Carbon dioxide capture from air leading to bis­[N-(5-methyl-1H-pyrazol-3-yl-κN2)carbamato-κO]copper(II) tetra­hydrate

Sirenko, V.Y.; Kuzevanova, I.S.; Vynohradov, O.S.; Naumova, D.D.; Shova, S.

doi:10.1107/S2056989023008575

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ISSN: 2056-9890

Volume 79| Part 11| November 2023| Pages 988-992

https://doi.org/10.1107/S2056989023008575

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Carbon dioxide capture from air leading to bis[N-(5-methyl-1H-pyrazol-3-yl-κN²)carbamato-κO]copper(II) tetrahydrate

Valerii Y. Sirenko,^a ^* Iryna S. Kuzevanova,^b,^c Oleksandr S. Vynohradov,^a Dina D. Naumova ^a and Sergiu Shova ^d

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, ^bDepartment of General and Inorganic Chemistry, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute", Peremogy Pr. 37, 03056 Kyiv, Ukraine, ^cInnovation Development Center ABN, Pirogov str. 2/37, 01030 Kyiv, Ukraine, and ^dDepartment of Inorganic polymers, "Petru Poni" Institute of Macromolecular Chemistry, Aleea Gr. Ghica, Voda 41A, 700487 Iasi, Romania
^*Correspondence e-mail: valerii_sirenko@knu.ua

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 18 September 2023; accepted 28 September 2023; online 5 October 2023)

A mononuclear square-planar Cu^II complex of (5-methyl-1H-pyrazol-3-yl)carbamate, [Cu(C₅H₆N₃O₂)₂]·4H₂O, was synthesized using a one-pot reaction from 5-methyl-3-pyrazolamine and copper(II) acetate in water under ambient conditions. The adsorption of carbon dioxide from air was facilitated by the addition of diethanolamine to the reaction mixture. While diethanolamine is not a component of the final product, it plays a pivotal role in the reaction by creating an alkaline environment, thereby enabling the adsorption of atmospheric carbon dioxide. The central copper(II) atom is in an (N₂O₂) square-planar coordination environment formed by two N atoms and two O atoms of two equivalent (5-methyl-1H-pyrazol-3-yl)carbamate ligands. Additionally, there are co-crystallized water molecules within the crystal structure of this compound. These co-crystallized water molecules are linked to the Cu^II mononuclear complex by O—H⋯O hydrogen bonds. According to Hirshfeld surface analysis, the most frequently observed weak intermolecular interactions are H⋯O/O⋯H (33.6%), H⋯C/C⋯H (11.3%) and H⋯N/N⋯H (9.0%) contacts.

Keywords: 5-methyl-3-pyrazolamine; copper(II) acetate; diethanolamine; Hirshfeld surface analysis; crystal structure; copper(II) complexes.

CCDC reference: 2298123

1. Chemical context

Currently, global warming stands out as the most significant environmental concern, leading to climate change and giving rise to a range of effects, including elevated sea levels, prolonged droughts, intensified hurricanes, and a surge in extreme weather occurrences (Ochedi et al., 2021 ). The primary cause of global warming in recent decades can be attributed to the heightened levels of greenhouse gases in the atmosphere, with particular emphasis on the concentration of CO₂ (Aghaie et al., 2018 ). Power plants, comprising more than 40% of CO₂ emissions, with coal-fired facilities accounting for 73% of fossil fuel-based power plant emissions (Cannone et al., 2021 ; Mikkelsen et al., 2010 ), are a significant contributor to the carbon footprint. Given the widespread use of fossil fuels, particularly coal, there is a strong need to develop effective methods for capturing and mitigating CO₂ emissions from power plant flue gases, to help stabilize the atmospheric CO₂ level (Wang et al., 2017 ).

Various technologies, including adsorption (Milner et al., 2017 ), absorption (Conway et al., 2013 ), membrane separations (Sreedhar et al., 2017 ), cryogenic distillation (Song et al., 2019 ), and chemical looping (Kronberger et al., 2004 ), are currently under research and development for capturing CO₂ from flue-gas streams. One potential strategy for reducing carbon emissions in the future involves the utilization of carbon capture and sequestration (CCS) materials.

The process of CCS entails the specific separation and subsequent storage of CO₂ taken from exhaust gas mixtures, which predominantly consist of N₂, CO₂, H₂O, and O₂, preventing their release into the atmosphere. Following this, the collected CO₂ is transported for either utilization or long-term storage. Amine scrubbing-based chemical capture methods have garnered significant focus and interest (Tang et al., 2005 ; Mani et al., 2006 ).

One of the methods for reducing carbon dioxide levels in the environment involves capturing it through the formation of carbamates (Conway et al., 2011 ; McCann et al., 2009 ; Zhang et al., 2017 ). Besides, carbamates can be used as catalysts or useful intermediates in the synthesis of other, more-valuable chemicals (Dell'Amico et al., 2003 ). Given the necessity of capturing CO₂ to address broader societal needs, in this article we report the synthesis, crystal structure and Hirshfeld surface analysis of a new mononuclear copper(II) complex with (5-methyl-1H-pyrazol-3-yl)carbamic acid – [Cu(5-MeHpzCarb)₂]·4H₂O.

2. Structural commentary

The title compound crystallizes in the monoclinic space group P2₁/c, and has a crystal structure built upon neutral mononuclear [Cu(5-MeHpzCarb)₂] units (Fig. 1). Co-crystallized water molecules are present in a 1:4 ratio to the complex as interstitial molecules. The asymmetric unit includes one copper site (SOF is 0.5, Wyckoff position 2a), one (5-methyl-1H-pyrazol-3-yl)carbamate ligand and two co-crystallized water molecules.

Figure 1
Representation of the [Cu(5-MeHpzCarb)₂] complex and co-crystallized water molecules, showing the atom-labelling scheme and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii. Symmetry codes: (i) −x, −y, −z; (ii) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.

The Cu^II ion displays a square-planar coordination environment (N₂O₂) formed by two nitrogen atoms of pyrazole rings and two oxygen atoms of carboxylate group of (5-methyl-1H-pyrazol-3-yl)carbamate ligands. The Cu1—N1 distances are 1.931 (2) Å while the Cu1–O1 distances are shorter and account to 1.9140 (17) Å. The O1–Cu1–O1ⁱ and N1—Cu1—N1ⁱ bond angles are 180°, which is typical for a square-planar arrangement (Fig. 1). At the same time, the N1—Cu1—O1ⁱ and N1—Cu1—O1 bond angles slightly deviate from the ideal value of 90°, which is the result of the formation of the six-membered chelate rings. Selected bond lengths and bond angles are given in Table 1. The Cu1 atom lies within the plane defined by N1—O1—N1ⁱ—O1ⁱ. Additionally, the Cu atom lies within the planes of the aromatic rings, whereas O1 and O1ⁱ are slightly above the plane, with an O1(O1ⁱ)-to-plane distance of 0.182 (3) Å.

Table 1
Selected bond lengths and bond angles (Å, °)

Cu1—O1	1.9140 (17)	Cu1—N1	1.931 (2)
N1ⁱ—Cu1—N1	180.0	O1—Cu1—N1ⁱ	91.08 (8)
O1—Cu1—N1	88.92 (8)	N2—N1—Cu1	126.70 (16)
Symmetry codes: (i) −x, −y, −z

In the crystal structure, monomeric [Cu(5-MeHpzCarb)₂] units form layers with Cu1 centres lying in the ab plane. The plane-normal-to-plane-normal angle between the horizontal N1—O1—N1ⁱ—O1ⁱ planes of two adjacent layers is 74.762 (2)°.

3. Supramolecular features

All the components of the structure are associated via intermolecular O—H⋯O and N—H⋯O hydrogen bonds, as well as weak C—H⋯O contacts (Figs. 2, 3). π–π contacts are also observed between neutral [Cu(5-MeHpzCarb)₂] molecular complexes (Fig. 2). The co-crystallized water molecules are interleaved with the supramolecular layers of the neutral [Cu(5-MeHpzCarb)₂] complexes along the c-axis. The O4 water molecule participates in four hydrogen bonds, two where it acts as a donor (O4—H4E⋯O2ⁱⁱ and O4—H4D⋯O3ⁱ, see Table 2 for details), and two as acceptor (O3—H3B⋯O4 and N2—H2⋯O4ⁱⁱⁱ, see Table 2 for details). At the same time, the O3 water molecule participates in three hydrogen bonds, two where it acts as a donor (O3—H3A⋯O2 and O3—H3B⋯O4, see Table 2 for details) and one as acceptor (O4—H4D⋯O3ⁱ, see Table 2 for details). In addition, the O3 water molecule participates in a weak C2—H2A⋯O3^iv contact with a C2⋯O3 distance of 3.340 (4) Å. According to this, the co-crystallized water molecules play an important role in providing cohesion between the neutral [Cu(5-MeHpzCarb)₂] molecular complexes. Geometric parameters for intermolecular hydrogen bonds are given in Table 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4D⋯O3ⁱ	0.87	1.80	2.664 (3)	171
O4—H4E⋯O1ⁱⁱ	0.87	2.44	2.930 (3)	116
O4—H4E⋯O2ⁱⁱ	0.87	2.02	2.873 (3)	167
N2—H2⋯O4ⁱⁱⁱ	0.88	1.99	2.863 (3)	169
N3—H3⋯O2^iv	0.88	2.02	2.889 (3)	169
O3—H3A⋯O2	0.87	1.89	2.756 (3)	176
O3—H3B⋯O4	0.87	1.92	2.783 (3)	169
C2—H2A⋯O3^iv	0.95	2.43	3.340 (4)	159
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Partial crystal packing of [Cu(5-MeHpzCarb)₂]·4H₂O showing intermolecular π–π and N—H⋯O contacts as green and red dashed lines, respectively.

Figure 3
Partial crystal packing of [Cu(5-MeHpzCarb)₂]·4H₂O showing the five-membered supramolecular ring formed by four water molecules and the carboxyl group of the (5-methyl-1H-pyrazol-3-yl)carbamate ligand.

Interestingly, four water molecules and the carboxyl group form a five-membered supramolecular ring (Fig. 3). In addition, π–π interactions are observed between the [Cu(5-MeHpzCarb)₂] neutral complexes. The plane-to-plane distance for these π–π contacts is 3.324 (3) Å with the plane-to-plane shift being 1.498 (5) Å. It is also worth noting very weak C—H⋯π contacts between two contiguous [Cu(5-MeHpzCarb)₂] units with a carbon-atom-to-plane distance of 3.586 (4) Å.

4. Hirshfeld surface analysis

The Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using Crystal Explorer 21.5 software (Spackman et al., 2021 ), with standard resolution of the three-dimensional d_norm surfaces plotted over a fixed colour scale of −0.6468 (red) to 1.1041 (blue) a.u. There are eight red spots on the d_norm surface (Fig. 4a). Visualizations were performed using a red–white–blue colour scheme, where red highlights shorter contacts, white is used for contacts around vdW separation, and blue depicts longer contacts. The red spots on the 3D d_norm Hirshfeld surfaces indicate the direction and strength of the intermolecular E—H⋯O hydrogen bonds (where E = N, O), as well as weak C—H⋯O and C—H⋯π contacts. The overall two-dimensional fingerprint plots for the selected interactions are shown in Fig. 4b.

Figure 4
(a) Hirshfeld surface representations with the function d_norm plotted onto the surface for the different interactions; (b) two-dimensional fingerprint plots, showing the contributions of different types of interactions.

The most significant contributions to the overall crystal packing are from H⋯H (32.2%), H⋯O/O⋯H (33.6%), H⋯C/C⋯H (11.3%), H⋯N/N⋯H (9.0%) and C⋯N/N⋯C (4.1%) interactions. The H⋯O/O⋯H contacts form a pair of spikes on the sides of the corresponding two-dimensional plot, which are indicative of strong intermolecular interactions between atoms. At the same time, the H⋯N/N⋯H and H⋯C/C⋯H contacts form less pronounced spikes, indicating that these interactions are weaker.

5. Database survey

A search of the Cambridge Structure Database (CSD version 5.44, last update June 2023; Groom et al., 2016 ) revealed that the structure has never been published before. 51 structures for the Cu(pyrazole)₂(CO₂)₂ moiety [four-coordinated copper atom with an N₂O₂ coordination environment] were found. Most similar to the title compound, complexes forming a four-coordinated N₂O₂ coordination environment, are trans-bis(3,5-dimethylpyrazole)bis(pivalato)copper(II) (DEFSAJ; Zhou et al., 2006 ), bis(1H-indazole-3-carboxylato)copper(II) (ETOVUH; Qin et al., 2017 ), trans-bis(4-nitrobenzoato-O)bis(3,5-dimethylpyrazole-N)copper(II) (KOKGIB; Sarma & Baruah, 2008 ) and bis(dimethylammonium) bis(μ₂-3,5-dicarboxylatopyrazolato)dicopper(II) (ALERIU; Demir et al., 2016 ).

6. Synthesis and crystallization

5-Methyl-3-pyrazolamine (0.015 g, 1.54 × 10 ⁻⁴ mol), copper(II) acetate (0.28 g, 1.54 × 10 ⁻⁴ mol) and diethanolamine (0.032 g, 3.08 × 10 ⁻⁴ mol) were mixed together, and dissolved in water. After 3 days, clear, light-violet crystals were collected by filtration, dried for less than a minute, and then placed under crystallographic oil for further measurements.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The H atoms of N_{(p, c)}—H, C_p—H and O_w—H groups (p = pyrazole, c = carbamide, w = water) were positioned geometrically and refined as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for C_p—H groups, N—H = 0.88 Å and U_iso(H) = 1.2U_eq(N) for N_{(p, c)}—H groups and O—H = 0.87 Å and U_iso(H) = 1.5U_eq(O) for O_w—H groups. Methyl H atoms were positioned geometrically and were allowed to ride on C atoms and rotate around the C—C bond, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for the CH₃ groups.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(C₅H₆N₃O₂)₂]·4H₂O
M_r	415.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	8.4623 (2), 5.64870 (16), 17.4536 (4)
β (°)	98.786 (2)
V (Å³)	824.51 (4)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.39
Crystal size (mm)	0.15 × 0.15 × 0.15

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.638, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5223, 1634, 1401
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.05
No. of reflections	1634
No. of parameters	116
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.57
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015b ), SHELXL2018/3 (Sheldrick, 2015a ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2298123

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023008575/tx2076sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023008575/tx2076Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.42.93a (Rigaku OD, 2023); cell refinement: CrysAlis PRO 1.171.42.93a (Rigaku OD, 2023); data reduction: CrysAlis PRO 1.171.42.93a (Rigaku OD, 2023); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015a); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

Bis[N-(5-methyl-1H-pyrazol-3-yl-κN²)carbamato-κO]copper(II) tetrahydrate top

Crystal data top

[Cu(C₅H₆N₃O₂)₂]·4H₂O	F(000) = 430
M_r = 415.86	D_x = 1.675 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 8.4623 (2) Å	Cell parameters from 2285 reflections
b = 5.64870 (16) Å	θ = 5.1–72.3°
c = 17.4536 (4) Å	µ = 2.39 mm⁻¹
β = 98.786 (2)°	T = 200 K
V = 824.51 (4) Å³	Block, clear light violet
Z = 2	0.15 × 0.15 × 0.15 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	1401 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.042
ω scans	θ_max = 76.8°, θ_min = 5.1°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	h = −10→10
T_min = 0.638, T_max = 1.000	k = −6→4
5223 measured reflections	l = −16→22
1634 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0636P)² + 0.4306P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1634 reflections	Δρ_max = 0.45 e Å⁻³
116 parameters	Δρ_min = −0.57 e Å⁻³
2 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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.000000	0.000000	0.000000	0.0327 (2)
O4	0.6601 (3)	0.2829 (4)	0.29517 (11)	0.0518 (6)
H4D	0.663197	0.160498	0.265176	0.078*
H4E	0.733747	0.377068	0.282986	0.078*
N2	−0.2338 (3)	0.3798 (4)	−0.05018 (12)	0.0354 (5)
H2	−0.253149	0.326001	−0.098018	0.042*
N1	−0.1348 (2)	0.2716 (4)	0.00870 (11)	0.0331 (5)
N3	−0.0507 (3)	0.3550 (4)	0.14235 (11)	0.0362 (5)
H3	−0.059104	0.455034	0.180169	0.043*
O3	0.3513 (3)	0.4313 (5)	0.30719 (12)	0.0567 (6)
H3A	0.280457	0.334940	0.282998	0.085*
H3B	0.442727	0.365820	0.303128	0.085*
C1	−0.1376 (3)	0.4090 (5)	0.07052 (14)	0.0327 (5)
C2	−0.2365 (3)	0.6047 (5)	0.05156 (15)	0.0368 (6)
H2A	−0.257394	0.729896	0.084961	0.044*
C4	−0.4112 (3)	0.7265 (6)	−0.07931 (17)	0.0455 (7)
H4A	−0.388986	0.707721	−0.132463	0.068*
H4B	−0.398069	0.893005	−0.063909	0.068*
H4C	−0.521048	0.676241	−0.076675	0.068*
C3	−0.2977 (3)	0.5781 (5)	−0.02590 (15)	0.0360 (6)
C5	0.0462 (3)	0.1642 (5)	0.16088 (13)	0.0339 (6)
O1	0.0677 (2)	0.0130 (3)	0.10968 (10)	0.0391 (5)
O2	0.1152 (2)	0.1456 (4)	0.22973 (9)	0.0400 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0378 (3)	0.0405 (4)	0.0182 (3)	0.0035 (2)	−0.0012 (2)	−0.0008 (2)
O4	0.0577 (12)	0.0586 (14)	0.0355 (10)	−0.0059 (11)	−0.0042 (9)	−0.0031 (9)
N2	0.0403 (11)	0.0409 (13)	0.0228 (10)	0.0015 (10)	−0.0020 (8)	0.0030 (9)
N1	0.0363 (11)	0.0417 (12)	0.0200 (9)	0.0032 (9)	−0.0003 (8)	0.0016 (9)
N3	0.0442 (12)	0.0438 (13)	0.0196 (9)	0.0015 (10)	0.0016 (8)	−0.0031 (9)
O3	0.0618 (14)	0.0628 (14)	0.0418 (12)	−0.0098 (12)	−0.0036 (10)	0.0008 (11)
C1	0.0341 (12)	0.0392 (14)	0.0245 (11)	−0.0040 (11)	0.0036 (9)	−0.0001 (11)
C2	0.0393 (13)	0.0412 (15)	0.0296 (12)	0.0004 (12)	0.0046 (10)	−0.0009 (11)
C4	0.0419 (14)	0.0491 (18)	0.0435 (15)	0.0032 (13)	−0.0004 (12)	0.0085 (13)
C3	0.0352 (12)	0.0391 (14)	0.0336 (13)	−0.0027 (11)	0.0048 (10)	0.0041 (12)
C5	0.0409 (13)	0.0417 (14)	0.0187 (11)	−0.0064 (12)	0.0031 (9)	0.0000 (10)
O1	0.0478 (11)	0.0465 (12)	0.0205 (9)	0.0065 (8)	−0.0028 (8)	−0.0009 (7)
O2	0.0491 (10)	0.0501 (11)	0.0183 (8)	−0.0039 (9)	−0.0026 (7)	0.0022 (8)

Geometric parameters (Å, º) top

Cu1—N1	1.931 (2)	N3—C5	1.363 (4)
Cu1—N1ⁱ	1.931 (2)	O3—H3A	0.8697
Cu1—O1	1.9140 (17)	O3—H3B	0.8700
Cu1—O1ⁱ	1.9140 (17)	C1—C2	1.396 (4)
O4—H4D	0.8701	C2—H2A	0.9500
O4—H4E	0.8698	C2—C3	1.380 (4)
N2—H2	0.8800	C4—H4A	0.9800
N2—N1	1.367 (3)	C4—H4B	0.9800
N2—C3	1.341 (4)	C4—H4C	0.9800
N1—C1	1.333 (3)	C4—C3	1.490 (4)
N3—H3	0.8800	C5—O1	1.269 (3)
N3—C1	1.387 (3)	C5—O2	1.258 (3)

N1ⁱ—Cu1—N1	180.0	N1—C1—C2	110.7 (2)
O1ⁱ—Cu1—N1ⁱ	88.92 (8)	N3—C1—C2	127.2 (2)
O1ⁱ—Cu1—N1	91.08 (8)	C1—C2—H2A	127.2
O1—Cu1—N1	88.92 (8)	C3—C2—C1	105.5 (2)
O1—Cu1—N1ⁱ	91.08 (8)	C3—C2—H2A	127.2
O1—Cu1—O1ⁱ	180.0	H4A—C4—H4B	109.5
H4D—O4—H4E	104.5	H4A—C4—H4C	109.5
N1—N2—H2	124.3	H4B—C4—H4C	109.5
C3—N2—H2	124.3	C3—C4—H4A	109.5
C3—N2—N1	111.5 (2)	C3—C4—H4B	109.5
N2—N1—Cu1	126.70 (16)	C3—C4—H4C	109.5
C1—N1—Cu1	127.60 (17)	N2—C3—C2	107.0 (2)
C1—N1—N2	105.3 (2)	N2—C3—C4	121.7 (2)
C1—N3—H3	116.4	C2—C3—C4	131.4 (3)
C5—N3—H3	116.4	O1—C5—N3	120.7 (2)
C5—N3—C1	127.2 (2)	O2—C5—N3	117.9 (2)
H3A—O3—H3B	104.5	O2—C5—O1	121.4 (3)
N1—C1—N3	122.1 (2)	C5—O1—Cu1	132.59 (17)

Cu1—N1—C1—N3	−7.3 (4)	C1—N3—C5—O1	1.3 (4)
Cu1—N1—C1—C2	172.53 (18)	C1—N3—C5—O2	−179.9 (2)
N2—N1—C1—N3	179.7 (2)	C1—C2—C3—N2	−1.3 (3)
N2—N1—C1—C2	−0.4 (3)	C1—C2—C3—C4	179.3 (3)
N1—N2—C3—C2	1.1 (3)	C3—N2—N1—Cu1	−173.46 (18)
N1—N2—C3—C4	−179.4 (2)	C3—N2—N1—C1	−0.5 (3)
N1—C1—C2—C3	1.1 (3)	C5—N3—C1—N1	0.0 (4)
N3—C1—C2—C3	−179.1 (3)	C5—N3—C1—C2	−179.9 (3)
N3—C5—O1—Cu1	5.3 (4)	O2—C5—O1—Cu1	−173.44 (18)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4D···O3ⁱⁱ	0.87	1.80	2.664 (3)	171
O4—H4E···O1ⁱⁱⁱ	0.87	2.44	2.930 (3)	116
O4—H4E···O2ⁱⁱⁱ	0.87	2.02	2.873 (3)	167
N2—H2···O4^iv	0.88	1.99	2.863 (3)	169
N3—H3···O2^v	0.88	2.02	2.889 (3)	169
O3—H3A···O2	0.87	1.89	2.756 (3)	176
O3—H3B···O4	0.87	1.92	2.783 (3)	169
C2—H2A···O3^v	0.95	2.43	3.340 (4)	159

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

Selected bond lengths and bond angles (Å, °) top

Cu1—O1	1.9140 (17)	Cu1—N1	1.931 (2)
N1ⁱ—Cu1—N1	180.0	O1—Cu1—N1ⁱ	91.08 (8)
O1—Cu1—N1	88.92 (8)	N2—N1—Cu1	126.70 (16)

Symmetry codes: (i) -x, -y, -z

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 22BF037-09 to Taras Shevchenko National University of Kyiv).

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