Crystal structure and Hirshfeld surface analysis of a copper(II) complex containing 2-nitro­benzoate and tetra­methyl­ethylenedi­amine ligands

Kansiz, S.; Qadir, A.M.; Dege, N.; Yongxin, L.; Saif, E.

doi:10.1107/S2056989021002802

research communications

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ISSN: 2056-9890

Volume 77| Part 4| April 2021| Pages 412-415

https://doi.org/10.1107/S2056989021002802

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Crystal structure and Hirshfeld surface analysis of a copper(II) complex containing 2-nitrobenzoate and tetramethylethylenediamine ligands

Sevgi Kansiz,^a ^* Adnan M. Qadir,^b Necmi Dege,^c Li Yongxin ^d and Eiad Saif ^e,^f ^*

^aDepartment of Fundamental Sciences, Faculty of Engineering, Samsun University, 55420, Samsun, Turkey, ^bDepartment of Chemistry, College of Science, Salahaddin University, Erbil, 44001, Iraq, ^cDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139, Samsun, Turkey, ^dDivision of Chemistry and Biological Chemistry, Nanyang Technological University, 637371, Singapore, ^eDepartment of Computer and Electronic Engineering Technology, Sana'a Community College, Sana'a, Yemen, and ^fDepartment of Electrical and Electronic Engineering, Faculty of Engineering, Ondokuz Mayıs University, 55139, Samsun, Turkey
^*Correspondence e-mail: sevgi.kansiz@samsun.edu.tr, eiad.saif@scc.edu.ye

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 24 February 2021; accepted 15 March 2021; online 19 March 2021)

The reaction of copper(II) sulfatepentahydrate with 2-nitrobenzoic acid and N,N,N′,N′-tetramethylethylenediamine (TMEDA) in basic solution produces the complex bis(2-nitrobenzoato-κO)(N,N,N′,N′-tetramethylethylenediamine-κ²N,N′)copper(II), [Cu(C₇H₄NO₄)₂(C₆H₁₆N₂)] or [Cu(2-nitrobenzoate)₂(tmeda)]. Each carboxylate group of the 2-nitrobenzoate ligand is coordinated by Cu^II atom in a monodentate fashion and two TMEDA ligand nitrogen atoms are coordinate by the metal center, giving rise to a distorted square-planar coordination environment. In the crystal, metal complexes are linked by centrosymmetric C—H⋯O hydrogen bonds, forming ribbons via a R₂²(10) ring motif. These ribbons are linked by further C—H⋯O hydrogen bonds, leading to two-dimensional hydrogen-bonded arrays parallel to the bc plane. Weak π–π stacking interactions provide additional stabilization of the crystal structure. Hirshfeld surface analysis, d_norm and two-dimensional fingerprint plots were examined to verify the contributions of the different intermolecular contacts within the supramolecular structure. The major interactions of the complex are O⋯H/H⋯O (44.9%), H⋯H (34%) and C⋯H (14.5%).

Keywords: crystal structure; copper(II); tetramethylethylenediamine; 2-nitrobenzoate; Hirshfeld surface.

CCDC reference: 1910225

1. Chemical context

Copper(II) carboxylate complexes continue to be of considerable interest on account of their biological properties such as antibacterial (Melník et al., 1982 ), antifungal (Kozlevčar et al., 1999 ), cytotoxic and antiviral activities (Ranford et al., 1993 ). Carboxylate ligands are versatile and can coordinate to metal centers in different modes such as monodentate, bidentate and bridging fashions. The bidentate coordination can be either symmetrical bidentate chelating, having the same C—O bond lengths, or asymmetrical bidentate chelating, having different C—O bond lengths. Carboxylate ligands have been used to generate units for developing supramolecular architectures. Copper is one of essential metals for human life. In the human body, various enzymes are copper-dependent such as Cytochrome c oxidase, superoxide dismutase, ferroxidases, monoamine oxidase, and dopamine β-monoxygenase (Brewer, 2009 ; Balamurugan & Schaffner, 2006 ). In this work, a new copper(II) complex involving 2-nitrobenzoic acid and N,N,N′,N′-tetramethylethylenediamine was synthesized, characterized by single crystal X-ray and studied by Hirshfeld surface analysis.

2. Structural commentary

Copper(II) acetate reacts with 2-nitrobenzoic acid and N,N,N′,N′-tetramethylethylenediamine (TMEDA) to give the mono-nuclear copper(II) complex (I). The asymmetric unit of the title compound contains one half of the metal complex, the central metal being located on the special position 4e (1/2, y, 1/4). The Cu^II atom has a distorted square-planar geometry with one oxygen atom each from two nitrobenzoic acid ligands and two TMEDA ligand nitrogen atoms (Figs. 1 and 2). The two nitro groups of the rings are oriented trans to each other, being symmetry-related to each other through a twofold axis. The structure of the complex is shown in Fig. 1. The Cu1—N1 and Cu1—O1 bond distances are 2.0269 (13) and 1.9589 (11) Å, respectively. The structural parameters of the TMEDA ligand, i.e. Cu—N bond lengths, are in agreement with a work reported by Gumienna-Kontecka et al. (2013 ). The C4—O1 and C4—O2 distances in the carboxyl group are 1.2772 (19) and 1.2388 (18) Å, respectively. Selected bond lengths are given in Table 1.

Table 1
Selected bond lengths (Å)

C1—N1	1.482 (2)	Cu1—O1	1.9589 (11)
C2—N1	1.483 (2)	Cu1—N1	2.0269 (13)
C3—N1	1.490 (2)	N2—O4	1.2206 (18)
C10—N2	1.4742 (19)	N2—O3	1.2249 (19)

Figure 1
The molecular structure of [Cu(2-nitrobenzoate)₂(tmeda)], with the atom labeling. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (i) −x + 1, y, −z + $[{1\over 2}]$ .

Figure 2
View of the two-dimensional hydrogen-bonded network in the structure of [Cu(2-nitrobenzoate)₂(tmeda) showing C9—H9⋯O4 hydrogen bonds [described by an R₂²(10) ring motif] as green dashed lines and C3—H3A⋯O3 hydrogen bonds as blue dashed lines.

3. Supramolecular features

The crystal packing of the title complex (Fig. 2) features intermolecular hydrogen bonds (C3—H3A⋯O3ⁱ and C9—H9⋯O4ⁱⁱ; symmetry codes as in Table 2). The metal complexes are self-assembled by centrosymmetric C9—H9⋯O4 hydrogen bonds along the c–axis direction, forming supramolecular ribbons linked via R₂²(10) ring motifs. Adjacent ribbons are connected by C3—H3A⋯O3 hydrogen bonds; these interactions lead to the formation of layers lying parallel to the bc plane. The three-dimensional network is stabilized by π–π stacking interactions with a centroid-to-centroid distance Cg1⋯Cg1ⁱⁱⁱ of 3.741 (2) Å, where Cg1 is the centroid of the C5–C10 ring [symmetry code: (iii) −x + 1, −y + 1, −z + 1].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O3ⁱ	0.99	2.59	3.531 (2)	158
C9—H9⋯O4ⁱⁱ	0.95	2.42	3.291 (2)	152
Symmetry codes: (i) $[-x+1, y-1, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.41, update of November 2019; Groom et al., 2016 ) for the title complex revealed four hits: catena-[(μ₂-terephthalato-O,O′,O′′,O′′′)(μ₂-terephthalato-O,O′′)bis[N-(2-aminoethyl)-3-amino-1-propanol]dicopper(II)] (FEMBEF; Mukherjee et al., 2004 ), bis[(μ₂-biphenyl-2,2′-dicarboxylato-O²,O^2′)[N-(pyrid;in-2-yl-N)pyridin-2-amine-N¹]]dicopper(II) tetrahydrate (GUCXOS; Kumagai et al., 2009 ), bis[(μ₂-biphenyl-2,2′-dicarboxylato-O²,O^2′)[N-(pyridin-2-yl-N)pyridin-2-amine-N¹]]dicopper(II) biphenyl-2,2′-dicarboxylic acid solvate monohydrate (GUCXUY; Kumagai et al., 2009) and bis(2-nitrobenzoato)bis(3,5-dimethyl-1H-pyrazole-N²)copper(II) (MIJFUH; Karmakar et al., 2007 ). The Cu—N and Cu—O bond lengths range from 1.973 to 2.022 Å and 1.955 to 1.987 Å, respectively. The Cu—N and Cu—O bond lengths in the title complex [2.0269 (13) and 1.9589 (11) Å, respectively] fall within these limits.

5. Hirshfeld surface analysis

Hirshfeld surface analysis and the associated two-dimensional fingerprint plots (Spackman & Jayatilaka, 2009 ) are very important for explaining the intermolecular contacts in the crystal structure (Demircioğlu et al., 2019 ; Ilmi et al., 2020 ). We performed the Hirshfeld surface analysis with CrystalExplorer17 (Turner et al., 2017 ). Fig. 3 shows the Hirshfeld surface mapped over d_norm (–0.2250 to 1.2935 a.u.) and the molecular electrostatic potentials (–0.2173 to 0.1248). In Fig. 3a, the red spots correspond to the O⋯H contacts. The electrostatic potential (Fig. 3b) shows donor (red) and acceptor (blue) regions. O⋯H/H⋯O (44.9%) contacts, seen as a pair of spikes of scattered points in the fingerprint plot, make the largest contribution to the total Hirshfeld surface in [Cu(2-nitrobenzoate)₂(tmeda)] (Fig. 4). The second most important interaction is H⋯H, contributing 34% to the overall crystal packing, which is shown in the 2D fingerprint of the (d_i, d_e) points related to the H atoms. Two symmetrical wings on the left and right sides are shown in the graph of C⋯H/H⋯C interactions (14.5%). The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of O⋯H, H⋯H and C⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major role in the crystal packing.

Figure 3
Hirshfeld surface of [Cu(2-nitrobenzoate)₂(tmeda)] mapped with (a) d_norm and (b) the molecular electrostatic potential.

Figure 4
Two-dimensional fingerprint plots for [Cu(2-nitrobenzoate)₂(tmeda)] showing all interactions and those delineated into O⋯H/H⋯O, H⋯H and C⋯H/H⋯C contacts (d_i is the closest internal distance from a given point on the Hirshfeld surface and d_e is the closest external contact).

6. Synthesis and crystallization

An aqueous solution of sodium 2-nitrobenzoate (5 mmol, 0.9 g) was added to an aqueous solution of CuSO₄·5H₂O (2.5 mmol, 0.6 g) under stirring. Tetramethylethylenediamine (2.5 mmol, 0.3 g) was added and the color changed from light blue to violet. The mixture was filtered and the filtrate was allowed to stand for slow evaporation. Single crystals suitable for X-ray were obtained after several days.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were positioned geometrically (C—H = 0.95, 0.98 and 0.99 Å) and refined using a riding model, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) otherwise.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(C₇H₄NO₄)₂(C₆H₁₆N₂)]
M_r	511.97
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	12.7286 (3), 7.4918 (2), 22.8967 (6)
β (°)	98.395 (1)
V (Å³)	2160.04 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.07
Crystal size (mm)	0.22 × 0.20 × 0.12

Data collection
Diffractometer	Bruker D8 Quest withPhoton II CPADs detector
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )
T_min, T_max	0.77, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	23494, 4737, 3573
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.808

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.092, 1.03
No. of reflections	4737
No. of parameters	152
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.63
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXT2014/5 (Sheldrick, 2015a ) and SHELXL2017/1 (Sheldrick, 2015b ).

Supporting information

CCDC reference: 1910225

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002802/zn2005sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002802/zn2005Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015b); software used to prepare material for publication: APEX3 (Bruker, 2017).

Bis(2-nitrobenzoato-κO)(N,N,N',N'-tetramethylethylenediamine-κ²N,N')copper(II) top

Crystal data top

[Cu(C₇H₄NO₄)₂(C₆H₁₆N₂)]	F(000) = 1060
M_r = 511.97	D_x = 1.574 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.7286 (3) Å	Cell parameters from 6607 reflections
b = 7.4918 (2) Å	θ = 3.2–34.7°
c = 22.8967 (6) Å	µ = 1.07 mm⁻¹
β = 98.395 (1)°	T = 100 K
V = 2160.04 (10) Å³	Block, blue
Z = 4	0.22 × 0.20 × 0.12 mm

Data collection top

Bruker D8 Quest withPhoton II CPADs detector diffractometer	4737 independent reflections
Radiation source: Incoatec microfocus source, Bruker D8 Quest	3573 reflections with I > 2σ(I)
Multilayer Mirror monochromator	R_int = 0.056
Detector resolution: 7.4074 pixels mm^-1	θ_max = 35.1°, θ_min = 3.2°
phi and ω scans	h = −20→20
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −12→12
T_min = 0.77, T_max = 0.88	l = −36→34
23494 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0258P)² + 3.2488P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4737 reflections	Δρ_max = 0.55 e Å⁻³
152 parameters	Δρ_min = −0.63 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
C1	0.29927 (12)	0.0971 (2)	0.26549 (9)	0.0226 (3)
H1A	0.282285	0.110738	0.222582	0.034*
H1B	0.282610	0.208122	0.284815	0.034*
H1C	0.257167	−0.000768	0.278536	0.034*
C2	0.43747 (14)	0.0376 (2)	0.34649 (8)	0.0227 (3)
H2A	0.395284	−0.060381	0.359361	0.034*
H2B	0.419573	0.148951	0.365245	0.034*
H2C	0.513178	0.011891	0.357879	0.034*
C3	0.44109 (12)	−0.1106 (2)	0.25164 (8)	0.0191 (3)
H3A	0.400440	−0.116874	0.211384	0.023*
H3B	0.422415	−0.215879	0.274155	0.023*
C4	0.51601 (12)	0.4529 (2)	0.34319 (7)	0.0161 (3)
C5	0.48616 (11)	0.56860 (19)	0.39205 (7)	0.0141 (3)
C6	0.37979 (12)	0.5852 (2)	0.39976 (7)	0.0164 (3)
H6	0.326473	0.529299	0.372478	0.020*
C7	0.35056 (12)	0.6815 (2)	0.44637 (8)	0.0196 (3)
H7	0.277599	0.693902	0.450177	0.024*
C8	0.42749 (12)	0.7599 (2)	0.48755 (7)	0.0205 (3)
H8	0.407256	0.823813	0.519973	0.025*
C9	0.53414 (12)	0.7451 (2)	0.48142 (7)	0.0188 (3)
H9	0.587555	0.797819	0.509431	0.023*
C10	0.56064 (11)	0.6518 (2)	0.43364 (7)	0.0151 (3)
Cu1	0.500000	0.25244 (3)	0.250000	0.01202 (6)
N1	0.41383 (10)	0.05640 (17)	0.28142 (6)	0.0152 (2)
N2	0.67360 (10)	0.65314 (18)	0.42590 (6)	0.0176 (3)
O1	0.44317 (9)	0.43232 (14)	0.29904 (5)	0.0165 (2)
O2	0.60401 (9)	0.37907 (16)	0.34882 (6)	0.0226 (2)
O3	0.69761 (10)	0.73929 (18)	0.38435 (6)	0.0275 (3)
O4	0.73708 (9)	0.57614 (18)	0.46249 (6)	0.0268 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0144 (6)	0.0213 (7)	0.0324 (10)	−0.0007 (6)	0.0050 (6)	−0.0020 (7)
C2	0.0297 (8)	0.0196 (7)	0.0197 (8)	−0.0011 (6)	0.0063 (7)	0.0039 (6)
C3	0.0187 (6)	0.0126 (6)	0.0265 (8)	−0.0024 (5)	0.0054 (6)	−0.0010 (6)
C4	0.0175 (6)	0.0128 (6)	0.0184 (7)	−0.0012 (5)	0.0039 (5)	−0.0002 (5)
C5	0.0144 (6)	0.0124 (6)	0.0159 (7)	0.0005 (5)	0.0030 (5)	0.0005 (5)
C6	0.0140 (6)	0.0167 (6)	0.0187 (7)	−0.0013 (5)	0.0025 (5)	0.0003 (6)
C7	0.0161 (6)	0.0231 (7)	0.0211 (8)	0.0007 (6)	0.0073 (6)	0.0002 (6)
C8	0.0201 (6)	0.0241 (7)	0.0189 (7)	0.0001 (6)	0.0073 (6)	−0.0038 (7)
C9	0.0178 (6)	0.0204 (6)	0.0181 (7)	−0.0009 (6)	0.0026 (5)	−0.0021 (6)
C10	0.0131 (6)	0.0149 (6)	0.0177 (7)	0.0004 (5)	0.0036 (5)	−0.0002 (5)
Cu1	0.01247 (10)	0.01009 (10)	0.01356 (12)	0.000	0.00210 (8)	0.000
N1	0.0149 (5)	0.0127 (5)	0.0186 (6)	−0.0002 (4)	0.0040 (5)	0.0006 (5)
N2	0.0145 (5)	0.0174 (6)	0.0214 (7)	−0.0017 (5)	0.0037 (5)	−0.0035 (5)
O1	0.0189 (5)	0.0143 (5)	0.0161 (5)	0.0004 (4)	0.0021 (4)	−0.0023 (4)
O2	0.0180 (5)	0.0237 (6)	0.0262 (6)	0.0038 (4)	0.0038 (5)	−0.0065 (5)
O3	0.0213 (5)	0.0332 (7)	0.0297 (7)	−0.0039 (5)	0.0092 (5)	0.0044 (6)
O4	0.0165 (5)	0.0295 (7)	0.0329 (7)	0.0040 (5)	−0.0013 (5)	0.0026 (6)

Geometric parameters (Å, º) top

C1—N1	1.482 (2)	C5—C6	1.396 (2)
C1—H1A	0.9800	C6—C7	1.383 (2)
C1—H1B	0.9800	C6—H6	0.9500
C1—H1C	0.9800	C7—C8	1.387 (2)
C2—N1	1.483 (2)	C7—H7	0.9500
C2—H2A	0.9800	C8—C9	1.389 (2)
C2—H2B	0.9800	C8—H8	0.9500
C2—H2C	0.9800	C9—C10	1.381 (2)
C3—N1	1.490 (2)	C9—H9	0.9500
C3—C3ⁱ	1.513 (3)	C10—N2	1.4742 (19)
C3—H3A	0.9900	Cu1—O1	1.9589 (11)
C3—H3B	0.9900	Cu1—O1ⁱ	1.9589 (11)
C4—O2	1.2388 (18)	Cu1—N1	2.0269 (13)
C4—O1	1.2772 (19)	Cu1—N1ⁱ	2.0269 (13)
C4—C5	1.508 (2)	N2—O4	1.2206 (18)
C5—C10	1.389 (2)	N2—O3	1.2249 (19)

N1—C1—H1A	109.5	C6—C7—H7	119.9
N1—C1—H1B	109.5	C8—C7—H7	119.9
H1A—C1—H1B	109.5	C7—C8—C9	120.04 (15)
N1—C1—H1C	109.5	C7—C8—H8	120.0
H1A—C1—H1C	109.5	C9—C8—H8	120.0
H1B—C1—H1C	109.5	C10—C9—C8	118.42 (14)
N1—C2—H2A	109.5	C10—C9—H9	120.8
N1—C2—H2B	109.5	C8—C9—H9	120.8
H2A—C2—H2B	109.5	C9—C10—C5	123.28 (14)
N1—C2—H2C	109.5	C9—C10—N2	116.55 (13)
H2A—C2—H2C	109.5	C5—C10—N2	120.05 (13)
H2B—C2—H2C	109.5	O1—Cu1—O1ⁱ	93.07 (7)
N1—C3—C3ⁱ	108.76 (11)	O1—Cu1—N1	91.76 (5)
N1—C3—H3A	109.9	O1ⁱ—Cu1—N1	165.06 (5)
C3ⁱ—C3—H3A	109.9	O1—Cu1—N1ⁱ	165.06 (5)
N1—C3—H3B	109.9	O1ⁱ—Cu1—N1ⁱ	91.76 (5)
C3ⁱ—C3—H3B	109.9	N1—Cu1—N1ⁱ	87.13 (7)
H3A—C3—H3B	108.3	C1—N1—C2	108.35 (13)
O2—C4—O1	124.71 (15)	C1—N1—C3	110.27 (12)
O2—C4—C5	120.10 (14)	C2—N1—C3	110.70 (13)
O1—C4—C5	115.09 (13)	C1—N1—Cu1	109.12 (10)
C10—C5—C6	116.79 (14)	C2—N1—Cu1	112.61 (10)
C10—C5—C4	123.09 (13)	C3—N1—Cu1	105.77 (9)
C6—C5—C4	119.95 (13)	O4—N2—O3	124.54 (14)
C7—C6—C5	121.26 (14)	O4—N2—C10	118.28 (14)
C7—C6—H6	119.4	O3—N2—C10	117.09 (13)
C5—C6—H6	119.4	C4—O1—Cu1	104.50 (9)
C6—C7—C8	120.18 (14)

O2—C4—C5—C10	24.2 (2)	C4—C5—C10—C9	−174.19 (15)
O1—C4—C5—C10	−159.09 (14)	C6—C5—C10—N2	−174.93 (13)
O2—C4—C5—C6	−150.89 (15)	C4—C5—C10—N2	9.9 (2)
O1—C4—C5—C6	25.8 (2)	C3ⁱ—C3—N1—C1	157.97 (16)
C10—C5—C6—C7	0.6 (2)	C3ⁱ—C3—N1—C2	−82.14 (18)
C4—C5—C6—C7	175.98 (15)	C3ⁱ—C3—N1—Cu1	40.11 (18)
C5—C6—C7—C8	−1.8 (2)	C9—C10—N2—O4	67.41 (19)
C6—C7—C8—C9	1.3 (3)	C5—C10—N2—O4	−116.36 (17)
C7—C8—C9—C10	0.2 (2)	C9—C10—N2—O3	−109.26 (17)
C8—C9—C10—C5	−1.5 (2)	C5—C10—N2—O3	66.97 (19)
C8—C9—C10—N2	174.64 (15)	O2—C4—O1—Cu1	4.07 (19)
C6—C5—C10—C9	1.0 (2)	C5—C4—O1—Cu1	−172.47 (10)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O3ⁱⁱ	0.99	2.59	3.531 (2)	158
C9—H9···O4ⁱⁱⁱ	0.95	2.42	3.291 (2)	152

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

Acknowledgements

Authors contributions are as follows. Methodology, AMQ; software, SK, ND, LY and ES; validation, SK, AMQ and ND; formal analysis, AMQ; investigation, SK, AMQ, ND and ES; resources, AMQ and ES; writing (review and editing), SK and AMQ; visualization, SK; supervision, SK and ND; funding acquisition, LY and ES.

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