Synthesis, crystal structure and Hirshfeld surface analysis of di-μ2-iodido-bis­[(2,2′-bi­quinoline-κ2N,N′)copper(I)]

Temesgen, A.W.; Novikov, A.P.; Tskhovrebov, A.G.; Kultyshkina, E.K.; Le, T.A.

doi:10.1107/S2056989023000634

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ISSN: 2056-9890

Volume 79| Part 3| March 2023| Pages 132-135

https://doi.org/10.1107/S2056989023000634

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Synthesis, crystal structure and Hirshfeld surface analysis of di-μ₂-iodido-bis[(2,2′-biquinoline-κ²N,N′)copper(I)]

Ayalew W. Temesgen,^a ^* Anton P. Novikov,^b,^c Alexander G. Tskhovrebov,^b Ekaterina K. Kultyshkina ^b and Tuan Anh Le ^d

^aDepartment of Chemistry, College of Natural and Computational Science, University of Gondar, Gondar 196, Ethiopia, ^bPeoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya, St, 117198, Moscow, Russian Federation, ^cFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospekt bldg 4, 119071 Moscow, Russian Federation, and ^dUniversity of Science, Vietnam National University, Hanoi, 334 Nguyen Trai, Thanh Xuan, 100000, Hanoi, Vietnam
^*Correspondence e-mail: wodajo.ayalew@uog.edu.et

Edited by G. Diaz de Delgado, Universidad de Los Andes Mérida, Venezuela (Received 5 September 2022; accepted 24 January 2023; online 7 February 2023)

This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.

The molecular and crystal structures of the title compound, [Cu₂I₂(C₁₈H₁₂N₂)₂], were examined by single-crystal X-ray diffraction and Hirshfeld surface analysis. The Cu atom is coordinated in a distorted tetrahedral geometry by two N atoms from the 2,2′-biquinoline ligands and the two μ₂-bridging iodide ligands. The molecules are in contact via π–π-stacking interactions. Hirshfeld surface analysis showed that the most important contributions to the intermolecular interactions are H⋯H (39.7%), H⋯I/I⋯H (17.8%), C⋯H/H⋯C (17.5%), C⋯C (16.5%), N⋯C/C⋯N (3.9%) and N⋯H/H⋯N (3.5%).

Keywords: crystal structure; Hirshfeld surface analysis; π–π stacking; biquinoline; copper complex.

CCDC reference: 2237760

1. Chemical context

Metal complexes with N-heterocyclic ligands find wide applications in various fields such as catalysis and medicine, among others (Delgado-Rebollo et al., 2019 ; Novikov et al., 2021 ; Fong, 2016 ; Artemjev et al., 2022 ). Copper(I) bypiridine complexes are of interest because of their structural peculiarities, cuprophilic interactions, and important photochemical properties. Therefore, bypyridine-type systems are often the ligands of choice to explore new metal complexes with potentially useful properties (Ferraro et al., 2022 ; Starosta et al., 2012 ; Vatsadze et al., 2010 ). 2,2′-Biquinoline is an important and widely employed diimine ligand. The geometry of the resulting metal derivatives depends on the ligand and counter-ion, the metal:ligand ratio and the solvent and synthetic conditions. Here we report the preparation and structural characterization of a copper iodide complex with 2,2′-biquinoline. We used Hirshfeld surface analysis to estimate the contribution of non-covalent interactions to the crystal structure.

2. Structural commentary

The title compound crystallizes in the centrosymmetric space group P $[\overline{1}]$ with one crystallographically independent molecule in the unit cell. The molecular structure is illustrated in Fig. 1. The Cu atom is coordinated in a distorted tetrahedral geometry (Table 1) by two nitrogen atoms from the 2,2′-biquinoline ligands and the two μ₂-bridged iodide ligands. The Cu1—I1 and Cu1ⁱ—I1 distances [symmetry code: (i) −x + 1, −y, −z + 1] are 2.5734 (2) and 2.6487 (2) Å, which are close to the distances in similar compounds (Sun et al., 2013 ; Starosta et al., 2012) with a substituted quinoline ligand. The Cu—N distances of 2.0930 (13) and 2.0900 (14) Å are almost equal within standard uncertainty.

Table 1
Selected geometric parameters (Å, °)

I1—Cu1	2.5734 (2)	Cu1—N2	2.0900 (14)
I1—Cu1ⁱ	2.6487 (2)	Cu1—N1	2.0930 (13)

Cu1—I1—Cu1ⁱ	68.829 (8)	N2—Cu1—I1ⁱ	110.91 (4)
N2—Cu1—N1	79.28 (5)	N1—Cu1—I1ⁱ	106.99 (4)
N2—Cu1—I1	122.14 (4)	I1—Cu1—I1ⁱ	111.171 (8)
N1—Cu1—I1	122.34 (4)
Symmetry code: (i) .

Figure 1
Molecular structure of the title compound, including atom and ring labelling. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x + 1, −y, −z + 1.]

The quinoline fragments in the biquinoline ligand adopt, as expected, a planar geometry. The maximum and minimum deviations of the atoms from these planes are between −0.018 (2) and 0.026 (2) Å. The angle between the quinolines described by rings 1/2 (as defined in Fig. 1) is 5.08 (9)° and between 3/4 is 0.59 (8)°. Then, the quinoline formed by rings 1 and 2 (ring 5) makes an angle of 7.56 (5)° with the quinoline described by rings 3/4 (ring 6).

3. Supramolecular features

The crystal packing is shown in Fig. 2, viewed down the c axis. Molecules both within the layers and between them are connected by π–π-stacking interactions between six-membered rings of the quinoline rings. The π–π-stacking interaction parameters are presented in Table 2. Ring 4, defined by N2/C18/C10–C13 in Fig. 1, participates in the shortest interactions. The contact with another ring 4, related by the symmetry operation −x, −y + 1, −z + 1, is perhaps the most efficient, based on the distance, the angle between the planes, and the shift between ring centroids.

Table 2
π–π-stacking interaction parameters (Å, °)

Ring 1	Ring No.	Ring 2	Ring No.	Angle	Centroid–centroid distance	Shift distance between ring centroids
C1–C6	1	C1–C6(−x + 1, −y, −z + 2)	1	0.000	3.874	1.459
C13–C18	3	N1/C1/C6–C9(−x + 1, −y + 1, −z + 1)	2	4.772	3.711	1.480
		N2/C18/C10–C13(−x, −y + 1, −z + 1)	4	0.590	3.665	1.602
N1/C1/C6–C9	2	N2/C18/C10–C13(−x + 1, −y + 1, −z + 1)	4	5.301	3.564	1.139
		C13–C18(−x + 1, −y + 1, −z + 1)	3	4.772	3.711	1.283
N2/C18/C10–C13	4	N2/C18/C10–C13(−x, −y + 1, −z + 1)	4	0.000	3.652	1.555
		C13–C18(−x, −y + 1, −z + 1)	3	0.590	3.665	1.579
		N1/C1/C6–C9(−x + 1, −y + 1, −z + 1)	2	5.301	3.564	1.068

Figure 2
View along the c axis of the crystal packing of the title compound, showing the stacking of layers formed by the Cu complex.

4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.43, update of 2022; Groom et al., 2016 ) showed only a few hits for bis[(μ₂-halogen)-2,2′-biquinoline-di-copper(I)]. We only found data for compounds with substituted quinoline rings in position-4 with carboxylate fragments. All compounds crystallize in the triclinic space group P $[\overline{1}]$ . In IRIVIP (Vatsadze et al., 2010), n-hexyl carboxylate groups are attached to the quinoline rings at position 4. In YIJFAA, YIJFEE, and YIJFII (Sun et al., 2013), ethyl carboxylate fragments are attached, and in PAYKIL (Starosta et al., 2012), there are methyl carboxylate fragments. In IRIVIP and YIJFAA, instead of the iodine atom, as in the title structure, there are chlorine atoms; in YIJFEE, there are bromine atoms. In other structures, the copper atoms are bonded through iodine atoms.

5. Hirshfeld surface analysis

Crystal Explorer21 was used to calculate the Hirshfeld surfaces and two-dimensional fingerprint plots (Spackman et al., 2021 ). The donor–acceptor groups are visualized using a standard (high) surface resolution and d_norm surfaces are mapped over a fixed colour scale from −0.0579 (red) to 1.3919 (blue) a.u., as illustrated in Fig. 3(a). Red spots on the surface correspond to C⋯C and I⋯H interactions. The presence of π-stacking interactions is confirmed by the characteristic red and blue triangles on the shape-index surface [Fig. 3(b)]. Fingerprint plots of the most important non-covalent interactions for the title compound are shown in Fig. 4. The largest contribution to the crystal packing is made by contacts of the H⋯H type (39.7%). Then contacts of the H⋯I/I⋯H and C⋯H/H⋯C types make approximately equal contributions (17.8 and 17.5%, respectively). C⋯C interactions responsible for π-stacking contribute 16.5%. Contacts that contribute less than 1% are not shown in Fig. 4.

Figure 3
Hirshfeld surface mapped over (a) d_norm and (b) shape-index to visualize the interactions in the title compound.

Figure 4
Two-dimensional fingerprint plots for the title compound divided into H⋯H (39.7%), H⋯I/I⋯H (17.8%), C⋯H/H⋯C (17.5%), C⋯C (16.5%), N⋯C/C⋯N (3.9%) and N⋯H/H⋯N (3.5%) interactions.

6. Synthesis and crystallization

The title compound was prepared by refluxing CuI with one equivalent of 2,2′-biquinoline in ethanol for 24 h. The compound precipitates as a purple solid in 87% yield. Found (%): C, 48.39; H, 2.71; N, 6.27. forC₃₆H₂₄Cu₂I₂N₄. Calculated (%): C, 48.61; H, 2.64; N, 6.19.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were placed at calculated positions (C—H = 0.95 Å) and refined using a riding model with [U_iso(H) = 1.2U_eq(C)].

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₂I₂(C₁₈H₁₂N₂)₂]
M_r	893.49
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.2032 (2), 9.4084 (3), 10.8312 (3)
α, β, γ (°)	70.9328 (8), 76.1237 (9), 74.2486 (9)
V (Å³)	749.84 (4)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	3.51
Crystal size (mm)	0.12 × 0.10 × 0.06

Data collection
Diffractometer	Bruker D8 QUEST PHOTON-III CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.656, 0.798
No. of measured, independent and observed [I > 2σ(I)] reflections	22231, 5464, 4875
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.050, 1.07
No. of reflections	5464
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.93, −1.00
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 2237760

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023000634/dj2055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023000634/dj2055Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Di-µ₂-iodido-bis[(2,2'-biquinoline-κ²N,N')copper(I)] top

Crystal data top

[Cu₂I₂(C₁₈H₁₂N₂)₂]	Z = 1
M_r = 893.49	F(000) = 432
Triclinic, P1	D_x = 1.979 Mg m⁻³
a = 8.2032 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4084 (3) Å	Cell parameters from 9951 reflections
c = 10.8312 (3) Å	θ = 2.3–32.6°
α = 70.9328 (8)°	µ = 3.51 mm⁻¹
β = 76.1237 (9)°	T = 100 K
γ = 74.2486 (9)°	Plate, red
V = 749.84 (4) Å³	0.12 × 0.10 × 0.06 mm

Data collection top

Bruker D8 QUEST PHOTON-III CCD diffractometer	4875 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.030
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 32.6°, θ_min = 2.3°
T_min = 0.656, T_max = 0.798	h = −12→12
22231 measured reflections	k = −14→14
5464 independent reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.050	w = 1/[σ²(F_o²) + (0.0241P)² + 0.2045P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5464 reflections	Δρ_max = 0.93 e Å⁻³
200 parameters	Δρ_min = −1.00 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: difference Fourier map	Extinction coefficient: 0.00061 (6)

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
I1	0.72676 (2)	0.05497 (2)	0.36228 (2)	0.01463 (4)
Cu1	0.47151 (3)	0.14895 (2)	0.52815 (2)	0.01482 (5)
N1	0.50362 (17)	0.22489 (16)	0.68043 (14)	0.0137 (2)
N2	0.32363 (17)	0.37275 (15)	0.48351 (13)	0.0126 (2)
C1	0.5986 (2)	0.14322 (19)	0.77875 (16)	0.0149 (3)
C2	0.7206 (2)	0.0086 (2)	0.76410 (18)	0.0188 (3)
H2	0.7335	−0.0253	0.6881	0.023*
C3	0.8205 (2)	−0.0730 (2)	0.86007 (19)	0.0225 (3)
H3	0.9050	−0.1616	0.8486	0.027*
C4	0.7991 (3)	−0.0268 (2)	0.97589 (19)	0.0235 (4)
H4	0.8658	−0.0869	1.0430	0.028*
C5	0.6831 (2)	0.1034 (2)	0.99178 (18)	0.0221 (3)
H5	0.6688	0.1333	1.0701	0.027*
C6	0.5837 (2)	0.1942 (2)	0.89164 (16)	0.0168 (3)
C7	0.4734 (2)	0.3365 (2)	0.89624 (17)	0.0204 (3)
H7	0.4603	0.3741	0.9702	0.024*
C8	0.3849 (2)	0.4209 (2)	0.79434 (17)	0.0186 (3)
H8	0.3134	0.5187	0.7954	0.022*
C9	0.4017 (2)	0.35984 (18)	0.68682 (16)	0.0134 (3)
C10	0.30656 (19)	0.44564 (18)	0.57445 (16)	0.0130 (3)
C11	0.2064 (2)	0.59515 (18)	0.56565 (17)	0.0151 (3)
H11	0.1989	0.6436	0.6318	0.018*
C12	0.1199 (2)	0.67017 (18)	0.46130 (17)	0.0161 (3)
H12	0.0505	0.7703	0.4552	0.019*
C13	0.1348 (2)	0.59756 (18)	0.36296 (16)	0.0135 (3)
C14	0.0488 (2)	0.6683 (2)	0.25249 (17)	0.0171 (3)
H14	−0.0225	0.7681	0.2431	0.021*
C15	0.0680 (2)	0.5933 (2)	0.15911 (17)	0.0183 (3)
H15	0.0103	0.6413	0.0850	0.022*
C16	0.1738 (2)	0.4440 (2)	0.17292 (17)	0.0181 (3)
H16	0.1868	0.3931	0.1074	0.022*
C17	0.2579 (2)	0.37192 (19)	0.27946 (17)	0.0162 (3)
H17	0.3279	0.2717	0.2876	0.019*
C18	0.23990 (19)	0.44731 (18)	0.37738 (16)	0.0129 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01422 (5)	0.01364 (5)	0.01633 (6)	−0.00129 (3)	−0.00081 (3)	−0.00714 (4)
Cu1	0.01437 (9)	0.01477 (9)	0.01559 (10)	0.00062 (7)	−0.00375 (7)	−0.00671 (7)
N1	0.0120 (6)	0.0154 (6)	0.0140 (6)	−0.0033 (5)	−0.0023 (5)	−0.0041 (5)
N2	0.0117 (5)	0.0134 (6)	0.0131 (6)	−0.0013 (5)	−0.0023 (4)	−0.0049 (5)
C1	0.0130 (7)	0.0179 (7)	0.0145 (7)	−0.0057 (6)	−0.0020 (5)	−0.0035 (6)
C2	0.0187 (8)	0.0184 (7)	0.0188 (8)	−0.0028 (6)	−0.0069 (6)	−0.0028 (6)
C3	0.0211 (8)	0.0196 (8)	0.0249 (9)	−0.0041 (7)	−0.0097 (7)	0.0003 (7)
C4	0.0250 (9)	0.0243 (9)	0.0207 (8)	−0.0102 (7)	−0.0117 (7)	0.0042 (7)
C5	0.0252 (9)	0.0282 (9)	0.0150 (7)	−0.0111 (7)	−0.0076 (6)	−0.0013 (7)
C6	0.0149 (7)	0.0234 (8)	0.0133 (7)	−0.0081 (6)	−0.0018 (5)	−0.0036 (6)
C7	0.0183 (8)	0.0309 (9)	0.0160 (8)	−0.0060 (7)	−0.0015 (6)	−0.0121 (7)
C8	0.0170 (7)	0.0244 (8)	0.0175 (8)	−0.0024 (6)	−0.0030 (6)	−0.0113 (7)
C9	0.0113 (6)	0.0162 (7)	0.0138 (7)	−0.0027 (5)	−0.0015 (5)	−0.0059 (6)
C10	0.0103 (6)	0.0148 (6)	0.0145 (7)	−0.0032 (5)	−0.0009 (5)	−0.0053 (5)
C11	0.0147 (7)	0.0140 (6)	0.0186 (7)	−0.0033 (5)	−0.0016 (5)	−0.0077 (6)
C12	0.0152 (7)	0.0118 (6)	0.0206 (8)	−0.0023 (5)	−0.0009 (6)	−0.0055 (6)
C13	0.0116 (6)	0.0118 (6)	0.0159 (7)	−0.0019 (5)	−0.0022 (5)	−0.0026 (5)
C14	0.0137 (7)	0.0162 (7)	0.0181 (8)	−0.0016 (6)	−0.0033 (6)	−0.0012 (6)
C15	0.0175 (7)	0.0188 (7)	0.0166 (7)	−0.0013 (6)	−0.0058 (6)	−0.0023 (6)
C16	0.0175 (7)	0.0212 (8)	0.0164 (7)	−0.0011 (6)	−0.0043 (6)	−0.0077 (6)
C17	0.0152 (7)	0.0162 (7)	0.0180 (7)	−0.0006 (6)	−0.0036 (6)	−0.0072 (6)
C18	0.0104 (6)	0.0135 (6)	0.0145 (7)	−0.0021 (5)	−0.0016 (5)	−0.0041 (5)

Geometric parameters (Å, º) top

I1—Cu1	2.5734 (2)	C7—C8	1.369 (3)
I1—Cu1ⁱ	2.6487 (2)	C7—H7	0.9500
Cu1—N2	2.0900 (14)	C8—C9	1.422 (2)
Cu1—N1	2.0930 (13)	C8—H8	0.9500
Cu1—I1ⁱ	2.6487 (2)	C9—C10	1.488 (2)
Cu1—Cu1ⁱ	2.9520 (4)	C10—C11	1.409 (2)
N1—C9	1.330 (2)	C11—C12	1.367 (2)
N1—C1	1.367 (2)	C11—H11	0.9500
N2—C10	1.3354 (19)	C12—C13	1.409 (2)
N2—C18	1.369 (2)	C12—H12	0.9500
C1—C2	1.414 (2)	C13—C14	1.415 (2)
C1—C6	1.421 (2)	C13—C18	1.423 (2)
C2—C3	1.374 (2)	C14—C15	1.369 (2)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.415 (3)	C15—C16	1.418 (2)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.365 (3)	C16—C17	1.372 (2)
C4—H4	0.9500	C16—H16	0.9500
C5—C6	1.418 (2)	C17—C18	1.418 (2)
C5—H5	0.9500	C17—H17	0.9500
C6—C7	1.406 (3)

Cu1—I1—Cu1ⁱ	68.829 (8)	C8—C7—H7	119.9
N2—Cu1—N1	79.28 (5)	C6—C7—H7	119.9
N2—Cu1—I1	122.14 (4)	C7—C8—C9	118.99 (16)
N1—Cu1—I1	122.34 (4)	C7—C8—H8	120.5
N2—Cu1—I1ⁱ	110.91 (4)	C9—C8—H8	120.5
N1—Cu1—I1ⁱ	106.99 (4)	N1—C9—C8	122.17 (15)
I1—Cu1—I1ⁱ	111.171 (8)	N1—C9—C10	116.58 (13)
N2—Cu1—Cu1ⁱ	141.62 (4)	C8—C9—C10	121.24 (15)
N1—Cu1—Cu1ⁱ	136.76 (4)	N2—C10—C11	122.82 (15)
I1—Cu1—Cu1ⁱ	56.791 (7)	N2—C10—C9	115.92 (14)
I1ⁱ—Cu1—Cu1ⁱ	54.380 (7)	C11—C10—C9	121.26 (14)
C9—N1—C1	119.18 (14)	C12—C11—C10	119.63 (14)
C9—N1—Cu1	113.35 (11)	C12—C11—H11	120.2
C1—N1—Cu1	126.92 (11)	C10—C11—H11	120.2
C10—N2—C18	118.23 (14)	C11—C12—C13	119.38 (15)
C10—N2—Cu1	113.89 (11)	C11—C12—H12	120.3
C18—N2—Cu1	127.82 (10)	C13—C12—H12	120.3
N1—C1—C2	118.85 (15)	C12—C13—C14	122.40 (15)
N1—C1—C6	121.75 (15)	C12—C13—C18	117.93 (15)
C2—C1—C6	119.33 (16)	C14—C13—C18	119.67 (14)
C3—C2—C1	119.82 (17)	C15—C14—C13	120.22 (16)
C3—C2—H2	120.1	C15—C14—H14	119.9
C1—C2—H2	120.1	C13—C14—H14	119.9
C2—C3—C4	120.78 (18)	C14—C15—C16	120.11 (16)
C2—C3—H3	119.6	C14—C15—H15	119.9
C4—C3—H3	119.6	C16—C15—H15	119.9
C5—C4—C3	120.43 (17)	C17—C16—C15	121.04 (15)
C5—C4—H4	119.8	C17—C16—H16	119.5
C3—C4—H4	119.8	C15—C16—H16	119.5
C4—C5—C6	120.13 (17)	C16—C17—C18	119.85 (15)
C4—C5—H5	119.9	C16—C17—H17	120.1
C6—C5—H5	119.9	C18—C17—H17	120.1
C7—C6—C5	122.99 (16)	N2—C18—C17	118.90 (14)
C7—C6—C1	117.63 (16)	N2—C18—C13	122.00 (14)
C5—C6—C1	119.34 (17)	C17—C18—C13	119.10 (15)
C8—C7—C6	120.15 (15)

C9—N1—C1—C2	−173.05 (15)	C18—N2—C10—C9	−179.42 (13)
Cu1—N1—C1—C2	16.1 (2)	Cu1—N2—C10—C9	3.07 (17)
C9—N1—C1—C6	3.8 (2)	N1—C9—C10—N2	4.8 (2)
Cu1—N1—C1—C6	−166.98 (11)	C8—C9—C10—N2	−175.83 (14)
N1—C1—C2—C3	178.35 (16)	N1—C9—C10—C11	−174.64 (14)
C6—C1—C2—C3	1.4 (3)	C8—C9—C10—C11	4.7 (2)
C1—C2—C3—C4	2.0 (3)	N2—C10—C11—C12	0.9 (2)
C2—C3—C4—C5	−2.6 (3)	C9—C10—C11—C12	−179.63 (15)
C3—C4—C5—C6	−0.4 (3)	C10—C11—C12—C13	−1.0 (2)
C4—C5—C6—C7	−174.13 (17)	C11—C12—C13—C14	179.90 (16)
C4—C5—C6—C1	3.8 (3)	C11—C12—C13—C18	0.2 (2)
N1—C1—C6—C7	−3.1 (2)	C12—C13—C14—C15	179.67 (15)
C2—C1—C6—C7	173.76 (16)	C18—C13—C14—C15	−0.7 (2)
N1—C1—C6—C5	178.82 (15)	C13—C14—C15—C16	0.2 (3)
C2—C1—C6—C5	−4.3 (2)	C14—C15—C16—C17	0.3 (3)
C5—C6—C7—C8	177.99 (17)	C15—C16—C17—C18	−0.3 (3)
C1—C6—C7—C8	0.0 (2)	C10—N2—C18—C17	179.51 (14)
C6—C7—C8—C9	2.2 (3)	Cu1—N2—C18—C17	−3.4 (2)
C1—N1—C9—C8	−1.5 (2)	C10—N2—C18—C13	−0.9 (2)
Cu1—N1—C9—C8	170.55 (12)	Cu1—N2—C18—C13	176.23 (11)
C1—N1—C9—C10	177.85 (13)	C16—C17—C18—N2	179.42 (15)
Cu1—N1—C9—C10	−10.14 (17)	C16—C17—C18—C13	−0.2 (2)
C7—C8—C9—N1	−1.6 (3)	C12—C13—C18—N2	0.7 (2)
C7—C8—C9—C10	179.14 (15)	C14—C13—C18—N2	−178.92 (15)
C18—N2—C10—C11	0.1 (2)	C12—C13—C18—C17	−179.65 (15)
Cu1—N2—C10—C11	−177.45 (12)	C14—C13—C18—C17	0.7 (2)

Symmetry code: (i) −x+1, −y, −z+1.

π–π-stacking interaction parameters (Å, °) top

Ring 1	Ring No.	Ring 2	Ring No.	Angle	Centroid–centroid distance	Shift distance between ring centroids
C1–C6	1	C1–C6(-x + 1, -y, -z + 2)	1	0.000	3.874	1.459
C13–C18	3	N1/C1/C6–C9(-x + 1, -y + 1, -z + 1)	2	4.772	3.711	1.480
		N2/C18/C10–C13(-x, -y + 1, -z + 1)	4	0.590	3.665	1.602
N1/C1/C6–C9	2	N2/C18/C10–C13(-x + 1, -y + 1, -z + 1)	4	5.301	3.564	1.139
		C13–C18(-x + 1, -y + 1, -z + 1)	3	4.772	3.711	1.283
N2/C18/C10–C13	4	N2/C18/C10–C13(-x, -y + 1, -z + 1)	4	0.000	3.652	1.555
		C13–C18(-x, -y + 1, -z + 1)	3	0.590	3.665	1.579
		N1/C1/C6–C9(-x + 1, -y + 1, -z + 1)	2	5.301	3.564	1.068

Acknowledgements

Authors contributions are as follows: Conceptualization, AWT, AGT and TAL; methodology, APN, AGT; validation: AWT, AGT; formal analysis: APN, AGT, TAL; investigation: AWT, AGT and TAL; resources, AGT, TAL; data curation, APN, EKK; writing (original draft), AWT; writing (review and editing), APN, AGT, TAL; visualization, AWT, TAL; supervision, AWT, AGT; project administration, AGT; funding acquisition, AGT, TAL.

Funding information

Funding for this research was provided by: Ministry of Science and Higher Education of the Russian Federation (subject No. 122011300061-3). This work was supported by the RUDN University Strategic Academic Leadership Program: Russian Foundation for Basic Research (grant No. 21-53-54001).

References

Artemjev, A. A., Novikov, A. P., Burkin, G. M., Sapronov, A. A., Kubasov, A. S., Nenajdenko, V. G., Khrustalev, V. N., Borisov, A. V., Kirichuk, A. A., Kritchenkov, A. S., Gomila, R. M., Frontera, A. & Tskhovrebov, A. G. (2022). Int. J. Mol. Sci. 23, 6372. Web of Science CSD CrossRef PubMed Google Scholar
Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2018). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Delgado-Rebollo, M., García-Morales, C., Maya, C., Prieto, A., Echavarren, A. M. & Pérez, P. J. (2019). J. Organomet. Chem. 898, 120856. Google Scholar
Ferraro, V., Castro, J., Trave, E. & Bortoluzzi, M. (2022). J. Organomet. Chem. 957, 122171. Web of Science CSD CrossRef Google Scholar
Fong, C. W. (2016). Free Radical Biol. Med. 95, 216–229. Web of Science CrossRef CAS 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
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
Novikov, A. P., Volkov, M. A., Safonov, A. V., Grigoriev, M. S. & Abkhalimov, E. V. (2021). Crystals, 11, 1417. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals 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
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Starosta, R., Komarnicka, U. K., Nagaj, J., Stokowa-Sołtys, K. & Bykowska, A. (2012). Acta Cryst. E68, m756–m757. CSD CrossRef IUCr Journals Google Scholar
Sun, X. M., Ning, W. H., Liu, J. L., Liu, S. X., Guo, P. C. & Ren, X. M. (2013). Chin. J. Inorg. Chem. 29, 2176–2182. CAS Google Scholar
Vatsadze, S. Z., Dolganov, A. V., Yakimanskii, A. V., Goikhman, M. Y., Podeshvo, I. V., Lyssenko, K. A., Maksimov, A. L. & Magdesieva, T. V. (2010). Russ. Chem. Bull. 59, 724–732. Web of Science CrossRef CAS Google Scholar

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