Synthesis, crystal structure and Hirshfeld surface analysis of a propyl 4-{[1-(2-methyl-4-nitro­phen­yl)-1H-1,2,3-triazol-4-yl]meth­oxy}benzoate copper(II) chloride complex

Hakimov, M.; Ortikov, I.; Sattarov, T.; Tashkhodjaev, B.; Tojiboev, A.

doi:10.1107/S2056989025001732

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ISSN: 2056-9890

Volume 81| Part 4| April 2025| Pages 271-274

https://doi.org/10.1107/S2056989025001732

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Synthesis, crystal structure and Hirshfeld surface analysis of a propyl 4-{[1-(2-methyl-4-nitrophenyl)-1H-1,2,3-triazol-4-yl]methoxy}benzoate copper(II) chloride complex

Muminjon Hakimov,^a ^* Ilkhomjon Ortikov,^b Tulkinjon Sattarov,^a Bakhodir Tashkhodjaev ^c and Akmaljon Tojiboev ^d

^aNamangan State University, Boburshoh str. 161, Namangan, 160107, Uzbekistan, ^bAlfraganus University, Yukari Karakamysh str. 2A 100190, Tashkent, Uzbekistan, ^cInstitute of the Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Mirzo Ulugbek Str. 77, Tashkent 100170, Uzbekistan, and ^dUniversity of Geological Sciences, Olimlar Str. 64, Tashkent 100170, Uzbekistan
^*Correspondence e-mail: hakimov1094@yahoo.com

Edited by G. Ferrence, Illinois State University, USA (Received 5 December 2024; accepted 24 February 2025; online 4 March 2025)

The core of the title complex, dichloridobis(propyl 4-{[1-(2-methyl-4-nitrophenyl)-1H-1,2,3-triazol-4-yl]methoxy}benzoate)copper(II), [CuCl₂(C₂₀H₂₀N₄O₅)₂], which belongs to the copper(II) complex family, consists of two C₂₀H₂₀N₄O₅ ligands and two chloride ligands arranged around the metal, forming a trans-dichlorido square-planar complex. In the crystal, the molecules are linked by C—H⋯Cl and C—H⋯O hydrogen bonds as well as by aromatic π–π stacking interactions into a three-dimensional network. To further analyse the intermolecular interactions, a Hirshfeld surface analysis was performed.

Keywords: crystal structure; copper (II) complex; 1,2,3-triazole; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 2426436

1. Chemical context

Transition-metal halides may be reacted with functionalized organic molecules (for example carboxylic acids, amides or amines) to produce neutral or ionic coordination compounds that combine and leverage the properties of both components (Constable et al., 2021 ). 1,2,3-Triazoles comprise an interesting class of heterocyclic compounds (Bozorov et al., 2019 ), and the synthesis of ligand-based 3d metal complexes from these compounds is of even greater interest (Dheer et al., 2017 ). The discovery by Sharpless and coworkers in 2001 (Kolb et al., 2001 ) of click chemistry, especially the copper-catalysed alkyne-azide cycloaddition (CuAAC) methodology for the preparation of triazole derivatives, has accelerated important advances in many scientific areas. This copper-catalysed process constituted a substantial development on the classical Huisgen-type thermal 1,3-dipolar cycloaddition as it permitted the regioselective preparation of 1,4- and 1,5-disubstituted 1,2,3-triazoles (Huisgen, 1963 ; Ling et al., 1996 ; Hein & Fokin, 2010 ; Liang & Astruc, 2011 ). Daniel Mendoza and co-worker reported the new copper(II) complexes supported by 2-mercapto and 4-mercaptopyridine-derived 1,2,3-triazole ligands. Their new complexes were tested in the CuAAC process under a variety of reaction conditions. The overall catalytic data demonstrated these complexes displayed the best CuAAC performance in alcoholic solvents without the need for an external reducing agent (Gonzalez-Silva et al., 2019 ). Herein, we report the synthesis of the coordination compound, 1, formed from propyl 4-{[1-(2-methyl-4-nitrophenyl)-1H-1,2,3-triazol-4-yl]methoxy}benzoate and copper(II) chloride and examined it using single-crystal X-ray diffraction and Hirshfeld surface studies as a part of our ongoing interest in 1,2,3-triazole derivatives, a continuation of our recently published work on the synthesis of triazole derivatives (Hakimov et al., 2024 ).

2. Structural commentary

Compound 1 crystallizes in the monoclinic space group P2₁/c. Fig. 1 depicts a perspective view of the mononuclear centrosymmetric complex, [(Cu)(L)₂(Cl)₂], where L = propyl 4-{[1-(2-methyl-4-nitrophenyl)-1H-1,2,3-triazol-4-yl]methoxy}benzoate, with the atom-labeling scheme. The asymmetric unit contains half of the molecule, with the copper atom coincident with an inversion center, which renders the two C₂₀H₂₀N₄O₅ ligands crystallographically equivalent. Likewise, the trans-chloride ligands are crystallographically equivalent. The copper(II) center is coordinated by a single nitrogen of each of the two 1H-1,2,3-triazole ligands with an N14—Cu bond length of 2.009 (2) Å and to two chlorine atoms with a Cu—Cl distances of 2.2460 (9) Å. Interestingly, the O10 atoms are located far away from the Cu center [4.451 (2) Å], ruling out a possible bidentate coordination of each 1,2,3-triazole ligand for the title compound. The coordination of the Cu metal center adopts a square-planar geometry, with τ₄ = 0 (Yang et al., 2007 ). According to the structural data for the title compound, the torsion angles O10—C11—C15—C16 and C16—N12—C17—C22 of the triazole ring with neighboring atoms are 53.6 (5) and −47.3 (5)°, respectively.

Figure 1
Ellipsoid plot of the title compound with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal structure of the title compound, no classical strong hydrogen bonds are observed. Some intermolecular C—H⋯O and C—H⋯Cl contacts (Table 1) can be identified as hydrogen bonds by Hirshfeld surface analysis (vide infra). For the complexes, a chain along the c-axis direction is observed due to stacking effects between the benzene rings (Fig. 2). These contacts link the molecules into a three-dimensional network, complemented by short ring-interactions with stacking between the triazole (centroid Cg1), propyl benzoate (centroid Cg2) rings and 1-methyl-5-nitrobenzene (centroid Cg3) rings [Cg1⋯Cg1′ = 5.5492 (18) Å, Cg2⋯Cg2′ = 4.009 (2) Å and Cg3⋯Cg3′ = 4.094 (2) Å, with slippages of 0.46, 1.799 and 2.091 Å, respectively].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O9	0.93	2.39	2.706 (4)	100
C22—H22⋯Clⁱ	0.93	2.78	3.689 (3)	167
C29—H29B⋯O8ⁱⁱ	0.96	2.59	3.531 (6)	168
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Crystal packing of the title compound. Hydrogen bonds are shown as blue dashed lines.

4. Hirshfeld surface analysis

A Hirshfeld surface analysis was performed using CrystalExplorer21 (Spackman et al., 2021 ). The Hirshfeld surface of molecule 1 mapped over d_norm is shown in Fig. 3. Intermolecular C—H⋯O and C—H⋯Cl contacts are shown, indicating close interactions (hydrogen bonds) as blue and red dashed lines, respectively. The 2D fingerprint plots (McKinnon et al., 2007 ), indicate that intermolecular H⋯H and O⋯H/H⋯O contacts make the largest contributions to the total Hirshfeld surface, 38.8% and 25.1%, respectively, with other significant contributions being H⋯C/C⋯H (10.0%), H⋯Cl/Cl⋯H (8.9%) and O⋯C/C⋯O (3.3%) (Fig. 4). The characteristic pair of spikes in the H⋯Cl/Cl⋯H and especially O⋯H/H⋯O plots shown in Fig. 4c and Fig. 4e are also indicative of hydrogen bonds. The Hirshfeld surface mapped over shape-index properties (Fig. 5) illustrates the π–π stacking interactions .

Figure 3
Hirshfeld surface of 1 mapped over d_norm and close intermolecular contacts.

Figure 4
Two-dimensional fingerprint plots of the intermolecular contacts in 1.

Figure 5
View of the Hirshfeld surface of the title compound plotted over shape-index: front and back views of middle molecule, respectively.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.46, November 2024; Groom et al., 2016 ) for the generalized 4-(phenoxymethyl)-1-phenyl-1H-1,2,3-triazole with triazole coordination to copper returned zero relevant hits. A search instead with 4-(pyridinesulfanylymethyl)-1-phenyl-1H-1,2,3-triazole returned one hit, CSD refcode GORBAT (Gonzalez-Silva et al., 2019). Four six-coordinate examples containing two bidentate 4-(pyridine)-1-phenyl-1H-1,2,3-triazole moieties and two chloride ligands have been reported (CSD refcodes KINNAZ, KINNED, KINNIH, KINNON and KINNUT; Conradie et al., 2018 ). The CSD returned less than 25 examples of four-coordinate copper(II) coordinated with exactly two chloride ligands and at least one N-coordinating triazole-derived ligand. Only eight examples have the chloride ligands in a trans or near-trans geometry, and of these, six include substituted benzotriazole ligands. The structure most similar to the title complex is bis{4-[(benzyloxy)methyl]-1-(4-chlorobenzyl)-1H-1,2,3-triazole}dichlorocopper(II) (CSD refcode QOCBAN; Mendoza-Espinosa et al., 2014 ).

6. Synthesis and crystallization

The starting reagents used for the synthesis of the title coordination compound – CuCl₂·2H₂O (chemical grade), 2-aminoethanol (MEA) (analytical grade) and ethyl alcohol (analytical grade) – were used as received. 40 mg (0.01 mmol) of C₂₀H₂₀N₄O₅ triazole ligand and 20 mg (0.12 mmol) of CuCl₂·2H₂O were added to 0.4 ml of C₂H₇NO and 4 ml of C₂H₆O solution in a glass vial. The mixture cleared and became a navy blue solution, without sediment. It was then stored in the dark at room temperature for two weeks, after which dark-pink prism-shaped crystals of the complex formed. The yield was 33 mg (55%), m.p. 491–499 K.

7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically and refined using a riding model with distance constraints of C—H = 0.93 Å (aromatic) and 0.97 Å (methylene) with U_iso(H) = 1.2U_eq(C); C—H = 0.96 Å (methyl) with U_iso(H) = 1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[CuCl₂(C₂₀H₂₀N₄O₅)₂]
M_r	927.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	15.8765 (4), 16.2381 (3), 8.0187 (2)
β (°)	92.984 (2)
V (Å³)	2064.45 (8)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.52
Crystal size (mm)	0.4 × 0.2 × 0.1

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	0.617, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11763, 3975, 3315
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.171, 1.08
No. of reflections	3975
No. of parameters	279
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.11, −0.73
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), OLEX2.solve (Bourhis et al., 2015 ), OLEX2 (Dolomanov et al., 2009 ), SHELXL2019/3 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2426436

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025001732/ej2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025001732/ej2010Isup2.hkl

checkCIF report

Computing details top

Dichloridobis(propyl 4-{[1-(2-methyl-4-nitrophenyl)-1H-1,2,3-triazol-4-yl]methoxy}benzoate)copper(II) top

Crystal data top

[CuCl₂(C₂₀H₂₀N₄O₅)₂]	F(000) = 958
M_r = 927.24	D_x = 1.492 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 15.8765 (4) Å	Cell parameters from 6038 reflections
b = 16.2381 (3) Å	θ = 2.8–71.2°
c = 8.0187 (2) Å	µ = 2.52 mm⁻¹
β = 92.984 (2)°	T = 295 K
V = 2064.45 (8) Å³	Prism, metallic pinkish pink
Z = 2	0.4 × 0.2 × 0.1 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	3315 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.034
scan	θ_max = 71.5°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	h = −18→19
T_min = 0.617, T_max = 1.000	k = −19→16
11763 measured reflections	l = −9→9
3975 independent reflections

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.171	w = 1/[σ²(F_o²) + (0.0806P)² + 2.7811P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3975 reflections	Δρ_max = 1.11 e Å⁻³
279 parameters	Δρ_min = −0.73 e Å⁻³
0 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
Cu	0.500000	1.000000	0.500000	0.0332 (2)
Cl	0.47301 (8)	0.90207 (6)	0.68768 (12)	0.0572 (3)
N14	0.51141 (17)	0.91436 (16)	0.3218 (3)	0.0326 (6)
N13	0.58540 (18)	0.90064 (16)	0.2623 (3)	0.0356 (6)
N12	0.57226 (17)	0.84290 (16)	0.1438 (3)	0.0335 (6)
C16	0.4907 (2)	0.8206 (2)	0.1295 (4)	0.0388 (7)
H16	0.466154	0.781814	0.056789	0.047*
C15	0.4514 (2)	0.86703 (19)	0.2442 (4)	0.0357 (7)
C11	0.3628 (2)	0.86819 (19)	0.2929 (5)	0.0406 (8)
H11A	0.356711	0.904300	0.387925	0.049*
H11B	0.325842	0.887620	0.201033	0.049*
O10	0.34212 (16)	0.78556 (14)	0.3351 (4)	0.0475 (6)
C5	0.2652 (2)	0.7721 (2)	0.3977 (4)	0.0373 (7)
C6	0.2435 (2)	0.6895 (2)	0.4118 (5)	0.0430 (8)
H6	0.279257	0.648799	0.375015	0.052*
C7	0.1692 (2)	0.6684 (2)	0.4801 (5)	0.0430 (8)
H7	0.155728	0.613122	0.492948	0.052*
C2	0.1138 (2)	0.7287 (2)	0.5304 (4)	0.0374 (7)
C3	0.1353 (2)	0.8107 (2)	0.5119 (5)	0.0444 (8)
H3	0.098309	0.851467	0.544037	0.053*
C4	0.2108 (2)	0.8329 (2)	0.4463 (5)	0.0450 (8)
H4	0.224769	0.888164	0.435060	0.054*
C1	0.0341 (2)	0.7081 (2)	0.6095 (5)	0.0417 (8)
O9	0.02717 (16)	0.62677 (16)	0.6325 (3)	0.0488 (6)
C27	−0.0424 (2)	0.5987 (2)	0.7267 (5)	0.0469 (9)
H27A	−0.095493	0.618928	0.677040	0.056*
H27B	−0.036330	0.618210	0.841093	0.056*
C28	−0.0399 (3)	0.5062 (2)	0.7216 (6)	0.0589 (11)
H28A	−0.051299	0.488279	0.607285	0.071*
H28B	−0.084449	0.484809	0.787746	0.071*
C29	0.0439 (4)	0.4699 (3)	0.7865 (7)	0.0789 (16)
H29A	0.087621	0.486837	0.715733	0.118*
H29B	0.040059	0.410879	0.786445	0.118*
H29C	0.056727	0.488996	0.898212	0.118*
C17	0.6440 (2)	0.8097 (2)	0.0661 (4)	0.0342 (7)
C22	0.6531 (2)	0.7246 (2)	0.0682 (4)	0.0358 (7)
H22	0.613273	0.690744	0.114771	0.043*
C21	0.7238 (2)	0.6921 (2)	−0.0018 (4)	0.0380 (7)
C20	0.7843 (2)	0.7405 (2)	−0.0689 (5)	0.0465 (8)
H20	0.831569	0.717168	−0.113705	0.056*
C19	0.7731 (2)	0.8247 (2)	−0.0681 (5)	0.0467 (9)
H19	0.813681	0.857969	−0.113702	0.056*
C18	0.7032 (2)	0.8617 (2)	−0.0014 (4)	0.0393 (8)
C26	0.6933 (3)	0.9537 (2)	−0.0065 (5)	0.0553 (10)
H26A	0.636487	0.967348	−0.043287	0.083*
H26B	0.731712	0.976626	−0.082638	0.083*
H26C	0.705328	0.975968	0.103051	0.083*
N23	0.7348 (2)	0.60191 (19)	0.0011 (4)	0.0469 (8)
O25	0.6897 (2)	0.56138 (16)	0.0887 (4)	0.0610 (8)
O24	0.7876 (2)	0.5722 (2)	−0.0855 (5)	0.0753 (10)
O8	−0.01809 (19)	0.75633 (18)	0.6508 (5)	0.0674 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0392 (4)	0.0267 (3)	0.0345 (4)	−0.0014 (3)	0.0092 (3)	−0.0058 (3)
Cl	0.0881 (8)	0.0353 (5)	0.0505 (5)	0.0033 (4)	0.0254 (5)	0.0041 (4)
N14	0.0386 (14)	0.0267 (13)	0.0330 (13)	−0.0035 (11)	0.0078 (11)	−0.0039 (10)
N13	0.0396 (15)	0.0324 (14)	0.0351 (14)	−0.0030 (12)	0.0053 (11)	−0.0094 (11)
N12	0.0409 (15)	0.0262 (12)	0.0339 (14)	−0.0016 (11)	0.0074 (11)	−0.0061 (10)
C16	0.0420 (18)	0.0297 (16)	0.0449 (18)	−0.0054 (14)	0.0030 (14)	−0.0080 (14)
C15	0.0413 (18)	0.0257 (15)	0.0403 (17)	−0.0024 (13)	0.0038 (14)	−0.0013 (13)
C11	0.0394 (18)	0.0260 (16)	0.057 (2)	−0.0019 (13)	0.0066 (15)	−0.0025 (15)
O10	0.0418 (13)	0.0270 (11)	0.0755 (18)	−0.0004 (10)	0.0185 (12)	0.0026 (11)
C5	0.0350 (17)	0.0317 (16)	0.0452 (18)	−0.0029 (13)	0.0020 (14)	0.0017 (14)
C6	0.0430 (19)	0.0295 (16)	0.057 (2)	0.0009 (14)	0.0102 (16)	−0.0007 (15)
C7	0.0456 (19)	0.0302 (17)	0.054 (2)	−0.0036 (15)	0.0050 (16)	0.0018 (15)
C2	0.0355 (17)	0.0356 (17)	0.0410 (18)	−0.0031 (14)	0.0002 (13)	0.0017 (14)
C3	0.0407 (19)	0.0318 (17)	0.061 (2)	0.0032 (15)	0.0078 (16)	−0.0012 (16)
C4	0.044 (2)	0.0292 (16)	0.063 (2)	−0.0011 (15)	0.0116 (17)	0.0023 (16)
C1	0.0415 (19)	0.0403 (18)	0.0433 (18)	−0.0015 (15)	0.0022 (15)	0.0019 (15)
O9	0.0464 (14)	0.0397 (13)	0.0622 (16)	−0.0055 (11)	0.0210 (12)	0.0031 (12)
C27	0.0420 (19)	0.052 (2)	0.048 (2)	−0.0043 (17)	0.0133 (16)	0.0029 (17)
C28	0.070 (3)	0.049 (2)	0.060 (3)	−0.022 (2)	0.027 (2)	−0.0047 (19)
C29	0.093 (4)	0.051 (3)	0.096 (4)	0.016 (3)	0.038 (3)	0.017 (3)
C17	0.0398 (17)	0.0303 (16)	0.0330 (16)	0.0001 (13)	0.0057 (13)	−0.0040 (13)
C22	0.0433 (18)	0.0307 (16)	0.0336 (16)	−0.0003 (14)	0.0043 (13)	−0.0019 (13)
C21	0.0429 (18)	0.0351 (17)	0.0357 (17)	0.0060 (14)	−0.0005 (14)	−0.0031 (14)
C20	0.0413 (19)	0.051 (2)	0.048 (2)	0.0038 (17)	0.0066 (15)	−0.0079 (17)
C19	0.046 (2)	0.051 (2)	0.044 (2)	−0.0079 (17)	0.0121 (16)	−0.0016 (16)
C18	0.051 (2)	0.0346 (17)	0.0329 (16)	−0.0049 (15)	0.0057 (14)	−0.0013 (13)
C26	0.078 (3)	0.0349 (19)	0.055 (2)	−0.0079 (19)	0.020 (2)	0.0034 (17)
N23	0.0530 (19)	0.0382 (16)	0.0492 (18)	0.0113 (14)	−0.0018 (15)	−0.0043 (14)
O25	0.093 (2)	0.0366 (14)	0.0546 (17)	0.0082 (14)	0.0110 (15)	0.0061 (12)
O24	0.064 (2)	0.0563 (18)	0.107 (3)	0.0209 (16)	0.0236 (18)	−0.0154 (18)
O8	0.0484 (17)	0.0448 (16)	0.111 (3)	0.0069 (13)	0.0250 (16)	0.0018 (16)

Geometric parameters (Å, º) top

Cu—Cl	2.2460 (9)	C1—O8	1.199 (5)
Cu—Clⁱ	2.2460 (9)	O9—C27	1.444 (4)
Cu—N14ⁱ	2.009 (2)	C27—H27A	0.9700
Cu—N14	2.009 (2)	C27—H27B	0.9700
N14—N13	1.310 (4)	C27—C28	1.503 (5)
N14—C15	1.350 (4)	C28—H28A	0.9700
N13—N12	1.344 (4)	C28—H28B	0.9700
N12—C16	1.344 (4)	C28—C29	1.522 (7)
N12—C17	1.432 (4)	C29—H29A	0.9600
C16—H16	0.9300	C29—H29B	0.9600
C16—C15	1.365 (5)	C29—H29C	0.9600
C15—C11	1.481 (5)	C17—C22	1.390 (4)
C11—H11A	0.9700	C17—C18	1.394 (5)
C11—H11B	0.9700	C22—H22	0.9300
C11—O10	1.426 (4)	C22—C21	1.385 (5)
O10—C5	1.361 (4)	C21—C20	1.373 (5)
C5—C6	1.390 (5)	C21—N23	1.475 (4)
C5—C4	1.383 (5)	C20—H20	0.9300
C6—H6	0.9300	C20—C19	1.378 (5)
C6—C7	1.369 (5)	C19—H19	0.9300
C7—H7	0.9300	C19—C18	1.393 (5)
C7—C2	1.391 (5)	C18—C26	1.502 (5)
C2—C3	1.384 (5)	C26—H26A	0.9600
C2—C1	1.483 (5)	C26—H26B	0.9600
C3—H3	0.9300	C26—H26C	0.9600
C3—C4	1.381 (5)	N23—O25	1.221 (4)
C4—H4	0.9300	N23—O24	1.216 (4)
C1—O9	1.338 (4)

Clⁱ—Cu—Cl	180.0	C1—O9—C27	117.0 (3)
N14ⁱ—Cu—Clⁱ	90.80 (8)	O9—C27—H27A	110.5
N14—Cu—Clⁱ	89.20 (8)	O9—C27—H27B	110.5
N14ⁱ—Cu—Cl	89.20 (8)	O9—C27—C28	106.2 (3)
N14—Cu—Cl	90.80 (8)	H27A—C27—H27B	108.7
N14ⁱ—Cu—N14	180.0	C28—C27—H27A	110.5
N13—N14—Cu	119.5 (2)	C28—C27—H27B	110.5
N13—N14—C15	111.1 (3)	C27—C28—H28A	108.8
C15—N14—Cu	129.4 (2)	C27—C28—H28B	108.8
N14—N13—N12	105.5 (2)	C27—C28—C29	113.7 (4)
N13—N12—C16	111.2 (3)	H28A—C28—H28B	107.7
N13—N12—C17	118.2 (3)	C29—C28—H28A	108.8
C16—N12—C17	130.3 (3)	C29—C28—H28B	108.8
N12—C16—H16	127.3	C28—C29—H29A	109.5
N12—C16—C15	105.4 (3)	C28—C29—H29B	109.5
C15—C16—H16	127.3	C28—C29—H29C	109.5
N14—C15—C16	106.8 (3)	H29A—C29—H29B	109.5
N14—C15—C11	121.9 (3)	H29A—C29—H29C	109.5
C16—C15—C11	131.2 (3)	H29B—C29—H29C	109.5
C15—C11—H11A	110.4	C22—C17—N12	116.9 (3)
C15—C11—H11B	110.4	C22—C17—C18	122.4 (3)
H11A—C11—H11B	108.6	C18—C17—N12	120.6 (3)
O10—C11—C15	106.5 (3)	C17—C22—H22	121.3
O10—C11—H11A	110.4	C21—C22—C17	117.3 (3)
O10—C11—H11B	110.4	C21—C22—H22	121.3
C5—O10—C11	117.4 (3)	C22—C21—N23	118.0 (3)
O10—C5—C6	114.6 (3)	C20—C21—C22	122.6 (3)
O10—C5—C4	125.1 (3)	C20—C21—N23	119.3 (3)
C4—C5—C6	120.3 (3)	C21—C20—H20	120.9
C5—C6—H6	120.1	C21—C20—C19	118.2 (3)
C7—C6—C5	119.8 (3)	C19—C20—H20	120.9
C7—C6—H6	120.1	C20—C19—H19	118.8
C6—C7—H7	119.6	C20—C19—C18	122.4 (3)
C6—C7—C2	120.7 (3)	C18—C19—H19	118.8
C2—C7—H7	119.6	C17—C18—C26	122.8 (3)
C7—C2—C1	122.1 (3)	C19—C18—C17	117.0 (3)
C3—C2—C7	118.8 (3)	C19—C18—C26	120.2 (3)
C3—C2—C1	119.0 (3)	C18—C26—H26A	109.5
C2—C3—H3	119.5	C18—C26—H26B	109.5
C4—C3—C2	121.1 (3)	C18—C26—H26C	109.5
C4—C3—H3	119.5	H26A—C26—H26B	109.5
C5—C4—H4	120.4	H26A—C26—H26C	109.5
C3—C4—C5	119.3 (3)	H26B—C26—H26C	109.5
C3—C4—H4	120.4	O25—N23—C21	118.1 (3)
O9—C1—C2	111.1 (3)	O24—N23—C21	118.0 (3)
O8—C1—C2	126.0 (3)	O24—N23—O25	123.9 (3)
O8—C1—O9	122.9 (3)

Cu—N14—N13—N12	−178.21 (19)	C6—C7—C2—C1	−178.1 (3)
Cu—N14—C15—C16	178.1 (2)	C7—C2—C3—C4	−0.7 (6)
Cu—N14—C15—C11	−4.7 (5)	C7—C2—C1—O9	3.6 (5)
N14—N13—N12—C16	−0.1 (3)	C7—C2—C1—O8	−177.3 (4)
N14—N13—N12—C17	−174.4 (3)	C2—C3—C4—C5	0.4 (6)
N14—C15—C11—O10	−122.9 (3)	C2—C1—O9—C27	172.7 (3)
N13—N14—C15—C16	0.2 (4)	C3—C2—C1—O9	−173.9 (3)
N13—N14—C15—C11	177.5 (3)	C3—C2—C1—O8	5.2 (6)
N13—N12—C16—C15	0.2 (4)	C4—C5—C6—C7	−2.5 (6)
N13—N12—C17—C22	125.8 (3)	C1—C2—C3—C4	176.9 (3)
N13—N12—C17—C18	−51.5 (4)	C1—O9—C27—C28	175.3 (3)
N12—C16—C15—N14	−0.3 (4)	O9—C27—C28—C29	56.2 (5)
N12—C16—C15—C11	−177.1 (3)	C17—N12—C16—C15	173.7 (3)
N12—C17—C22—C21	−177.9 (3)	C17—C22—C21—C20	1.1 (5)
N12—C17—C18—C19	177.2 (3)	C17—C22—C21—N23	179.3 (3)
N12—C17—C18—C26	−3.8 (5)	C22—C17—C18—C19	0.1 (5)
C16—N12—C17—C22	−47.3 (5)	C22—C17—C18—C26	179.1 (3)
C16—N12—C17—C18	135.4 (4)	C22—C21—C20—C19	−0.9 (5)
C16—C15—C11—O10	53.6 (5)	C22—C21—N23—O25	−12.1 (5)
C15—N14—N13—N12	−0.1 (3)	C22—C21—N23—O24	167.0 (3)
C15—C11—O10—C5	174.7 (3)	C21—C20—C19—C18	0.3 (6)
C11—O10—C5—C6	170.4 (3)	C20—C21—N23—O25	166.1 (3)
C11—O10—C5—C4	−10.0 (5)	C20—C21—N23—O24	−14.8 (5)
O10—C5—C6—C7	177.1 (3)	C20—C19—C18—C17	0.1 (5)
O10—C5—C4—C3	−178.4 (4)	C20—C19—C18—C26	−178.9 (4)
C5—C6—C7—C2	2.2 (6)	C18—C17—C22—C21	−0.7 (5)
C6—C5—C4—C3	1.2 (6)	N23—C21—C20—C19	−179.1 (3)
C6—C7—C2—C3	−0.6 (6)	O8—C1—O9—C27	−6.4 (6)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O9	0.93	2.39	2.706 (4)	100
C22—H22···Clⁱⁱ	0.93	2.78	3.689 (3)	167
C29—H29B···O8ⁱⁱⁱ	0.96	2.59	3.531 (6)	168

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

Acknowledgements

The authors thank the Institute of Bioorganic Chemistry of the Academy Sciences of Uzbekistan, Tashkent, Uzbekistan, for providing the single-crystal XRD facility.

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