Synthesis, crystal structure and Hirshfeld surface analysis of a new copper(II) complex based on diethyl 2,2′-(4H-1,2,4-triazole-3,5-di­yl)di­acetate

Vynohradov, O.S.; Vashchenko, O.V.; Khomenko, D.M.; Doroshchuk, R.O.; Raspertova, I.V.; Lampeka, R.D.; Stoica, A.-C.

doi:10.1107/S2056989024008259

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ISSN: 2056-9890

Volume 80| Part 9| September 2024| Pages 976-980

https://doi.org/10.1107/S2056989024008259

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Synthesis, crystal structure and Hirshfeld surface analysis of a new copper(II) complex based on diethyl 2,2′-(4H-1,2,4-triazole-3,5-diyl)diacetate

Oleksandr S. Vynohradov,^a ^* Oleksandr V. Vashchenko,^a Dmytro M. Khomenko,^a ‡ Roman O. Doroshchuk,^a ‡ Ilona V. Raspertova,^a Rostyslav D. Lampeka ^a and Alexandru-Constantin Stoica ^b

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, and ^b"PetruPoni" Institute of Macromolecular Chemistry, Aleea Gr., Ghica Voda 41A, 700487 Iasi, Romania
^*Correspondence e-mail: oleksandr.vynohradov@knu.ua

Edited by S.-L. Zheng, Harvard University, USA (Received 15 July 2024; accepted 21 August 2024; online 30 August 2024)

The title compound, bis[μ-2,2′-(4H-1,2,4-triazole-3,5-diyl)diacetato]bis[diaquacopper(II)] dihydrate, [Cu₂(C₆H₅N₃O₄)₂(H₂O)₄]·2H₂O, is a dinuclear octahedral Cu^II triazole-based complex. The central copper atoms are hexa-coordinated by two nitrogen atoms in the equatorial positions, two equatorial oxygen atoms of two carboxylate substituents in position 3 and 5 of the 1,2,4-triazole ring, and two axial oxygen atoms of two water molecules. Two additional solvent water molecules are linked to the title molecule by O—H⋯N and O⋯H—O hydrogen bonds. The crystal structure is built up from the parallel packing of discrete supramolecular chains running along the a-axis direction. Hirshfeld surface analysis suggests that the most important contributions to the surface contacts are from H⋯O/O⋯H (53.5%), H⋯H (28.1%), O⋯O (6.3%) and H⋯C/C⋯H (6.2%) interactions. The crystal studied was twinned by a twofold rotation around [100].

Keywords: copper; copper(II) complex; crystal structure; 1,2,4-triazole; Hirshfeld surface analysis.

CCDC reference: 2378887

1. Chemical context

1,2,4-Triazole-based organic compounds have been widely used as ligands for the synthesis of transition-metal complexes (Haasnoot, 2000 ; Aromí et al., 2011 ; Farooq, 2021 ). Depending on the substituents on the azole core, the title ligands can coordinate not only in a monodentate manner (Cudziło et al., 2011 ; Zaleski et al., 2005 ), but also as a linker binding two metal ions (Drabent et al., 2001 ; Zhang et al., 2005 ) and thus play an important role in the design of new polynuclear coordination compounds. In particular, copper(II) coordination compounds based on 1,2,4-triazoles have attracted the interest of chemists due to their magnetic properties (Petrenko et al., 2020 ; Kaase et al., 2014 ), bioactivity (Hernández-Gil et al., 2013 ; Ferrer et al., 2004 ) and catalysis (Thorseth et al., 2013 ; Li et al., 2015 ). Dinuclear copper(II) complexes can promote single- and double-strand DNA cleavage in both aerobic and anaerobic conditions (Li et al., 2010 ). Being much cheaper than most metals, copper(II) coordination compounds are promising substances for exploration as catalysts. Previously we reported that a dinuclear Cu^II complex based on 5-methyl-3-(2-pyridyl)-1,2,4-triazole as a ligand can selectively catalyse the oxidation of styrene towards benzaldehyde and of cyclohexane to KA oil (a mixture of cyclohexanol and cyclohexanone; Petrenko et al., 2021 ). Finally, Cu^II complexes can exhibit urease inhibitory activities (Xu et al., 2015 ). Since dinuclear copper(II) complexes with triazole bridges can exhibit catalytic properties, we decided to continue our research in this direction. Herein, we describe the synthesis, crystal structure, and results of Hirshfeld surface analysis of the title compound, [Cu₂(C₆H₅N₃O₄)₂(H₂O)₄]·2H₂O, which potentially exhibits catalytic, inhibitory, and magnetic properties.

2. Structural commentary

The title compound (Fig. 1), a dinuclear copper(II) 1,2,4-triazole-based complex, crystallizes in the monoclinic, P2₁/n space group. The asymmetric unit consists of one copper(II) ion, one 4H-1,2,4-triazole-3,5-dicarboxylate ligand, two coordinated water molecules and one solvent water molecule. The structure of the title compound can be described as a neutral complex of formula [Cu₂(C₆H₅N₃O₄)₂(H₂O)₄]·2H₂O in which the triazole ligand is coordinated in a tetradentate way. The Cu^II ion has a distorted N₂O₄ octahedral geometry formed by two nitrogen atoms in the equatorial positions with Cu1—N1 = 1.982 (3) Å and Cu1—N2ⁱ [symmetry code: (i) −x + 1, −y + 1, −z + 1)] = 1.990 (4) Å bond distances, two equatorial oxygen atoms of two carboxylate substituents in position 3 and 5 of the triazole ring [Cu1—O1 = 1.962 (3) Å and Cu1—O3ⁱ = 1.974 (3) Å], and two axial oxygen atoms of two water molecules with Cu1—O1W = 2.497 (3) Å and Cu1—O2W = 2.484 (3) Å bond distances. The Cu1—Cu1ⁱ intermetallic distance in the complex molecule is 3.9866 (15) Å. Two copper atoms bridged by two 4H-1,2,4-triazole-3,5-dicarboxylate ligands form a non-planar six-membered bimetallic ring. In addition, four six-membered non-planar chelate rings are formed due to the presence of carboxylate substituents at the 3 and 5 positions of the 1,2,4-triazole rings. There are medium strength intermolecular O—H⋯O hydrogen bonds between the main compound and solvent water molecules. Intermolecular N—H⋯O and C—H⋯O hydrogen bonds between two complex molecules are also observed (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4ⁱ	0.87	1.91	2.762 (5)	165
O1W—H1WB⋯O3W	0.87	1.94	2.797 (5)	169
O2W—H2WA⋯O1Wⁱⁱ	0.85	2.03	2.880 (4)	170
O2W—H2WB⋯O2ⁱⁱⁱ	0.87	1.89	2.744 (4)	167
N3—H3⋯O4^iv	0.88	1.81	2.670 (5)	165
C5—H5B⋯O3^iv	0.99	2.32	3.257 (6)	158
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

The crystal structure is built up from the parallel packing of discrete supramolecular chains running along the a-axis direction with a Cu⋯Cu separation of 6.5248 (11) Å (Fig. 2). Within the chain, the complex molecules interact through O—H⋯O hydrogen bonds, while the association with the interstitial water molecules occurs via O—H⋯O and N—H⋯O hydrogen bonds (Fig. 3, Table 1).

Figure 2
One-dimensional supramolecular chain running parallel to the a axis and viewed along the b axis. Solvent water molecules are shown in green, O—H⋯O and O—H⋯N hydrogen bonds are shown as red and blue dotted lines, respectively.

Figure 3
Partial view of the crystal packing showing hydrogen-bond contacts between adjacent molecules.

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.41, update of November 2021; Groom et al., 2016 ) for the Cu₂(C₂N₃)₂O₄ moiety (two 1,2,4-triazole ring skeletons connected via two Cu atoms; each copper atom is coordinated by two oxygen atoms) revealed 48 hits. Most similar to the title compound are dinuclear copper(II) complexes with following database refcodes: COCZAV (Ferrer et al., 1999 ), DODRET and DODRIX (Prins et al., 1985 ), FIVGEY (Matthews et al., 2003 ), JOZXAX (van Koningsbruggen et al., 1992 ) and VALZOA (Doroschuk, 2016 ). All coordination compounds have many common characteristics, but there are also some minor differences between them. All these dinuclear copper(II) complexes contain two 1,2,4-triazole-based ligands. The triazole derivatives have two substituents at positions 3 and 5 of the triazole ring. The substituents containing donor atoms also participate in coordination with the copper atom. These ligands exhibit bridging functions and link two copper atoms at distances in the range of 3.85 to 4.09 Å. Two six-coordinated copper atoms are involved in the formation of a six-membered ring. There are two water molecules in the axial positions of the central copper atom in the title compound and the compound JOZXAX. In other complexes, one axial position in the geometric environment of the copper atom is occupied by a water molecule, while the second axial position is typically occupied by an anion of an inorganic salt. The title compound crystallizes in the monoclinic P2₁/n space group. Five complexes crystallized in the triclinic, P $[\overline{1}]$ space group, while JOZXAX crystallized in the monoclinic C2/c space group.

5. Hirshfeld surface analysis

The Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using Crystal Explorer 17.5 software (Spackman et al., 2021 ), with a standard resolution of the three-dimensional d_norm surfaces (shown in Figs. 4 and 5). The dark-red spots 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 for the H⋯O/O⋯H, H⋯H, O⋯O, H⋯C/C⋯H, H⋯N/N⋯H and O⋯C/C⋯O contacts (Fig. 6), the overall two-dimensional fingerprint plot and the decomposed two-dimensional fingerprint plots are given in Fig. 7. Two pairs of N3—H3⋯O4 interatomic contacts with lengths of 1.696 Å are the shortest. The most significant contributions to the overall crystal packing are from H⋯O/O⋯H (53.5%), H⋯H (28.1%), O⋯O (6.3%) and H⋯C/C⋯H (6.2%) contacts. The predominance of contributions from H⋯H and H⋯O contacts to the overall crystal packing is typical not only for the title compound and other dinuclear copper(II) complexes with triazole-containing ligands but also of copper(II) coordination compounds with azole-based ligands in general. There is a small contribution from H⋯N/N⋯H (3.5%) and O⋯C/C⋯O (2.3%) weak intermolecular contacts. The relative percentage contributions to the overall Hirshfeld surface by elements: H⋯all atoms = 55.4%, O⋯all atoms = 35.6%, C⋯all atoms = 6.1%, N⋯all atoms = 3.0% and Cu⋯all atoms = 0%. In addition, quantitative physical properties of the Hirshfeld surface for this compound were obtained, such as molecular volume (444.48 Å³), surface area (384.06 Å²), globularity (0.733) and asphericity (0.063). The asphericity value for the title compound at 0.063 is close to zero, indicating a near isotropic nature. The globularity value (0.733) is less than one, suggesting a modest deviation from a spherical surface and indicating that this molecular surface is more structured compared to a sphere.

Figure 4
(a) Two projections of the Hirshfeld surfaces mapped over d_norm showing the intermolecular interactions within the molecule and (b) an illustration of selected O—H⋯O and O—H⋯N interactions depicted by green and yellow dashed lines, respectively.

Figure 5
Hirshfeld surface representations with the function d_norm plotted onto the surface for the different interactions.

Figure 6
The overall two-dimensional fingerprint plot and those delineated into specified interactions.

6. Synthesis and crystallization

[Cu₂(HL)₂(H₂O)₄]·2H₂O. An aqueous solution (2 ml) of Cu(NO₃)₂·6H₂O (0.296 g, 1 mmol) was added to 2 ml of an aqueous solution of ethyl 2,2′-(1H-1,2,4-triazole-3,5-diyl)diacetate (0.241 g, 1 mmol) to give a clear blue solution. The blue crystals that precipitated after 2 days were filtered off, washed with water, and dried in air (Kiseleva et al., 1990 ). Yield 0.247 g (82.18%). IR data (in KBr, cm⁻¹): 3404, 3224, 1638, 1620, 1606, 1568, 1540, 1454, 1418, 1400, 1386, 1274, 1250, 1052, 956, 752, 644, 578. Analysis calculated for C₁₂H₂₂Cu₂N₆O₁₄ (601.43): C, 23.96%; H, 3.69%; N, 13.97%. Found: C, 23.88%; H, 3.72%; N, 13.88%.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal studied was twinned by a twofold rotation around [100]. The corresponding HKLF5 generated by the CrysAlis program was used for refinement. The O- and N-bound hydrogen atoms were identified in difference-Fourier maps and refined isotropically with positional restraints. All other H atoms were placed in calculated positions and refined using a riding model with C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂(C₆H₅N₃O₄)₂(H₂O)₄]·2H₂O
M_r	601.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	6.5176 (13), 9.4854 (19), 15.967 (2)
β (°)	93.035 (15)
V (Å³)	985.7 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.25
Crystal size (mm)	0.56 × 0.37 × 0.33 × 0.22 (radius)

Data collection
Diffractometer	Xcalibur, Eos
Absorption correction	For a sphere (CrysAlis PRO; Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.488, 0.498
No. of measured, independent and observed [I > 2σ(I)] reflections	2569, 2569, 1969
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.096, 1.00
No. of reflections	2569
No. of parameters	159
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.53
Computer programs: CrysAlis PRO (Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2378887

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024008259/oi2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024008259/oi2010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024008259/oi2010Isup3.cdx

FT-IR spectrum of the title compound. DOI: https://doi.org/10.1107/S2056989024008259/oi2010sup4.jpg

Powder X-ray diffraction pattern of the title compound. DOI: https://doi.org/10.1107/S2056989024008259/oi2010sup5.jpg

checkCIF report

Computing details top

Bis[µ-2,2'-(4H-1,2,4-triazole-3,5-diyl)diacetato]bis[diaquacopper(II)] dihydrate top

Crystal data top

[Cu₂(C₆H₅N₃O₄)₂(H₂O)₄]·2H₂O	F(000) = 612
M_r = 601.44	D_x = 2.026 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.5176 (13) Å	Cell parameters from 833 reflections
b = 9.4854 (19) Å	θ = 2.5–28.3°
c = 15.967 (2) Å	µ = 2.25 mm⁻¹
β = 93.035 (15)°	T = 200 K
V = 985.7 (3) Å³	Prism, clear intense green
Z = 2	0.56 × 0.37 × 0.33 × 0.22 (radius) mm

Data collection top

Xcalibur, Eos diffractometer	1969 reflections with I > 2σ(I)
Detector resolution: 16.1593 pixels mm^-1	R_int = 0.053
ω scans	θ_max = 29.2°, θ_min = 2.5°
Absorption correction: for a sphere (CrysAlisPro; Rigaku OD, 2024)	h = −8→8
T_min = 0.488, T_max = 0.498	k = −12→12
2569 measured reflections	l = −21→21
2569 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0483P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2569 reflections	Δρ_max = 0.63 e Å⁻³
159 parameters	Δρ_min = −0.53 e Å⁻³
18 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. Refined as a 2-component twin.

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

	x	y	z	U_iso*/U_eq
Cu1	0.48120 (9)	0.59062 (7)	0.61179 (3)	0.01441 (17)
O1	0.4081 (5)	0.7706 (4)	0.66289 (18)	0.0196 (8)
O1W	0.8274 (4)	0.6812 (4)	0.57854 (18)	0.0176 (8)
H1WA	0.849334	0.760096	0.605348	0.026*
H1WB	0.826653	0.704497	0.525777	0.026*
O2	0.3198 (5)	0.9950 (4)	0.67791 (19)	0.0167 (8)
O2W	0.1424 (5)	0.4979 (4)	0.65012 (18)	0.0220 (8)
H2WA	0.058325	0.553892	0.624170	0.033*
H2WB	0.134335	0.500812	0.704360	0.033*
O3	0.3906 (5)	0.4446 (3)	0.27539 (18)	0.0181 (8)
O3W	0.8739 (6)	0.7755 (4)	0.4147 (2)	0.0255 (9)
H3WA	0.888191	0.700243	0.386753	0.038*
H3WB	0.812698	0.836952	0.383823	0.038*
O4	0.3227 (4)	0.5597 (3)	0.15734 (18)	0.0148 (8)
N1	0.3931 (5)	0.6605 (4)	0.4985 (2)	0.0110 (9)
N2	0.4400 (5)	0.6031 (4)	0.42206 (19)	0.0104 (8)
N3	0.3370 (5)	0.8181 (4)	0.4021 (2)	0.0115 (9)
H3	0.302775	0.898014	0.377062	0.014*
C1	0.3396 (6)	0.8877 (6)	0.6350 (3)	0.0114 (11)
C2	0.2603 (7)	0.8982 (5)	0.5444 (3)	0.0190 (12)
H2A	0.108417	0.894494	0.543222	0.023*
H2B	0.298467	0.992262	0.523253	0.023*
C3	0.3309 (6)	0.7904 (6)	0.4839 (3)	0.0112 (11)
C4	0.4041 (6)	0.7029 (5)	0.3657 (3)	0.0126 (11)
C5	0.4403 (7)	0.6970 (5)	0.2737 (3)	0.0134 (11)
H5A	0.587709	0.714517	0.265692	0.016*
H5B	0.360820	0.773275	0.244772	0.016*
C6	0.3793 (6)	0.5556 (6)	0.2329 (3)	0.0145 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0258 (3)	0.0090 (3)	0.0082 (2)	0.0024 (3)	−0.0025 (2)	0.0000 (3)
O1	0.0343 (19)	0.0125 (18)	0.0119 (15)	0.0043 (18)	0.0005 (15)	−0.0056 (15)
O1W	0.0274 (17)	0.013 (2)	0.0122 (15)	−0.0017 (18)	−0.0028 (13)	−0.0004 (17)
O2	0.0299 (18)	0.0093 (19)	0.0107 (16)	0.0032 (18)	0.0007 (14)	−0.0018 (15)
O2W	0.0337 (19)	0.019 (2)	0.0129 (16)	0.012 (2)	−0.0023 (14)	0.0013 (17)
O3	0.034 (2)	0.008 (2)	0.0124 (16)	−0.0008 (17)	−0.0041 (14)	0.0030 (15)
O3W	0.038 (2)	0.017 (2)	0.0212 (17)	0.000 (2)	−0.0018 (16)	−0.0045 (19)
O4	0.0280 (17)	0.010 (2)	0.0061 (15)	−0.0003 (16)	−0.0051 (12)	0.0013 (15)
N1	0.0183 (19)	0.008 (2)	0.0063 (17)	−0.0002 (19)	−0.0012 (15)	0.0007 (17)
N2	0.0103 (16)	0.015 (2)	0.0066 (14)	0.003 (2)	0.0029 (14)	−0.0029 (19)
N3	0.019 (2)	0.008 (2)	0.0077 (18)	0.0014 (19)	−0.0009 (15)	0.0053 (18)
C1	0.013 (2)	0.017 (3)	0.0041 (19)	−0.003 (2)	0.0056 (16)	0.000 (2)
C2	0.026 (3)	0.013 (3)	0.018 (2)	0.005 (3)	0.0021 (18)	−0.001 (3)
C3	0.014 (2)	0.012 (3)	0.007 (2)	0.000 (2)	−0.0001 (17)	0.004 (2)
C4	0.014 (2)	0.013 (3)	0.012 (2)	−0.003 (2)	0.0015 (18)	0.003 (2)
C5	0.019 (2)	0.010 (3)	0.011 (2)	0.001 (2)	−0.0012 (19)	−0.001 (2)
C6	0.011 (2)	0.018 (3)	0.016 (2)	0.004 (2)	0.0031 (17)	−0.001 (2)

Geometric parameters (Å, º) top

Cu1—O1	1.962 (3)	O4—C6	1.243 (5)
Cu1—O1W	2.497 (3)	N1—N2	1.385 (4)
Cu1—O2W	2.484 (3)	N1—C3	1.314 (6)
Cu1—O3ⁱ	1.974 (3)	N2—C4	1.319 (5)
Cu1—N1	1.982 (3)	N3—H3	0.8800
Cu1—N2ⁱ	1.990 (4)	N3—C3	1.336 (5)
O1—C1	1.269 (5)	N3—C4	1.323 (6)
O1W—H1WA	0.8703	C1—C2	1.514 (6)
O1W—H1WB	0.8707	C2—H2A	0.9900
O2—C1	1.238 (5)	C2—H2B	0.9900
O2W—H2WA	0.8546	C2—C3	1.495 (6)
O2W—H2WB	0.8709	C4—C5	1.502 (5)
O3—C6	1.253 (5)	C5—H5A	0.9900
O3W—H3WA	0.8491	C5—H5B	0.9900
O3W—H3WB	0.8489	C5—C6	1.534 (6)

O1—Cu1—O1W	91.79 (13)	C4—N2—N1	106.2 (4)
O1—Cu1—O2W	88.11 (12)	C3—N3—H3	126.4
O1—Cu1—O3ⁱ	82.43 (13)	C4—N3—H3	126.4
O1—Cu1—N1	91.35 (14)	C4—N3—C3	107.1 (4)
O1—Cu1—N2ⁱ	171.18 (13)	O1—C1—C2	119.3 (4)
O2W—Cu1—O1W	177.86 (9)	O2—C1—O1	124.8 (4)
O3ⁱ—Cu1—O1W	84.77 (12)	O2—C1—C2	115.8 (5)
O3ⁱ—Cu1—O2W	93.10 (12)	C1—C2—H2A	107.8
O3ⁱ—Cu1—N1	167.83 (15)	C1—C2—H2B	107.8
O3ⁱ—Cu1—N2ⁱ	89.34 (13)	H2A—C2—H2B	107.1
N1—Cu1—O1W	84.98 (13)	C3—C2—C1	118.1 (4)
N1—Cu1—O2W	97.16 (13)	C3—C2—H2A	107.8
N1—Cu1—N2ⁱ	97.31 (14)	C3—C2—H2B	107.8
N2ⁱ—Cu1—O1W	90.61 (13)	N1—C3—N3	109.5 (4)
N2ⁱ—Cu1—O2W	89.17 (13)	N1—C3—C2	129.0 (4)
C1—O1—Cu1	134.8 (3)	N3—C3—C2	121.5 (4)
Cu1—O1W—H1WA	108.5	N2—C4—N3	110.2 (4)
Cu1—O1W—H1WB	109.5	N2—C4—C5	127.5 (4)
H1WA—O1W—H1WB	104.5	N3—C4—C5	122.2 (4)
Cu1—O2W—H2WA	102.5	C4—C5—H5A	108.9
Cu1—O2W—H2WB	109.6	C4—C5—H5B	108.9
H2WA—O2W—H2WB	113.0	C4—C5—C6	113.5 (4)
C6—O3—Cu1ⁱ	130.3 (3)	H5A—C5—H5B	107.7
H3WA—O3W—H3WB	109.5	C6—C5—H5A	108.9
N2—N1—Cu1	127.3 (3)	C6—C5—H5B	108.9
C3—N1—Cu1	123.1 (3)	O3—C6—C5	119.8 (4)
C3—N1—N2	107.0 (4)	O4—C6—O3	123.9 (5)
N1—N2—Cu1ⁱ	132.4 (3)	O4—C6—C5	116.2 (4)
C4—N2—Cu1ⁱ	121.1 (3)

Cu1—O1—C1—O2	−173.2 (3)	N2—N1—C3—N3	−0.2 (5)
Cu1—O1—C1—C2	11.6 (7)	N2—N1—C3—C2	179.4 (4)
Cu1ⁱ—O3—C6—O4	168.2 (3)	N2—C4—C5—C6	41.1 (6)
Cu1ⁱ—O3—C6—C5	−11.0 (6)	N3—C4—C5—C6	−142.1 (4)
Cu1—N1—N2—Cu1ⁱ	24.3 (5)	C1—C2—C3—N1	26.4 (7)
Cu1—N1—N2—C4	−161.7 (3)	C1—C2—C3—N3	−154.0 (4)
Cu1—N1—C3—N3	162.8 (3)	C3—N1—N2—Cu1ⁱ	−173.6 (3)
Cu1—N1—C3—C2	−17.6 (7)	C3—N1—N2—C4	0.4 (5)
Cu1ⁱ—N2—C4—N3	174.4 (3)	C3—N3—C4—N2	0.2 (5)
Cu1ⁱ—N2—C4—C5	−8.4 (6)	C3—N3—C4—C5	−177.1 (4)
O1—C1—C2—C3	−21.3 (6)	C4—N3—C3—N1	0.0 (5)
O2—C1—C2—C3	163.0 (4)	C4—N3—C3—C2	−179.7 (4)
N1—N2—C4—N3	−0.4 (5)	C4—C5—C6—O3	−30.0 (6)
N1—N2—C4—C5	176.8 (4)	C4—C5—C6—O4	150.8 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ⁱⁱ	0.87	1.91	2.762 (5)	165
O1W—H1WB···O3W	0.87	1.94	2.797 (5)	169
O2W—H2WA···O1Wⁱⁱⁱ	0.85	2.03	2.880 (4)	170
O2W—H2WB···O2^iv	0.87	1.89	2.744 (4)	167
N3—H3···O4^v	0.88	1.81	2.670 (5)	165
C5—H5B···O3^v	0.99	2.32	3.257 (6)	158

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

Footnotes

‡Additional address: Enamine Ltd., Winston Churchill Street 78, Kyiv 02094, Ukraine.

Funding information

Funding for this research was provided by grants 22BF037–06 obtained from the Ministry of Education and Science of Ukraine.

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