Synthesis, crystal structure and Hirshfeld surface analysis of bis­(acetyl­acetonato-κ2O,O′)(2-amino-1-methyl-1H-benzimidazole-κN3)copper(II)

Siddikova, K.; Ziyatov, D.; Tojiboev, A.; Ashurov, J.; Kadirova, Z.; Daminova, S.

doi:10.1107/S2056989024011538

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Volume 81| Part 1| January 2025| Pages 1-5

https://doi.org/10.1107/S2056989024011538

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Synthesis, crystal structure and Hirshfeld surface analysis of bis(acetylacetonato-κ²O,O′)(2-amino-1-methyl-1H-benzimidazole-κN³)copper(II)

Kyzlarkhan Siddikova,^a Daminbek Ziyatov,^b ^* Akmaljon Tojiboev,^c,^d Jamshid Ashurov,^e Zukhra Kadirova ^f and Shahlo Daminova ^b,^f

^aKarshi Engineering Economics Institute, Mustakillik Avenue 225, Karshi 180100, Uzbekistan, ^bNational University of Uzbekistan named after Mirzo Ulugbek, University Street 4, Tashkent 100174, Uzbekistan, ^cUniversity of Geological Sciences, Olimlar Street 64, Tashkent 100125, Uzbekistan, ^dNamangan State University, Boburshox Street 161, Namangan 160107, Uzbekistan, ^eInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, Mirzo Ulugbek Street 83, Tashkent 100125, Uzbekistan, and ^fUzbek-Japan Innovation Center of Youth, University Street 2B, Tashkent 100095, Uzbekistan
^*Correspondence e-mail: ziatovdamin@gmail.com

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 11 September 2024; accepted 26 November 2024; online 1 January 2025)

The title compound, [Cu(C₅H₇O₂)₂(C₈H₉N₃)], crystallizes in the orthorhombic space group Pnma. In the crystal structure, the Cu^II ion is coordinated by two acetylacetonate ligands and one 2-amino-1-methyl-1H-benzimidazole ligand. The crystal structure features intramolecular N—H⋯O and intermolecular N—H⋯O hydrogen bonds, which contribute to the overall cohesion of the crystal. Hirshfeld surface analysis and two-dimensional fingerprint plots were utilized to quantify the intermolecular interactions, revealing the relative contributions of H⋯H (61.1%), H⋯C/C⋯H (21.3%), and O⋯H/H⋯O (11.3%) contacts to the crystal packing.

Keywords: benzimidazole; acetylacetone; copper complex; crystal structure; Hirshfeld surface analysis.

CCDC reference: 2405560

1. Chemical context

Transition-metal complexes containing Schiff base ligands have garnered significant attention in recent years due to their promising catalytic activity in various reactions (Sheikhshoaie et al., 2009 ; Hatefi et al., 2010 ; Rezaeifard et al., 2010 ). Benzimidazole derivatives have also attracted considerable interest due to their diverse biological and therapeutic activities, including antimicrobial properties against bacteria such as methicillin-resistant staphylococcus aureus (Gatadi et al., 2019 ), escherichia coli (Mishra et al., 2019 ), and bacillus subtilis (Song & Ma, 2016 ). The discovery of new benzimidazole compounds with novel antibacterial mechanisms is of paramount importance in addressing the growing threat of antibiotic resistance (Khalafi-Nezhad et al., 2005 ). Recent research has focused on the synthesis and characterization of benzimidazole-based complexes with d-block metals (Jabborova et al., 2024 ) and f-block metals (Ruzieva et al., 2022 ), further expanding the potential applications of these compounds.

The coordination chemistry of rare-earth metals with β-diketonate ligands has been extensively studied due to their versatility and ease of use (Binnemans, 2005 ). β-Dicarbonyl compounds, known for their keto–enol tautomerism, are among the most widely investigated tautomeric systems (Tighadouini et al., 2022 ; Harris, 2001 ). Metal acetylacetonates have found applications in diverse fields, including redox flow batteries (Suttil et al., 2015 ) and as corrosion inhibitors for mild steel (Mahdavian & Attar, 2009 ). Notably, Cu^II, Ni^II, Co^II, and Zn^II complexes with acetylacetone ligands have demonstrated enhanced antimicrobial activity compared to the free ligand (Raman et al., 2003 ). In light of the potential biological significance of the title compound, [Cu(C₅H₇O₂)₂(C₈H₉N₃)], a detailed investigation of its crystal structure is presented.

2. Structural commentary

The title compound, bis(acetylacetonato-κ²O,O′)(2-amino-1-methyl-1H-benzimidazole-κN³)copper(II) (I), crystallizes in the orthorhombic space group Pnma (Fig. 1). The asymmetric unit consists of one molecule of 2-amino-1-methyl-1H-benzimidazole (MAB) and one acetylacetonate (acac) ligand, both coordinated to the central copper(II) ion. The Cu^II ion adopts a square-pyramidal coordination geometry (coordination number 5), with the equatorial plane defined by the oxygen atoms of two bidentate β-diketonate molecules [Cu1—O1 = 1.9378 (16) Å; Cu1—O2 = 1.9546 (16) Å; Table 1]. The observed elongation of the Cu—O bonds is attributed to the Jahn–Teller effect, a common phenomenon in copper-based complexes (Halcrow, 2013 ). The benzimidazole moiety is essentially planar and lies in the plane of symmetry (Fig. 2). The N1 atom of the benzimidazole ligand coordinates axially to the Cu^II ion with a bond distance of 2.196 (2) Å. The observed Cu—N1, Cu—O1, and Cu—O2 bond lengths are consistent with those reported for related Cu^II complexes (Geiger et al., 2017 ; Wong et al., 2009 ). The root-mean-square deviation of the equatorial plane (defined by O1, O2, Cu1, and their symmetry-related counterparts O1ⁱ and O2ⁱ) is 0.118 Å, with out-of-plane distances of 0.0596 (16) Å for O1 and 0.0582 (16) Å for O2. The largest deviation from the plane is observed for the Cu^II ion [0.2357 (4) Å], which is attributed to the presence of only one axial ligand (Fig. 1). The molecular structure of I exhibits intramolecular N—H⋯O hydrogen bonds (Table 2), which contribute to the stability of the individual molecules. These hydrogen bonds form a characteristic S₁¹(6) graph-set motif (Etter et al., 1990 ).

Table 1
Selected bond lengths (Å)

Cu1—O1ⁱ	1.9378 (16)	Cu1—O2	1.9546 (16)
Cu1—O1	1.9378 (16)	Cu1—O2ⁱ	1.9546 (16)
Cu1—N1	2.196 (2)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C2/N3/C3A/C7A ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2	0.86	2.44	3.077 (3)	131
N2—H2B⋯O2ⁱⁱ	0.86	2.44	3.167 (3)	142
C5B—H5BA⋯Cg1ⁱⁱⁱ	0.96	2.74	3.682 (4)	166
Symmetry codes: (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Figure 1
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. The hydrogen atoms and symmetry-generated atoms are not labeled.

Figure 2
(a) The asymmetric unit in the crystal of I. (b) Emphasis on the benzimidazole planarity.

3. Supramolecular features

Intermolecular N—H⋯O hydrogen bonds play a crucial role in establishing the overall crystal packing. These intermolecular interactions link the molecules into a zigzag chain running along the crystallographic a-axis direction, as depicted in Fig. 3. The graph-set descriptors for these chains are C₁¹(6) and R₂¹(4), further illustrating the connectivity of the hydrogen-bonded network.

Figure 3
Crystal packing of I along the c axis. Intramolecular N—H⋯O hydrogen bonds are shown as red and intermolecular N—H⋯O hydrogen bonds as light-blue dashed lines. Dashed green lines denote C—H⋯Cg1 contacts. For clarity, H atoms not involved in these interactions have been omitted.

The structure also features π-ring interactions between adjacent chains, which contribute to the overall cohesion of the crystal. These interactions involve C—H⋯π contacts, where the C5—H5C bond of one molecule interacts with the centroid (Cg1) of the N1/C2/N3/C3A/C7A ring of a neighbouring molecule. The distance between the hydrogen atom (H5C) and the ring centroid (Cg1) is 2.743 (16) Å, indicating a significant interaction.

The combination of intramolecular and intermolecular hydrogen bonds, along with π-ring interactions, results in a robust three-dimensional supramolecular network in the crystal structure of I. These interactions not only contribute to the overall cohesion of the crystal but may also influence the physical and chemical properties of the compound.

4. Hirshfeld surface analysis

Hirshfeld surface analysis was conducted using CrystalExplorer 21.5 (Spackman et al., 2021 ) to gain further insights into the intermolecular interactions in the crystal structure of I. The d_norm surface, shown in Fig. 4, is mapped over −0.2120 to −1.5316 arbitrary units (a.u.), with red, white, and blue regions representing contacts shorter, equal to, or longer than the sum of van der Waals radii, respectively(Venkatesan et al., 2016 ).

Figure 4
View of the three-dimensional Hirshfeld surface of I plotted over d_norm.

The overall two-dimensional fingerprint plot (Fig. 5a) and its decomposed components illustrate the relative contributions of different intermolecular contacts to the Hirshfeld surface. As expected, H⋯H contacts (Fig. 5b) constitute the most significant contribution, accounting for 61.1% of the total Hirshfeld surface area. H⋯C/C⋯H contacts (Fig. 5c) comprise 21.3%, followed by O⋯H/H⋯O contacts (Fig. 5d) at 11.3%. The remaining contributions, including N⋯H/H⋯N (4.6%), Cu⋯C (1.0%), and C⋯C (0.7%), are relatively minor. These results highlight the dominance of van der Waals interactions in the crystal packing of I.

Figure 5
The full two-dimensional fingerprint plots for I, showing (a) all interactions and (b)–(d) delineated into separate interactions.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.45, November 2023; Groom et al., 2016 ) revealed two related structures: bis(acetylacetonato-κ²O,O′)(2-amino-1-methyl-1H-benzimidazole-κN)oxidovanadium(IV) (Kadirova et al., 2009 ; CSD refcode BOVMAB) and aqua(benzimidazole-N)bis(2,4-pentanedionato-O,O′)cobalt(II) (Lin & Feng, 2003 ; CSD refcode ESUZUN). In both cases, the benzimidazole ligand coordinates to the central metal ion through the sp² nitrogen atom (N3), as observed in I. However, the coordination geometries and overall structural features differ due to the presence of different metal centers and additional ligands in these related complexes.

6. Synthesis and crystallization

All reagents and solvents were of analytical grade and used as received. Elemental analysis was performed using a FlashSmart™ Elemental Analyzer. The Fourier-transform infrared (FT–IR) spectrum was recorded on a Spectrum Two N FT–IR Spectrometer at room temperature.

Solutions of 0.1 mmol (0.0261 g) of CuCl₂·6H₂O in ethanol (solution A), 0.2 mmol (0.0294 g) of 2-amino-1-methyl-1H-benzimidazole (MAB) in ethanol (solution B), and 0.2 mmol (0.0205 mL, ρ = 0.975 g mL⁻¹) of acetylacetone (solution C) were prepared. Solution B was added dropwise to solution A with stirring at room temperature for 30 minutes; no immediate changes being observed. Subsequently, solution C was added dropwise to the mixture, followed by stirring for 12 h. The resulting solution was then allowed to stand undisturbed at room temperature. Blue–green crystals formed over several days, which were then filtered, washed with ethanol, and recrystallized from dimethyl sulfoxide to yield light-green crystals suitable for X-ray diffraction analysis.

Elemental analysis: Calculated for C₁₈H₂₃CuN₃O₄: C, 52.88; H, 5.67; N, 10.28%. Found: C, 53.06; H, 5.33; N, 10.59%.

FT–IR (cm⁻¹): 3448s, 3341s, 3054s, 2935m, 1654s, 1612s, 1584s, 1551s, 1522s, 1499s, 1399s, 1319s, 1289s, 1200m, 1108s, 1089m, 1018s, 934s, 894m, 787s, 746s, 674m, 657s, 587s, 566m, 429m.

7. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3. Hydrogen atoms bonded to carbon were positioned geometrically (C—H = 0.93 Å for aromatic, 0.96 Å for methyl, and 0.97 Å for methylene) and refined using a riding model, with U_iso(H) = 1.5U_eq(C) for methyl hydrogens and 1.2U_eq(C) for all others. The amine group (–NH₂) hydrogen atoms were located in a difference-Fourier map and refined with an N—H distance restraint of 0.86 (2) Å and U_iso(H) = 1.5U_eq(N).

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(C₅H₇O₂)₂(C₈H₉N₃)]
M_r	408.93
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	9.0322 (2), 13.9740 (3), 16.0004 (4)
V (Å³)	2019.51 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.70
Crystal size (mm)	0.3 × 0.24 × 0.18

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.517, 1.000
No. of measured, independent and observed [I ≥ 2σ(I)] reflections	19729, 2050, 1693
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.109, 1.04
No. of reflections	2050
No. of parameters	146
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.34
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015 ), OLEX2.refine (Bourhis et al., 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2405560

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024011538/tx2089sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024011538/tx2089Isup2.hkl

checkCIF report

Computing details top

Bis(acetylacetonato-κ²O,O')(2-amino-1-methyl-1H-\ benzimidazole-κN³)copper(II) top

Crystal data top

[Cu(C₅H₇O₂)₂(C₈H₉N₃)]	D_x = 1.345 Mg m⁻³
M_r = 408.93	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pnma	Cell parameters from 5665 reflections
a = 9.0322 (2) Å	θ = 2.8–69.5°
b = 13.9740 (3) Å	µ = 1.70 mm⁻¹
c = 16.0004 (4) Å	T = 298 K
V = 2019.51 (8) Å³	Block, clear light green
Z = 4	0.3 × 0.24 × 0.18 mm
F(000) = 846.676

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	1693 reflections with I ≥ 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.066
ω scans	θ_max = 71.5°, θ_min = 4.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −11→10
T_min = 0.517, T_max = 1.000	k = −17→17
19729 measured reflections	l = −19→19
2050 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0585P)² + 0.436P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.109	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.27 e Å⁻³
2050 reflections	Δρ_min = −0.33 e Å⁻³
146 parameters	Extinction correction: SHELXL2016/6 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00034 (14)

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	0.58425 (4)	0.250000	0.42118 (3)	0.04582 (19)
O1	0.66063 (18)	0.34444 (12)	0.49868 (10)	0.0623 (4)
N1	0.3473 (2)	0.250000	0.45198 (15)	0.0466 (6)
O2	0.56911 (18)	0.34360 (12)	0.33081 (10)	0.0615 (4)
N2	0.2624 (3)	0.250000	0.31270 (17)	0.0819 (10)
H2A	0.350932	0.250000	0.292910	0.098*
H2B	0.187784	0.250000	0.279310	0.098*
C3	0.2406 (3)	0.250000	0.39601 (18)	0.0492 (7)
C7A	0.2752 (3)	0.250000	0.52873 (17)	0.0440 (6)
C8	−0.0378 (5)	0.250000	0.3850 (3)	0.0828 (14)
C3A	0.1225 (3)	0.250000	0.5159 (2)	0.0507 (7)
C4B	0.6857 (3)	0.43114 (19)	0.48236 (19)	0.0713 (7)
C5	0.0806 (4)	0.250000	0.6613 (3)	0.0798 (12)
H5	0.017475	0.250000	0.707242	0.096*
C2B	0.5995 (3)	0.4322 (2)	0.33641 (19)	0.0724 (7)
N3	0.1028 (3)	0.250000	0.43016 (16)	0.0534 (7)
C3B	0.6587 (4)	0.4754 (2)	0.4067 (2)	0.0907 (10)
H3B	0.682585	0.539925	0.402560	0.109*
C4	0.0195 (4)	0.250000	0.5807 (2)	0.0701 (10)
H4	−0.082124	0.250000	0.571234	0.105*
C5B	0.7560 (5)	0.4878 (3)	0.5527 (2)	0.1149 (14)
H5BA	0.760146	0.554218	0.537488	0.172*
H5BB	0.854430	0.464517	0.562579	0.172*
H5BC	0.697939	0.480611	0.602556	0.172*
C6	0.2322 (4)	0.250000	0.6747 (2)	0.0671 (9)
H6	0.267621	0.250000	0.729239	0.080*
C7	0.3321 (4)	0.250000	0.6096 (2)	0.0550 (7)
H7	0.433621	0.250000	0.619289	0.066*
C1B	0.5684 (6)	0.4893 (2)	0.2591 (2)	0.1206 (15)
H1BA	0.574813	0.556314	0.271846	0.181*
H1BB	0.470795	0.474659	0.239196	0.181*
H1BC	0.639781	0.473498	0.216864	0.181*
H8A	−0.049 (6)	0.199 (3)	0.353 (3)	0.19 (2)*
H8B	−0.100 (8)	0.250000	0.420 (4)	0.14 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0410 (3)	0.0525 (3)	0.0439 (3)	0.000	0.00055 (16)	0.000
O1	0.0659 (10)	0.0630 (10)	0.0580 (9)	0.0026 (8)	−0.0107 (7)	−0.0074 (8)
N1	0.0368 (12)	0.0605 (14)	0.0426 (12)	0.000	0.0026 (10)	0.000
O2	0.0728 (11)	0.0612 (10)	0.0505 (9)	−0.0109 (7)	0.0010 (7)	0.0085 (7)
N2	0.0433 (16)	0.160 (3)	0.0422 (14)	0.000	−0.0035 (12)	0.000
C3	0.0360 (14)	0.0645 (18)	0.0471 (15)	0.000	0.0009 (12)	0.000
C7A	0.0464 (15)	0.0420 (13)	0.0435 (14)	0.000	0.0033 (12)	0.000
C8	0.041 (2)	0.137 (5)	0.070 (3)	0.000	−0.0072 (19)	0.000
C3A	0.0441 (15)	0.0556 (17)	0.0524 (17)	0.000	0.0055 (13)	0.000
C4B	0.0746 (17)	0.0566 (14)	0.0828 (18)	0.0047 (12)	−0.0081 (14)	−0.0184 (13)
C5	0.071 (3)	0.114 (3)	0.055 (2)	0.000	0.0223 (17)	0.000
C2B	0.0847 (19)	0.0593 (15)	0.0731 (17)	−0.0010 (13)	0.0100 (14)	0.0128 (13)
N3	0.0374 (13)	0.0733 (18)	0.0494 (14)	0.000	−0.0018 (10)	0.000
C3B	0.129 (3)	0.0480 (14)	0.095 (2)	−0.0085 (16)	−0.009 (2)	−0.0014 (14)
C4	0.050 (2)	0.097 (3)	0.064 (2)	0.000	0.0117 (15)	0.000
C5B	0.148 (4)	0.078 (2)	0.119 (3)	0.000 (2)	−0.038 (3)	−0.039 (2)
C6	0.073 (2)	0.083 (2)	0.0449 (16)	0.000	0.0051 (15)	0.000
C7	0.0554 (19)	0.0618 (19)	0.0477 (16)	0.000	−0.0022 (14)	0.000
C1B	0.187 (4)	0.083 (2)	0.092 (3)	−0.013 (2)	−0.004 (2)	0.036 (2)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.9378 (16)	C3A—C4	1.393 (5)
Cu1—O1	1.9378 (16)	C4B—C3B	1.381 (4)
Cu1—N1	2.196 (2)	C4B—C5B	1.516 (4)
Cu1—O2	1.9546 (16)	C5—H5	0.9300
Cu1—O2ⁱ	1.9546 (16)	C5—C4	1.404 (6)
O1—C4B	1.260 (3)	C5—C6	1.385 (5)
N1—C3	1.316 (4)	C2B—C3B	1.383 (4)
N1—C7A	1.390 (3)	C2B—C1B	1.498 (4)
O2—C2B	1.272 (3)	C3B—H3B	0.9300
N2—H2A	0.8600	C4—H4	0.9300
N2—H2B	0.8600	C5B—H5BA	0.9600
N2—C3	1.348 (4)	C5B—H5BB	0.9600
C3—N3	1.360 (4)	C5B—H5BC	0.9600
C7A—C3A	1.395 (4)	C6—H6	0.9300
C7A—C7	1.392 (4)	C6—C7	1.378 (5)
C8—N3	1.461 (5)	C7—H7	0.9300
C8—H8A	0.89 (5)	C1B—H1BA	0.9600
C8—H8Aⁱ	0.89 (5)	C1B—H1BB	0.9600
C8—H8B	0.79 (7)	C1B—H1BC	0.9600
C3A—N3	1.383 (4)

O1ⁱ—Cu1—O1	85.85 (10)	C3B—C4B—C5B	119.4 (3)
O1—Cu1—N1	101.73 (7)	C4—C5—H5	119.0
O1ⁱ—Cu1—N1	101.73 (7)	C6—C5—H5	119.0
O1—Cu1—O2	92.44 (7)	C6—C5—C4	122.0 (3)
O1ⁱ—Cu1—O2ⁱ	92.44 (7)	O2—C2B—C3B	124.4 (3)
O1—Cu1—O2ⁱ	162.56 (7)	O2—C2B—C1B	114.8 (3)
O1ⁱ—Cu1—O2	162.56 (7)	C3B—C2B—C1B	120.8 (3)
O2—Cu1—N1	95.61 (7)	C3—N3—C8	126.6 (3)
O2ⁱ—Cu1—N1	95.61 (7)	C3—N3—C3A	106.3 (2)
O2ⁱ—Cu1—O2	84.01 (10)	C3A—N3—C8	127.1 (3)
C4B—O1—Cu1	125.89 (18)	C4B—C3B—C2B	125.9 (3)
C3—N1—Cu1	124.14 (19)	C4B—C3B—H3B	117.1
C3—N1—C7A	105.0 (2)	C2B—C3B—H3B	117.1
C7A—N1—Cu1	130.90 (19)	C3A—C4—C5	114.9 (3)
C2B—O2—Cu1	125.76 (18)	C3A—C4—H4	122.5
H2A—N2—H2B	120.0	C5—C4—H4	122.5
C3—N2—H2A	120.0	C4B—C5B—H5BA	109.5
C3—N2—H2B	120.0	C4B—C5B—H5BB	109.5
N1—C3—N2	124.5 (3)	C4B—C5B—H5BC	109.5
N1—C3—N3	113.4 (3)	H5BA—C5B—H5BB	109.5
N2—C3—N3	122.1 (3)	H5BA—C5B—H5BC	109.5
N1—C7A—C3A	109.5 (3)	H5BB—C5B—H5BC	109.5
N1—C7A—C7	130.4 (3)	C5—C6—H6	119.0
C7—C7A—C3A	120.1 (3)	C7—C6—C5	122.1 (3)
N3—C8—H8Aⁱ	112 (3)	C7—C6—H6	119.0
N3—C8—H8A	112 (3)	C7A—C7—H7	121.3
N3—C8—H8B	105 (5)	C6—C7—C7A	117.4 (3)
H8A—C8—H8Aⁱ	108 (6)	C6—C7—H7	121.3
H8A—C8—H8B	109 (4)	C2B—C1B—H1BA	109.5
H8B—C8—H8Aⁱ	109 (4)	C2B—C1B—H1BB	109.5
N3—C3A—C7A	105.9 (2)	C2B—C1B—H1BC	109.5
N3—C3A—C4	130.7 (3)	H1BA—C1B—H1BB	109.5
C4—C3A—C7A	123.5 (3)	H1BA—C1B—H1BC	109.5
O1—C4B—C3B	125.5 (3)	H1BB—C1B—H1BC	109.5
O1—C4B—C5B	115.1 (3)

Cu1—O1—C4B—C3B	2.1 (4)	C3—N1—C7A—C7	180.000 (1)
Cu1—O1—C4B—C5B	−175.7 (2)	C7A—N1—C3—N2	180.000 (1)
Cu1—N1—C3—N2	0.000 (1)	C7A—N1—C3—N3	0.000 (1)
Cu1—N1—C3—N3	180.000 (1)	C7A—C3A—N3—C3	0.000 (1)
Cu1—N1—C7A—C3A	180.000 (1)	C7A—C3A—N3—C8	180.000 (1)
Cu1—N1—C7A—C7	0.000 (1)	C7A—C3A—C4—C5	0.000 (1)
Cu1—O2—C2B—C3B	4.8 (4)	C3A—C7A—C7—C6	0.000 (1)
Cu1—O2—C2B—C1B	−176.0 (2)	C5—C6—C7—C7A	0.000 (1)
O1—C4B—C3B—C2B	0.3 (6)	N3—C3A—C4—C5	180.000 (1)
N1—C3—N3—C8	180.000 (1)	C4—C3A—N3—C3	180.000 (1)
N1—C3—N3—C3A	0.000 (1)	C4—C3A—N3—C8	0.000 (1)
N1—C7A—C3A—N3	0.000 (1)	C4—C5—C6—C7	0.000 (1)
N1—C7A—C3A—C4	180.000 (1)	C5B—C4B—C3B—C2B	178.0 (4)
N1—C7A—C7—C6	180.000 (1)	C6—C5—C4—C3A	0.000 (1)
O2—C2B—C3B—C4B	−4.1 (6)	C7—C7A—C3A—N3	180.000 (1)
N2—C3—N3—C8	0.000 (1)	C7—C7A—C3A—C4	0.000 (1)
N2—C3—N3—C3A	180.000 (1)	C1B—C2B—C3B—C4B	176.9 (4)
C3—N1—C7A—C3A	0.000 (1)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C2/N3/C3A/C7A ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2	0.86	2.44	3.077 (3)	131
N2—H2B···O2ⁱⁱ	0.86	2.44	3.167 (3)	142
C5B—H5BA···Cg1ⁱⁱⁱ	0.96	2.74	3.682 (4)	166

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

Acknowledgements

The authors acknowledge support from the MIRAI FUND (JICA) and technical equipment support provided by the Institute of Bioorganic Chemistry of Academy Sciences of Uzbekistan.

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