Crystal structure and Hirshfeld surface analysis of di-μ-chlorido-bis­[(aceto­nitrile-κN)chlorido­(ethyl 5-methyl-1H-pyrazole-3-carboxyl­ate-κ2N2,O)copper(II)]

Vynohradov, O.S.; Pavlenko, V.A.; Kucheriv, O.I.; Golenya, I.A.; Petlovanyi, D.; Shova, S.

doi:10.1107/S2056989021010653

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ISSN: 2056-9890

Volume 77| Part 11| November 2021| Pages 1153-1157

https://doi.org/10.1107/S2056989021010653

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Crystal structure and Hirshfeld surface analysis of di-μ-chlorido-bis[(acetonitrile-κN)chlorido(ethyl 5-methyl-1H-pyrazole-3-carboxylate-κ²N²,O)copper(II)]

Oleksandr S. Vynohradov,^a Vadim A. Pavlenko,^a Olesia I. Kucheriv,^a Irina A. Golenya,^a ^* Denys Petlovanyi ^b and Sergiu Shova ^c

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, ^bEnamine Ltd, Oleksandra Matrosova Str. 23, Kyiv 01103, Ukraine, and ^c"Poni Petru" Institute of Macromolecular Chemistry, Aleea Gr. Ghica, Voda 41A, 700487 Iasi, Romania
^*Correspondence e-mail: igolenya@ua.fm

Edited by O. Blacque, University of Zürich, Switzerland (Received 7 October 2021; accepted 14 October 2021; online 26 October 2021)

The title compound, [Cu₂Cl₄(C₅H₁₀N₂O₂)₂(CH₃CN)₂] or [Cu₂(μ₂-Cl)₂(CH₃—Pz-COOCH₂CH₃)₂Cl₂(CH₃CN)₂], was synthesized using a one-pot reaction of copper powder, copper(II) chloride dihydrate and ethyl 5-methyl-1H-pyrazole-3-carboxylate (CH₃—Pz-COOCH₂CH₃) in acetonitrile under ambient conditions. This complex consists of discrete binuclear molecules with a {Cu₂(μ₂-Cl)₂} core, in which the Cu⋯Cu distance is 3.8002 (7) Å. The pyrazole-based ligands are bidentate coordinated, leading to the formation of two five-membered chelate rings. The coordination geometry of both copper atoms (ON₂Cl₃) can be described as distorted octahedral on account of the acetonitrile coordination. A Hirshfeld surface analysis suggests that the most important contributions to the surface contacts are from H⋯H (40%), H⋯Cl/Cl⋯H (24.3%), H⋯O/O⋯H (11.8%), H⋯C/C⋯H (9.2%) and H⋯N/N⋯H (8.3%) interactions.

Keywords: copper; copper complexes; crystal structure; pyrazole; X-ray crystallography; Hirshfeld surface analysis; one-pot reaction; direct synthesis; oxidative dissolution.

CCDC reference: 2115608

1. Chemical context

Pyrazoles can form structures of various nuclearities, ranging from mononuclear (Mighell et al., 1975 ; Liu et al., 2001 ; Małecka et al., 2003 ) to polynuclear complexes (He, 2011 ; Contaldi et al., 2009 ; Chandrasekhar et al., 2008 ) and metallacycles (Vynohradov et al., 2020a ; Surmann et al., 2016 ; Galassi et al., 2012 ) with specific molecular topologies. By performing the synthesis of metal complexes by oxidative dissolution of metals, commonly known as direct synthesis (Kokozay et al., 2018 ; Plyuta et al., 2020 ; Sirenko et al., 2020 ; Li et al., 2021 ), copper can be introduced in a zerovalent state. Copper powder can be oxidized in solution in the presence of proton-donating agents, such as pyrazoles, to form polynuclear complexes, where two copper atoms are connected by a bidentate-bridging deprotonated pyrazole (Vynohradov et al., 2020b ; Davydenko et al., 2013 ). Many examples of copper coordination compounds have been synthesized and described in which two copper atoms are connected by halogen bridges, for example, through chlorine anions, deprotonated ligand molecules and also hydroxyl groups (Vincent et al., 2018 ; Wei et al., 2012 ; Mezei et al., 2004 ). Copper(II) pyrazolate complexes have attracted considerable interest for their interesting magnetic properties (Malinkin et al., 2012 ; Spodine et al., 1999 ) and abilities to bind DNA (Vafazadeh et al., 2015 ; Kulkarni et al., 2011 ). Finally, the antioxidant (Kupcewicz et al., 2013 ) and anticancer (Santini et al., 2014 ) activities of these compounds should be noted. Relatively few unsymmetrical pyrazole-containing ligands with different chelating arms in the 3- and 5-positions and their coordination compounds have been investigated so far (Konrad et al., 2001 ; Dubs et al., 2006 ; Krämer et al., 2002 ; Röder et al., 2002 ; Penkova et al., 2010 ). Considering the above, we understand the importance of accumulating a theoretical information base on such coordination compounds, and therefore in this article we report the synthesis, crystal structure and Hirshfeld surface analysis of a new binuclear copper(II) complex with unsymmetrical pyrazole ethyl 5-methyl-1H-pyrazole-3-carboxylate – [Cu₂(μ₂-Cl)₂(CH₃-Pz-COOCH₂CH₃)₂Cl₂(CH₃CN)₂].

2. Structural commentary

The title compound (Fig. 1) is a binuclear cyclic copper(II) pyrazole-containing complex which crystallized in the monoclinic P2₁/c space group. The asymmetric unit consists of one copper ion, one ethyl 5-methyl-1H-pyrazole-3-carboxylate ligand, one coordinated acetonitrile molecule and two chlorine ions. One of these chlorine ions bridges two metal centers, thus connecting two symmetry-generated fragments. The structure of this complex can be described as a dimer of formula [CuCl₂(C₇H₁₀N₂O₂)(CH₃CN)]₂ in which the CH₃-Pz-COOCH₂CH₃ ligand is coordinated in a bidentate way and remains protonated. The copper atom has a distorted octahedral coordination environment formed by three chlorine atoms, one nitrogen atom of the acetonitrile molecule and two atoms of the unsymmetrical pyrazole ligand – the pyridine-like N1 atom and atom O 1 of the ester substituent in position 3 of the pyrazole ring. The bidentate coordination of the pyrazole ligand leads to the formation of a five-membered chelate ring. The atoms in the ring deviate only slightly from planarity [the Cu1 atom is out of the Cu1/N1/C4/C5/O1 plane by 0.0222 (8) Å; N1 by −0.0406 (14) Å; C4 by 0.0326 (15) Å; C5 by 0.0031 (18) Å and O1 by −0.0172 (14) Å]. Both the copper atoms and the bridging chlorine atoms lie in the same plane without deviations from planarity. The intermetallic distance in the dimer unit is 3.8002 (7) Å while the chlorine–chlorine separation in the four-membered bimetallic cycle is 3.5894 (15) Å.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Irrelevant hydrogen atoms were omitted for clarity.

An overlay of the asymmetric units of the structures of the title compound (red) and a similar complex with methyl 5-methyl-1H-pyrazole-3-carboxylate (green) is presented in Fig. 2. The structures were compared using OLEX2 software (Dolomanov et al., 2009 ). It was found that the structure of the complex does not change regardless of the organic radical R in the COOR ester group, whether –CH₃ or –CH₂—CH₃. The crystal structures of these compounds are also similar. In addition, the intermetallic distance in the above structures differs approximately by 0.1 Å and the chlorine–chlorine separation in the four-membered bimetallic ring differs by 0.05 Å [Cu⋯Cu = 3.7047 (7) Å and Cl⋯Cl = 3.5364 (11) Å for the methyl analogue]. The molecular structure is stabilized by intramolecular N—H⋯Cl and C—H⋯Cl hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1ⁱ	0.80 (2)	2.72 (2)	3.281 (2)	129 (2)
N2—H2⋯Cl2ⁱ	0.80 (2)	2.59 (2)	3.273 (2)	145 (1)
C7—H7A⋯Cl2ⁱⁱ	0.96	2.79	3.662 (4)	151
Symmetry codes: (i) ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Overlay diagram of the asymmetric units of the structures of the title compound (red) and of a similar complex with methyl 5-methyl-1H-pyrazole-3-carboxylate (green) which shows the similarity of the structure regardless of the organic radical R in the COOR ester group of the substituent on the pyrazole ring.

3. Supramolecular features

The crystal packing of the title compound (Fig. 3) consists of discrete binuclear molecules with a {Cu₂(μ₂-Cl)₂} core, which form a planar bimetallic ring. The four-membered Cu1/Cl1/Cu1ⁱ/Cl1ⁱ planes of the bimetallic rings are situated perpendicular to the b axis, while the chelate ring planes are located approximately parallel. No intermolecular hydrogen bonds were identified in the crystal structure. The minimum separation between the Cl atoms of neighbouring molecules inside one unit cell is 4.4013 (13) Å for Cl1ⁱ and Cl1ⁱⁱ [symmetry codes: (i) 1 − x, 1 − y, 2 − z; (ii) x, y, −1 + z] while the minimum distance between two copper atoms is 7.6498 (3) Å for Cu1 and Cu1ⁱⁱ.

Figure 3
Crystal packing of the title compound viewed along (a) the a- and (b) the b-axis directions. Selected hydrogen atoms were omitted for clarity.

4. Hirshfeld surface analysis

The Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were performed using Crystal Explorer 17.5 (Turner et al., 2018 ), with a standard resolution of the three-dimensional d_norm surfaces plotted over a fixed colour scale of −0.1996 (red) to 1.1926 (blue) a.u. The pale-red spots in Fig. 4 represent short contacts and negative d_norm values on the surface corresponding to the interactions described above. The Hirshfeld surfaces mapped over d_norm are shown for the H⋯H, H⋯Cl/Cl⋯H, H⋯O/O⋯H, H⋯C/C⋯H and H⋯N/N⋯H contacts, the overall two-dimensional fingerprint plot and the decomposed two-dimensional fingerprint plots are given in Fig. 5. Twelve short interatomic contacts in the range 2.34–2.8 Å are indicated by the faint red spots. Two pairs of intermolecular C—H⋯O contacts between the O1 atom of the ester substituent and the hydrogen atom of the methyl group of the coordinated acetonitrile were the shortest. Also, four intermolecular C—H⋯Cl contacts with a length of 2.685 Å, which are present between the terminal chlorine atoms and the hydrogen atoms of the ethyl group (hydrogen atom near C7) of the ester substituent are also short. Finally, four intermolecular C—H⋯Cl contacts with a length of 2.8 Å are observed between the terminal chlorine atoms and the hydrogen atoms of the –CH₃ group of the acetonitrile molecule. For the title compound, the most significant contributions to the overall crystal packing are from H⋯H (40%), H⋯Cl/Cl⋯H (24.3%), H⋯O/O⋯H (11.8%), H⋯C/C⋯H (9.2%) and H⋯N/N⋯H (8.3%) contacts. The small contribution of the other weak intermolecular C⋯C (2.9%), C⋯O/O⋯C (2.1%), C⋯N/N⋯C (0.8%), C⋯Cl/Cl⋯C (0.3%), O⋯N/N⋯O (0.3%) and Cl⋯Cl (0.1%) contacts has a negligible effect on the packing. In addition, quantitative physical properties of the Hirshfeld surface for the title compound were obtained, such as molecular volume (657.89 Å³), surface area (571.56 Å²), globularity (0.640), as well as asphericity (0.147).

Figure 4
Two projections of Hirshfeld surfaces mapped over d_norm showing the intermolecular interactions within the molecule.

Figure 5
The overall two-dimensional fingerprint plot and those delineated into specified interactions. Hirshfeld surface representations with the function d_norm plotted onto the surface for the different interactions.

5. Database survey

Six similar structures are registered in the Cambridge Structural Database (Version 2021.1; Groom et al., 2016 ): two reports of complexes with methyl 5-methyl-1H-pyrazole-3-carboxylate [UMUXEI (Rheingold, 2021 ) and ZEQGUZ (Shakirova et al., 2012 )], two reports of the free ligand ethyl 5-methyl-1H-pyrazole-3-carboxylate [FAQSAR01 (Mague et al., 2018 ) and FAQSAR02 (Kusakiewicz-Dawid et al., 2019 )] and two structure reports of the same ligand with a different name and cell parameters (Elguero et al., 1999 ) [3-ethoxycarbonyl-5-methylpyrazole (FAQSAR) and 4-bromo-3-ethoxycarbonyl-5-methylpyrazole (FAQTAS)].

6. Synthesis and crystallization

[Cu₂(μ₂-Cl)₂(CH₃-Pz-COOCH₂CH₃)₂Cl₂(CH₃CN)₂] was synthesized at room temperature by the oxidative dissolution method by the addition of a copper powder (1.56 mmol, 0.1 g) and copper(II) chloride dihydrate (3.1 mmol, 0.53 g) mixture to an acetonitrile (9 ml) solution of ethyl 5-methyl-1H-pyrazole-3-carboxylate (4.67 mmol, 0.72 g). The mixture was stirred without heating for three h with free air access until dissolution of the copper powder and a green precipitate of the product was obtained. The precipitate was filtered off and re-dissolved in acetonitrile. Green crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent. The IR spectra of the starting pyrazole ligand and the obtained green crystals of the title coordination compound are given in the supporting information.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were positioned geometrically (C—H = 0.93–0.97) and refined as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl). N-bound H atoms were refined with U_iso(H) = 1.2U_eq(N).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂Cl₄(C₅H₁₀N₂O₂)₂(C₂H₃N)₂]
M_r	659.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.3934 (4), 15.9822 (5), 7.6498 (3)
β (°)	106.226 (4)
V (Å³)	1337.48 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.03
Crystal size (mm)	0.45 × 0.2 × 0.1

Data collection
Diffractometer	Rigaku Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 )
T_min, T_max	0.839, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9132, 3062, 2380
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.083, 1.04
No. of reflections	3062
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.34
Computer programs: CrysAlis PRO (Rigaku OD, 2021), SHELXLT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009).

Supporting information

CCDC reference: 2115608

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021010653/zq2267sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021010653/zq2267Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021010653/zq2267Isup3.cdx

IR spectrum of the title compound. DOI: https://doi.org/10.1107/S2056989021010653/zq2267sup4.txt

IR spectrum of the free ligand. DOI: https://doi.org/10.1107/S2056989021010653/zq2267sup5.txt

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXLT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Di-µ-chlorido-bis[(acetonitrile-κN)chlorido(ethyl 5-methyl-1H-pyrazole-3-carboxylate-κ²N²,O)copper(II)] top

Crystal data top

[Cu₂Cl₄(C₅H₁₀N₂O₂)₂(C₂H₃N)₂]	F(000) = 668
M_r = 659.33	D_x = 1.637 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.3934 (4) Å	Cell parameters from 3607 reflections
b = 15.9822 (5) Å	θ = 2.3–27.2°
c = 7.6498 (3) Å	µ = 2.03 mm⁻¹
β = 106.226 (4)°	T = 293 K
V = 1337.48 (9) Å³	Block, green
Z = 2	0.45 × 0.2 × 0.1 mm

Data collection top

Rigaku Xcalibur, Eos diffractometer	3062 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2380 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 16.1593 pixels mm^-1	θ_max = 28.3°, θ_min = 1.9°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	k = −18→21
T_min = 0.839, T_max = 1.000	l = −9→9
9132 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0338P)² + 0.250P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3062 reflections	Δρ_max = 0.30 e Å⁻³
158 parameters	Δρ_min = −0.34 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	0.32946 (3)	0.47882 (2)	0.91290 (4)	0.03655 (12)
Cl1	0.45100 (6)	0.48716 (4)	1.20189 (9)	0.04438 (18)
Cl2	0.23810 (6)	0.60138 (4)	0.93837 (10)	0.04752 (19)
O1	0.14691 (18)	0.38325 (11)	0.9411 (3)	0.0501 (5)
O2	0.12145 (16)	0.24499 (11)	0.9610 (3)	0.0471 (5)
N1	0.37558 (18)	0.35720 (12)	0.9058 (3)	0.0359 (5)
N2	0.4841 (2)	0.32429 (13)	0.9131 (3)	0.0406 (6)
H2	0.541 (2)	0.3509 (10)	0.9021 (5)	0.049*
N3	0.2412 (2)	0.47671 (13)	0.6418 (3)	0.0452 (6)
C1	0.4879 (2)	0.24100 (15)	0.9412 (4)	0.0414 (7)
C2	0.6021 (3)	0.19159 (18)	0.9591 (5)	0.0628 (10)
H2A	0.624715	0.194792	0.847440	0.094*
H2B	0.588090	0.134232	0.984660	0.094*
H2C	0.666779	0.214025	1.056683	0.094*
C3	0.3747 (2)	0.21906 (15)	0.9510 (4)	0.0417 (6)
H3	0.347635	0.165569	0.967998	0.050*
C4	0.3075 (2)	0.29279 (15)	0.9307 (3)	0.0356 (6)
C5	0.1848 (2)	0.31277 (16)	0.9433 (4)	0.0375 (6)
C6	0.0021 (2)	0.2595 (2)	0.9877 (4)	0.0567 (8)
H6A	−0.049565	0.289751	0.884815	0.068*
H6B	0.009748	0.292321	1.096964	0.068*
C7	−0.0522 (3)	0.1761 (2)	1.0052 (5)	0.0624 (9)
H7A	−0.071569	0.147755	0.890001	0.094*
H7B	−0.125387	0.183416	1.042309	0.094*
H7C	0.005383	0.143312	1.094653	0.094*
C8	0.1955 (3)	0.48097 (15)	0.4916 (4)	0.0417 (6)
C9	0.1373 (4)	0.4863 (2)	0.2988 (4)	0.0710 (10)
H9A	0.150266	0.435166	0.241128	0.107*
H9B	0.171560	0.532163	0.248413	0.107*
H9C	0.051142	0.495250	0.278268	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0379 (2)	0.03067 (19)	0.0376 (2)	0.00332 (12)	0.00486 (14)	−0.00063 (12)
Cl1	0.0504 (4)	0.0426 (4)	0.0359 (4)	0.0007 (3)	0.0049 (3)	0.0039 (3)
Cl2	0.0448 (4)	0.0378 (4)	0.0559 (5)	0.0095 (3)	0.0074 (3)	−0.0022 (3)
O1	0.0491 (12)	0.0414 (11)	0.0637 (14)	0.0052 (9)	0.0224 (10)	−0.0034 (9)
O2	0.0351 (10)	0.0452 (11)	0.0642 (14)	−0.0029 (8)	0.0190 (9)	0.0025 (9)
N1	0.0305 (11)	0.0312 (11)	0.0449 (14)	−0.0011 (9)	0.0088 (10)	−0.0021 (9)
N2	0.0329 (12)	0.0353 (12)	0.0544 (16)	−0.0048 (9)	0.0133 (11)	−0.0057 (10)
N3	0.0471 (14)	0.0425 (13)	0.0431 (15)	0.0053 (10)	0.0077 (12)	−0.0029 (10)
C1	0.0382 (15)	0.0301 (13)	0.0526 (18)	0.0006 (11)	0.0074 (13)	−0.0075 (11)
C2	0.0442 (17)	0.0463 (17)	0.094 (3)	0.0062 (13)	0.0121 (18)	−0.0150 (16)
C3	0.0399 (15)	0.0311 (13)	0.0517 (18)	−0.0041 (11)	0.0085 (13)	−0.0003 (11)
C4	0.0338 (13)	0.0329 (13)	0.0382 (16)	−0.0032 (10)	0.0069 (11)	−0.0037 (10)
C5	0.0370 (14)	0.0385 (15)	0.0368 (16)	−0.0040 (11)	0.0101 (12)	−0.0034 (11)
C6	0.0422 (17)	0.073 (2)	0.059 (2)	0.0066 (14)	0.0209 (16)	0.0057 (16)
C7	0.0416 (17)	0.084 (2)	0.062 (2)	−0.0189 (15)	0.0156 (16)	−0.0033 (17)
C8	0.0464 (16)	0.0391 (15)	0.0406 (18)	0.0057 (11)	0.0136 (13)	−0.0044 (11)
C9	0.090 (3)	0.083 (2)	0.038 (2)	0.0103 (19)	0.0133 (19)	−0.0022 (16)

Geometric parameters (Å, º) top

Cu1—Cl1ⁱ	2.9242 (8)	C2—H2A	0.9600
Cu1—Cl1	2.2609 (7)	C2—H2B	0.9600
Cu1—Cl2	2.2521 (7)	C2—H2C	0.9600
Cu1—O1	2.637 (2)	C3—H3	0.9300
Cu1—N1	2.0182 (19)	C3—C4	1.390 (3)
Cu1—N3	2.036 (2)	C4—C5	1.462 (4)
O1—C5	1.205 (3)	C6—H6A	0.9700
O2—C5	1.330 (3)	C6—H6B	0.9700
O2—C6	1.449 (3)	C6—C7	1.492 (4)
N1—N2	1.330 (3)	C7—H7A	0.9600
N1—C4	1.335 (3)	C7—H7B	0.9600
N2—H2	0.80 (3)	C7—H7C	0.9600
N2—C1	1.347 (3)	C8—C9	1.441 (4)
N3—C8	1.123 (4)	C9—H9A	0.9600
C1—C2	1.495 (4)	C9—H9B	0.9600
C1—C3	1.360 (4)	C9—H9C	0.9600

Cl1—Cu1—Cl1ⁱ	86.62 (3)	H2A—C2—H2C	109.5
Cl1—Cu1—O1	103.64 (5)	H2B—C2—H2C	109.5
Cl2—Cu1—Cl1	92.05 (3)	C1—C3—H3	127.0
Cl2—Cu1—Cl1ⁱ	108.61 (3)	C1—C3—C4	106.1 (2)
Cl2—Cu1—O1	95.89 (5)	C4—C3—H3	127.0
O1—Cu1—Cl1ⁱ	153.19 (4)	N1—C4—C3	110.2 (2)
N1—Cu1—Cl1	89.44 (6)	N1—C4—C5	116.5 (2)
N1—Cu1—Cl1ⁱ	85.41 (6)	C3—C4—C5	133.2 (2)
N1—Cu1—Cl2	165.96 (7)	O1—C5—O2	124.1 (2)
N1—Cu1—O1	70.22 (7)	O1—C5—C4	123.3 (2)
N1—Cu1—N3	90.84 (8)	O2—C5—C4	112.6 (2)
N3—Cu1—Cl1	171.83 (7)	O2—C6—H6A	110.2
N3—Cu1—Cl1ⁱ	85.27 (7)	O2—C6—H6B	110.2
N3—Cu1—Cl2	89.66 (6)	O2—C6—C7	107.4 (2)
N3—Cu1—O1	84.12 (8)	H6A—C6—H6B	108.5
C5—O1—Cu1	104.76 (17)	C7—C6—H6A	110.2
C5—O2—C6	116.2 (2)	C7—C6—H6B	110.2
N2—N1—Cu1	128.73 (16)	C6—C7—H7A	109.5
N2—N1—C4	105.05 (19)	C6—C7—H7B	109.5
C4—N1—Cu1	124.95 (17)	C6—C7—H7C	109.5
N1—N2—H2	123.6	H7A—C7—H7B	109.5
N1—N2—C1	112.7 (2)	H7A—C7—H7C	109.5
C1—N2—H2	123.6	H7B—C7—H7C	109.5
C8—N3—Cu1	175.2 (2)	N3—C8—C9	179.8 (4)
N2—C1—C2	121.7 (2)	C8—C9—H9A	109.5
N2—C1—C3	105.9 (2)	C8—C9—H9B	109.5
C3—C1—C2	132.4 (2)	C8—C9—H9C	109.5
C1—C2—H2A	109.5	H9A—C9—H9B	109.5
C1—C2—H2B	109.5	H9A—C9—H9C	109.5
C1—C2—H2C	109.5	H9B—C9—H9C	109.5
H2A—C2—H2B	109.5

Cu1—O1—C5—O2	178.2 (2)	N2—C1—C3—C4	−1.0 (3)
Cu1—O1—C5—C4	−0.4 (3)	C1—C3—C4—N1	1.1 (3)
Cu1—N1—N2—C1	167.66 (19)	C1—C3—C4—C5	−174.1 (3)
Cu1—N1—C4—C3	−168.89 (18)	C2—C1—C3—C4	177.7 (3)
Cu1—N1—C4—C5	7.2 (3)	C3—C4—C5—O1	171.4 (3)
N1—N2—C1—C2	−178.3 (3)	C3—C4—C5—O2	−7.4 (4)
N1—N2—C1—C3	0.5 (3)	C4—N1—N2—C1	0.2 (3)
N1—C4—C5—O1	−3.7 (4)	C5—O2—C6—C7	−179.7 (2)
N1—C4—C5—O2	177.6 (2)	C6—O2—C5—O1	−3.1 (4)
N2—N1—C4—C3	−0.8 (3)	C6—O2—C5—C4	175.7 (2)
N2—N1—C4—C5	175.3 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	0.80 (2)	2.72 (2)	3.281 (2)	129 (2)
N2—H2···Cl2ⁱ	0.80 (2)	2.59 (2)	3.273 (2)	145 (1)
C7—H7A···Cl2ⁱⁱ	0.96	2.79	3.662 (4)	151

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, y−1/2, −z+3/2.

Funding information

This work was supported by the Ministry of Education and Science of Ukraine: Grant of the Ministry of Education and Science of Ukraine for perspective development of a scientific direction "Mathematical sciences and natural sciences" at Taras Shevchenko National University of Kyive (grant No. 21BNN-06).

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