Synthesis, crystal structure and Hirshfeld surface analysis of a copper(II) complex involving 3-methyl­benzoate and 2,2′-bi­pyridine ligands

Qadir, A.

doi:10.1107/S2056989023006904

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Volume 79| Part 9| September 2023| Pages 804-807

https://doi.org/10.1107/S2056989023006904

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Synthesis, crystal structure and Hirshfeld surface analysis of a copper(II) complex involving 3-methylbenzoate and 2,2′-bipyridine ligands

Adnan Qadir ^a ^*

^aDepartment of Chemistry, College of Science, Salahaddin University, Erbil 44001, Iraq
^*Correspondence e-mail: adnan.qadir@su.edu.krd

Edited by G. Diaz de Delgado, Universidad de Los Andes Mérida, Venezuela (Received 24 January 2023; accepted 5 August 2023; online 15 August 2023)

3-Methylbenzoic acid (3-mbH) and 2,2′-bipyridine (bipy) reacted with a copper(II) salt forming a new mixed ligand complex, aqua(2,2′-bipyridine-κ²N,N′)bis(3-methylbenzoato)-κ²O,O′;κO-copper(II) 0.68-hydrate, [Cu(C₈H₇O₂)₂(C₁₀H₈N₂)(H₂O)]·0.68H₂O or [Cu(3-mb)₂(bipy)(H₂O)]·0.68H₂O. The coordination environment of Cu^II is a distorted octahedron. The metal atom is attached to two 3-mb moieties, which bind in monodentate and bidentate fashions. One of the 3-mb units is disordered. The coordination environment is completed by one bipy ligand and a water molecule. A second water molecule is outside the coordination sphere of the Cu^II atom and its occupancy refined to 0.68. The structure consists of chains along the b-axis direction formed by complex units joined via hydrogen bonds between the coordinated water molecule and an O atom of a coordinated 3-mb unit. Hirshfeld surface analysis indicates that the most abundant contacts are H⋯H (56.8%), H⋯C/C⋯H (21.7%) and H⋯O/O⋯H (13.7%).

Keywords: crystal structure; coordination compound; Hirshfeld surface analysis; 3-methylbenzoate.

CCDC reference: 2117143

1. Chemical context

The coordination chemistry of mixed-ligand copper(II) complexes continues to be of interest. Copper is an important part of various metalloenzymes. It takes part in many metabolic processes such as iron metabolism, mitochondrial oxidative phosphorylation and catecholamine production (Chen et al., 2020 ; De Freitas et al., 2003 ). Mixed-ligand copper(II) carboxylates containing nitrogen donor ligands have been reported to display a variety of pharmacological and superoxide dismutase activities. For example, the bis(acetato)bis(imidazole)copper(II) complex exhibits antitumor activity (Tamura et al., 1987 ) and copper(II) salicylate with imidazoles have dismutase activities (Abuhijleh, 2010 ). Incorporating nitrogen donor ligands in metal complexes has resulted in enhancement of the biological activity of these complexes (Patel et al., 2012 ). It has been reported that the steric effect of a substituent on the phenyl group of carboxylate ligands in metal complexes affects the coordination number of the metal, the geometry of the complex and the coordination mode of the ligand (Saini et al., 2015 ). In our previous contribution, the Cu^II complex with 3-mb and N,N,N,N-tetramethylethylenediamine (tmeda), [Cu(3-mb)₂(tmeda)(H₂O)₂], was prepared and characterized by single-crystal X-ray diffraction. The complex was octahedral with 3-mb acting as monodentate (Kansız et al., 2021 ). In view of the above information, a new Cu^II carboxylate containing 2,2′-bipyridine was synthesized, characterized by X-ray crystallographic analysis and studied by Hirshfeld surface analysis.

2. Structural commentary

Complex 1 (Fig. 1) crystallizes in the monoclinic system in the P2₁/c space group. The Cu^II atom has a distorted octahedral environment with the central copper atom coordinated by N₂O₄ donor sets. The Cu—N bond lengths range from 2.0071 (18) to 2.0131 (18) Å and the N1—Cu1—N2 angle is 80.58 (7)° (Table 1). The Cu1—O_carboxylate distances are 1.842 (17)–2.2988 (18) Å. The Cu—O and Cu—N values are very close to those reported for copper(II) complexes involving benzoate (BZA) as a ligand, for example [Cu(BZA)₂(bipy)(H₂O)] [Cu—O = 1.9951 (12)–1.9633 (12) Å and Cu—N = 2.0064 (14)–2.0111 (13) Å; Devereux et al., 2007 ]. This indicates that the presence of the methyl substituent has little or no effect on the Cu—O and Cu—N bond lengths. The 3-mb ligand defined by O3/O4/C9–C16 is disordered over two orientations related by an approximately 180° rotation.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O2	0.85	1.93	2.643 (3)	140
O5—H5B⋯O4^aⁱ	0.85	2.09	2.694 (10)	128
C20—H20⋯O4^aⁱⁱ	0.93	2.40	3.324 (10)	171
C23—H23⋯O4^aⁱⁱ	0.93	2.51	3.405 (7)	163
C18—H18⋯O2ⁱⁱⁱ	0.93	2.51	3.371 (4)	154
C24—H24⋯O6ⁱⁱ	0.93	2.36	3.200 (5)	151
C26—H26⋯O3^a	0.93	2.48	2.984 (13)	115
C17—H17⋯O1	0.93	2.59	3.093 (3)	115
C7—H7⋯O6	0.93	2.72	3.405 (6)	131
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) .

Figure 1
Molecular structure of complex 1 with ellipsoids drawn at the 50% probability level. Only the major component of disorder is shown.

3. Supramolecular features

In the crystal, hydrogen bonding between H atoms of the coordinated water molecule and the O atoms of the coordinated 3-mb (O5—H5B⋯O4) leads to the formation of a linear chain in the b-axis direction (Fig. 2 and Table 1). The chains interdigitate with other chains related by a screw-axis, connected via C—H⋯O interactions between O atoms of the 3-mb ligand and H atoms of the bipy ligand (Table 1), further consolidating the crystal. The occupancy of the solvent water (H6A—O6—H6B) refined to 0.68, which seems to be due to water escaping the crystal through the channels that run along the b-axis direction.

Figure 2
Partial view of the packing arrangement in compound 1 showing O—H⋯O interactions along the b-axis direction.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42; Groom et al., 2016 ) for compounds containing only Cu, O, N, C, and H resulted in 634 compounds containing bipy and 15 compounds containing 3-mb. In both lists, a dimeric compound containing bipy and 3-mb was identified (refcode PIGZAH; Li et al., 2007 ). Other related compounds are AJEFEB (Wen, 2009 ), DUDYIN (He et al., 2019 ), FERCOV (Wang et al., 2005 ), GELXAX (Stephenson & Hardie, 2006 ), LEBOR (Tian et al., 2011 ), QETNEJ (Chen et al., 2006 ) and TOFZIZ (Gopalakrishnan et al., 2014 ).

5. Hirshfeld surface analysis

CrystalExplorer (Turner et al., 2017 ) was used for Hirshfeld surface analysis and to generate the fingerprint plots. The purpose of using Hirshfeld surfaces, mapped onto d_norm, is to provide additional insight into intermolecular interactions. Close contacts shorter than van der Waals radii are shown as red spots on the surface. The closest contacts are responsible for directional supramolecular interactions. The blue areas in the surface map represent weak contacts that are longer than the sum of the van der Waals radii. The Hirshfeld surface mapped onto d_norm, is presented in Fig. 3. It displays several red spots due to O—H⋯O and C—H⋯O contacts. The intense spot near the coordinated water molecule in the complex is assigned to the O5—H5⋯O hydrogen bond, as confirmed by the X-ray analysis (Table 1). Fingerprint plots for the contacts are shown in Fig. 4. The contributions of the H⋯H (Fig. 4b), H⋯C/C⋯H (Fig. 4c) and H⋯O/O⋯H (Fig. 4d) contacts are 56.8, 21.7 and 13.7%, respectively.

Figure 3
Hirshfeld surface map for the title complex.

Figure 4
Fingerprint plot of the title compound showing all interactions and delineated into the most important intermolecular contacts.

6. Synthesis and crystallization

3-Methylbenzoic acid (4 mmol, 0.54 g) and sodium hydroxide (4 mmol, 0.16 g) in water (20 ml) were added to a solution of Cu(NO₃)₂·3H₂O (2 mmol, 0.48 g) in water (20 ml) under stirring. A solution of 2,2′-bipyridine (2 mmol, 0.3 g) in EtOH (25 ml) was added and the color changed from greenish blue to blue. The precipitate was filtered off, washed with water and dried. Blue single crystals of the title complex suitable for X-ray diffraction studies were obtained after evaporation of an ethanol solution after several days.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. One of the 3-methylbenzoates (O3/O4/C9–C16) is disordered over two positions related by a 180° rotation. The occupancies of the two components refined to 0.664 (4):0.336 (4). The occupancy of the water molecule H6A–O6–H6B refined to 0.680 (10). The coordinates of the ordered water atom were refined with U_iso(H) = 1.5U_eq(O). All other H atoms were positioned geometrically and refined as riding with U_iso(H) = 1.2–1.5U_eq(parent atom).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₈HH₇O₂)₂(C₁₀H₈N₂)(H₂O)]·0.68H₂O
M_r	520.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	16.754 (3), 7.0021 (12), 22.103 (4)
β (°)	106.522 (6)
V (Å³)	2485.9 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.92
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	63716, 6171, 4874
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.106, 1.09
No. of reflections	6171
No. of parameters	418
No. of restraints	347
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.40
Computer programs: APEX2 (Bruker, 2013 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and Mercury (Macrae et al., 2020 ).

Supporting information

CCDC reference: 2117143

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023006904/dj2063sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023006904/dj2063Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: APEX2 (Bruker, 2013); data reduction: APEX2 (Bruker, 2013); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020).

Aqua(2,2'-bipyridineκ²N,N')bis(3-methylbenzoato)-κ²O,O';κO-copper(II) 0.68-hydrate, top

Crystal data top

[Cu(C₈HH₇O₂)₂(C₁₀H₈N₂)(H₂O)]·0.68H₂O	F(000) = 1079
M_r = 520.26	D_x = 1.390 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.754 (3) Å	Cell parameters from 9233 reflections
b = 7.0021 (12) Å	θ = 2.5–26.6°
c = 22.103 (4) Å	µ = 0.92 mm⁻¹
β = 106.522 (6)°	T = 293 K
V = 2485.9 (8) Å³	Block, blue
Z = 4	0.20 × 0.15 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.035
φ and ω scans	θ_max = 28.5°, θ_min = 2.5°
63716 measured reflections	h = −22→22
6171 independent reflections	k = −9→9
4874 reflections with I > 2σ(I)	l = −29→29

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0389P)² + 1.6967P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
6171 reflections	Δρ_max = 0.30 e Å⁻³
418 parameters	Δρ_min = −0.40 e Å⁻³
347 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	Occ. (<1)
Cu1	0.34763 (2)	0.84495 (4)	0.31767 (2)	0.03879 (9)
O1	0.32781 (10)	0.7602 (3)	0.39681 (8)	0.0519 (4)
O2	0.26638 (14)	1.0161 (2)	0.42229 (9)	0.0664 (5)
N1	0.47164 (11)	0.8619 (2)	0.35426 (8)	0.0391 (4)
N2	0.38047 (11)	0.8817 (2)	0.23762 (8)	0.0377 (4)
C1	0.27773 (13)	0.8419 (3)	0.42213 (10)	0.0392 (4)
C2	0.23017 (13)	0.7151 (3)	0.45422 (9)	0.0372 (4)
C3	0.18273 (14)	0.7973 (3)	0.48953 (10)	0.0422 (5)
H3	0.182368	0.929463	0.493519	0.051*
C4	0.13590 (17)	0.6878 (4)	0.51900 (12)	0.0563 (6)
C5	0.1379 (2)	0.4918 (5)	0.51221 (15)	0.0735 (9)
H5	0.107167	0.415128	0.531672	0.088*
C6	0.1844 (2)	0.4077 (4)	0.47736 (17)	0.0801 (10)
H6	0.184782	0.275525	0.473485	0.096*
C7	0.23037 (18)	0.5186 (4)	0.44812 (13)	0.0571 (6)
H7	0.261503	0.461430	0.424335	0.069*
C8	0.0844 (2)	0.7820 (6)	0.55660 (18)	0.0969 (12)
H8A	0.113429	0.775074	0.600751	0.145*
H8B	0.031860	0.717351	0.548780	0.145*
H8C	0.074998	0.913325	0.544171	0.145*
O3	0.2315 (6)	0.7725 (11)	0.2675 (5)	0.0456 (16)	0.664 (4)
O4	0.2993 (4)	0.4976 (13)	0.2761 (4)	0.0443 (13)	0.664 (4)
C9	0.2338 (3)	0.5930 (10)	0.2581 (4)	0.0401 (12)	0.664 (4)
C10	0.1531 (2)	0.4981 (6)	0.2230 (2)	0.0427 (9)	0.664 (4)
C11	0.0787 (3)	0.5949 (7)	0.21325 (19)	0.0493 (9)	0.664 (4)
H11	0.079230	0.717697	0.229388	0.059*	0.664 (4)
C12	0.0028 (3)	0.5143 (9)	0.1799 (2)	0.0644 (12)	0.664 (4)
C13	0.0051 (3)	0.3318 (9)	0.1573 (3)	0.0746 (14)	0.664 (4)
H13	−0.044531	0.273815	0.135003	0.090*	0.664 (4)
C14	0.0781 (3)	0.2330 (8)	0.1666 (2)	0.0792 (13)	0.664 (4)
H14	0.077331	0.110027	0.150537	0.095*	0.664 (4)
C15	0.1529 (3)	0.3148 (7)	0.1996 (2)	0.0616 (11)	0.664 (4)
H15	0.202420	0.247440	0.206067	0.074*	0.664 (4)
C16	−0.0769 (3)	0.6241 (10)	0.1687 (3)	0.099 (2)	0.664 (4)
H16A	−0.100922	0.642619	0.124164	0.148*	0.664 (4)
H16B	−0.065780	0.745972	0.189242	0.148*	0.664 (4)
H16C	−0.115080	0.553947	0.185422	0.148*	0.664 (4)
O3'	0.2373 (12)	0.789 (2)	0.2796 (10)	0.040 (2)	0.336 (4)
O4'	0.2799 (8)	0.498 (3)	0.2621 (9)	0.047 (3)	0.336 (4)
C9'	0.2241 (6)	0.618 (2)	0.2594 (9)	0.042 (2)	0.336 (4)
C10'	0.1349 (5)	0.5677 (11)	0.2262 (4)	0.0430 (16)	0.336 (4)
C11'	0.1173 (5)	0.3862 (12)	0.2021 (4)	0.0552 (16)	0.336 (4)
H11'	0.160250	0.298071	0.207060	0.066*	0.336 (4)
C12'	0.0359 (6)	0.3330 (15)	0.1703 (6)	0.068 (2)	0.336 (4)
C13'	−0.0260 (6)	0.4669 (14)	0.1651 (5)	0.067 (2)	0.336 (4)
H13'	−0.080912	0.432829	0.145436	0.081*	0.336 (4)
C14'	−0.0089 (5)	0.6484 (14)	0.1879 (4)	0.0641 (19)	0.336 (4)
H14'	−0.051704	0.737327	0.182021	0.077*	0.336 (4)
C15'	0.0720 (4)	0.7003 (13)	0.2197 (4)	0.0503 (16)	0.336 (4)
H15'	0.083741	0.822434	0.236369	0.060*	0.336 (4)
C16'	0.0144 (7)	0.1356 (13)	0.1463 (5)	0.090 (3)	0.336 (4)
H16D	−0.002135	0.136810	0.101007	0.135*	0.336 (4)
H16E	−0.030539	0.088314	0.160979	0.135*	0.336 (4)
H16F	0.062117	0.054395	0.161428	0.135*	0.336 (4)
C17	0.51321 (16)	0.8587 (4)	0.41546 (12)	0.0524 (6)
H17	0.483401	0.844910	0.444839	0.063*
C18	0.59886 (18)	0.8753 (4)	0.43692 (14)	0.0647 (7)
H18	0.626326	0.873196	0.479876	0.078*
C19	0.64208 (17)	0.8947 (4)	0.39341 (15)	0.0650 (8)
H19	0.699777	0.905457	0.406664	0.078*
C20	0.60063 (14)	0.8983 (3)	0.33014 (13)	0.0507 (6)
H20	0.629658	0.911990	0.300250	0.061*
C21	0.51485 (13)	0.8811 (3)	0.31178 (11)	0.0369 (4)
C22	0.46312 (13)	0.8851 (3)	0.24534 (10)	0.0370 (4)
C23	0.49461 (16)	0.8923 (3)	0.19373 (12)	0.0492 (6)
H23	0.551776	0.893392	0.199385	0.059*
C24	0.4399 (2)	0.8979 (4)	0.13391 (13)	0.0593 (7)
H24	0.459856	0.901430	0.098753	0.071*
C25	0.35603 (19)	0.8982 (4)	0.12654 (12)	0.0591 (7)
H25	0.318396	0.904644	0.086519	0.071*
C26	0.32842 (16)	0.8888 (3)	0.17930 (11)	0.0501 (6)
H26	0.271393	0.887348	0.174260	0.060*
O5	0.33408 (13)	1.1632 (2)	0.33836 (11)	0.0676 (5)
H5A	0.311059	1.174260	0.367935	0.101*
H5B	0.299885	1.215072	0.306576	0.101*
O6	0.4289 (3)	0.4219 (8)	0.4465 (3)	0.119 (2)	0.680 (10)
H6A	0.441 (6)	0.309 (10)	0.446 (4)	0.178*	0.680 (10)
H6B	0.435 (6)	0.490 (13)	0.478 (4)	0.178*	0.680 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03652 (14)	0.03638 (15)	0.04663 (16)	0.00129 (11)	0.01693 (11)	0.00307 (11)
O1	0.0532 (9)	0.0548 (10)	0.0559 (10)	0.0099 (8)	0.0286 (8)	0.0131 (8)
O2	0.1003 (15)	0.0395 (10)	0.0768 (13)	0.0003 (9)	0.0534 (12)	0.0043 (9)
N1	0.0404 (9)	0.0344 (9)	0.0418 (10)	−0.0003 (7)	0.0107 (8)	−0.0015 (7)
N2	0.0392 (9)	0.0334 (9)	0.0409 (9)	−0.0016 (7)	0.0118 (7)	0.0026 (7)
C1	0.0423 (11)	0.0412 (12)	0.0339 (10)	0.0002 (9)	0.0105 (8)	0.0004 (9)
C2	0.0405 (11)	0.0386 (11)	0.0321 (10)	−0.0017 (9)	0.0095 (8)	−0.0013 (8)
C3	0.0492 (12)	0.0418 (12)	0.0359 (11)	0.0028 (10)	0.0126 (9)	−0.0023 (9)
C4	0.0593 (15)	0.0674 (18)	0.0479 (14)	−0.0020 (13)	0.0244 (12)	−0.0018 (12)
C5	0.088 (2)	0.0661 (19)	0.080 (2)	−0.0222 (16)	0.0450 (17)	0.0024 (16)
C6	0.120 (3)	0.0390 (14)	0.097 (2)	−0.0164 (16)	0.056 (2)	−0.0061 (15)
C7	0.0755 (17)	0.0394 (13)	0.0652 (16)	−0.0015 (12)	0.0343 (14)	−0.0083 (12)
C8	0.104 (3)	0.112 (3)	0.102 (3)	0.003 (2)	0.073 (2)	−0.006 (2)
O3	0.0315 (18)	0.047 (2)	0.055 (4)	0.0020 (17)	0.007 (2)	0.005 (2)
O4	0.035 (3)	0.0400 (18)	0.057 (4)	0.002 (2)	0.011 (2)	0.006 (2)
C9	0.038 (2)	0.044 (2)	0.044 (2)	−0.006 (2)	0.0222 (19)	0.007 (2)
C10	0.0408 (19)	0.051 (2)	0.0411 (17)	−0.0051 (17)	0.0202 (15)	0.0005 (18)
C11	0.0437 (19)	0.063 (2)	0.0424 (18)	−0.005 (2)	0.0149 (15)	−0.0017 (19)
C12	0.049 (2)	0.092 (3)	0.049 (2)	−0.014 (2)	0.0094 (19)	−0.002 (2)
C13	0.066 (3)	0.096 (3)	0.058 (3)	−0.029 (3)	0.011 (2)	−0.010 (2)
C14	0.088 (3)	0.077 (3)	0.072 (3)	−0.023 (3)	0.023 (2)	−0.022 (2)
C15	0.064 (2)	0.059 (2)	0.065 (2)	−0.010 (2)	0.024 (2)	−0.0119 (19)
C16	0.041 (2)	0.159 (6)	0.085 (3)	0.001 (3)	0.000 (2)	−0.008 (4)
O3'	0.035 (4)	0.046 (4)	0.041 (5)	−0.001 (3)	0.015 (3)	−0.006 (3)
O4'	0.032 (5)	0.050 (4)	0.054 (7)	0.001 (4)	0.005 (4)	0.010 (4)
C9'	0.036 (3)	0.048 (4)	0.044 (3)	0.000 (3)	0.018 (3)	0.005 (3)
C10'	0.038 (3)	0.053 (4)	0.043 (3)	−0.007 (3)	0.020 (3)	0.000 (3)
C11'	0.051 (3)	0.065 (3)	0.053 (3)	−0.009 (3)	0.021 (3)	−0.003 (3)
C12'	0.058 (4)	0.084 (4)	0.060 (4)	−0.019 (4)	0.016 (3)	−0.005 (3)
C13'	0.054 (4)	0.089 (4)	0.055 (4)	−0.024 (4)	0.010 (3)	−0.002 (4)
C14'	0.046 (3)	0.087 (4)	0.058 (4)	−0.002 (4)	0.012 (3)	0.000 (4)
C15'	0.038 (3)	0.066 (4)	0.048 (3)	−0.002 (3)	0.014 (2)	−0.003 (3)
C16'	0.088 (6)	0.093 (7)	0.084 (6)	−0.028 (5)	0.017 (5)	−0.025 (5)
C17	0.0596 (15)	0.0513 (14)	0.0447 (13)	−0.0019 (12)	0.0123 (11)	−0.0024 (11)
C18	0.0619 (16)	0.0594 (17)	0.0576 (16)	−0.0058 (13)	−0.0075 (13)	−0.0029 (13)
C19	0.0416 (13)	0.0574 (16)	0.085 (2)	−0.0084 (12)	0.0003 (13)	0.0048 (15)
C20	0.0394 (12)	0.0397 (12)	0.0741 (17)	−0.0039 (9)	0.0179 (12)	0.0059 (11)
C21	0.0387 (10)	0.0227 (9)	0.0512 (12)	−0.0009 (8)	0.0160 (9)	0.0010 (8)
C22	0.0446 (11)	0.0198 (9)	0.0494 (12)	−0.0021 (8)	0.0177 (9)	0.0015 (8)
C23	0.0557 (14)	0.0368 (12)	0.0641 (16)	−0.0040 (10)	0.0312 (12)	−0.0008 (11)
C24	0.094 (2)	0.0431 (13)	0.0502 (15)	−0.0102 (13)	0.0362 (15)	−0.0023 (11)
C25	0.0802 (19)	0.0492 (14)	0.0423 (13)	−0.0130 (13)	0.0084 (13)	0.0026 (11)
C26	0.0501 (13)	0.0444 (13)	0.0507 (14)	−0.0057 (10)	0.0061 (11)	0.0054 (10)
O5	0.0899 (14)	0.0395 (9)	0.0894 (14)	0.0115 (9)	0.0516 (12)	0.0108 (9)
O6	0.103 (3)	0.113 (4)	0.157 (5)	0.023 (3)	0.064 (3)	0.043 (4)

Geometric parameters (Å, º) top

Cu1—O3'	1.842 (17)	C16—H16A	0.9600
Cu1—O1	1.9628 (16)	C16—H16B	0.9600
Cu1—N1	2.0072 (18)	C16—H16C	0.9600
Cu1—O3	2.011 (8)	O3'—C9'	1.275 (8)
Cu1—N2	2.0131 (18)	O4'—C9'	1.248 (8)
Cu1—O5	2.2988 (18)	C9'—C10'	1.509 (7)
O1—C1	1.269 (3)	C10'—C11'	1.377 (8)
O2—C1	1.235 (3)	C10'—C15'	1.381 (8)
N1—C17	1.334 (3)	C11'—C12'	1.396 (9)
N1—C21	1.346 (3)	C11'—H11'	0.9300
N2—C26	1.336 (3)	C12'—C13'	1.378 (9)
N2—C22	1.346 (3)	C12'—C16'	1.488 (10)
C1—C2	1.499 (3)	C13'—C14'	1.367 (10)
C2—C7	1.382 (3)	C13'—H13'	0.9300
C2—C3	1.387 (3)	C14'—C15'	1.387 (8)
C3—C4	1.385 (3)	C14'—H14'	0.9300
C3—H3	0.9300	C15'—H15'	0.9300
C4—C5	1.382 (4)	C16'—H16D	0.9600
C4—C8	1.510 (4)	C16'—H16E	0.9600
C5—C6	1.373 (4)	C16'—H16F	0.9600
C5—H5	0.9300	C17—C18	1.382 (4)
C6—C7	1.377 (4)	C17—H17	0.9300
C6—H6	0.9300	C18—C19	1.365 (4)
C7—H7	0.9300	C18—H18	0.9300
C8—H8A	0.9600	C19—C20	1.373 (4)
C8—H8B	0.9600	C19—H19	0.9300
C8—H8C	0.9600	C20—C21	1.383 (3)
O3—C9	1.277 (5)	C20—H20	0.9300
O4—C9	1.250 (5)	C21—C22	1.478 (3)
C9—C10	1.508 (5)	C22—C23	1.387 (3)
C10—C11	1.380 (5)	C23—C24	1.379 (4)
C10—C15	1.384 (5)	C23—H23	0.9300
C11—C12	1.395 (6)	C24—C25	1.367 (4)
C11—H11	0.9300	C24—H24	0.9300
C12—C13	1.377 (7)	C25—C26	1.373 (4)
C12—C16	1.499 (7)	C25—H25	0.9300
C13—C14	1.369 (7)	C26—H26	0.9300
C13—H13	0.9300	O5—H5A	0.8517
C14—C15	1.383 (6)	O5—H5B	0.8515
C14—H14	0.9300	O6—H6A	0.82 (7)
C15—H15	0.9300	O6—H6B	0.82 (7)

O3'—Cu1—O1	86.6 (7)	C10—C15—H15	120.4
O3'—Cu1—N1	170.4 (5)	C12—C16—H16A	109.5
O1—Cu1—N1	94.41 (7)	C12—C16—H16B	109.5
O1—Cu1—O3	91.9 (4)	H16A—C16—H16B	109.5
N1—Cu1—O3	164.9 (3)	C12—C16—H16C	109.5
O3'—Cu1—N2	96.6 (7)	H16A—C16—H16C	109.5
O1—Cu1—N2	168.42 (7)	H16B—C16—H16C	109.5
N1—Cu1—N2	80.58 (7)	C9'—O3'—Cu1	114.1 (12)
O3—Cu1—N2	90.7 (3)	O4'—C9'—O3'	124.5 (10)
O3'—Cu1—O5	98.8 (5)	O4'—C9'—C10'	119.3 (9)
O1—Cu1—O5	93.69 (7)	O3'—C9'—C10'	116.1 (9)
N1—Cu1—O5	90.69 (7)	C11'—C10'—C15'	120.5 (7)
O3—Cu1—O5	102.7 (2)	C11'—C10'—C9'	118.6 (7)
N2—Cu1—O5	96.79 (7)	C15'—C10'—C9'	120.9 (7)
C1—O1—Cu1	123.87 (15)	C10'—C11'—C12'	120.8 (8)
C17—N1—C21	118.7 (2)	C10'—C11'—H11'	119.6
C17—N1—Cu1	126.13 (17)	C12'—C11'—H11'	119.6
C21—N1—Cu1	115.18 (14)	C13'—C12'—C11'	117.7 (8)
C26—N2—C22	119.2 (2)	C13'—C12'—C16'	120.1 (8)
C26—N2—Cu1	125.89 (16)	C11'—C12'—C16'	122.0 (9)
C22—N2—Cu1	114.78 (14)	C14'—C13'—C12'	121.9 (8)
O2—C1—O1	124.6 (2)	C14'—C13'—H13'	119.1
O2—C1—C2	118.7 (2)	C12'—C13'—H13'	119.1
O1—C1—C2	116.66 (19)	C13'—C14'—C15'	120.1 (8)
C7—C2—C3	119.0 (2)	C13'—C14'—H14'	119.9
C7—C2—C1	121.8 (2)	C15'—C14'—H14'	119.9
C3—C2—C1	119.2 (2)	C10'—C15'—C14'	118.9 (8)
C4—C3—C2	121.8 (2)	C10'—C15'—H15'	120.5
C4—C3—H3	119.1	C14'—C15'—H15'	120.5
C2—C3—H3	119.1	C12'—C16'—H16D	109.5
C5—C4—C3	117.6 (2)	C12'—C16'—H16E	109.5
C5—C4—C8	121.9 (3)	H16D—C16'—H16E	109.5
C3—C4—C8	120.4 (3)	C12'—C16'—H16F	109.5
C6—C5—C4	121.5 (3)	H16D—C16'—H16F	109.5
C6—C5—H5	119.3	H16E—C16'—H16F	109.5
C4—C5—H5	119.3	N1—C17—C18	122.6 (3)
C5—C6—C7	120.2 (3)	N1—C17—H17	118.7
C5—C6—H6	119.9	C18—C17—H17	118.7
C7—C6—H6	119.9	C19—C18—C17	118.3 (3)
C6—C7—C2	119.9 (2)	C19—C18—H18	120.9
C6—C7—H7	120.1	C17—C18—H18	120.9
C2—C7—H7	120.1	C18—C19—C20	120.2 (2)
C4—C8—H8A	109.5	C18—C19—H19	119.9
C4—C8—H8B	109.5	C20—C19—H19	119.9
H8A—C8—H8B	109.5	C19—C20—C21	118.7 (2)
C4—C8—H8C	109.5	C19—C20—H20	120.7
H8A—C8—H8C	109.5	C21—C20—H20	120.7
H8B—C8—H8C	109.5	N1—C21—C20	121.6 (2)
C9—O3—Cu1	105.6 (6)	N1—C21—C22	114.54 (18)
O4—C9—O3	122.6 (5)	C20—C21—C22	123.8 (2)
O4—C9—C10	120.4 (5)	N2—C22—C23	121.0 (2)
O3—C9—C10	117.0 (5)	N2—C22—C21	114.65 (18)
C11—C10—C15	119.4 (4)	C23—C22—C21	124.4 (2)
C11—C10—C9	120.1 (4)	C24—C23—C22	119.0 (2)
C15—C10—C9	120.5 (4)	C24—C23—H23	120.5
C10—C11—C12	122.1 (5)	C22—C23—H23	120.5
C10—C11—H11	119.0	C25—C24—C23	119.7 (2)
C12—C11—H11	119.0	C25—C24—H24	120.2
C13—C12—C11	116.9 (5)	C23—C24—H24	120.2
C13—C12—C16	122.1 (5)	C24—C25—C26	118.8 (2)
C11—C12—C16	121.0 (5)	C24—C25—H25	120.6
C14—C13—C12	122.0 (5)	C26—C25—H25	120.6
C14—C13—H13	119.0	N2—C26—C25	122.4 (2)
C12—C13—H13	119.0	N2—C26—H26	118.8
C13—C14—C15	120.5 (5)	C25—C26—H26	118.8
C13—C14—H14	119.8	Cu1—O5—H5A	109.4
C15—C14—H14	119.8	Cu1—O5—H5B	109.3
C14—C15—C10	119.2 (5)	H5A—O5—H5B	104.4
C14—C15—H15	120.4	H6A—O6—H6B	126 (9)

Cu1—O1—C1—O2	−36.8 (3)	O4'—C9'—C10'—C15'	−176.9 (19)
Cu1—O1—C1—C2	143.68 (16)	O3'—C9'—C10'—C15'	−1 (2)
O2—C1—C2—C7	170.4 (2)	C15'—C10'—C11'—C12'	0.4 (13)
O1—C1—C2—C7	−10.0 (3)	C9'—C10'—C11'—C12'	−179.2 (10)
O2—C1—C2—C3	−7.7 (3)	C10'—C11'—C12'—C13'	−1.1 (17)
O1—C1—C2—C3	171.8 (2)	C10'—C11'—C12'—C16'	−177.2 (10)
C7—C2—C3—C4	0.3 (4)	C11'—C12'—C13'—C14'	2.3 (19)
C1—C2—C3—C4	178.4 (2)	C16'—C12'—C13'—C14'	178.5 (11)
C2—C3—C4—C5	0.1 (4)	C12'—C13'—C14'—C15'	−2.7 (17)
C2—C3—C4—C8	−179.4 (3)	C11'—C10'—C15'—C14'	−0.7 (13)
C3—C4—C5—C6	−0.2 (5)	C9'—C10'—C15'—C14'	178.9 (9)
C8—C4—C5—C6	179.3 (3)	C13'—C14'—C15'—C10'	1.9 (14)
C4—C5—C6—C7	0.0 (6)	C21—N1—C17—C18	0.3 (3)
C5—C6—C7—C2	0.4 (5)	Cu1—N1—C17—C18	−178.59 (19)
C3—C2—C7—C6	−0.5 (4)	N1—C17—C18—C19	−0.3 (4)
C1—C2—C7—C6	−178.6 (3)	C17—C18—C19—C20	0.3 (4)
Cu1—O3—C9—O4	−2.8 (14)	C18—C19—C20—C21	−0.3 (4)
Cu1—O3—C9—C10	177.9 (6)	C17—N1—C21—C20	−0.3 (3)
O4—C9—C10—C11	168.3 (9)	Cu1—N1—C21—C20	178.71 (16)
O3—C9—C10—C11	−12.4 (11)	C17—N1—C21—C22	−179.34 (19)
O4—C9—C10—C15	−12.5 (11)	Cu1—N1—C21—C22	−0.3 (2)
O3—C9—C10—C15	166.7 (9)	C19—C20—C21—N1	0.3 (3)
C15—C10—C11—C12	−0.5 (7)	C19—C20—C21—C22	179.3 (2)
C9—C10—C11—C12	178.6 (5)	C26—N2—C22—C23	−1.2 (3)
C10—C11—C12—C13	0.4 (8)	Cu1—N2—C22—C23	174.20 (16)
C10—C11—C12—C16	−178.6 (5)	C26—N2—C22—C21	178.66 (18)
C11—C12—C13—C14	−0.2 (9)	Cu1—N2—C22—C21	−5.9 (2)
C16—C12—C13—C14	178.7 (6)	N1—C21—C22—N2	4.1 (2)
C12—C13—C14—C15	0.2 (10)	C20—C21—C22—N2	−174.88 (19)
C13—C14—C15—C10	−0.2 (8)	N1—C21—C22—C23	−175.98 (19)
C11—C10—C15—C14	0.4 (7)	C20—C21—C22—C23	5.0 (3)
C9—C10—C15—C14	−178.7 (5)	N2—C22—C23—C24	0.6 (3)
O1—Cu1—O3'—C9'	−89.7 (18)	C21—C22—C23—C24	−179.2 (2)
N2—Cu1—O3'—C9'	79.1 (18)	C22—C23—C24—C25	0.7 (4)
O5—Cu1—O3'—C9'	177.1 (17)	C23—C24—C25—C26	−1.4 (4)
Cu1—O3'—C9'—O4'	−3 (3)	C22—N2—C26—C25	0.5 (3)
Cu1—O3'—C9'—C10'	−178.4 (11)	Cu1—N2—C26—C25	−174.38 (19)
O4'—C9'—C10'—C11'	3 (2)	C24—C25—C26—N2	0.8 (4)
O3'—C9'—C10'—C11'	178.4 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2	0.85	1.93	2.643 (3)	140
O5—H5B···O4^aⁱ	0.85	2.09	2.694 (10)	128
C20—H20···O4^aⁱⁱ	0.93	2.40	3.324 (10)	171
C23—H23···O4^aⁱⁱ	0.93	2.51	3.405 (7)	163
C18—H18···O2ⁱⁱⁱ	0.93	2.51	3.371 (4)	154
C24—H24···O6ⁱⁱ	0.93	2.36	3.200 (5)	151
C26—H26···O3^a	0.93	2.48	2.984 (13)	115
C17—H17···O1	0.93	2.59	3.093 (3)	115
C7—H7···O6	0.93	2.72	3.405 (6)	131

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

Acknowledgements

The author acknowledges the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the Bruker APEXII CCD diffractometer.

Funding information

Funding for this research was provided by: Salahaddin University-Erbil.

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