Crystal structure and Hirshfeld surface analysis of 2,2′-{(1E,1′E)-[ethane-1,2-diylbis(aza­nylyl­idene)]bis­(methanylyl­idene)}bis­[4-(tri­fluoro­meth­oxy)phenol]copper(II) hydro­quinone hemisolvate

Kansiz, S.; Meral, S.; Dege, N.; Agar, A.A.; Fritsky, I.O.

doi:10.1107/S2056989019014294

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1729-1733

https://doi.org/10.1107/S2056989019014294

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Crystal structure and Hirshfeld surface analysis of 2,2′-{(1E,1′E)-[ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[4-(trifluoromethoxy)phenol]copper(II) hydroquinone hemisolvate

Sevgi Kansiz,^a ^* Seher Meral,^b Necmi Dege,^a Aysen Alaman Agar ^c and Igor O. Fritsky ^d ^*

^aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Kurupelit, Samsun, Turkey, ^bBoyabat Vocational School, Sinop University, 57200 Sinop, Turkey, ^cDepartment of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Kurupelit, Samsun, Turkey, and ^dDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64 Vladimirska Str., Kiev 01601, Ukraine
^*Correspondence e-mail: sevgi.kansiz85@gmail.com, ifritsky@univ.kiev.ua

Edited by A. J. Lough, University of Toronto, Canada (Received 9 October 2019; accepted 20 October 2019; online 29 October 2019)

In the title complex, [Cu(C₁₈H₁₂F₆N₂O₄)]·0.5C₆H₆O₂, the Cu^II ion has a square-planar coordination geometry, being ligated by two N and two O atoms of the tetradentate open-chain Schiff base ligand 6,6′-{(1E,1′E)-[ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[2-(trifluoromethoxy)phenol]. The crystal packing is stabilized by intramolecular O—H⋯O and intermolecular C—H⋯F, C—H⋯O and C—H⋯π hydrogen bonds. In addition, weak π–π interactions form a three-dimensional structure. Hirshfeld surface analysis and two-dimensional fingerprint plots were performed and created to analyze the intermolecular interactions present in the crystal, indicating that the most important contributions for the crystal packing are from F⋯H/H⋯F (25.7%), H⋯H (23.5%) and C⋯H/H⋯C (12.6%) interactions.

Keywords: crystal structure; copper (II); salen-type Schiff base; Hirshfeld surface.

CCDC references: 1900670; 1900670

1. Chemical context

Metal complexes of Schiff bases have different applications because of their different heteroatoms (N, S, Cl etc.), functional groups, π-electron density, isomer structures and easy synthesis (El-Samanody et al., 2017 ). Metal complexes with less oxophilic character exhibit attractive properties, such as targeting catalysts in many polymerization reactions (Ng et al., 2016 ). On the other hand, in nature, metal complexes are encountered in many reactions, such as binding to DNA or enzymes (Li et al., 2010 ). For this reason, metal complexes are of increasing interest in the fields of medicine and chemical synthesis with attractive functional properties and stable structures. Salen-type Schiff bases [salen is N,N′-bis(salicylidene)ethylenediamine] have been synthesized by many research groups from different diamines and derivatives of benzaldehyde (Prushan et al., 2007 ). In addition, salen-type Schiff bases derived from 2-hydroxy-3-methoxybenzaldehyde (also called o-vanillin) are very effective ligands for many metal ions due to the two different binding sites, because of the presence of the methoxy group near the –OH group (Andruh, 2015 ). Each transition metal has different biological properties depending on the geometry of the complex and the structure of the ligand, so the biological activity of a drug may be controlled by changing the metal ion or the chemical structure of the ligand. Recently, it was reported that synthesized Schiff bases indicate antibacterial properties, more pronounced in the case of metal complexes compared to the free Schiff bases (Wu et al., 2011 ).

In this study, a salen-type Schiff base has been synthesized from 2-hydroxy-5-(trifluoromethoxy)benzaldehyde with ethylenediamine by a condensation reaction. The synthesized Schiff base was used as an O,N,N′,O′-type tetradentate ligand, and a copper(II) complex was obtained and the structure confirmed by single-crystal X-ray diffraction analysis. In this study, we describe the crystal structure and Hirshfeld surface analysis of the title compound, as determined by X-ray crystallographic analysis.

2. Structural commentary

Fig. 1 illustrates the title metal complex formed by a Cu^II ion chelated by a doubly deprotonated tetradentate Schiff base ligand and a hydrogen-bonded molecule of hydroquinone. The Cu1 ion is coordinated by two imine N atoms (N6 and N7) and two phenoxo O atoms (O2 and O3) of the tetradentate Schiff base ligand 6,6′-{(1E,1′E)-[ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[2-(trifluoromethoxy)phenol] (L1). The hydroquinone molecule is located on an inversion centre and is linked to neighbouring complex cations via O—H⋯O hydrogen bonds. The bond lengths Cu1—O2 and Cu1—O3 [1.883 (4) and 1.906 (4) Å, respectively] and Cu1—N1 and Cu1—N2 [1.929 (5) and 1.927 (5) Å, respectively] are close to the values observed for related copper(II) complexes reported in the literature (Şen et al., 2017 ; Fritsky et al., 2004 ; Strotmeyer et al., 2003 ). Selected geometric parameters of the title compound are listed in Table 1.

Table 1
Selected geometric parameters (Å, °)

Cu1—O2	1.883 (4)	N3—C10	1.455 (8)
Cu1—O3	1.906 (4)	N2—C8	1.275 (8)
Cu1—N2	1.927 (5)	O4—C18	1.269 (12)
Cu1—N3	1.929 (5)	O1—C1	1.267 (9)
O2—C5	1.309 (7)	F2—C1	1.271 (9)
O3—C17	1.317 (7)	F4—C18	1.265 (11)

O2—Cu1—O3	87.54 (17)	O2—Cu1—N3	177.82 (18)
O2—Cu1—N2	94.40 (18)	O3—Cu1—N3	93.9 (2)
O3—Cu1—N2	176.2 (2)	N2—Cu1—N3	84.3 (2)

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond. [Symmetry code: (i) −x, −y, −z + 1.]

3. Supramolecular features

The crystal packing of the title compound is stabilized by intermolecular C—H⋯O, C—H⋯F and C—H⋯Cg1 (Cg1 is the centroid of the C19–C21/C19ⁱ–C21ⁱ ring) hydrogen bonds (Table 2 and Fig. 2). In addition, weak π–π interactions connect the molecules into a three-dimensional supramolecular architecture (Fig. 3). The Cg2⋯Cg3 distance is 3.507 (2) Å, where Cg2 and Cg3 are the centroids of the Cu1/O2/C5/C6/C8/N2 and Cu1/O3/C17/C12/C11/N1 rings, respectively.

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C19–C21/C19ⁱ–C21ⁱ ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O3	0.82	2.20	2.993 (8)	165
C11—H11⋯F2ⁱ	0.93	2.63	3.513 (8)	159
C10—H10A⋯O5ⁱⁱ	0.97	2.53	3.469 (11)	162
C15—H15⋯O5ⁱⁱⁱ	0.93	2.55	3.345 (9)	144
C8—H8⋯Cg1^iv	0.93	2.82	3.740 (8)	173
Symmetry codes: (i) x+1, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y, -z+1; (iv) x, y+1, z.

Figure 2
A view of the crystal packing of the title compound. Dashed lines denote intermolecular O—H⋯O, C—H⋯F and C—H⋯π hydrogen bonds.

Figure 3
A view of the crystal packing of the title compound. The π–π interactions are shown as pink dashed lines. [The direction of the unitcell parameters is missing. It might be better to show the unitcell outline]

4. Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots were performed and created with CrystalExplorer17 (Turner et al., 2017 ). The Hirshfeld surface was mapped with d_norm (Fig. 4). The view of surface were obtained in the range −0.4385 to 1.6105 a.u. (d_norm). The blue, white and red colour conventions used for the d_norm-mapped Hirshfeld surfaces recognize the interatomic contacts as longer, at van der Waals separations and short interatomic contacts, respectively.

Figure 4
The d_norm-mapped Hirshfeld surface for visualizing the intermolecular contacts of the title compound.

A fingerprint plot delineated into specific interatomic contacts contains information related to specific intermolecular interactions. The blue colour refers to the frequency of occurrence of the (d_i, d_e) pair with the full fingerprint plot outlined in gray. Fig. 5(a) shows the two-dimensional fingerprint plot of the sum of the contacts contributing to the Hirshfeld surface represented in normal mode. The most significant contribution to the Hirshfeld surface is from F⋯H/H⋯F contacts (25.7%) (Fig. 5b). Here, H⋯H interactions are only the second most significant contribution to the total Hirshfeld surface (23.5%). In addition, C⋯H/H⋯C and O⋯H/H⋯O contacts contribute 12.6 and 11.2% to the Hirshfeld surface, respectively.

Figure 5
Two-dimensional fingerprint plots of the title compound.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.40, update of February 2019; Groom et al., 2016 ) related to the title complex revealed six hits. These structures are Cu(5-hexyloxySalen)·CHCl₃ (FAGLOP; Paschke et al., 2002 ), C₃₀H₅₄Cu₂F₁₂N₁₀O₂P₂ (ICUHEU; Margraf et al., 2006 ), C₃₈H₄₄Cu₂N₄O₁₀ (PIFKOE01; Liu, 2016 ), C₃₆H₃₆Cu₂N₄O₈·2CH₄O (PIFKOE02; Zhang, 2016 ), C₁₈H₁₈CuN₂O₄·1.5H₂O (QARPAB; Yao et al., 2005 ) and C₁₈H₁₈CuN₂O₄ (XOZZUH; Atria et al., 2002 ). All of these structures have square-planar environments, as in the title copper(II) complex. The Cu—O and Cu—N bond lengths range from ca 1.898 to 1.915 Å and from ca 1.936 to 2.271 Å, respectively. In the title complex, the Cu—N bond lengths [1.927 (5) and 1.929 (5) Å] fall within these limits. While the Cu1—O3 and C1—O2 bond length [1.906 (4) and 1.883 (4) Å, respectively] are within and close to these limits, respectively, the Cu1—O2 bond length is outside these limits, with a shorter value of 1.883 (4) Å.

6. Synthesis and crystallization

2,2′-{(1E,1′E)-[Ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[4-(trifluoromethoxy)phenol] (H₂L1) was synthesized by condensation of 2-hydroxy-5-(trifluoromethoxy)benzaldehyde (0.0095 mmol) and 1,2-ethanediamine (0.0095 mmol) in ethanol under reflux for about 18 h. The yellow product was washed with ether and dried at room temperature. 0.0080 mmol H₂L1 was dissolved in 20 ml ethanol and 0.0080 mmol Cu(CH₃COO)₂·H₂O was dissolved in 20 ml ethanol. The metal solution was added dropwise to the Schiff base solution and the resulting solution refluxed for about 6 h. The product (CuL1) was washed with toluene and crystallized from ethanol at room temperature. 2,2′-{(1E,1′E)-[Ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[4-(trifluoromethoxy)phenol]copper(II) hydroquinone hemisolvate was obtained even after 0.0040 mmol hydroquinone was added to 0.0040 mmol CuL1 in 20 ml ethanol and refluxed for about 6 h. A purple crystal suitable for X-ray diffraction analysis was obtained from the reaction (m.p. 568 K; yield 80%) (Fig. 6).

Figure 6
The synthesis of the title compound.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were fixed geometrically and treated as riding, with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene, C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic, C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for methine, and O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O) for hydroxy H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(C₁₈H₁₂F₆N₂O₄)]·0.5C₆H₆O₂
M_r	552.89
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.3167 (10), 10.0363 (10), 11.8052 (13)
α, β, γ (°)	92.633 (9), 97.310 (9), 98.670 (9)
V (Å³)	1080.0 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.10
Crystal size (mm)	0.57 × 0.25 × 0.06

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.695, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	9277, 4105, 2818
R_int	0.105
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.217, 1.08
No. of reflections	4105
No. of parameters	317
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.43
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXT2017 (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC references: 1900670; 1900670

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989019014294/lh5932sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019014294/lh5932Isup2.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2017 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).

2,2'-{(1E,1'E)-[Ethane-1,2-diylbis(azanylylidene)]bis(methanylylidene)}bis[4-(trifluoromethoxy)phenol]copper(II) hydroquinone hemisolvate top

Crystal data top

[Cu(C₁₈H₁₂F₆N₂O₄)]·0.5C₆H₆O₂	Z = 2
M_r = 552.89	F(000) = 556
Triclinic, P1	D_x = 1.700 Mg m⁻³
a = 9.3167 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0363 (10) Å	Cell parameters from 9488 reflections
c = 11.8052 (13) Å	θ = 2.1–31.6°
α = 92.633 (9)°	µ = 1.10 mm⁻¹
β = 97.310 (9)°	T = 296 K
γ = 98.670 (9)°	Stick, orange
V = 1080.0 (2) Å³	0.57 × 0.25 × 0.06 mm

Data collection top

Stoe IPDS 2 diffractometer	4105 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2818 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.105
rotation method scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −11→11
T_min = 0.695, T_max = 0.944	k = −11→12
9277 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.067	H-atom parameters constrained
wR(F²) = 0.217	w = 1/[σ²(F_o²) + (0.1271P)²] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
4105 reflections	Δρ_max = 0.88 e Å⁻³
317 parameters	Δρ_min = −0.43 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Cu1	0.34081 (8)	0.48948 (6)	0.55458 (5)	0.0543 (3)
O2	0.2235 (5)	0.4083 (4)	0.4202 (3)	0.0623 (10)
O3	0.4268 (5)	0.3290 (4)	0.5642 (3)	0.0725 (12)
N3	0.4629 (6)	0.5787 (5)	0.6891 (4)	0.0615 (12)
N2	0.2498 (5)	0.6496 (4)	0.5547 (4)	0.0599 (11)
O4	0.8058 (6)	0.1792 (5)	0.9159 (5)	0.0941 (16)
O1	−0.2353 (6)	0.5831 (6)	0.1519 (6)	0.1072 (19)
F2	−0.3405 (7)	0.6958 (6)	0.0275 (5)	0.1250 (19)
C5	0.1234 (6)	0.4598 (5)	0.3559 (5)	0.0562 (12)
C17	0.5157 (6)	0.2963 (6)	0.6508 (5)	0.0594 (13)
C12	0.5756 (7)	0.3861 (6)	0.7474 (5)	0.0607 (14)
C13	0.6693 (7)	0.3408 (6)	0.8348 (5)	0.0656 (14)
H13	0.708436	0.398326	0.898891	0.079*
C11	0.5502 (7)	0.5230 (6)	0.7574 (5)	0.0652 (15)
H11	0.602434	0.576870	0.819803	0.078*
C4	0.0563 (7)	0.3889 (6)	0.2529 (5)	0.0640 (14)
H4	0.086152	0.308254	0.231398	0.077*
O5	0.2281 (8)	0.1271 (6)	0.3981 (7)	0.133 (3)
H5	0.291517	0.170047	0.446142	0.199*
C6	0.0774 (7)	0.5844 (5)	0.3848 (5)	0.0600 (13)
C8	0.1441 (7)	0.6725 (6)	0.4822 (5)	0.0637 (14)
H8	0.107514	0.752591	0.493445	0.076*
C14	0.7035 (7)	0.2153 (6)	0.8275 (6)	0.0701 (16)
C20	0.1237 (8)	0.0623 (7)	0.5681 (7)	0.083 (2)
H20	0.206608	0.107143	0.614594	0.099*
F5	0.8619 (9)	0.0840 (7)	1.0705 (6)	0.165 (3)
C2	−0.1012 (8)	0.5510 (7)	0.2184 (6)	0.0809 (19)
C16	0.5574 (8)	0.1686 (6)	0.6466 (6)	0.0716 (16)
H16	0.521840	0.109651	0.582720	0.086*
C1	−0.2238 (10)	0.6854 (8)	0.0927 (6)	0.089 (2)
F4	0.6940 (12)	−0.0204 (7)	0.9451 (6)	0.213 (5)
C9	0.3081 (9)	0.7467 (6)	0.6522 (6)	0.0793 (19)
H9A	0.243130	0.737135	0.710360	0.095*
H9B	0.313865	0.838005	0.627497	0.095*
C3	−0.0517 (8)	0.4351 (7)	0.1834 (6)	0.0784 (19)
H3	−0.091257	0.389063	0.113585	0.094*
F3	−0.1763 (13)	0.7969 (6)	0.1498 (6)	0.220 (5)
C19	0.0109 (9)	−0.0032 (6)	0.6171 (6)	0.084 (2)
H19	0.019589	−0.007714	0.696149	0.101*
C7	−0.0395 (8)	0.6257 (7)	0.3149 (6)	0.0793 (19)
H7	−0.074097	0.704473	0.335183	0.095*
C10	0.4551 (9)	0.7224 (6)	0.7003 (6)	0.086 (2)
H10A	0.528371	0.772004	0.660172	0.104*
H10B	0.475229	0.754184	0.780449	0.104*
F1	−0.1335 (8)	0.6744 (10)	0.0196 (7)	0.179 (3)
C21	0.1175 (9)	0.0633 (6)	0.4511 (7)	0.085 (2)
C15	0.6497 (7)	0.1268 (7)	0.7341 (6)	0.0730 (16)
H15	0.675021	0.040716	0.729992	0.088*
F6	0.6605 (12)	0.1453 (14)	1.0406 (8)	0.215 (5)
C18	0.7608 (15)	0.0945 (11)	0.9851 (10)	0.122 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0612 (5)	0.0452 (4)	0.0562 (4)	0.0114 (3)	0.0058 (3)	−0.0023 (2)
O2	0.073 (3)	0.0482 (19)	0.064 (2)	0.0178 (17)	−0.0043 (18)	−0.0075 (16)
O3	0.094 (3)	0.059 (2)	0.064 (2)	0.037 (2)	−0.012 (2)	−0.0105 (18)
N3	0.068 (3)	0.052 (2)	0.060 (3)	0.002 (2)	0.003 (2)	−0.0008 (19)
N2	0.062 (3)	0.046 (2)	0.071 (3)	0.012 (2)	0.004 (2)	−0.006 (2)
O4	0.088 (3)	0.082 (3)	0.106 (4)	0.015 (3)	−0.022 (3)	0.029 (3)
O1	0.091 (4)	0.096 (4)	0.132 (5)	0.013 (3)	−0.005 (3)	0.038 (4)
F2	0.130 (4)	0.118 (4)	0.120 (4)	0.043 (3)	−0.042 (3)	0.018 (3)
C5	0.054 (3)	0.054 (3)	0.062 (3)	0.011 (2)	0.009 (2)	0.004 (2)
C17	0.054 (3)	0.062 (3)	0.068 (3)	0.026 (3)	0.010 (3)	0.003 (3)
C12	0.065 (4)	0.054 (3)	0.060 (3)	0.003 (3)	0.002 (3)	0.007 (2)
C13	0.065 (4)	0.059 (3)	0.071 (3)	0.008 (3)	0.003 (3)	0.006 (3)
C11	0.061 (3)	0.068 (4)	0.062 (3)	0.006 (3)	0.000 (3)	−0.003 (3)
C4	0.061 (3)	0.056 (3)	0.074 (3)	0.018 (3)	0.002 (3)	−0.008 (3)
O5	0.146 (6)	0.068 (3)	0.188 (7)	−0.016 (3)	0.094 (6)	−0.049 (4)
C6	0.062 (3)	0.049 (3)	0.070 (3)	0.016 (2)	0.002 (3)	0.005 (2)
C8	0.069 (4)	0.048 (3)	0.076 (4)	0.021 (3)	0.008 (3)	−0.004 (2)
C14	0.067 (4)	0.063 (3)	0.078 (4)	0.012 (3)	−0.004 (3)	0.018 (3)
C20	0.070 (4)	0.057 (4)	0.119 (6)	0.017 (3)	0.004 (4)	−0.029 (4)
F5	0.219 (7)	0.133 (5)	0.126 (4)	0.032 (5)	−0.067 (5)	0.044 (4)
C2	0.081 (5)	0.068 (4)	0.090 (4)	0.025 (3)	−0.018 (4)	0.007 (3)
C16	0.078 (4)	0.061 (3)	0.077 (4)	0.025 (3)	0.000 (3)	−0.003 (3)
C1	0.105 (6)	0.093 (5)	0.060 (4)	0.004 (4)	−0.007 (4)	0.014 (4)
F4	0.351 (12)	0.082 (4)	0.151 (6)	−0.054 (5)	−0.078 (7)	0.038 (4)
C9	0.102 (5)	0.054 (3)	0.077 (4)	0.020 (3)	−0.008 (4)	−0.013 (3)
C3	0.090 (5)	0.063 (4)	0.075 (4)	0.011 (3)	−0.010 (3)	−0.005 (3)
F3	0.390 (13)	0.087 (4)	0.149 (5)	0.083 (6)	−0.138 (7)	−0.026 (4)
C19	0.117 (6)	0.055 (3)	0.081 (4)	0.022 (4)	0.009 (4)	−0.008 (3)
C7	0.088 (5)	0.059 (3)	0.090 (4)	0.023 (3)	−0.006 (4)	0.001 (3)
C10	0.112 (6)	0.051 (3)	0.085 (4)	0.002 (3)	−0.012 (4)	−0.008 (3)
F1	0.151 (6)	0.259 (10)	0.144 (6)	0.038 (6)	0.057 (5)	0.058 (6)
C21	0.093 (5)	0.047 (3)	0.114 (6)	0.007 (3)	0.026 (4)	−0.021 (3)
C15	0.076 (4)	0.061 (3)	0.085 (4)	0.021 (3)	0.003 (3)	0.016 (3)
F6	0.202 (9)	0.316 (14)	0.137 (6)	0.034 (9)	0.043 (6)	0.097 (7)
C18	0.149 (10)	0.098 (7)	0.101 (6)	−0.003 (6)	−0.028 (7)	0.026 (5)

Geometric parameters (Å, º) top

Cu1—O2	1.883 (4)	O5—H5	0.8200
Cu1—O3	1.906 (4)	C6—C7	1.407 (9)
Cu1—N2	1.927 (5)	C6—C8	1.431 (8)
Cu1—N3	1.929 (5)	C8—H8	0.9300
O2—C5	1.309 (7)	C14—C15	1.375 (9)
O3—C17	1.317 (7)	C20—C19	1.361 (11)
N3—C11	1.279 (8)	C20—C21	1.375 (11)
N3—C10	1.455 (8)	C20—H20	0.9300
N2—C8	1.275 (8)	F5—C18	1.309 (11)
N2—C9	1.465 (7)	C2—C7	1.348 (10)
O4—C18	1.269 (12)	C2—C3	1.379 (10)
O4—C14	1.419 (7)	C16—C15	1.381 (9)
O1—C1	1.267 (9)	C16—H16	0.9300
O1—C2	1.475 (8)	C1—F3	1.268 (9)
F2—C1	1.271 (9)	C1—F1	1.292 (10)
C5—C4	1.403 (8)	F4—C18	1.265 (11)
C5—C6	1.423 (8)	C9—C10	1.474 (11)
C17—C16	1.395 (8)	C9—H9A	0.9700
C17—C12	1.420 (8)	C9—H9B	0.9700
C12—C13	1.403 (8)	C3—H3	0.9300
C12—C11	1.431 (9)	C19—C21ⁱ	1.392 (11)
C13—C14	1.346 (9)	C19—H19	0.9300
C13—H13	0.9300	C7—H7	0.9300
C11—H11	0.9300	C10—H10A	0.9700
C4—C3	1.366 (9)	C10—H10B	0.9700
C4—H4	0.9300	C15—H15	0.9300
O5—C21	1.366 (9)	F6—C18	1.353 (15)

O2—Cu1—O3	87.54 (17)	C21—C20—H20	119.4
O2—Cu1—N2	94.40 (18)	C7—C2—C3	122.2 (6)
O3—Cu1—N2	176.2 (2)	C7—C2—O1	120.4 (7)
O2—Cu1—N3	177.82 (18)	C3—C2—O1	117.0 (6)
O3—Cu1—N3	93.9 (2)	C15—C16—C17	122.2 (6)
N2—Cu1—N3	84.3 (2)	C15—C16—H16	118.9
C5—O2—Cu1	127.1 (3)	C17—C16—H16	118.9
C17—O3—Cu1	127.0 (4)	F3—C1—O1	114.8 (7)
C11—N3—C10	122.4 (5)	F3—C1—F2	109.4 (8)
C11—N3—Cu1	125.0 (4)	O1—C1—F2	113.7 (7)
C10—N3—Cu1	112.3 (4)	F3—C1—F1	105.7 (9)
C8—N2—C9	120.3 (5)	O1—C1—F1	110.6 (9)
C8—N2—Cu1	125.9 (4)	F2—C1—F1	101.6 (7)
C9—N2—Cu1	113.8 (4)	N2—C9—C10	109.6 (6)
C18—O4—C14	118.9 (7)	N2—C9—H9A	109.7
C1—O1—C2	118.1 (6)	C10—C9—H9A	109.7
O2—C5—C4	118.9 (5)	N2—C9—H9B	109.7
O2—C5—C6	123.6 (5)	C10—C9—H9B	109.7
C4—C5—C6	117.5 (5)	H9A—C9—H9B	108.2
O3—C17—C16	118.8 (5)	C4—C3—C2	119.0 (6)
O3—C17—C12	123.4 (5)	C4—C3—H3	120.5
C16—C17—C12	117.8 (5)	C2—C3—H3	120.5
C13—C12—C17	118.7 (6)	C20—C19—C21ⁱ	119.9 (7)
C13—C12—C11	118.3 (5)	C20—C19—H19	120.0
C17—C12—C11	123.0 (5)	C21ⁱ—C19—H19	120.0
C14—C13—C12	121.1 (6)	C2—C7—C6	119.8 (6)
C14—C13—H13	119.5	C2—C7—H7	120.1
C12—C13—H13	119.5	C6—C7—H7	120.1
N3—C11—C12	126.5 (5)	N3—C10—C9	109.9 (5)
N3—C11—H11	116.7	N3—C10—H10A	109.7
C12—C11—H11	116.7	C9—C10—H10A	109.7
C3—C4—C5	121.9 (6)	N3—C10—H10B	109.7
C3—C4—H4	119.1	C9—C10—H10B	109.7
C5—C4—H4	119.1	H10A—C10—H10B	108.2
C21—O5—H5	109.5	O5—C21—C20	123.4 (7)
C7—C6—C5	119.3 (5)	O5—C21—C19ⁱ	117.9 (8)
C7—C6—C8	117.1 (5)	C20—C21—C19ⁱ	118.7 (7)
C5—C6—C8	123.6 (5)	C14—C15—C16	118.5 (6)
N2—C8—C6	125.1 (5)	C14—C15—H15	120.7
N2—C8—H8	117.5	C16—C15—H15	120.7
C6—C8—H8	117.5	F4—C18—O4	118.6 (10)
C13—C14—C15	121.7 (6)	F4—C18—F5	111.2 (9)
C13—C14—O4	117.9 (6)	O4—C18—F5	112.4 (10)
C15—C14—O4	120.2 (6)	F4—C18—F6	103.2 (13)
C19—C20—C21	121.3 (7)	O4—C18—F6	108.5 (10)
C19—C20—H20	119.4	F5—C18—F6	101.1 (11)

O3—Cu1—O2—C5	179.3 (5)	C18—O4—C14—C15	−74.5 (11)
N2—Cu1—O2—C5	2.6 (5)	C1—O1—C2—C7	74.4 (11)
Cu1—O2—C5—C4	174.2 (4)	C1—O1—C2—C3	−111.7 (9)
Cu1—O2—C5—C6	−6.2 (8)	O3—C17—C16—C15	−179.8 (6)
Cu1—O3—C17—C16	174.3 (5)	C12—C17—C16—C15	2.2 (10)
Cu1—O3—C17—C12	−7.8 (9)	C2—O1—C1—F3	−61.3 (13)
O3—C17—C12—C13	−180.0 (6)	C2—O1—C1—F2	171.7 (7)
C16—C17—C12—C13	−2.0 (9)	C2—O1—C1—F1	58.2 (10)
O3—C17—C12—C11	−2.9 (10)	C8—N2—C9—C10	−161.6 (6)
C16—C17—C12—C11	175.0 (6)	Cu1—N2—C9—C10	21.2 (7)
C17—C12—C13—C14	0.6 (10)	C5—C4—C3—C2	−3.4 (11)
C11—C12—C13—C14	−176.5 (6)	C7—C2—C3—C4	4.9 (12)
C10—N3—C11—C12	−173.9 (7)	O1—C2—C3—C4	−168.9 (6)
Cu1—N3—C11—C12	0.6 (10)	C21—C20—C19—C21ⁱ	−4.1 (12)
C13—C12—C11—N3	−176.2 (6)	C3—C2—C7—C6	−1.4 (12)
C17—C12—C11—N3	6.8 (10)	O1—C2—C7—C6	172.2 (6)
O2—C5—C4—C3	178.2 (6)	C5—C6—C7—C2	−3.6 (10)
C6—C5—C4—C3	−1.5 (9)	C8—C6—C7—C2	176.2 (7)
O2—C5—C6—C7	−174.7 (6)	C11—N3—C10—C9	−153.1 (6)
C4—C5—C6—C7	4.9 (9)	Cu1—N3—C10—C9	31.8 (8)
O2—C5—C6—C8	5.5 (9)	N2—C9—C10—N3	−33.6 (9)
C4—C5—C6—C8	−174.8 (6)	C19—C20—C21—O5	−179.7 (7)
C9—N2—C8—C6	−179.2 (6)	C19—C20—C21—C19ⁱ	4.1 (12)
Cu1—N2—C8—C6	−2.3 (9)	C13—C14—C15—C16	−0.6 (11)
C7—C6—C8—N2	179.2 (6)	O4—C14—C15—C16	−176.1 (6)
C5—C6—C8—N2	−1.0 (10)	C17—C16—C15—C14	−0.9 (11)
C12—C13—C14—C15	0.7 (11)	C14—O4—C18—F4	56.4 (17)
C12—C13—C14—O4	176.3 (6)	C14—O4—C18—F5	−171.6 (9)
C18—O4—C14—C13	109.8 (10)	C14—O4—C18—F6	−60.7 (11)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O3	0.82	2.20	2.993 (8)	165
C11—H11···F2ⁱⁱ	0.93	2.63	3.513 (8)	159
C10—H10A···O5ⁱⁱⁱ	0.97	2.53	3.469 (11)	162
C15—H15···O5^iv	0.93	2.55	3.345 (9)	144
C8—H8···Cg1^v	0.93	2.82	3.740 (8)	173

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

Funding information

Funding for this research was provided by: Ondokuz Mayıs University (award No. PYO.FEN.1906.19.001).

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