Crystal structure and Hirshfeld surface analysis of a new polymorph of chlorido­bis­(1,10-phenan­throline-κ2N,N′)copper(II) perchlorate

Plutenko, M.O.; Vynohradov, O.S.; Haukka, M.; Golenya, I.A.; Gaidai, S.V.

doi:10.1107/S2056989025000209

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ISSN: 2056-9890

Volume 81| Part 2| February 2025| Pages 140-143

https://doi.org/10.1107/S2056989025000209

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Crystal structure and Hirshfeld surface analysis of a new polymorph of chloridobis(1,10-phenanthroline-κ²N,N′)copper(II) perchlorate

Maksym O. Plutenko,^a ^* Oleksandr S. Vynohradov,^a Matti Haukka,^b Irina A. Golenya ^a and Snizhana V. Gaidai ^a

^aDepartment of Chemistry, National Taras Shevchenko University, Volodymyrska, Street 64, 01601 Kyiv, Ukraine, and ^bDepartment of Chemistry, University of Jyväskylä, PO Box 35, Jyväskylä, FI-40014, Finland
^*Correspondence e-mail: plutenkom@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 November 2024; accepted 9 January 2025; online 14 January 2025)

The title salt (systematic name: 2-methyl-4-oxo-3,4-dihydroquinazolin-1-ium chloride), [CuCl(C₁₂H₈N₂)₂](ClO₄), is comprised of a mononuclear complex cation [Cu(phen)₂Cl]⁺ (phen is 1,10-phenanthroline) and a perchlorate anion, ClO₄⁻, both with point group symmetry 2. The Cu^II atom has a slightly distorted trigonal–bipyramidal coordination environment, defined by a N₄Cl coordination set with the Cl atom and two N atoms at the equatorial sites. In the crystal, each phen ring is parallel to neighboring phen rings. The resulting significant π–π stacking interactions lead to zigzag chains extending parallel to [001]. Hirshfeld surface analysis suggests that the most important contributions to the surface contacts are from H⋯H (32.1%), H⋯C/C⋯H (18.2%), H⋯O/O⋯H (14.6%), H⋯Cl/Cl⋯H (12.7%) and C⋯C (10.6%) interactions.

Keywords: copper; copper(II) complex; crystal structure; 1,10-phenanthroline; Hirshfeld surface analysis.

CCDC reference: 2415829

1. Chemical context

1,10-Phenanthroline (phen) is one of the most extensively studied chelating N-heterocyclic ligands. Copper(II) complexes of phen, particularly those exhibiting a coordination environment with coordination number 5, have garnered significant attention due to their diverse biological (Barceló-Oliver et al., 2009 ; Pradeep et al., 2014 ), redox catalytic (Huang & Batey, 2007 ; Liu et al., 2024 ), and photochemical (Freitag et al., 2016 ) activities. Furthermore, complexes formed between copper and phen (in both 1:1 and 1:2 metal-to-ligand ratios) have been actively investigated as DNA-binding and oxidative DNA-cleaving agents (Bales et al., 2005 ; Zhang et al., 2006 ; Pradeep et al., 2014). In this context, structural studies of five-coordinate Cu^II complexes based on phen are of considerable interest for enhancing the understanding of the geometric features of the CuN₄X chromophore and for elucidating the structure–property relationships of these compounds.

Here, we report on synthesis, crystal structure, and Hirshfeld surface analysis of the compound [CuCl(phen)₂]ClO₄, crystallizing as a novel polymorph.

2. Structural commentary

The asymmetric unit of the title compound consists of half a [Cu(phen)₂Cl]⁺ complex cation (point group symmetry 2) and half of a perchlorate anion ClO₄⁻ (point group symmetry 2). The Cu^II ion in the complex cation has a slightly distorted trigonal–bipyramidal coordination environment (τ₅ = 0.921; Addison et al., 1984 ) formed by four nitrogen atoms from two phen ligands and one Cl⁻ ligand (Fig. 1). The equatorial plane is defined by atoms Cl1, N1 and N1ⁱ whereas the axial positions are occupied by atoms N2 and N2ⁱ [symmetry code: (i) −x, y, −z + $[{1\over 2}]$ ]. The Cu—N bond lengths to the equatorial N atoms are shorter by about 0.11 Å in comparison to the axial N atoms (Table 1). The crystallographically unique phen molecule retains its planarity [maximum deviation from the least-squares plane is 0.034 (3) Å for atom C2] and forms a five-membered [Cu—N—C—C—N] chelate ring due to its bidentate coordination. The dihedral angle between the two phen planes coordinating to Cu1 is 59.55 (6)°. The twist angle between the planes is 48.32 (5)°, the fold angle between the planes is 39.10 (8)°, whereby the twist angle refers to the rotation of one phen plane relative to the other, while the fold angle describes the bending between the planes.

Table 1
Selected bond lengths (Å)

Cu1—N1	1.988 (2)	Cl2—O2	1.418 (3)
Cu1—N2	2.100 (2)	Cl2—O1	1.420 (2)
Cu1—Cl1	2.3402 (12)

Figure 1
The structures of the molecular entities of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The dashed line represents a C—H⋯O hydrogen bond. [Symmetry code: (i) −x, y, −z + $[{1\over 2}]$ .]

3. Supramolecular features

In the crystal structure of the title compound (Fig. 2), each phen ring is parallel to its neighboring phen ring. The resulting significant π–π stacking with an inter-planar distance of 3.5085 (16) Å leads to a zigzag chain structure extending parallel to [001]. There are additional weak intermolecular C—H⋯O hydrogen bonds that link the complex cation to the perchlorate anion. Numerical details of these interactions are compiled in Table 2. The shortest Cu⋯Cu separation within the unit cell is 7.7779 (3) Å.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1ⁱ	0.95	2.43	3.253 (4)	145
C3—H3⋯O2ⁱⁱ	0.95	2.48	3.368 (5)	157
Symmetry codes: (i) $[-x, y, -z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Packing of the molecular components in the title compound in a view along the a axis. C—H⋯O hydrogen bonds are shown as black dashed lines.

4. Hirshfeld analysis

Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using CrystalExplorer (Spackman et al., 2021 ). The dark-red spots in Fig. 3 arise as a result of short interatomic contacts and represent negative d_norm values on the surface, while the other weaker intermolecular interactions appear as light-red spots. The Hirshfeld surfaces mapped over d_norm are shown individually for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, H⋯Cl/Cl⋯H, C⋯C and C⋯O/O⋯C contacts (Fig. 4). The overall two-dimensional fingerprint plot and those decomposed into individual contacts are given in Fig. 5. The most significant contributions to the overall crystal packing are from H⋯H (32.1%), H⋯C/C⋯H (18.2%), H⋯O/O⋯H (14.6%), H⋯Cl/Cl⋯H (12.7%) and C⋯C (10.6%) contacts. There are also small contributions from C⋯O/O⋯C (5.2%), H⋯N/N⋯H (2.4%), C⋯N/N⋯C (2.2%), O⋯N/N⋯O (1.8%) and O⋯Cl/Cl⋯O (0.3%) intermolecular contacts.

Figure 3
Hirshfeld surface mapped over d_norm in a projection along the b axis (front and back view).

Figure 4
Hirshfeld surface representations with the function d_norm plotted onto the surface for individual interactions.

Figure 5
The overall two-dimensional fingerprint plot and those delineated into specified interactions.

In the context of the Hirshfeld surface analysis, quantitative physical properties for the title compound were obtained, such as molecular volume (460.76 Å³), surface area (398.28 Å²), globularity (0.724) and asphericity (0.097). The asphericity value for the title compound is nearly zero, indicating an almost isotropic nature. The globularity value, being less than one, points to a slight deviation from a spherical shape.

5. Database survey

A search conducted in the Cambridge Structural Database (CSD, version 5.44, updated June 2023; Groom et al., 2016 ) identified a total of 118 entries corresponding to compounds containing the [CuCl(phen)₂]⁺ cation. Among these, five entries specifically pertain to compounds that include both the [CuCl(phen)₂]⁺ cation and the perchlorate anion. Notably, one structure was identified with the same formula as the title compound, [CuCl(phen)₂]ClO₄ (CLPLCU, Boys et al., 1981 ; CLPLCU01, Daizhi et al., 2006 ), revealing that this compound is at least dimorphic. The other matches have formulas [CuCl(phen)₂]ClO₄·0.5H₂O (ASUCOG, Wei & Yang, 2004 ) and [CuCl(phen)₂]ClO₄·H₂O (FUVWUP, Chang et al., 2008 ; JATRAA, Crispini et al., 2018 ).

CLPLCU and ASUCOG crystallize in space group P2₁/c, FUVWUP in P2₁/n and JATRAA in P $[\overline{1}]$ . The cell volumes are 4490.3 Å³ for ASUCOG (Z = 8), 2283.0 Å³ for CLPLCU (Z = 4), 2335.18 Å³ for FUVWUP (Z = 4), 1185.88 Å³ for JATRAA (Z = 2), and 2153.12 Å³ for the title compound (C2/c, Z = 4). Thus, the title compound has the smallest volume per formula unit.

ASUCOG contains two crystallographically unique [CuCl(phen)₂]⁺ cations, while all other structures contain only one crystallographically unique complex cation. In general, bond lengths and angles of the [CuCl(phen)₂]⁺ cation are very similar for all described complexes. Cu—N bond lengths lie in the range 1.970–2.135 Å, in good agreement with the title complex, whereas Cu—Cl bond lengths (2.269–2.326 Å) are slightly shorter than in the title compound. The crystal structures of all hydrous compounds (ASUCOG, FUVWUP, JATRAA) include Cu—Cl⋯HOH⋯O—Cl hydrogen-bond motifs.

6. Synthesis and crystallization

The title compound was obtained during an attempt to synthesize a trinuclear complex based on the polypyridyl ligand L, which includes one tetradentate and two bidentate metal-binding sites (Fig. 6; Fritsky et al., 2003 ; Strotmeyer et al., 2003 ). Copper(II) chloride dihydrate (0.034 g, 0.2 mmol) dissolved in methanol (5 ml) was added to a solution of 1,10-phenanthroline (0.036 g, 0.2 mmol) in methanol (5 ml). Separately, [Cu(L-H)(MeOH)]ClO₄ (0.070 g, 0.1 mmol), prepared according to Fritsky et al. (2001 ), was dissolved in a 1:1 (v:v) methanol–water mixture (10 ml). The two solutions were combined, stirred in air for 30 min. while heated (323 K), then cooled, filtered, and left at room temperature for crystallization. X-ray-quality, small green block-like crystals formed after two weeks. Yield: 0.034 g (61%).

Figure 6
The polypyridyl ligand involved in the synthesis of the title compound.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The positions of H atoms were positioned geometrically and refined isotropically using a riding model with C—H = 0.95 Å; U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[CuCl(C₁₂H₈N₂)₂](ClO₄)
M_r	558.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	15.7143 (5), 11.6386 (4), 13.0138 (5)
β (°)	115.227 (2)
V (Å³)	2153.12 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.31
Crystal size (mm)	0.13 × 0.13 × 0.09

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.642, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections	21362, 2471, 1947
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.105, 1.06
No. of reflections	2471
No. of parameters	160
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.57
Computer programs: COLLECT (Bruker, 2004 ), DENZO/SCALEPACK (Otwinowski & Minor, 1997 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2019/2 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2415829

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025000209/wm5744sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025000209/wm5744Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025000209/wm5744Isup3.cdx

checkCIF report

Computing details top

Chloridobis(1,10-phenanthroline-κ²N,N')copper(II) perchlorate top

Crystal data top

[CuCl(C₁₂H₈N₂)₂](ClO₄)	F(000) = 1132
M_r = 558.85	D_x = 1.724 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.7143 (5) Å	Cell parameters from 1037 reflections
b = 11.6386 (4) Å	θ = 3.1–27.5°
c = 13.0138 (5) Å	µ = 1.31 mm⁻¹
β = 115.227 (2)°	T = 120 K
V = 2153.12 (13) Å³	Block, green
Z = 4	0.13 × 0.13 × 0.09 mm

Data collection top

Nonius KappaCCD diffractometer	2471 independent reflections
Radiation source: fine-focus sealed tube	1947 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm^-1	R_int = 0.050
φ scans and ω scans with κ offset	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −20→20
T_min = 0.642, T_max = 0.880	k = −15→15
21362 measured reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0393P)² + 5.6416P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2471 reflections	Δρ_max = 0.70 e Å⁻³
160 parameters	Δρ_min = −0.56 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
Cu1	0.000000	0.24858 (4)	0.250000	0.03782 (18)
Cl1	0.000000	0.04751 (9)	0.250000	0.0380 (3)
Cl2	0.000000	0.37251 (8)	−0.250000	0.0303 (2)
O1	0.07641 (18)	0.4406 (2)	−0.2458 (3)	0.0632 (8)
O2	0.0293 (2)	0.3002 (3)	−0.1533 (3)	0.0819 (10)
N1	−0.10679 (18)	0.2549 (2)	0.2935 (2)	0.0364 (6)
N2	−0.09691 (17)	0.33812 (19)	0.1083 (2)	0.0320 (5)
C1	−0.1099 (2)	0.2086 (3)	0.3852 (3)	0.0430 (7)
H1	−0.055627	0.170922	0.439318	0.052*
C2	−0.1913 (2)	0.2140 (3)	0.4040 (3)	0.0438 (8)
H2	−0.191784	0.179833	0.470096	0.053*
C3	−0.2694 (2)	0.2679 (3)	0.3281 (3)	0.0399 (7)
H3	−0.324559	0.271466	0.340803	0.048*
C4	−0.2683 (2)	0.3186 (2)	0.2303 (2)	0.0349 (7)
C5	−0.3467 (2)	0.3764 (3)	0.1452 (3)	0.0415 (7)
H5	−0.403151	0.384501	0.154666	0.050*
C6	−0.3421 (2)	0.4199 (3)	0.0512 (3)	0.0405 (7)
H6	−0.395219	0.458075	−0.004311	0.049*
C7	−0.2578 (2)	0.4090 (2)	0.0343 (3)	0.0343 (6)
C8	−0.2487 (2)	0.4508 (2)	−0.0620 (3)	0.0382 (7)
H8	−0.300060	0.487821	−0.121269	0.046*
C9	−0.1647 (2)	0.4373 (2)	−0.0691 (3)	0.0385 (7)
H9	−0.157107	0.466637	−0.132784	0.046*
C10	−0.0908 (2)	0.3806 (2)	0.0169 (3)	0.0359 (7)
H10	−0.033379	0.371728	0.010016	0.043*
C11	−0.1797 (2)	0.3536 (2)	0.1167 (2)	0.0308 (6)
C12	−0.1844 (2)	0.3084 (2)	0.2167 (2)	0.0320 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0417 (3)	0.0452 (3)	0.0423 (3)	0.000	0.0331 (3)	0.000
Cl1	0.0354 (5)	0.0433 (6)	0.0415 (6)	0.000	0.0222 (5)	0.000
Cl2	0.0319 (5)	0.0321 (5)	0.0365 (5)	0.000	0.0239 (4)	0.000
O1	0.0645 (16)	0.0475 (14)	0.112 (2)	−0.0249 (12)	0.0710 (17)	−0.0274 (14)
O2	0.0681 (18)	0.123 (3)	0.0741 (19)	0.0427 (18)	0.0489 (16)	0.0583 (19)
N1	0.0428 (14)	0.0412 (13)	0.0388 (13)	−0.0026 (11)	0.0303 (12)	−0.0019 (11)
N2	0.0399 (13)	0.0307 (12)	0.0373 (13)	−0.0015 (10)	0.0278 (11)	−0.0046 (10)
C1	0.0514 (19)	0.0477 (17)	0.0452 (18)	−0.0009 (15)	0.0352 (16)	0.0023 (14)
C2	0.057 (2)	0.0477 (17)	0.0468 (18)	−0.0089 (15)	0.0414 (17)	−0.0061 (15)
C3	0.0404 (17)	0.0485 (18)	0.0453 (17)	−0.0152 (14)	0.0321 (15)	−0.0160 (14)
C4	0.0384 (16)	0.0372 (15)	0.0397 (16)	−0.0130 (12)	0.0269 (14)	−0.0174 (13)
C5	0.0330 (15)	0.0512 (18)	0.0486 (18)	−0.0122 (13)	0.0254 (14)	−0.0187 (15)
C6	0.0333 (15)	0.0471 (18)	0.0437 (18)	−0.0033 (13)	0.0190 (14)	−0.0113 (14)
C7	0.0367 (15)	0.0327 (14)	0.0389 (16)	−0.0083 (12)	0.0211 (13)	−0.0129 (12)
C8	0.0434 (17)	0.0359 (15)	0.0383 (17)	−0.0038 (13)	0.0202 (14)	−0.0067 (12)
C9	0.0538 (19)	0.0337 (15)	0.0377 (16)	−0.0058 (14)	0.0288 (15)	−0.0025 (13)
C10	0.0455 (17)	0.0347 (15)	0.0403 (16)	−0.0030 (13)	0.0305 (14)	−0.0028 (12)
C11	0.0383 (15)	0.0281 (13)	0.0355 (15)	−0.0089 (11)	0.0248 (13)	−0.0122 (11)
C12	0.0383 (15)	0.0312 (14)	0.0357 (15)	−0.0089 (12)	0.0246 (13)	−0.0116 (12)

Geometric parameters (Å, º) top

Cu1—N1	1.988 (2)	C3—C4	1.409 (4)
Cu1—N1ⁱ	1.988 (2)	C3—H3	0.9500
Cu1—N2ⁱ	2.100 (2)	C4—C12	1.408 (4)
Cu1—N2	2.100 (2)	C4—C5	1.426 (5)
Cu1—Cl1	2.3402 (12)	C5—C6	1.355 (5)
Cl2—O2ⁱⁱ	1.418 (3)	C5—H5	0.9500
Cl2—O2	1.418 (3)	C6—C7	1.438 (4)
Cl2—O1	1.420 (2)	C6—H6	0.9500
Cl2—O1ⁱⁱ	1.420 (2)	C7—C11	1.397 (4)
N1—C1	1.330 (4)	C7—C8	1.406 (4)
N1—C12	1.354 (4)	C8—C9	1.370 (4)
N2—C10	1.329 (3)	C8—H8	0.9500
N2—C11	1.363 (3)	C9—C10	1.389 (4)
C1—C2	1.403 (4)	C9—H9	0.9500
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.358 (5)	C11—C12	1.435 (4)
C2—H2	0.9500

N1—Cu1—N1ⁱ	175.73 (14)	C2—C3—H3	120.1
N1—Cu1—N2ⁱ	96.66 (9)	C4—C3—H3	120.1
N1ⁱ—Cu1—N2ⁱ	81.20 (9)	C12—C4—C3	116.8 (3)
N1—Cu1—N2	81.20 (9)	C12—C4—C5	119.2 (3)
N1ⁱ—Cu1—N2	96.66 (9)	C3—C4—C5	124.0 (3)
N2ⁱ—Cu1—N2	120.50 (12)	C6—C5—C4	121.0 (3)
N1—Cu1—Cl1	92.13 (7)	C6—C5—H5	119.5
N1ⁱ—Cu1—Cl1	92.13 (7)	C4—C5—H5	119.5
N2ⁱ—Cu1—Cl1	119.75 (6)	C5—C6—C7	120.9 (3)
N2—Cu1—Cl1	119.75 (6)	C5—C6—H6	119.6
O2ⁱⁱ—Cl2—O2	107.1 (3)	C7—C6—H6	119.6
O2ⁱⁱ—Cl2—O1	108.37 (15)	C11—C7—C8	117.0 (3)
O2—Cl2—O1	110.36 (19)	C11—C7—C6	119.2 (3)
O2ⁱⁱ—Cl2—O1ⁱⁱ	110.36 (19)	C8—C7—C6	123.8 (3)
O2—Cl2—O1ⁱⁱ	108.37 (15)	C9—C8—C7	119.2 (3)
O1—Cl2—O1ⁱⁱ	112.1 (2)	C9—C8—H8	120.4
C1—N1—C12	118.9 (3)	C7—C8—H8	120.4
C1—N1—Cu1	126.8 (2)	C8—C9—C10	119.9 (3)
C12—N1—Cu1	114.29 (18)	C8—C9—H9	120.1
C10—N2—C11	117.2 (3)	C10—C9—H9	120.1
C10—N2—Cu1	132.0 (2)	N2—C10—C9	122.9 (3)
C11—N2—Cu1	110.81 (18)	N2—C10—H10	118.5
N1—C1—C2	121.6 (3)	C9—C10—H10	118.5
N1—C1—H1	119.2	N2—C11—C7	123.8 (2)
C2—C1—H1	119.2	N2—C11—C12	116.4 (3)
C3—C2—C1	120.2 (3)	C7—C11—C12	119.9 (2)
C3—C2—H2	119.9	N1—C12—C4	122.9 (3)
C1—C2—H2	119.9	N1—C12—C11	117.3 (2)
C2—C3—C4	119.7 (3)	C4—C12—C11	119.8 (3)

C12—N1—C1—C2	0.0 (5)	C10—N2—C11—C12	−179.2 (2)
Cu1—N1—C1—C2	−176.8 (2)	Cu1—N2—C11—C12	0.4 (3)
N1—C1—C2—C3	−0.3 (5)	C8—C7—C11—N2	−0.2 (4)
C1—C2—C3—C4	−0.1 (5)	C6—C7—C11—N2	179.5 (2)
C2—C3—C4—C12	0.8 (4)	C8—C7—C11—C12	−179.7 (2)
C2—C3—C4—C5	179.5 (3)	C6—C7—C11—C12	0.0 (4)
C12—C4—C5—C6	1.0 (4)	C1—N1—C12—C4	0.8 (4)
C3—C4—C5—C6	−177.7 (3)	Cu1—N1—C12—C4	178.0 (2)
C4—C5—C6—C7	0.0 (5)	C1—N1—C12—C11	−177.7 (3)
C5—C6—C7—C11	−0.5 (4)	Cu1—N1—C12—C11	−0.5 (3)
C5—C6—C7—C8	179.1 (3)	C3—C4—C12—N1	−1.2 (4)
C11—C7—C8—C9	−1.2 (4)	C5—C4—C12—N1	180.0 (3)
C6—C7—C8—C9	179.2 (3)	C3—C4—C12—C11	177.3 (2)
C7—C8—C9—C10	1.5 (4)	C5—C4—C12—C11	−1.5 (4)
C11—N2—C10—C9	−1.0 (4)	N2—C11—C12—N1	0.1 (4)
Cu1—N2—C10—C9	179.5 (2)	C7—C11—C12—N1	179.6 (2)
C8—C9—C10—N2	−0.4 (4)	N2—C11—C12—C4	−178.5 (2)
C10—N2—C11—C7	1.3 (4)	C7—C11—C12—C4	1.0 (4)
Cu1—N2—C11—C7	−179.1 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱⁱ	0.95	2.43	3.253 (4)	145
C3—H3···O2ⁱⁱⁱ	0.95	2.48	3.368 (5)	157

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

Funding information

Funding for this research was provided by: the Ministry of Education and Science of Ukraine through grants No. 22BF037-09 and 24DF037-04N (RN/61-2024) .

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