Crystal structure and Hirshfeld surface analysis of bis­(2-amino-1-methyl­benzimidazole-κN3)bis­(salicylato-κ2O,O′)copper(II)

Mukhammadiev, S.; Fayzullayeva, F.; Kadirova, Z.; Tojiboev, A.; Ashurov, J.; Daminova, S.

doi:10.1107/S2056989025007960

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 81| Part 10| October 2025| Pages 968-971

https://doi.org/10.1107/S2056989025007960

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Crystal structure and Hirshfeld surface analysis of bis(2-amino-1-methylbenzimidazole-κN³)bis(salicylato-κ²O,O′)copper(II)

Salmon Mukhammadiev,^a ^* Feruza Fayzullayeva,^a Zukhra Kadirova,^a Akmaljon Tojiboev,^b Jamshid Ashurov ^c and Shahlo Daminova ^d

^aUzbekistan Japan Innovation Center of Youth, University Street 2B, Tashkent 100095, Uzbekistan, ^bUniversity of Geological Sciences, Olimlar street, 64, Mirzo Ulug`bek district, Tashkent, Uzbekistan, ^cInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, 100125, M.,Ulug`bek Str, 83, Tashkent, Uzbekistan, and ^dUzbekistan Japan Innovation Center of Youth, University Street 2B, Tashkent 100095, National University of Uzbekistan named after Mirzo Ulugbek, University Street 4, Tashkent 100174, Uzbekistan
^*Correspondence e-mail: [email protected]

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 June 2025; accepted 5 September 2025; online 19 September 2025)

The title complex, [Cu(C₇H₅O₃)₂(C₈H₉N₃)₂], crystallizes in the monoclinic space group C2/c. The Cu^II cation is located on an inversion center and adopts a distorted octahedral coordination environment defined by two aromatic N atoms from neutral 2-amino-1-methylbenzimidazole ligands and by four O atoms from two bidentate salicylate anions coordinating via their carboxylate groups. The tri-periodic supramolecular network features intra- and intermolecular O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, along with π–π stacking and C—H⋯π interactions. Hirshfeld surface analysis indicates that H⋯H (43.7% contribution), C⋯H/H⋯C (35.8%), and O⋯H/H⋯O (14.1%) contacts dominate the intermolecular interactions.

Keywords: crystal structure; copper(II) complex; 2-amino-1-methylbenzimidazole; salicylate ligand; void analysis; supramolecular interactions; hydrogen bonding.

CCDC reference: 2485535

1. Chemical context

Salicylic acid or derivatives thereof form stable complexes with the central metal cation (e.g. copper) via strong coordination bonds either in a monodentate or bidentate fashion, forming bonds to the oxygen atoms of the carboxyl group and/or the hydroxyl group (Iravani et al., 2013 ; Hoang et al., 1992 ). Corresponding complexes exhibit distinctive magnetic and optical properties, influenced by the electronic configuration of the central metal cation and the π-electron system of the ligand, thereby enhancing potential applications in catalysis, optical materials, or biological systems (Costes et al., 2003 ).

Copper(II) complexes formed by salicylic acid and a co-ligand, such as benzimidazole and its derivatives, have continued to attract attention due to their structural diversity and biological potential. In these mixed N,O-donor ligand systems, salicylic acid can coordinate via its hydroxyl and carboxylate groups, while aromatic amines bind through nitrogen atoms (Lawal et al., 2017 ). These combinations of ligands provide favorable coordination environments, influencing the crystal packing and stability of the resulting complexes.

In the context given above, we report here on the crystal structure, Hirshfeld and void analysis of a new Cu^II complex derived from salicylic acid and benzimidazole, [Cu(C₇H₅O₃)₂(C₈H₉N₃)₂] (Fig. 1).

Figure 1
Molecular structure of the title complex. Displacement ellipsoids are drawn at the 50% probability level; non-labeled atoms are generated by symmetry operation $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z.

2. Structural commentary

The asymmetric unit of the title complex comprises one half of the [Cu(C₇H₅O₃)₂(C₈H₉N₃)₂] molecule, the complete complex being generated by inversion symmetry. The central Cu^II cation adopts a distorted octahedral coordination environment defined by two nitrogen atoms [N1, N1ⁱ; symmetry code: (i) −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1] from two neutral 2-amino-1-methylbenzimidazole (MAB) ligands and four oxygen atoms from two bidentate salicylate ligands, coordinating in a κ²O,O′ fashion (O1, O2; O1ⁱ, O2ⁱ) through the carboxylate groups. The Cu—N and Cu—O bond lengths fall within expected ranges for the typical Jahn–Teller distortion, with the Cu1—N1, Cu1—O1, and Cu1—O2 distances being 1.9781 (16), 1.9849 (14), and 2.5672 (15) Å, respectively. The salicylate ligand forms a four-membered chelate ring with a bite angle of 56.60 (5)° for O1—Cu1—O2 and a cis angle of 123.40 (5)° for O1—Cu1—O2ⁱ. Within the salicylate ligand an intramolecular O—H⋯O hydrogen bond between the phenolic hydroxyl group (O3—H3) and the adjacent carboxylate oxygen atom (O2) helps to consolidate the molecular conformation (Table 1). The N—Cu1—O angles are 88.95 (6) and 91.05 (6)°. These values are consistent with those observed in previously reported Cu^II complexes bearing mixed N,O-donor ligands (Puchoňová et al., 2017 ). The dihedral angle between the benzimidazole ring of the MAB ligand and the aromatic ring of the coordinated salicylate ligand is 82.68 (11)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.81 (1)	1.81 (1)	2.538 (2)	150 (1)
N3—H3a⋯O3ⁱ	0.88 (1)	2.33 (1)	3.046 (3)	139 (1)
N3—H3b⋯O1	0.88 (1)	2.49 (1)	3.020 (3)	119 (1)
C4—H4⋯O2ⁱⁱ	0.95 (1)	2.57 (1)	3.373 (2)	143 (1)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

3. Supramolecular features

The title compound exhibits a tri-periodic supramolecular network defined by a variety of non-covalent interactions. Two key intermolecular N—H⋯O hydrogen bonds (Table 1) are observed between the amino group of the benzimidazole ligand (N3) and neighboring salicylate oxygen atoms (O3). Additional weaker C—H⋯O contacts further contribute to the supramolecular cohesion (Table 1). π–π stacking interactions are observed between aromatic rings N1/C6/C1/N2/C7 (centroid Cg3) and C1–C6 (Cg4) with a centroid-to-centroid distances of 3.8831 (13) Å for Cg3⋯Cg4(1 − x, 1 − y, 1 − z; slippage = 1.769 Å), as shown in Fig. 2. Furthermore, a weak C—H⋯π interactions is present between the C11—H11 group and the π-systems represented by Cg4. The H11⋯Cg distance is 2.637 (3), the C11⋯Cg distance is 3.543 (3) and the C11—H11⋯Cg angle is 159.6 (3)°.

Figure 2
The molecular packing of the title compound along [010]. Intra- and intermolecular hydrogen bonds are shown as dashed lines. π–π stacking interactions are indicated as follows: Cg3⋯Cg3 in green, Cg3⋯Cg4 in pink, and Cg4⋯Cg4 in red.

4. Hirshfeld surface and void analysis

In order to quantify and visualize intermolecular interactions, a Hirshfeld surface (HS) analysis (Spackman & Jayatilaka, 2009 ) was performed and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) calculated with CrystalExplorer21 (Spackman et al., 2021 ). The HS mapped with d_norm is represented in Fig. 3, where white regions indicate contacts at van der Waals separations, red spots denote shorter contacts (e.g. hydrogen bonds) and blue areas longer contacts. The overall two-dimensional fingerprint plot is shown in Fig. 4a. H⋯H contacts make the largest contribution (43.7%, Fig. 4b) to the HS. Other significant contacts are H⋯C/C⋯H (35.8%, Fig. 4c) and H⋯O/O⋯H (14.1%, Fig. 4d), while H⋯N/N⋯H (3%, Fig. 4e), C⋯C (2%, Fig. 4f) and C⋯N/N⋯C (1.4%, Fig. 4g) contacts contribute only to a minor amount.

Figure 3
HS plotted over d_norm (a) along [100], (b) along [010] and (c) along [001].

Figure 4
Two-dimensional fingerprint plots for (a) all interactions and (b)–(g) individual interatomic contacts.

Void analysis was performed using CrystalExplorer with a probe radius of 1.2 Å and a grid spacing of 0.2 Å. The total void volume within the unit cell was calculated to be 327.6 Å³, which corresponds to 11.7% of the unit-cell volume. The voids are visualized as transparent isosurfaces in the crystal packing diagram (Fig. 5).

Figure 5
The void surface packing in a view along [010].

5. Database survey

A search of the Cambridge Structural Database (CSD, version 5.46, updated November 2024; Groom et al., 2016 ) for similar coordination environments (bidentate carboxylate group and an aromatic monodentate N-donor ligand) yielded several complexes including the first-row transition metal complex: catena-[bis(μ-carbonato)tetrakis(2,4′-bipyridine)bis(aqua)dicopper(II) dihydrate] (RITBEE01; Mulrooney et al., 2018 ), which features a bidentate binding and bridging carbonate anion and monodentately binding 2,2′-bipyridine entities, resulting in the formation of a polymeric chain.

6. Synthesis and crystallization

An aqueous solution of copper(II) sulfate pentahydrate (0.05 M, 10 ml) was prepared by dissolving the salt in distilled water. An ethanolic solution of salicylic acid (0.1 M, 10 ml) was added, and the resulting mixture stirred magnetically at room temperature for 4 h. No noticeable color change was observed during this step. Subsequently, an ethanolic solution of 2-amino-1-methylbenzimidazole (0.1 M, 10 ml) was added, and stirring was continued for additional 4 h, resulting in a green-colored solution. The reaction mixture was then filtered and left to stand at room temperature for 2–3 weeks to allow the growth of green crystals suitable for X-ray diffraction analysis.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were positioned geometrically (aromatic C—H = 0.95 Å, N—H = 0.89 Å, O—H = 0.84 Å and methyl C—H = 0.98 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(aromatic C, N) or 1.5U_eq(methyl C, O).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₇H₅O₃)₂(C₈H₉N₃)₂]
M_r	632.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	16.7892 (5), 9.0355 (2), 19.2315 (6)
β (°)	106.011 (3)
V (Å³)	2804.23 (14)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.58
Crystal size (mm)	0.54 × 0.18 × 0.06

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 )
T_min, T_max	0.710, 1.000
No. of measured, independent and observed [I ≥ 2u(I)] reflections	13358, 2710, 2351
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.108, 1.02
No. of reflections	2710
No. of parameters	197
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.44
Computer programs: CrysAlis PRO (Rigaku OD, 2023), OLEX2.solve (Bourhis et al., 2015 ), SHELXL (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2485535

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025007960/wm5761sup1.cif

checkCIF report

Computing details top

Bis(2-hydroxybenzoato-κ²O¹,O^1')bis(1-methyl-1H-1,3-benzodiazol-2-amine-κN³)copper(II) top

Crystal data top

[Cu(C₇H₅O₃)₂(C₈H₉N₃)₂]	F(000) = 1308.0
M_r = 632.14	D_x = 1.497 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 16.7892 (5) Å	Cell parameters from 6926 reflections
b = 9.0355 (2) Å	θ = 4.8–71.0°
c = 19.2315 (6) Å	µ = 1.58 mm⁻¹
β = 106.011 (3)°	T = 150 K
V = 2804.23 (14) Å³	Block, dark green
Z = 4	0.54 × 0.18 × 0.06 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	2710 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2351 reflections with I ≥ 2u(I)
Mirror monochromator	R_int = 0.046
Detector resolution: 10.0000 pixels mm^-1	θ_max = 71.7°, θ_min = 4.8°
ω scans	h = −20→17
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −11→10
T_min = 0.710, T_max = 1.000	l = −23→23
13358 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	25 constraints
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0592P)² + 2.8103P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = −0.001
2710 reflections	Δρ_max = 0.36 e Å⁻³
197 parameters	Δρ_min = −0.44 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Cu1	0.25	0.75	0.5	0.02441 (15)
O1	0.24551 (8)	0.80636 (16)	0.59860 (8)	0.0287 (3)
O2	0.17132 (9)	0.60031 (16)	0.57333 (8)	0.0331 (4)
O3	0.09241 (9)	0.50418 (17)	0.65918 (9)	0.0385 (4)
H3	0.10951 (9)	0.50901 (17)	0.62385 (9)	0.0577 (6)*
N1	0.35479 (10)	0.64351 (19)	0.54380 (9)	0.0284 (4)
N2	0.48415 (10)	0.5937 (2)	0.60893 (10)	0.0321 (4)
N3	0.43028 (12)	0.8317 (2)	0.62124 (12)	0.0469 (6)
H3a	0.47667 (12)	0.8575 (2)	0.65315 (12)	0.0563 (7)*
H3b	0.38887 (12)	0.8948 (2)	0.60864 (12)	0.0563 (7)*
C1	0.45469 (12)	0.4673 (2)	0.57009 (12)	0.0292 (5)
C2	0.49118 (14)	0.3304 (3)	0.56638 (13)	0.0367 (5)
H2	0.54675 (14)	0.3105 (3)	0.59311 (13)	0.0441 (6)*
C3	0.44333 (16)	0.2248 (3)	0.52229 (14)	0.0401 (6)
H3c	0.46642 (16)	0.1301 (3)	0.51867 (14)	0.0481 (7)*
C4	0.36121 (16)	0.2540 (2)	0.48257 (14)	0.0386 (5)
H4	0.32941 (16)	0.1784 (2)	0.45334 (14)	0.0463 (7)*
C5	0.32582 (14)	0.3926 (2)	0.48553 (12)	0.0334 (5)
H5	0.27066 (14)	0.4134 (2)	0.45803 (12)	0.0401 (6)*
C6	0.37341 (12)	0.4982 (2)	0.52959 (11)	0.0276 (4)
C7	0.42262 (12)	0.6952 (2)	0.59162 (12)	0.0308 (5)
C8	0.56419 (14)	0.6094 (3)	0.66364 (14)	0.0458 (6)
H8a	0.5682 (5)	0.5360 (14)	0.7020 (5)	0.0686 (9)*
H8b	0.60917 (14)	0.594 (2)	0.6410 (3)	0.0686 (9)*
H8c	0.5687 (5)	0.7091 (8)	0.6844 (8)	0.0686 (9)*
C9	0.22167 (13)	0.8228 (2)	0.73737 (12)	0.0310 (5)
H9	0.25920 (13)	0.8908 (2)	0.72568 (12)	0.0373 (5)*
C10	0.20417 (14)	0.8346 (3)	0.80299 (12)	0.0380 (5)
H10	0.22939 (14)	0.9099 (3)	0.83627 (12)	0.0456 (6)*
C11	0.14918 (15)	0.7351 (3)	0.82013 (13)	0.0387 (6)
H11	0.13671 (15)	0.7428 (3)	0.86527 (13)	0.0464 (7)*
C12	0.11264 (13)	0.6251 (3)	0.77193 (12)	0.0362 (5)
H12	0.07531 (13)	0.5577 (3)	0.78424 (12)	0.0434 (6)*
C13	0.13000 (12)	0.6125 (2)	0.70566 (12)	0.0298 (5)
C14	0.18537 (12)	0.7131 (2)	0.68769 (11)	0.0259 (4)
C15	0.20180 (12)	0.7050 (2)	0.61594 (11)	0.0270 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0213 (2)	0.0226 (2)	0.0293 (2)	0.00500 (15)	0.00676 (17)	0.00076 (16)
O1	0.0257 (7)	0.0291 (7)	0.0324 (8)	0.0017 (6)	0.0101 (6)	0.0006 (6)
O2	0.0384 (8)	0.0271 (8)	0.0333 (8)	0.0027 (6)	0.0088 (6)	−0.0039 (6)
O3	0.0366 (8)	0.0323 (8)	0.0444 (9)	−0.0093 (7)	0.0078 (7)	−0.0011 (7)
N1	0.0253 (8)	0.0253 (9)	0.0344 (9)	0.0051 (7)	0.0077 (7)	−0.0008 (7)
N2	0.0231 (8)	0.0331 (10)	0.0371 (10)	0.0025 (7)	0.0033 (7)	0.0011 (8)
N3	0.0320 (10)	0.0344 (11)	0.0650 (14)	0.0041 (8)	−0.0020 (9)	−0.0167 (10)
C1	0.0251 (10)	0.0291 (11)	0.0348 (11)	0.0050 (8)	0.0108 (8)	0.0060 (9)
C2	0.0328 (11)	0.0354 (12)	0.0432 (13)	0.0124 (9)	0.0124 (10)	0.0083 (10)
C3	0.0488 (14)	0.0290 (12)	0.0448 (13)	0.0147 (10)	0.0169 (11)	0.0021 (10)
C4	0.0480 (14)	0.0267 (12)	0.0409 (13)	0.0040 (9)	0.0121 (11)	−0.0047 (9)
C5	0.0329 (11)	0.0305 (11)	0.0355 (12)	0.0043 (9)	0.0073 (9)	−0.0015 (9)
C6	0.0281 (10)	0.0248 (10)	0.0314 (11)	0.0054 (8)	0.0107 (8)	0.0030 (8)
C7	0.0250 (10)	0.0296 (11)	0.0373 (12)	0.0029 (8)	0.0075 (8)	−0.0013 (9)
C8	0.0262 (11)	0.0501 (15)	0.0516 (15)	0.0027 (10)	−0.0052 (10)	0.0012 (12)
C9	0.0267 (10)	0.0312 (11)	0.0339 (11)	−0.0019 (8)	0.0062 (8)	0.0003 (9)
C10	0.0397 (12)	0.0388 (13)	0.0322 (12)	0.0003 (10)	0.0042 (10)	−0.0056 (10)
C11	0.0381 (12)	0.0495 (15)	0.0300 (12)	0.0081 (10)	0.0119 (10)	0.0049 (10)
C12	0.0290 (10)	0.0412 (13)	0.0394 (12)	0.0017 (9)	0.0111 (9)	0.0119 (10)
C13	0.0242 (9)	0.0261 (10)	0.0364 (11)	0.0023 (8)	0.0038 (8)	0.0041 (9)
C14	0.0212 (9)	0.0251 (10)	0.0309 (11)	0.0030 (7)	0.0063 (8)	0.0022 (8)
C15	0.0223 (9)	0.0251 (10)	0.0315 (11)	0.0074 (8)	0.0039 (8)	0.0026 (8)

Geometric parameters (Å, º) top

Cu1—O1	1.9849 (14)	C3—H3c	0.9500
Cu1—O1ⁱ	1.9849 (14)	C3—C4	1.405 (3)
Cu1—O2	2.5672 (15)	C4—H4	0.9500
Cu1—N1	1.9781 (16)	C4—C5	1.394 (3)
Cu1—N1ⁱ	1.9781 (16)	C5—H5	0.9500
O1—C15	1.274 (3)	C5—C6	1.376 (3)
O2—C15	1.264 (3)	C8—H8a	0.9800
O3—H3	0.8084	C8—H8b	0.9800
O3—C13	1.358 (3)	C8—H8c	0.9800
N1—C6	1.394 (3)	C9—H9	0.9500
N1—C7	1.335 (3)	C9—C10	1.376 (3)
N2—C1	1.380 (3)	C9—C14	1.395 (3)
N2—C7	1.352 (3)	C10—H10	0.9500
N2—C8	1.467 (3)	C10—C11	1.392 (3)
N3—H3a	0.8800	C11—H11	0.9500
N3—H3b	0.8800	C11—C12	1.381 (3)
N3—C7	1.350 (3)	C12—H12	0.9500
C1—C2	1.391 (3)	C12—C13	1.388 (3)
C1—C6	1.400 (3)	C13—C14	1.410 (3)
C2—H2	0.9500	C14—C15	1.482 (3)
C2—C3	1.377 (4)

O1—Cu1—O2ⁱ	123.40 (5)	C1—C6—N1	108.42 (18)
O1—Cu1—O2	56.60 (5)	C5—C6—N1	130.57 (19)
O1ⁱ—Cu1—O1	180.0	C5—C6—C1	121.01 (19)
N1ⁱ—Cu1—O1ⁱ	88.95 (6)	N2—C7—N1	112.40 (19)
N1ⁱ—Cu1—O1	91.05 (6)	N3—C7—N1	125.03 (19)
N1—Cu1—O1ⁱ	91.05 (6)	N3—C7—N2	122.56 (19)
N1—Cu1—O1	88.95 (6)	H8a—C8—N2	109.5
N1ⁱ—Cu1—N1	180.0	H8b—C8—N2	109.5
C15—O1—Cu1	104.01 (13)	H8b—C8—H8a	109.5
C13—O3—H3	107.8	H8c—C8—N2	109.5
C6—N1—Cu1	126.57 (14)	H8c—C8—H8a	109.5
C7—N1—Cu1	127.78 (14)	H8c—C8—H8b	109.5
C7—N1—C6	105.64 (16)	C10—C9—H9	119.36 (13)
C7—N2—C1	107.01 (17)	C14—C9—H9	119.36 (13)
C8—N2—C1	126.06 (19)	C14—C9—C10	121.3 (2)
C8—N2—C7	126.7 (2)	H10—C10—C9	120.31 (13)
H3b—N3—H3a	120.0	C11—C10—C9	119.4 (2)
C7—N3—H3a	120.0	C11—C10—H10	120.31 (14)
C7—N3—H3b	120.0	H11—C11—C10	119.79 (14)
C2—C1—N2	131.8 (2)	C12—C11—C10	120.4 (2)
C6—C1—N2	106.52 (18)	C12—C11—H11	119.79 (14)
C6—C1—C2	121.6 (2)	H12—C12—C11	119.72 (14)
H2—C2—C1	121.41 (13)	C13—C12—C11	120.6 (2)
C3—C2—C1	117.2 (2)	C13—C12—H12	119.72 (13)
C3—C2—H2	121.41 (13)	C12—C13—O3	119.12 (19)
H3c—C3—C2	119.23 (13)	C14—C13—O3	121.4 (2)
C4—C3—C2	121.5 (2)	C14—C13—C12	119.4 (2)
C4—C3—H3c	119.23 (13)	C13—C14—C9	118.9 (2)
H4—C4—C3	119.61 (13)	C15—C14—C9	120.95 (19)
C5—C4—C3	120.8 (2)	C15—C14—C13	120.10 (19)
C5—C4—H4	119.61 (14)	O2—C15—O1	121.9 (2)
H5—C5—C4	121.09 (14)	C14—C15—O1	118.49 (18)
C6—C5—C4	117.8 (2)	C14—C15—O2	119.64 (19)
C6—C5—H5	121.09 (12)

Cu1—O1—C15—O2	−0.95 (13)	N3—C7—N2—C1	178.8 (2)
Cu1—O1—C15—C14	−179.75 (10)	N3—C7—N2—C8	4.1 (3)
Cu1—N1—C6—C1	178.22 (18)	C1—C2—C3—C4	0.1 (3)
Cu1—N1—C6—C5	−2.4 (2)	C1—C6—N1—C7	−0.6 (2)
Cu1—N1—C7—N2	−178.35 (19)	C1—C6—C5—C4	0.0 (2)
Cu1—N1—C7—N3	2.8 (2)	C2—C1—N2—C7	179.4 (3)
O1—C15—C14—C9	−4.6 (2)	C2—C1—N2—C8	−5.8 (3)
O1—C15—C14—C13	173.06 (17)	C2—C1—C6—C5	1.4 (3)
O2—C15—C14—C9	176.60 (18)	C2—C3—C4—C5	1.2 (3)
O2—C15—C14—C13	−5.8 (2)	C3—C2—C1—C6	−1.4 (3)
O3—C13—C12—C11	−179.33 (19)	C3—C4—C5—C6	−1.2 (3)
O3—C13—C14—C9	179.50 (19)	C5—C6—N1—C7	178.7 (3)
O3—C13—C14—C15	1.8 (2)	C6—C1—N2—C7	−0.2 (2)
N1—C6—C1—N2	0.55 (18)	C6—C1—N2—C8	174.49 (18)
N1—C6—C1—C2	−179.18 (18)	C9—C10—C11—C12	0.2 (3)
N1—C6—C5—C4	−179.3 (3)	C9—C14—C13—C12	0.3 (2)
N1—C7—N2—C1	−0.2 (2)	C10—C9—C14—C13	−0.2 (2)
N1—C7—N2—C8	−174.86 (19)	C10—C9—C14—C15	177.42 (19)
N2—C1—C2—C3	178.9 (3)	C10—C11—C12—C13	−0.2 (3)
N2—C1—C6—C5	−178.89 (17)	C11—C10—C9—C14	0.0 (3)
N2—C7—N1—C6	0.5 (2)	C11—C12—C13—C14	−0.1 (3)
N3—C7—N1—C6	−178.4 (3)	C12—C13—C14—C15	−177.40 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.81 (1)	1.81 (1)	2.538 (2)	150 (1)
N3—H3a···O3ⁱⁱ	0.88 (1)	2.33 (1)	3.046 (3)	139 (1)
N3—H3b···O1	0.88 (1)	2.49 (1)	3.020 (3)	119 (1)
C4—H4···O2ⁱⁱⁱ	0.95 (1)	2.57 (1)	3.373 (2)	143 (1)
C8—H8c···N3	0.98 (1)	2.56 (1)	2.957 (3)	104 (1)

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

Acknowledgements

The authors gratefully acknowledge the technical equipment support provided by the Institute of Bioorganic Chemistry of the Academy of Sciences of Uzbekistan, Tashkent, Uzbekistan. The authors are also grateful to the FAIRE programme provided by the Cambridge Crystallographic Data Centre (CCDC) for the opportunity to use the Cambridge Structural Database (CSD) and associated software.

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