Synthesis, crystal structure and Hirshfeld surface analysis of [Cu(H2L)2(μ-Cl)CuCl3]·H2O [H2L = 2-hy­droxy-N′-(propan-2-yl­idene)benzohydrazide]

Boulguemh, I.; Lehleh, A.; Beghidja, C.; Beghidja, A.

doi:10.1107/S2056989024007941

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Volume 80| Part 9| September 2024| Pages 961-966

https://doi.org/10.1107/S2056989024007941

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Synthesis, crystal structure and Hirshfeld surface analysis of [Cu(H₂L)₂(μ-Cl)CuCl₃]·H₂O [H₂L = 2-hydroxy-N′-(propan-2-ylidene)benzohydrazide]

Imededdine Boulguemh,^a Asma Lehleh,^a Chahrazed Beghidja ^a and Adel Beghidja ^a ^*

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Constantine 1 - Frères Mentouri, 25017, Constantine, Algeria
^*Correspondence e-mail: beghidja@umc.edu.dz

Edited by S. P. Kelley, University of Missouri-Columbia, USA (Received 13 May 2024; accepted 12 August 2024; online 20 August 2024)

The present study focuses on the synthesis and structural characterization of a novel dinuclear Cu^II complex, [trichloridocopper(II)]-μ-chlorido-{bis[2-hydroxy-N′-(propan-2-ylidene)benzohydrazide]copper(II)} monohydrate, [Cu₂Cl₄(C₁₀H₁₂N₂O₂)₂]·H₂O or [Cu(H₂L)₂(μ-Cl)CuCl₃]·H₂O [H₂L = 2-hydroxy-N′-(propan-2-ylidene)benzohydrazide]. The complex crystallizes in the monoclinic space group P2₁/n with one molecule of water, which forms interactions with the ligands. The first copper ion is penta-coordinated to two benzohydrazine-derived ligands via two nitrogen and two oxygen atoms, and one bridging chloride, which is also coordinated by the second copper ion alongside three terminal chlorines in a distorted tetrahedral geometry. The arrangement around the first copper ion exhibits a distorted geometry intermediate between trigonal bipyramidal and square pyramidal. In the crystal, chains are formed via intermolecular interactions along the a-axis direction, with subsequent layers constructed through hydrogen-bonding interactions parallel to the ac plane, and through slipped π–π stacking interactions parallel to the ab plane, resulting in a three-dimensional network. The intermolecular interactions in the crystal structure were quantified and analysed using Hirshfeld surface analysis. Residual electron density from disordered methanol molecules in the void space could not be reasonably modelled, thus a solvent mask was applied.

Keywords: hydrazone; crystal structure; copper complexes; Hirshfeld surface; hydrogen bonds.

CCDC reference: 2377149

1. Chemical context

Schiff bases are organic compounds that have important applications in many areas of chemistry, including organic synthesis and inorganic chemistry (Sinicropi et al., 2022 ). Over the years, Schiff bases have gained a lot of popularity as chelating ligands in coordination chemistry with transition metals, due to their versatility and ability to act as multiple linkers and their stability under various oxidizing and reducing conditions (DeepikaVerma et al., 2023 ). These ligands make excellent coordination molecules and can show variety in structures with metal complexes (Guo et al., 2011 ), thus leading to a variety of properties (DeepikaVerma et al., 2023).

Hydrazone ligands constitute a distinct category of Schiff bases, arising from the condensation reaction involving hydrazine and either an aldehyde or a ketone in the presence of an acid or a base. The literature has reported that coordination complexes formed between hydrazones and metals can be used in several areas, such as in catalysis for various reactions (Dile et al., 2016 ), as materials for gas adsorption (Roztocki et al., 2016 ), for the detection of heavy metals in the environment (Sharma et al., 2019 ), in electrochemistry (Toledano-Magaña et al., 2015 ) and in molecular magnetism (Sadhukhan et al., 2018 ). In addition, these complexes are widely studied in pharmaceutical chemistry, (Haider & Khan, 2022 ) due to their potential as bioactive compounds, especially as anticancer (Šermukšnytė et al., 2022 ; Gaur et al., 2022 ), antituberculosis (Mathew et al., 2015 ; Teneva et al., 2023 ) and antifungal agents (Kajal et al., 2014 ) (Yankin et al., 2022 ), as well as for the design of drugs against Alzheimer's disease (Boulguemh et al., 2020 ) and Parkinson's disease (Kondeva-Burdina et al., 2022 ).

As a continuation of our research on the synthesis and the study of the biological and magnetic properties of new Schiff base-type ligands and their complexes (Ouilia et al., 2012 ; Boussadia et al., 2020 ; Boulguemh et al., 2020), we report here the synthesis, structural characterization and Hirshfeld surface analysis of a new dinuclear copper(II) complex [Cu(H₂L)₂(μ-Cl)CuCl₃]·H₂O with a hydrazine ligand (H₂L = 2-hydroxy-N′-(propan-2-ylidene)benzohydrazide).

2. Structural commentary

The asymmetric unit of the title compound, which comprises a dinuclear Cu^II complex and one water solvation molecule, is illustrated in Fig. 1. The first copper ion Cu1 is in pentacoordinated environment with trigonality index parameter τ₅ = 0.516. The tau value for pentacoordinated complexes is calculated using the equation elaborated by Addison et al. (1984 ): τ₅ = (β − α)/60, where α and β are the largest basal angles. τ₅ equals 1 for an ideal trigonal bipyramid and 0 for a square-pyramidal coordination. The coordination geometry around the Cu1 ion lies between a distorted trigonal bipyramidal and square pyramidal. The copper ion Cu1 is coordinated to the two carbonyl oxygen atoms O1 and O3, and the two imine nitrogens N2 and N4 from two bidentate chelating H₂L ligands. The fifth coordination site is occupied by a bridging chloride Cl1 with a Cu1—Cl1 distance of 2.5001 (14) Å, consistent with literature values (Comba et al., 1988 ). The Cu1—O bond lengths are Cu1—O1 = 1.971 (3) Å and Cu1—O3 = 1.959 (3) Å, while the Cu1—N2 and Cu1—N4 bond lengths are 1.999 (4) and 2.009 (4) Å, respectively. The distorted tetrahedral site around the second copper ion, Cu2, is occupied by three terminal chloride ions, Cl2, Cl3, and Cl4 and a bridging chloride ion Cl1. The terminal Cu—Cl bond distances range from 2.2209 (16) to 2.2601 (12) Å, while the Cu—Cl bridging bond is slightly longer, with a Cu2—Cl1 distance of 2.2897 (15) Å (Table 1). These distances are comparable to those observed for other tetrachlorometallate (Vasilevesky et al., 1991 ; Ramos Silva et al., 2005 ; Comba et al., 1988). The geometry index for tetracoordinated copper ions, τ₄, is calculated as [360° − (α + β)]/141° (Yang et al., 2007 ), inspired by the τ₅ index for five-coordinate complexes developed by Addison and Reedijk (Addison et al., 1984). The values of τ₄ range from 1 for a perfect tetrahedral geometry to 0 for a perfect square-planar geometry. For the tetracoordinated coordination geometry around the Cu2 ion, τ₄ = 0.61, indicating a very distorted tetrahedral geometry (Yang et al., 2007). This distortion has been noted in numerous salts containing [CuCl₄]²⁻ ions, with some displaying thermochromic properties attributed to the deformation of tetrachlorometallate ions in response to temperature changes (Willett et al., 1974 ).

Table 1
Selected geometric parameters (Å, °)

Cu1—Cl1	2.5001 (14)	Cu2—Cl1	2.2897 (15)
Cu1—O1	1.971 (3)	Cu2—Cl2	2.2601 (12)
Cu1—O3	1.959 (3)	Cu2—Cl3	2.2209 (16)
Cu1—N2	1.999 (4)	Cu2—Cl4	2.2269 (13)
Cu1—N4	2.009 (4)

Cl1—Cu1—O1	108.38 (10)	N2—Cu1—N4	173.85 (15)
Cl1—Cu1—O3	108.44 (11)	Cl1—Cu2—Cl2	99.52 (5)
Cl1—Cu1—N2	96.87 (11)	Cl1—Cu2—Cl3	135.68 (6)
Cl1—Cu1—N4	89.26 (11)	Cl1—Cu2—Cl4	94.92 (5)
O1—Cu1—O3	143.06 (14)	Cl2—Cu2—Cl3	98.34 (5)
O1—Cu1—N2	81.01 (13)	Cl2—Cu2—Cl4	137.89 (5)
O1—Cu1—N4	96.61 (13)	Cl3—Cu2—Cl4	98.32 (5)
O3—Cu1—N2	97.49 (13)	Cu1—Cl1—Cu2	135.00 (5)
O3—Cu1—N4	80.97 (12)

Figure 1
The title compound showing the atom-labelling scheme with ellipsoids drawn at the 50% probability level and H atoms shown as small spheres of arbitrary radii.

The Cu1—Cl1—Cu2 bridging angle of 135.00 (5)° is larger than those observed in the literature for yellow terminal tetrachlorometallate ligands (Ramos Silva et al., 2005). However, the intermetallic Cu⋯Cu distance observed in the title compound [4.426 (8) Å] is within the range observed for similar compounds (Comba et al., 1988; Ramos Silva et al., 2005). Some correlations between the magnetic and structural parameters for mono-μ-chloro–copper chains have been observed, while the magnetic and structural data suggest a limited number of exchange pathways (van Albada et al., 2004 ; Alves et al., 2009 ). However, following these correlations, overall ferromagnetic behaviour can be expected for values of the quotient φ/R (where φ is the Cu—Cl—Cu bridge angle and R is the Cu—Cl long bond length) lower than approximately 40 and higher than 57, whereas antiferromagnetic behaviour is observed when this quotient φ/R is between these two values. However, the terminal halometallate counter-ion has no impact on the nature of the interaction. In the title compound, the Cu—Cl—Cu bond angle is 135.00 (5)°, with Cu—Cl distances of 2.5001 (14) and 2.2897 (15) Å, resulting in φ/R ratios of 54 and 59, respectively. These values suggest antiferromagnetic behaviour.

3. Supramolecular features

In the crystal, the supramolecular network consists of an extensive set of intra- and intermolecular hydrogen-bonding interactions (numerical details are given in Table 2). Two intramolecular hydrogen bonds are formed between the imine N1 and N3 atoms and phenolic O2, O4 atoms of the ligand via the respective hydrogen atoms H1 and H3 (Fig. 1). While the carbon donor atoms C10 and C20 of the methyl groups are involved in hydrogen bonds with the acceptor atoms O3 and O1, respectively, of the carbonyl groups via the H10C and H20C atoms (Fig. 1). The solvent water molecule is linked to the complex molecule via the oxygen atom O2 of the phenolic group by a O2—H2⋯O1W hydrogen bond (Fig. 1).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1W	0.82	1.79	2.606 (6)	171
N1—H1⋯O2	0.86	1.94	2.597 (5)	132
N3—H3⋯O4	0.86	1.96	2.612 (5)	132
O1W—H1WA⋯O3ⁱ	0.85	2.53	3.375 (6)	170
O1W—H1WA⋯N3ⁱ	0.85	2.59	3.303 (7)	142
O1W—H1WB⋯Cl3ⁱⁱ	0.85	2.38	3.195 (6)	160
O4—H4⋯Cl2ⁱⁱⁱ	0.82	2.40	3.215 (3)	175
C7—H7⋯O1	0.93	2.44	2.762 (5)	1
C10—H10C⋯O3	0.96	2.35	3.099 (6)	135
C20—H20C⋯O1	0.96	2.41	3.043 (5)	123
Symmetry codes: (i) ; (ii) ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

The complex molecules are connected via two hydrogen bonds involving the water molecule, O1W—H1WB⋯Cl3 and O1W—H1WA⋯O3, leading to chains propagating along the a-axis direction (Fig. 2). The two-dimensional arrangement parallel to the ac plane is established by connecting two adjacent chains through two types of patterns. The first arrangement is formed by a succession of R₄⁴(20) and R₄⁴(24) rings, and the second one through a succession of R₆⁴(30) rings (Fig. 3). The first two ring structures are formed by two water and two complex molecules, except for the third ring, which is formed by two solvent water and four complex molecules.

Figure 2
Partial view of the crystal structure showing the intermolecular hydrogen bonds (indicated by green dashed lines) forming infinite chains propagating along the a-axis direction.

Figure 3
Molecular view of the arrangement of chains (a) via R⁴₄(20) and R₄⁴(24) rings and (b) R₄⁶(30) rings along the ac plane. Hydrogen bonds are shown as dashed green lines.

In the first arrangement, the two water molecules act as acceptor and donor, forming R₄⁴(20) and R₄⁴(24) rings. O2—H2⋯O1W—H1WA⋯O3 interactions are observed in the first ring and O2—H2⋯O1W—H1WB⋯Cl3 in the second ring (Fig. 3a). The second arrangement of interconnected chains is generated by a succession of R₆⁴(30) rings, where the two water molecules act as donors in Cl3⋯ H1WB —O1W—H1WA⋯O3 interactions, and two phenol donor groups in O4—H4⋯Cl2 interactions (Fig. 3b).

The junction between the resulting two double chains via hydrogen bonds O4—H4⋯Cl2 and C10—H10A⋯Cl4 establishes two-dimensional layers parallel to the ac plane (Fig. 4). Slipped π–π stacking interactions are also observed in this structure, involving the aromatic rings of the ligands with an intercentroid distance Cg1⋯·Cg2( $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) of 3.683 (3) Å (where Cg1 and Cg2 are the centroids of the C2–C7 and C12–C17 rings, respectively), resulting in a three-dimensional network by linking chains along the b axis (Fig. 5).

Figure 4
Crystal packing of the title compound shown in a projection of the two-dimensional network connected through hydrogen bonds (shown as dashed green lines).

Figure 5
Crystal packing of the title compound showing the 3D network and the chains parallel to the b axis formed by π–π stacking interactions between the aromatic rings of the ligands (shown in red).

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.45, updated in November 2023; Groom et al., 2016 ), revealed that crystal structures have been reported for complexes of several hydrazone derivatives with various metal ions, such as copper (Balsa et al., 2021 ), zinc (Dasgupta et al., 2020 ), cadmium (Govindaiah et al., 2021 ), cobalt (Han et al., 2020 ), magnesium (Khandar et al., 2019 ). Only one complex based on copper and benzoic acid, 2-(1-methylethylidene)hydrazide has been reported (Mohamad et al., 2019 ). No complexes containing two copper ions connected to each other by a chlorine atom and coordinated to two molecules of acetone hydrazone have been documented in the CSD.

To the best of our knowledge, there are only a few examples of asymmetric binuclear copper-based complexes reported in the CSD with some instances where a copper complex is bridged by any type of tetrametallate (Barz et al., 1998 ; Shi et al., 2014 ; Alves et al., 2014 ; Kaur et al., 2019 ; Singh et al., 2014 ; Comba et al., 1988; Ramos Silva et al., 2005).

5. Hirshfeld surface analysis

For further characterization of the intermolecular interactions in the title compound, we carried out a Hirshfeld surface (HS) analysis (Spackman & Jayatilaka, 2009 ) using Crystal Explorer 21 (Spackman et al., 2021 ) and generated the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ). The HS of the title compound mapped over d_norm in the range 0.4396 to +2.3676 a.u. is illustrated in Fig. 6 using colour to indicate contacts that are shorter (red areas), equal to (white areas), or longer than (blue areas) the sum of the van der Waals radii (Ashfaq et al., 2021 ). The red spots on the surface mapped over d_norm (Fig. 6a) indicate the involvement of atoms in hydrogen-bonding interactions. The HS mapped over shape-index (Fig. 6b) is used to check for the presence of interactions such as C—H⋯π and π–π stacking (Ashfaq et al., 2021). The existence of adjacent red and blue triangular regions around the aromatic rings conforms to the presence of π–π stacking interactions in the title compound (Fig. 6b), and the curvedness plots (Fig. 6c) show flat surface patches characteristic of planar stacking. The two-dimensional fingerprint plots provide unique information about the non-covalent interactions and the crystal packing in terms of the percentage contribution of the interatomic contacts (Spackman & McKinnon, 2002 ; Ashfaq et al., 2021). Fig. 7 shows the two-dimensional fingerprint plot for the overall interactions with their relative contributions to the Hirshfeld surface. The most important interatomic contact is H⋯Cl as it makes the highest contribution to the crystal packing (35.6%, Fig. 7b). The other major contributor is H⋯H interactions (32.3%, Fig. 7c). Other interactions contributing less to the crystal packing are C⋯H (9.9%, Fig. 7d), O⋯H (6.7%, Fig. 7e), C⋯C (4.7%, Fig. 7f), N⋯H (2.8%, Fig. 7g), C⋯O (1.7%, Fig. 7h), Cl⋯O (1.7%, Fig. 7i), N⋯C (1.5%, Fig. 7j) and O⋯O (0.8%, Fig. 7k). Other contacts make a contribution of 2.3% in total and are not discussed in this work.

Figure 6
A view of the Hirshfeld surface mapped over (a) d_norm, (b) shape-index and (c) curvedness.

Figure 7
Two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) Cl⋯H/H⋯Cl, (c) H⋯H, (d) C⋯H/ H⋯C, (e) O⋯H/ H⋯O, (f) C⋯C, (g) N⋯H/H⋯N, (h) O⋯C/C⋯O, (i) N⋯C/C⋯N and (j) O⋯O interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

6. Synthesis and crystallization

A mixture of CuCl₂·2H₂O (0.170 g, 1mmol) with salicylhydrazide (0.304 g, 2 mmol) and NaOH (0.08 g, 2 mmol), was dissolved in 10 mL of a mixed methanol/acetone (3/1) solution then stirred for 2 h at room temperature. Yellow crystals suitable for X-ray analysis were obtained after 5 days in (0.022 g, 52%).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were placed in calculated positions with C—H = 0.93–0.95 Å, N—H = 0.86 Å, O—H = 0.82–0.85 Å and refined using a riding model with U_iso(H) = 1.2–1.5U_eq(C,N,O). A solvent mask was calculated via the SQUEEZE routine in PLATON (Spek, 2015 , 2020 ) and 120 electrons were found in a volume of 234 Å³ in two voids per unit cell. This is consistent with the presence of 1[H₂O], 1.5[CH₃OH] per formula unit, which account for 122 electrons per unit cell.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₂Cl₄(C₁₀H₁₂N₂O₂)₂]·2H₂O·1.5CH₄O
M_r	737.40
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	273
a, b, c (Å)	11.6514 (4), 20.1507 (8), 12.8149 (4)
β (°)	110.858 (2)
V (Å³)	2811.56 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.94
Crystal size (mm)	0.14 × 0.12 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.673, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	21699, 5708, 3843
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.146, 1.06
No. of reflections	5708
No. of parameters	324
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.53
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXT2018/3 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and PLATON (Spek, 2020).

Supporting information

CCDC reference: 2377149

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989024007941/ev2007sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024007941/ev2007Isup2.hkl

checkCIF report

Computing details top

[Trichloridocopper(II)]-µ-chlorido-{bis[2-hydroxy-N'-(propan-2-ylidene)benzohydrazide]copper(II)} monohydrate top

Crystal data top

[Cu₂Cl₄(C₁₀H₁₂N₂O₂)₂]·2H₂O·1.5CH₄O	F(000) = 1360
M_r = 737.40	D_x = 1.704 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3635 reflections
a = 11.6514 (4) Å	θ = 2.6–23.4°
b = 20.1507 (8) Å	µ = 1.94 mm⁻¹
c = 12.8149 (4) Å	T = 273 K
β = 110.858 (2)°	Block, yellow
V = 2811.56 (18) Å³	0.14 × 0.12 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5708 independent reflections
Radiation source: MoKα	3843 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 18.4 pixels mm^-1	θ_max = 26.4°, θ_min = 2.0°
φ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −21→25
T_min = 0.673, T_max = 0.745	l = −16→14
21699 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.146	W = 1/[Σ²(FO²) + (0.0793P)²] WHERE P = (FO² + 2FC²)/3
S = 1.06	(Δ/σ)_max = 0.001
5708 reflections	Δρ_max = 0.71 e Å⁻³
324 parameters	Δρ_min = −0.53 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All N(H) groups At 1.5 times of: All C(H,H,H) groups, All O(H) groups, All O(H,H) groups

2. Uiso/Uaniso restraints and constraints Uanis(C21) ~ Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002 Uanis(O5) ~ Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002

3.a Free rotating group: O1W(H1WA,H1WB)

3.b Aromatic/amide H refined with riding coordinates: N1(H1), N3(H3), C4(H4A), C5(H5), C6(H6), C7(H7), C14(H14), C15(H15), C16(H16), C17(H17)

3.c Idealised Me refined as rotating group: C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C19(H19A,H19B,H19C), C20(H20A,H20B, H20C), C21(H21A,H21B,H21C)

3.d Idealised tetrahedral OH refined as rotating group: O2(H2), O4(H4), O5(H5A).

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

	x	y	z	U_iso*/U_eq
Cu1	0.75452 (5)	0.61586 (3)	0.24378 (4)	0.0340 (2)
Cu2	0.36066 (5)	0.63824 (3)	0.19419 (4)	0.0381 (2)
Cl1	0.52667 (11)	0.61036 (6)	0.14739 (9)	0.0440 (4)
Cl2	0.40338 (12)	0.57786 (6)	0.35215 (9)	0.0498 (4)
Cl3	0.29411 (16)	0.72976 (7)	0.25093 (11)	0.0676 (5)
Cl4	0.22690 (12)	0.63604 (6)	0.01947 (10)	0.0521 (4)
O1	0.8210 (3)	0.52516 (15)	0.2546 (2)	0.0384 (10)
O2	0.8882 (3)	0.42800 (17)	0.5540 (3)	0.0529 (11)
O3	0.8022 (3)	0.70917 (14)	0.2734 (2)	0.0365 (10)
O4	0.8657 (3)	0.81403 (15)	0.0217 (2)	0.0467 (10)
N1	0.8076 (3)	0.52971 (17)	0.4240 (3)	0.0343 (11)
N2	0.7577 (3)	0.59260 (17)	0.3964 (3)	0.0329 (11)
N3	0.8051 (3)	0.70518 (17)	0.1001 (3)	0.0340 (11)
N4	0.7711 (3)	0.63902 (16)	0.0973 (3)	0.0307 (11)
C1	0.8365 (4)	0.4970 (2)	0.3474 (3)	0.0304 (12)
O1W	0.9308 (4)	0.3537 (3)	0.7302 (4)	0.119 (2)
C2	0.8862 (4)	0.4296 (2)	0.3687 (3)	0.0343 (12)
C3	0.9105 (4)	0.3962 (2)	0.4704 (4)	0.0395 (14)
C4	0.9573 (4)	0.3314 (2)	0.4824 (4)	0.0517 (17)
C5	0.9782 (5)	0.3009 (3)	0.3947 (5)	0.0585 (19)
C6	0.9532 (5)	0.3324 (3)	0.2941 (4)	0.0539 (17)
C7	0.9075 (4)	0.3963 (2)	0.2808 (4)	0.0429 (17)
C8	0.7218 (4)	0.6229 (2)	0.4683 (4)	0.0376 (14)
C9	0.7308 (5)	0.5926 (3)	0.5773 (4)	0.0523 (17)
C10	0.6685 (5)	0.6909 (2)	0.4417 (4)	0.0503 (17)
C11	0.8230 (4)	0.7382 (2)	0.1949 (3)	0.0310 (12)
C12	0.8656 (4)	0.8069 (2)	0.2065 (3)	0.0311 (12)
C13	0.8874 (4)	0.8439 (2)	0.1218 (3)	0.0328 (12)
C14	0.9286 (4)	0.9088 (2)	0.1416 (3)	0.0366 (14)
C15	0.9450 (4)	0.9386 (2)	0.2436 (4)	0.0404 (14)
C16	0.9226 (4)	0.9033 (2)	0.3277 (4)	0.0412 (16)
C17	0.8840 (4)	0.8387 (2)	0.3086 (3)	0.0356 (14)
C18	0.7490 (4)	0.6063 (2)	0.0057 (4)	0.0396 (14)
C19	0.7628 (7)	0.6374 (3)	−0.0940 (4)	0.074 (3)
C20	0.7147 (5)	0.5358 (2)	0.0012 (4)	0.0455 (16)
H1	0.81939	0.51265	0.48846	0.0410*
H2	0.89569	0.40190	0.60509	0.0800*
H3	0.81424	0.72404	0.04332	0.0410*
H4	0.87029	0.84159	−0.02370	0.0700*
H4A	0.97419	0.30903	0.54971	0.0620*
H5	1.00988	0.25806	0.40383	0.0700*
H6	0.96696	0.31086	0.23543	0.0640*
H7	0.89049	0.41769	0.21267	0.0520*
H9A	0.66940	0.55874	0.56479	0.0790*
H9B	0.71815	0.62622	0.62517	0.0790*
H9C	0.81082	0.57334	0.61213	0.0790*
H10A	0.72080	0.72206	0.49371	0.0750*
H10B	0.58840	0.69159	0.44692	0.0750*
H10C	0.66221	0.70267	0.36723	0.0750*
H14	0.94531	0.93246	0.08641	0.0440*
H15	0.97101	0.98253	0.25575	0.0490*
H16	0.93375	0.92321	0.39606	0.0500*
H17	0.86953	0.81523	0.36510	0.0430*
H19A	0.70856	0.67474	−0.11693	0.1110*
H19B	0.74279	0.60553	−0.15355	0.1110*
H19C	0.84614	0.65190	−0.07606	0.1110*
H20A	0.78488	0.50873	0.00817	0.0680*
H20B	0.65036	0.52658	−0.06878	0.0680*
H20C	0.68640	0.52596	0.06132	0.0680*
H1WA	0.99407	0.33290	0.72978	0.1790*
H1WB	0.88009	0.32335	0.73023	0.1790*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0510 (4)	0.0231 (3)	0.0307 (3)	0.0007 (2)	0.0181 (2)	0.0037 (2)
Cu2	0.0512 (4)	0.0320 (3)	0.0345 (3)	0.0030 (2)	0.0193 (3)	−0.0012 (2)
Cl1	0.0426 (6)	0.0525 (7)	0.0402 (6)	0.0021 (5)	0.0188 (5)	0.0021 (5)
Cl2	0.0742 (9)	0.0429 (7)	0.0369 (6)	0.0065 (6)	0.0256 (6)	0.0047 (5)
Cl3	0.1140 (12)	0.0390 (7)	0.0589 (8)	0.0198 (7)	0.0419 (8)	−0.0043 (6)
Cl4	0.0633 (8)	0.0474 (8)	0.0386 (6)	0.0069 (6)	0.0094 (6)	−0.0016 (5)
O1	0.0520 (19)	0.0294 (16)	0.0341 (16)	0.0060 (14)	0.0156 (14)	0.0043 (13)
O2	0.073 (2)	0.044 (2)	0.0352 (18)	0.0046 (18)	0.0113 (17)	0.0127 (15)
O3	0.058 (2)	0.0241 (16)	0.0315 (15)	−0.0039 (14)	0.0209 (14)	0.0020 (12)
O4	0.083 (2)	0.0310 (17)	0.0346 (16)	−0.0098 (17)	0.0313 (17)	−0.0014 (13)
N1	0.045 (2)	0.0292 (19)	0.0293 (17)	0.0012 (16)	0.0140 (16)	0.0057 (15)
N2	0.043 (2)	0.0222 (18)	0.0344 (19)	−0.0030 (15)	0.0149 (16)	−0.0018 (14)
N3	0.050 (2)	0.0257 (19)	0.0301 (18)	−0.0050 (16)	0.0189 (16)	0.0010 (14)
N4	0.042 (2)	0.0212 (18)	0.0294 (18)	0.0000 (15)	0.0132 (15)	0.0016 (13)
C1	0.035 (2)	0.024 (2)	0.032 (2)	−0.0045 (17)	0.0116 (18)	−0.0001 (17)
O1W	0.069 (3)	0.195 (6)	0.096 (3)	0.026 (3)	0.032 (3)	0.098 (4)
C2	0.034 (2)	0.026 (2)	0.036 (2)	−0.0033 (18)	0.0040 (18)	0.0020 (17)
C3	0.043 (3)	0.030 (2)	0.037 (2)	−0.0046 (19)	0.004 (2)	0.0007 (18)
C4	0.047 (3)	0.032 (3)	0.059 (3)	0.002 (2)	−0.002 (2)	0.015 (2)
C5	0.051 (3)	0.028 (3)	0.080 (4)	0.007 (2)	0.003 (3)	−0.002 (3)
C6	0.055 (3)	0.040 (3)	0.062 (3)	0.008 (2)	0.015 (3)	−0.008 (2)
C7	0.049 (3)	0.035 (3)	0.042 (3)	0.002 (2)	0.013 (2)	−0.004 (2)
C8	0.040 (3)	0.031 (2)	0.040 (2)	−0.0055 (19)	0.012 (2)	−0.0015 (19)
C9	0.068 (3)	0.060 (3)	0.035 (3)	−0.002 (3)	0.026 (2)	−0.001 (2)
C10	0.070 (3)	0.034 (3)	0.057 (3)	−0.001 (2)	0.035 (3)	−0.007 (2)
C11	0.036 (2)	0.025 (2)	0.031 (2)	0.0014 (17)	0.0106 (18)	0.0023 (16)
C12	0.037 (2)	0.023 (2)	0.034 (2)	−0.0007 (17)	0.0137 (18)	0.0025 (16)
C13	0.042 (2)	0.028 (2)	0.029 (2)	−0.0001 (18)	0.0135 (18)	0.0033 (17)
C14	0.046 (3)	0.031 (2)	0.035 (2)	−0.006 (2)	0.017 (2)	0.0061 (18)
C15	0.048 (3)	0.028 (2)	0.042 (2)	−0.003 (2)	0.012 (2)	−0.0041 (19)
C16	0.054 (3)	0.035 (3)	0.034 (2)	−0.005 (2)	0.015 (2)	−0.0057 (19)
C17	0.046 (3)	0.032 (2)	0.030 (2)	−0.0027 (19)	0.0151 (19)	0.0025 (17)
C18	0.058 (3)	0.027 (2)	0.032 (2)	−0.001 (2)	0.014 (2)	0.0025 (18)
C19	0.138 (6)	0.052 (4)	0.037 (3)	−0.025 (4)	0.036 (3)	−0.003 (2)
C20	0.066 (3)	0.032 (3)	0.036 (2)	−0.005 (2)	0.015 (2)	−0.0033 (19)

Geometric parameters (Å, º) top

Cu1—Cl1	2.5001 (14)	C11—C12	1.460 (6)
Cu1—O1	1.971 (3)	C12—C13	1.412 (6)
Cu1—O3	1.959 (3)	C12—C17	1.403 (5)
Cu1—N2	1.999 (4)	C13—C14	1.385 (6)
Cu1—N4	2.009 (4)	C14—C15	1.389 (6)
Cu2—Cl1	2.2897 (15)	C15—C16	1.391 (7)
Cu2—Cl2	2.2601 (12)	C16—C17	1.371 (6)
Cu2—Cl3	2.2209 (16)	C18—C19	1.482 (7)
Cu2—Cl4	2.2269 (13)	C18—C20	1.471 (6)
O1—C1	1.271 (5)	O1W—H1WB	0.8500
O2—C3	1.351 (6)	O1W—H1WA	0.8500
O3—C11	1.260 (5)	C4—H4A	0.9300
O4—C13	1.357 (5)	C5—H5	0.9300
N1—N2	1.387 (5)	C6—H6	0.9300
N1—C1	1.322 (5)	C7—H7	0.9300
N2—C8	1.293 (6)	C9—H9A	0.9600
O2—H2	0.8200	C9—H9C	0.9600
N3—C11	1.335 (5)	C9—H9B	0.9600
N3—N4	1.388 (5)	C10—H10B	0.9600
N4—C18	1.290 (6)	C10—H10C	0.9600
O4—H4	0.8200	C10—H10A	0.9600
N1—H1	0.8600	C14—H14	0.9300
C1—C2	1.464 (6)	C15—H15	0.9300
C2—C3	1.403 (6)	C16—H16	0.9300
C2—C7	1.407 (6)	C17—H17	0.9300
N3—H3	0.8600	C19—H19B	0.9600
C3—C4	1.402 (6)	C19—H19C	0.9600
C4—C5	1.377 (8)	C19—H19A	0.9600
C5—C6	1.372 (8)	C20—H20C	0.9600
C6—C7	1.381 (7)	C20—H20A	0.9600
C8—C10	1.493 (6)	C20—H20B	0.9600
C8—C9	1.494 (7)

Cl1—Cu1—O1	108.38 (10)	C13—C12—C17	117.8 (4)
Cl1—Cu1—O3	108.44 (11)	C11—C12—C17	117.5 (4)
Cl1—Cu1—N2	96.87 (11)	C12—C13—C14	120.2 (3)
Cl1—Cu1—N4	89.26 (11)	O4—C13—C14	121.9 (4)
O1—Cu1—O3	143.06 (14)	O4—C13—C12	117.9 (4)
O1—Cu1—N2	81.01 (13)	C13—C14—C15	120.2 (4)
O1—Cu1—N4	96.61 (13)	C14—C15—C16	120.5 (4)
O3—Cu1—N2	97.49 (13)	C15—C16—C17	119.2 (4)
O3—Cu1—N4	80.97 (12)	C12—C17—C16	122.1 (4)
N2—Cu1—N4	173.85 (15)	C19—C18—C20	119.1 (4)
Cl1—Cu2—Cl2	99.52 (5)	N4—C18—C19	121.4 (4)
Cl1—Cu2—Cl3	135.68 (6)	N4—C18—C20	119.5 (4)
Cl1—Cu2—Cl4	94.92 (5)	H1WA—O1W—H1WB	104.00
Cl2—Cu2—Cl3	98.34 (5)	C3—C4—H4A	120.00
Cl2—Cu2—Cl4	137.89 (5)	C5—C4—H4A	120.00
Cl3—Cu2—Cl4	98.32 (5)	C6—C5—H5	119.00
Cu1—Cl1—Cu2	135.00 (5)	C4—C5—H5	119.00
Cu1—O1—C1	113.7 (3)	C5—C6—H6	120.00
Cu1—O3—C11	114.4 (2)	C7—C6—H6	120.00
N2—N1—C1	117.5 (3)	C6—C7—H7	119.00
Cu1—N2—N1	108.9 (3)	C2—C7—H7	119.00
Cu1—N2—C8	133.5 (3)	C8—C9—H9A	110.00
N1—N2—C8	117.6 (4)	C8—C9—H9C	109.00
C3—O2—H2	109.00	H9A—C9—H9B	109.00
N4—N3—C11	116.9 (3)	H9A—C9—H9C	109.00
Cu1—N4—N3	108.7 (3)	H9B—C9—H9C	109.00
N3—N4—C18	118.5 (4)	C8—C9—H9B	109.00
Cu1—N4—C18	132.6 (3)	C8—C10—H10A	109.00
C13—O4—H4	109.00	C8—C10—H10C	109.00
O1—C1—N1	118.9 (4)	H10A—C10—H10B	110.00
N2—N1—H1	121.00	C8—C10—H10B	109.00
C1—N1—H1	121.00	H10B—C10—H10C	109.00
N1—C1—C2	120.9 (3)	H10A—C10—H10C	109.00
O1—C1—C2	120.3 (4)	C13—C14—H14	120.00
C1—C2—C7	117.7 (3)	C15—C14—H14	120.00
C3—C2—C7	118.7 (4)	C16—C15—H15	120.00
C1—C2—C3	123.6 (4)	C14—C15—H15	120.00
O2—C3—C4	122.1 (4)	C15—C16—H16	120.00
C2—C3—C4	119.4 (4)	C17—C16—H16	120.00
C11—N3—H3	122.00	C16—C17—H17	119.00
O2—C3—C2	118.5 (4)	C12—C17—H17	119.00
N4—N3—H3	122.00	C18—C19—H19A	110.00
C3—C4—C5	120.1 (5)	C18—C19—H19B	109.00
C4—C5—C6	121.4 (5)	H19A—C19—H19B	110.00
C5—C6—C7	119.4 (5)	H19A—C19—H19C	110.00
C2—C7—C6	121.1 (4)	C18—C19—H19C	109.00
C9—C8—C10	118.3 (4)	H19B—C19—H19C	109.00
N2—C8—C9	122.7 (4)	C18—C20—H20B	110.00
N2—C8—C10	119.0 (4)	C18—C20—H20C	110.00
O3—C11—N3	118.9 (4)	C18—C20—H20A	110.00
N3—C11—C12	120.2 (4)	H20A—C20—H20C	109.00
O3—C11—C12	120.9 (3)	H20B—C20—H20C	109.00
C11—C12—C13	124.7 (3)	H20A—C20—H20B	109.00

O1—Cu1—Cl1—Cu2	119.83 (11)	C11—N3—N4—Cu1	2.0 (5)
O3—Cu1—Cl1—Cu2	−63.23 (12)	C11—N3—N4—C18	177.7 (4)
N2—Cu1—Cl1—Cu2	37.05 (13)	N4—N3—C11—O3	−3.7 (6)
N4—Cu1—Cl1—Cu2	−143.46 (12)	N4—N3—C11—C12	176.6 (4)
Cl1—Cu1—O1—C1	−95.8 (3)	Cu1—N4—C18—C19	176.3 (4)
O3—Cu1—O1—C1	89.0 (4)	Cu1—N4—C18—C20	−6.5 (7)
N2—Cu1—O1—C1	−1.5 (3)	N3—N4—C18—C19	1.8 (7)
N4—Cu1—O1—C1	172.8 (3)	N3—N4—C18—C20	179.0 (4)
Cl1—Cu1—O3—C11	−87.9 (3)	O1—C1—C2—C3	177.4 (4)
O1—Cu1—O3—C11	87.3 (3)	O1—C1—C2—C7	−4.3 (7)
N2—Cu1—O3—C11	172.3 (3)	N1—C1—C2—C3	−2.3 (7)
N4—Cu1—O3—C11	−1.7 (3)	N1—C1—C2—C7	176.0 (4)
Cl1—Cu1—N2—N1	110.0 (3)	C1—C2—C3—O2	−0.7 (7)
Cl1—Cu1—N2—C8	−68.4 (4)	C1—C2—C3—C4	179.5 (4)
O1—Cu1—N2—N1	2.4 (3)	C7—C2—C3—O2	−179.0 (4)
O1—Cu1—N2—C8	−176.0 (5)	C7—C2—C3—C4	1.2 (7)
O3—Cu1—N2—N1	−140.3 (3)	C1—C2—C7—C6	−179.4 (5)
O3—Cu1—N2—C8	41.3 (5)	C3—C2—C7—C6	−1.0 (7)
Cl1—Cu1—N4—N3	108.6 (3)	O2—C3—C4—C5	179.8 (5)
Cl1—Cu1—N4—C18	−66.3 (4)	C2—C3—C4—C5	−0.5 (8)
O1—Cu1—N4—N3	−143.0 (3)	C3—C4—C5—C6	−0.6 (9)
O1—Cu1—N4—C18	42.2 (5)	C4—C5—C6—C7	0.8 (9)
O3—Cu1—N4—N3	−0.2 (3)	C5—C6—C7—C2	0.0 (8)
O3—Cu1—N4—C18	−175.1 (5)	O3—C11—C12—C13	−177.9 (4)
Cl2—Cu2—Cl1—Cu1	−55.79 (9)	O3—C11—C12—C17	0.9 (7)
Cl3—Cu2—Cl1—Cu1	56.67 (11)	N3—C11—C12—C13	1.9 (7)
Cl4—Cu2—Cl1—Cu1	163.90 (8)	N3—C11—C12—C17	−179.3 (4)
Cu1—O1—C1—N1	0.2 (5)	C11—C12—C13—O4	1.0 (7)
Cu1—O1—C1—C2	−179.5 (3)	C11—C12—C13—C14	−179.6 (4)
Cu1—O3—C11—N3	3.4 (5)	C17—C12—C13—O4	−177.8 (4)
Cu1—O3—C11—C12	−176.8 (3)	C17—C12—C13—C14	1.6 (7)
C1—N1—N2—Cu1	−3.2 (5)	C11—C12—C17—C16	−179.3 (4)
C1—N1—N2—C8	175.5 (4)	C13—C12—C17—C16	−0.4 (7)
N2—N1—C1—O1	2.2 (6)	O4—C13—C14—C15	177.4 (4)
N2—N1—C1—C2	−178.2 (4)	C12—C13—C14—C15	−2.1 (7)
Cu1—N2—C8—C9	177.6 (4)	C13—C14—C15—C16	1.3 (7)
Cu1—N2—C8—C10	−2.2 (7)	C14—C15—C16—C17	−0.1 (7)
N1—N2—C8—C9	−0.7 (7)	C15—C16—C17—C12	−0.3 (7)
N1—N2—C8—C10	179.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1W	0.82	1.79	2.606 (6)	171
N1—H1···O2	0.86	1.94	2.597 (5)	132
N3—H3···O4	0.86	1.96	2.612 (5)	132
O1W—H1WA···O3ⁱ	0.85	2.53	3.375 (6)	170
O1W—H1WA···N3ⁱ	0.85	2.59	3.303 (7)	142
O1W—H1WB···Cl3ⁱⁱ	0.85	2.38	3.195 (6)	160
O4—H4···Cl2ⁱⁱⁱ	0.82	2.40	3.215 (3)	175
C7—H7···O1	0.93	2.44	2.762 (5)	1
C10—H10C···O3	0.96	2.35	3.099 (6)	135
C17—H17···O3	0.93	2.43	2.760 (5)	101
C20—H20C···O1	0.96	2.41	3.043 (5)	123

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

Acknowledgements

The authors are grateful to University Constantine 1- Frères Mentouri, MESRS (Algeria). The Algerian PRFU project (2023–2026: grant No. B00L01UN250120230004) is also acknowledged.

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