin-2-yl)imidazo[1,5-a]pyridine, a neutral L molecule lacking the methyl group, was reported to crystallize in orthorhombic space group P2₁2₁2₁ (PRIMPY; Golic et al., 1980 ). It acts as a κ²(N,N) chelator to form an Mn^II complex (Álvarez et al., 2012 ) but can be easily released from the complex by boiling its suspension in water.

The ubiquitous Cd tetrachloride anion is found in more than 300 CSD structures. The mean Cd—Cl bond length of 2.46 Å in (I) is comparable to distances found in the database for other salts containing isolated CdCl₄^2– tetrahedral anions (Cd—Cl distances for this anion vary from 2.38 to 2.57 Å with the average lengths falling in the narrow range 2.43–2.48 Å).

5. Photoluminescence measurements

The photoluminescence spectrum of the crystalline powder sample of (I) excited at 364 nm (spectrofluorophotometer RF-6000, Shimadzu) shows a broad intense unsymmetrical band with maximum at 403 nm and a full width at half maximum of 51 nm (Fig. 4). The spectroscopic data are strictly comparable to those of the monoclinic form of (I) (Vassilyeva et al., 2021), indicating that the structural variations of the two polymorphs of (I) are insufficient to result in different photophysical properties.

Figure 4
The excitation (dotted) and emission spectra (solid) of a powdered sample of the triclinic polymorph of [L]₂[CdCl₄] at room temperature.

6. Synthesis and crystallization

2-PCA (0.19 ml, 2.0 mmol) was added dropwise to CH₃NH₂·HCl (0.27 g, 4.0 mmol) and 2-hydroxy-3-methoxybenzaldehyde (0.30 g, 2.0 mmol) dissolved in 10 ml of methanol in a 50 ml conical flask. The solution was stirred magnetically for half an hour at 323 K. Then, solid CdCl₂·2.5H₂O (0.23 g, 1.0 mmol) was added to the flask and the reaction mixture was stirred for another half an hour at 323 K, filtered and left to evaporate. Colourless shiny blocks of (I) suitable for X-ray crystallography formed in several hours. The crystals were filtered off, washed with diethyl ether and dried in air. Yield: 0.16 g, 23% (based on cadmium). ¹H NMR (400 MHz, DMSO-d₆): δ (ppm) 8.93 (d, 1H, J = 3.9 Hz, H3), 8.70 (d, 1H, J = 9.3 Hz, H8), 8.56 (s, 1H, H3), 8.25–8.19 (m, 2H, H10+H11), 8.03 (d, 1H, J = 9.3 Hz, H5), 7.76–7.73 (m, 1H, H2), 7.37 (t, 1H, J = 8.1 Hz, H6), 7.23 (t, 1H, J = 7.1 Hz, H7), 4.31 (s, 3H, CH₃). Analysis calculated for C₂₆H₂₄Cl₄N₆Cd (674.73): C 46.28; H 3.59; N 12.46%. Found: C 45.78; H 3.68; N 12.28%.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Anisotropic displacement parameters were employed for the non-hydrogen atoms. All hydrogen atoms were added at calculated positions and refined by use of a riding model with isotropic displacement parameters based on those of the parent atom (C—H = 0.95 Å, U_iso(H) = 1.2U_eqC for CH, C—H = 0.98 Å, U_iso(H) = 1.5U_eqC for CH₃). Idealized methyl groups were refined as rotating groups.

Table 3
Experimental details

Crystal data
Chemical formula	(C₁₃H₁₂N₃)₂[CdCl₄]
M_r	674.71
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	9.6288 (3), 11.5103 (4), 13.0302 (5)
α, β, γ (°)	78.734 (3), 81.153 (3), 77.708 (3)
V (Å³)	1374.33 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.21
Crystal size (mm)	0.44 × 0.27 × 0.20

Data collection
Diffractometer	New Gemini, Dual, Cu at home/near, Atlas
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.713, 0.852
No. of measured, independent and observed [I > 2σ(I)] reflections	23842, 6206, 5235
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.065, 1.09
No. of reflections	6206
No. of parameters	336
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.54
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXT2014/4 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2388010

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009654/ej2007sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009654/ej2007Isup2.hkl

checkCIF report

Computing details top

Bis[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] tetrachloridocadmium(II) top

Crystal data top

(C₁₃H₁₂N₃)₂[CdCl₄]	Z = 2
M_r = 674.71	F(000) = 676
Triclinic, P1	D_x = 1.630 Mg m⁻³
a = 9.6288 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5103 (4) Å	Cell parameters from 12802 reflections
c = 13.0302 (5) Å	θ = 2.5–28.5°
α = 78.734 (3)°	µ = 1.21 mm⁻¹
β = 81.153 (3)°	T = 150 K
γ = 77.708 (3)°	Irregular, yellow
V = 1374.33 (9) Å³	0.44 × 0.27 × 0.20 mm

Data collection top

New Gemini, Dual, Cu at home/near, Atlas diffractometer	6206 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	5235 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 10.6426 pixels mm^-1	θ_max = 28.9°, θ_min = 2.2°
ω scans	h = −13→12
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2023)	k = −14→15
T_min = 0.713, T_max = 0.852	l = −17→16
23842 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0175P)² + 0.519P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
6206 reflections	Δρ_max = 0.67 e Å⁻³
336 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints

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.

Refinement. 1. Fixed Uiso At 1.2 times of: All C(H) groups At 1.5 times of: All C(H,H,H) groups 2.a Aromatic/amide H refined with riding coordinates: C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24), C25(H25), C26(H26) 2.b Idealised Me refined as rotating group: C4(H4A,H4B,H4C), C17(H17A,H17B,H17C)

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

	x	y	z	U_iso*/U_eq
Cd1	0.55171 (2)	0.71231 (2)	0.76703 (2)	0.01848 (6)
Cl1	0.46428 (8)	0.71615 (6)	0.59977 (5)	0.03304 (17)
Cl2	0.63522 (6)	0.50197 (5)	0.84357 (5)	0.02149 (13)
Cl3	0.37442 (6)	0.81359 (5)	0.89287 (5)	0.02465 (14)
Cl4	0.73342 (7)	0.84425 (5)	0.73399 (5)	0.02646 (15)
N1	0.2818 (2)	0.23733 (16)	0.94071 (16)	0.0168 (4)
N2	0.1226 (2)	0.39279 (17)	0.88997 (16)	0.0181 (4)
N3	0.1461 (2)	0.09936 (16)	0.83280 (16)	0.0187 (4)
C1	0.1543 (2)	0.2704 (2)	0.90398 (19)	0.0169 (5)
C2	0.2345 (3)	0.4354 (2)	0.9184 (2)	0.0196 (5)
C3	0.3324 (3)	0.3361 (2)	0.95090 (19)	0.0188 (5)
H3	0.420091	0.335580	0.976096	0.023*
C4	0.3592 (3)	0.1135 (2)	0.9694 (2)	0.0238 (6)
H4A	0.404112	0.081565	0.905313	0.036*
H4B	0.292051	0.062933	1.008614	0.036*
H4C	0.433169	0.113245	1.013424	0.036*
C5	0.2286 (3)	0.5618 (2)	0.9053 (2)	0.0223 (6)
H5	0.303810	0.592783	0.923318	0.027*
C6	0.1138 (3)	0.6367 (2)	0.8666 (2)	0.0262 (6)
H6	0.108142	0.721477	0.857448	0.031*
C7	0.0009 (3)	0.5911 (2)	0.8392 (2)	0.0256 (6)
H7	−0.079016	0.645928	0.812363	0.031*
C8	0.0050 (3)	0.4727 (2)	0.8504 (2)	0.0251 (6)
H8	−0.071002	0.443354	0.831666	0.030*
C9	0.0679 (2)	0.1897 (2)	0.87987 (19)	0.0167 (5)
C10	−0.0786 (3)	0.2061 (2)	0.9062 (2)	0.0232 (6)
H10	−0.128823	0.270389	0.941296	0.028*
C11	−0.1499 (3)	0.1252 (2)	0.8796 (2)	0.0284 (6)
H11	−0.250913	0.134240	0.894811	0.034*
C12	−0.0721 (3)	0.0318 (2)	0.8310 (2)	0.0297 (6)
H12	−0.118633	−0.024474	0.811981	0.036*
C13	0.0742 (3)	0.0213 (2)	0.8105 (2)	0.0242 (6)
H13	0.127099	−0.044787	0.778788	0.029*
N4	0.2726 (2)	0.08422 (17)	0.58031 (17)	0.0225 (5)
N5	0.3173 (2)	0.23872 (17)	0.63174 (16)	0.0183 (4)
N6	0.0130 (2)	0.34248 (19)	0.63388 (17)	0.0285 (5)
C14	0.2197 (3)	0.2002 (2)	0.5887 (2)	0.0210 (5)
C15	0.4022 (3)	0.0479 (2)	0.6177 (2)	0.0240 (6)
H15	0.460532	−0.030079	0.620321	0.029*
C16	0.4329 (3)	0.1443 (2)	0.65074 (19)	0.0203 (5)
C17	0.2027 (3)	0.0022 (2)	0.5410 (2)	0.0327 (7)
H17A	0.214666	0.017799	0.463828	0.049*
H17B	0.100473	0.015804	0.567009	0.049*
H17C	0.246445	−0.081565	0.566185	0.049*
C18	0.5494 (3)	0.1647 (2)	0.6946 (2)	0.0262 (6)
H18	0.628307	0.101148	0.709293	0.031*
C19	0.5467 (3)	0.2756 (2)	0.7152 (2)	0.0275 (6)
H19	0.624016	0.289983	0.745308	0.033*
C20	0.4292 (3)	0.3712 (2)	0.6923 (2)	0.0258 (6)
H20	0.430482	0.449280	0.705267	0.031*
C21	0.3161 (3)	0.3527 (2)	0.6525 (2)	0.0217 (5)
H21	0.237135	0.416540	0.638813	0.026*
C22	0.0784 (3)	0.2703 (2)	0.5643 (2)	0.0222 (5)
C23	0.0180 (3)	0.2607 (2)	0.4770 (2)	0.0317 (6)
H23	0.069903	0.212218	0.427328	0.038*
C24	−0.1193 (3)	0.3230 (3)	0.4639 (2)	0.0376 (7)
H24	−0.164382	0.316423	0.405925	0.045*
C25	−0.1891 (3)	0.3942 (3)	0.5354 (2)	0.0367 (7)
H25	−0.284419	0.436304	0.529123	0.044*
C26	−0.1179 (3)	0.4039 (3)	0.6174 (2)	0.0369 (7)
H26	−0.165158	0.457220	0.664470	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01851 (10)	0.01593 (10)	0.02228 (11)	−0.00275 (7)	−0.00489 (7)	−0.00489 (7)
Cl1	0.0463 (4)	0.0322 (4)	0.0245 (4)	−0.0092 (3)	−0.0153 (3)	−0.0035 (3)
Cl2	0.0204 (3)	0.0156 (3)	0.0287 (4)	−0.0012 (2)	−0.0057 (3)	−0.0044 (3)
Cl3	0.0189 (3)	0.0210 (3)	0.0350 (4)	0.0002 (2)	−0.0018 (3)	−0.0122 (3)
Cl4	0.0227 (3)	0.0189 (3)	0.0393 (4)	−0.0075 (2)	−0.0048 (3)	−0.0040 (3)
N1	0.0156 (11)	0.0138 (9)	0.0216 (11)	−0.0020 (8)	−0.0046 (8)	−0.0037 (8)
N2	0.0142 (10)	0.0168 (10)	0.0255 (12)	−0.0008 (8)	−0.0058 (9)	−0.0079 (9)
N3	0.0222 (11)	0.0131 (10)	0.0214 (12)	−0.0042 (8)	−0.0026 (9)	−0.0036 (9)
C1	0.0153 (13)	0.0165 (11)	0.0203 (13)	−0.0031 (9)	−0.0019 (10)	−0.0063 (10)
C2	0.0176 (13)	0.0195 (12)	0.0255 (14)	−0.0041 (10)	−0.0053 (10)	−0.0097 (11)
C3	0.0175 (13)	0.0157 (12)	0.0260 (14)	−0.0053 (10)	−0.0075 (10)	−0.0040 (11)
C4	0.0248 (14)	0.0130 (11)	0.0331 (16)	0.0000 (10)	−0.0101 (12)	−0.0011 (11)
C5	0.0265 (14)	0.0181 (12)	0.0253 (15)	−0.0093 (11)	−0.0030 (11)	−0.0051 (11)
C6	0.0342 (16)	0.0144 (12)	0.0304 (16)	−0.0003 (11)	−0.0064 (12)	−0.0068 (11)
C7	0.0240 (14)	0.0220 (13)	0.0285 (15)	0.0053 (11)	−0.0078 (11)	−0.0058 (11)
C8	0.0199 (14)	0.0255 (14)	0.0321 (16)	−0.0016 (11)	−0.0103 (11)	−0.0077 (12)
C9	0.0192 (13)	0.0172 (12)	0.0152 (13)	−0.0077 (10)	−0.0037 (10)	−0.0003 (10)
C10	0.0194 (14)	0.0278 (14)	0.0250 (15)	−0.0070 (11)	−0.0013 (11)	−0.0091 (12)
C11	0.0197 (14)	0.0370 (16)	0.0322 (16)	−0.0156 (12)	−0.0021 (12)	−0.0044 (13)
C12	0.0358 (17)	0.0301 (15)	0.0313 (16)	−0.0214 (13)	−0.0083 (13)	−0.0050 (13)
C13	0.0356 (16)	0.0161 (12)	0.0242 (15)	−0.0082 (11)	−0.0054 (12)	−0.0059 (11)
N4	0.0279 (12)	0.0167 (10)	0.0235 (12)	−0.0037 (9)	−0.0035 (9)	−0.0051 (9)
N5	0.0217 (11)	0.0153 (10)	0.0168 (11)	−0.0033 (8)	0.0008 (8)	−0.0021 (8)
N6	0.0257 (13)	0.0306 (12)	0.0241 (13)	0.0019 (10)	−0.0006 (10)	−0.0026 (10)
C14	0.0237 (14)	0.0206 (12)	0.0182 (14)	−0.0035 (10)	−0.0023 (10)	−0.0029 (11)
C15	0.0253 (15)	0.0188 (12)	0.0246 (15)	0.0017 (10)	−0.0019 (11)	−0.0031 (11)
C16	0.0236 (14)	0.0160 (12)	0.0184 (13)	−0.0007 (10)	0.0007 (10)	−0.0012 (10)
C17	0.0463 (18)	0.0232 (14)	0.0331 (17)	−0.0091 (12)	−0.0103 (14)	−0.0090 (12)
C18	0.0233 (14)	0.0266 (14)	0.0266 (15)	−0.0001 (11)	−0.0022 (11)	−0.0053 (12)
C19	0.0257 (15)	0.0318 (15)	0.0267 (15)	−0.0109 (12)	−0.0018 (11)	−0.0039 (12)
C20	0.0300 (15)	0.0211 (13)	0.0271 (15)	−0.0090 (11)	0.0031 (12)	−0.0066 (11)
C21	0.0259 (14)	0.0133 (12)	0.0236 (14)	−0.0019 (10)	0.0017 (11)	−0.0028 (10)
C22	0.0232 (14)	0.0192 (12)	0.0219 (14)	−0.0038 (10)	−0.0020 (11)	0.0010 (11)
C23	0.0366 (17)	0.0300 (15)	0.0280 (16)	−0.0036 (12)	−0.0081 (13)	−0.0033 (13)
C24	0.0360 (18)	0.0420 (17)	0.0339 (18)	−0.0085 (14)	−0.0133 (14)	0.0042 (14)
C25	0.0230 (15)	0.0453 (18)	0.0331 (18)	−0.0020 (13)	−0.0030 (13)	0.0095 (14)
C26	0.0288 (16)	0.0429 (17)	0.0296 (17)	0.0052 (13)	0.0033 (13)	−0.0018 (14)

Geometric parameters (Å, º) top

Cd1—Cl1	2.4436 (7)	C12—C13	1.376 (4)
Cd1—Cl2	2.4448 (6)	C13—H13	0.9500
Cd1—Cl3	2.4496 (7)	N4—C14	1.343 (3)
Cd1—Cl4	2.4895 (6)	N4—C15	1.361 (3)
N1—C1	1.339 (3)	N4—C17	1.474 (3)
N1—C3	1.365 (3)	N5—C14	1.353 (3)
N1—C4	1.467 (3)	N5—C16	1.395 (3)
N2—C1	1.359 (3)	N5—C21	1.388 (3)
N2—C2	1.400 (3)	N6—C22	1.344 (3)
N2—C8	1.395 (3)	N6—C26	1.333 (3)
N3—C9	1.341 (3)	C14—C22	1.473 (3)
N3—C13	1.341 (3)	C15—H15	0.9500
C1—C9	1.475 (3)	C15—C16	1.367 (3)
C2—C3	1.360 (3)	C16—C18	1.414 (3)
C2—C5	1.421 (3)	C17—H17A	0.9800
C3—H3	0.9500	C17—H17B	0.9800
C4—H4A	0.9800	C17—H17C	0.9800
C4—H4B	0.9800	C18—H18	0.9500
C4—H4C	0.9800	C18—C19	1.350 (4)
C5—H5	0.9500	C19—H19	0.9500
C5—C6	1.348 (3)	C19—C20	1.424 (4)
C6—H6	0.9500	C20—H20	0.9500
C6—C7	1.421 (4)	C20—C21	1.347 (3)
C7—H7	0.9500	C21—H21	0.9500
C7—C8	1.334 (3)	C22—C23	1.387 (4)
C8—H8	0.9500	C23—H23	0.9500
C9—C10	1.381 (3)	C23—C24	1.382 (4)
C10—H10	0.9500	C24—H24	0.9500
C10—C11	1.389 (3)	C24—C25	1.364 (4)
C11—H11	0.9500	C25—H25	0.9500
C11—C12	1.377 (4)	C25—C26	1.389 (4)
C12—H12	0.9500	C26—H26	0.9500

Cl1—Cd1—Cl2	108.30 (2)	N3—C13—C12	123.6 (2)
Cl1—Cd1—Cl3	113.98 (2)	N3—C13—H13	118.2
Cl1—Cd1—Cl4	108.24 (2)	C12—C13—H13	118.2
Cl2—Cd1—Cl3	110.40 (2)	C14—N4—C15	110.5 (2)
Cl2—Cd1—Cl4	115.56 (2)	C14—N4—C17	126.9 (2)
Cl3—Cd1—Cl4	100.36 (2)	C15—N4—C17	122.6 (2)
C1—N1—C3	110.67 (19)	C14—N5—C16	109.32 (19)
C1—N1—C4	126.46 (19)	C14—N5—C21	129.3 (2)
C3—N1—C4	122.86 (19)	C21—N5—C16	121.3 (2)
C1—N2—C2	109.13 (19)	C26—N6—C22	116.7 (2)
C1—N2—C8	130.01 (19)	N4—C14—N5	106.7 (2)
C8—N2—C2	120.81 (19)	N4—C14—C22	127.3 (2)
C9—N3—C13	116.4 (2)	N5—C14—C22	125.9 (2)
N1—C1—N2	106.48 (18)	N4—C15—H15	126.3
N1—C1—C9	126.6 (2)	N4—C15—C16	107.5 (2)
N2—C1—C9	126.9 (2)	C16—C15—H15	126.3
N2—C2—C5	119.3 (2)	N5—C16—C18	119.2 (2)
C3—C2—N2	106.19 (19)	C15—C16—N5	106.1 (2)
C3—C2—C5	134.5 (2)	C15—C16—C18	134.8 (2)
N1—C3—H3	126.2	N4—C17—H17A	109.5
C2—C3—N1	107.5 (2)	N4—C17—H17B	109.5
C2—C3—H3	126.2	N4—C17—H17C	109.5
N1—C4—H4A	109.5	H17A—C17—H17B	109.5
N1—C4—H4B	109.5	H17A—C17—H17C	109.5
N1—C4—H4C	109.5	H17B—C17—H17C	109.5
H4A—C4—H4B	109.5	C16—C18—H18	120.5
H4A—C4—H4C	109.5	C19—C18—C16	119.1 (2)
H4B—C4—H4C	109.5	C19—C18—H18	120.5
C2—C5—H5	120.8	C18—C19—H19	119.7
C6—C5—C2	118.5 (2)	C18—C19—C20	120.6 (2)
C6—C5—H5	120.8	C20—C19—H19	119.7
C5—C6—H6	119.5	C19—C20—H20	119.4
C5—C6—C7	121.1 (2)	C21—C20—C19	121.1 (2)
C7—C6—H6	119.5	C21—C20—H20	119.4
C6—C7—H7	119.4	N5—C21—H21	120.6
C8—C7—C6	121.3 (2)	C20—C21—N5	118.7 (2)
C8—C7—H7	119.4	C20—C21—H21	120.6
N2—C8—H8	120.5	N6—C22—C14	114.6 (2)
C7—C8—N2	119.0 (2)	N6—C22—C23	123.2 (2)
C7—C8—H8	120.5	C23—C22—C14	122.3 (2)
N3—C9—C1	113.4 (2)	C22—C23—H23	120.7
N3—C9—C10	124.4 (2)	C24—C23—C22	118.6 (3)
C10—C9—C1	122.2 (2)	C24—C23—H23	120.7
C9—C10—H10	121.2	C23—C24—H24	120.5
C9—C10—C11	117.6 (2)	C25—C24—C23	119.1 (3)
C11—C10—H10	121.2	C25—C24—H24	120.5
C10—C11—H11	120.4	C24—C25—H25	120.7
C12—C11—C10	119.1 (2)	C24—C25—C26	118.7 (3)
C12—C11—H11	120.4	C26—C25—H25	120.7
C11—C12—H12	120.6	N6—C26—C25	123.7 (3)
C13—C12—C11	118.9 (2)	N6—C26—H26	118.1
C13—C12—H12	120.6	C25—C26—H26	118.1

N1—C1—C9—N3	−40.5 (3)	N4—C14—C22—N6	138.5 (3)
N1—C1—C9—C10	138.2 (3)	N4—C14—C22—C23	−40.7 (4)
N2—C1—C9—N3	137.1 (2)	N4—C15—C16—N5	0.0 (3)
N2—C1—C9—C10	−44.3 (4)	N4—C15—C16—C18	−178.8 (3)
N2—C2—C3—N1	0.9 (3)	N5—C14—C22—N6	−36.2 (4)
N2—C2—C5—C6	0.7 (4)	N5—C14—C22—C23	144.6 (3)
N3—C9—C10—C11	−1.7 (4)	N5—C16—C18—C19	−1.1 (4)
C1—N1—C3—C2	−0.7 (3)	N6—C22—C23—C24	−3.7 (4)
C1—N2—C2—C3	−0.8 (3)	C14—N4—C15—C16	−0.2 (3)
C1—N2—C2—C5	176.8 (2)	C14—N5—C16—C15	0.1 (3)
C1—N2—C8—C7	−176.7 (3)	C14—N5—C16—C18	179.2 (2)
C1—C9—C10—C11	179.8 (2)	C14—N5—C21—C20	−177.3 (2)
C2—N2—C1—N1	0.4 (3)	C14—C22—C23—C24	175.4 (2)
C2—N2—C1—C9	−177.6 (2)	C15—N4—C14—N5	0.2 (3)
C2—N2—C8—C7	0.5 (4)	C15—N4—C14—C22	−175.3 (2)
C2—C5—C6—C7	−0.1 (4)	C15—C16—C18—C19	177.6 (3)
C3—N1—C1—N2	0.2 (3)	C16—N5—C14—N4	−0.2 (3)
C3—N1—C1—C9	178.2 (2)	C16—N5—C14—C22	175.4 (2)
C3—C2—C5—C6	177.5 (3)	C16—N5—C21—C20	−0.4 (4)
C4—N1—C1—N2	178.9 (2)	C16—C18—C19—C20	−0.6 (4)
C4—N1—C1—C9	−3.1 (4)	C17—N4—C14—N5	177.9 (2)
C4—N1—C3—C2	−179.5 (2)	C17—N4—C14—C22	2.3 (4)
C5—C2—C3—N1	−176.2 (3)	C17—N4—C15—C16	−177.9 (2)
C5—C6—C7—C8	−0.3 (4)	C18—C19—C20—C21	2.0 (4)
C6—C7—C8—N2	0.1 (4)	C19—C20—C21—N5	−1.4 (4)
C8—N2—C1—N1	177.8 (2)	C21—N5—C14—N4	177.0 (2)
C8—N2—C1—C9	−0.2 (4)	C21—N5—C14—C22	−7.4 (4)
C8—N2—C2—C3	−178.5 (2)	C21—N5—C16—C15	−177.4 (2)
C8—N2—C2—C5	−0.9 (4)	C21—N5—C16—C18	1.7 (3)
C9—N3—C13—C12	1.6 (4)	C22—N6—C26—C25	1.8 (4)
C9—C10—C11—C12	1.5 (4)	C22—C23—C24—C25	1.7 (4)
C10—C11—C12—C13	0.2 (4)	C23—C24—C25—C26	1.7 (4)
C11—C12—C13—N3	−1.8 (4)	C24—C25—C26—N6	−3.6 (5)
C13—N3—C9—C1	178.8 (2)	C26—N6—C22—C14	−177.2 (2)
C13—N3—C9—C10	0.2 (4)	C26—N6—C22—C23	1.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4C···Cl3ⁱ	0.98	2.72	3.664 (3)	162
C5—H5···Cl3	0.95	2.71	3.446 (2)	135
C7—H7···Cl4ⁱⁱ	0.95	2.72	3.651 (3)	166
C8—H8···Cl2ⁱⁱ	0.95	2.75	3.518 (3)	138
C12—H12···Cl4ⁱⁱⁱ	0.95	2.70	3.644 (2)	171
C17—H17A···Cl4^iv	0.98	2.79	3.695 (3)	155
C17—H17C···Cl1^v	0.98	2.80	3.721 (3)	158
C23—H23···Cl4^iv	0.95	2.69	3.576 (3)	156
C26—H26···Cl2ⁱⁱ	0.95	2.84	3.689 (3)	149

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

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant for the perspective development of the scientific direction ‘Mathematical Sciences and Natural Sciences’ at the Taras Shevchenko National University of Kyiv).

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