Crystal structure and Hirshfeld surface analysis of one-dimensional copper(II) coordination polymer incorporating succinate and tetra­methyl­ethylene­diamine ligands

Qadir, A.M.; Kansiz, S.; Dege, N.; Rosair, G.M.; Iskenderov, T.S.

doi:10.1107/S2056989020007227

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ISSN: 2056-9890

Volume 76| Part 7| July 2020| Pages 1038-1041

https://doi.org/10.1107/S2056989020007227

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Crystal structure and Hirshfeld surface analysis of one-dimensional copper(II) coordination polymer incorporating succinate and tetramethylethylenediamine ligands

Adnan M. Qadir,^a Sevgi Kansiz,^b ^* Necmi Dege,^c Georgina M. Rosair ^d and Turganbay S. Iskenderov ^e ^*

^aDepartment of Chemistry, College of Science, Salahaddin University, Erbil, 44001, Iraq, ^bDepartment of Fundamental Sciences, Faculty of Engineering, Samsun University, Samsun, 55420, Turkey, ^cDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun, 55139, Turkey, ^dInstitute of Chemical Sciences, School of Engineering & Physical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK, and ^eDepartment of Chemistry, National Taras Shevchenko University of Kyiv, 64, Vladimirska Str., Kiev 01601, Ukraine
^*Correspondence e-mail: sevgi.kansiz85@gmail.com, tiskenderov@ukr.net

Edited by S. Parkin, University of Kentucky, USA (Received 1 May 2020; accepted 29 May 2020; online 9 June 2020)

The reaction of copper nitrate with succinic acid (succH) and N,N,N′,N′-tetramethylethylenediamine (TMEDA) in basic solution produces the complex catena-poly[[[(N,N,N′,N′-tetramethylethylenediamine-κ²N,N′)copper(II)]-μ-succinato-κ²O¹:O⁴] tetrahydrate], {[Cu(C₄H₄O₄)(C₆H₁₆N₂)]·4H₂O}_n or {[Cu(succ)(tmeda)]·4H₂O}_n. Each carboxylate group of the succinate ligand coordinates to a Cu^II atom in a monodentate fashion, giving rise to a distorted square-planar geometry. The succinate ligands bridge the Cu^II centres, forming one-dimensional polymeric chains. Hydrogen bonds between the ligands and water molecules link these chains into sheets that lie parallel to the ac plane. 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.

Keywords: crystal structure; copper(II); polymer; tetramethylethylenediamine; Hirshfeld surface.

CCDC reference: 2006634

1. Chemical context

Coordination polymers are a key area of development in supramolecular chemistry. Aliphatic saturated dicarboxylates are versatile linkage ligands for construction of supramolecular frameworks. These possess conformational freedom and coordinating ability owing to the single carbon chain. Aliphatic dicarboxylate anions exhibit different coordination modes such as uni-bidentate, bis-monodentate, bis-bidentate, tridentate or tetradentate, linking metal atoms into 1-D coordination polymers, 2-D layers or 3-D networks. Copper(II) carboxylate complexes are known to possess various biological activities including antifungal (Melník et al., 1982 ), antibacterial (Mojumdar et al., 2005 ), antiviral and cytotoxic activities (Ranford et al., 1993 ). Copper(II) is present at the active site some of proteins. The proteins containing copper(II) display biological functions such as electron transfer, dioxygen transfer, oxygenation, reduction, oxidation and disproportionation (Mukherjee, 2003 ). In this work, the synthesis, single crystal structure and Hirshfeld surface analysis of a copper(II) complex involving N,N,N′,N′-tetramethylethylenediamine and succinate ligands are reported.

2. Structural commentary

The asymmetric unit of the title compound (1) is illustrated in Fig. 1. In the complex {[Cu(succ)₂(tmeda)]·4H₂O}_n, the central metal atom has distorted square-planar geometry with one oxygen atom each from two succ ligands and two TMEDA ligand nitrogen atoms (Figs. 2 and 3). There are two longer axial Cu⋯O contacts of 2.590 (2) and 2.432 (2) Å. In the square-plane, the Cu—O and Cu—N bond lengths are in the range 1.964 (2)–2.038 (2) Å (Table 1). The structural parameters in the TMEDA ligand, i.e. the Cu—N bond lengths, are in agreement with those reported for the [Cu₃(PyDHA-2H)(tmeda)₃](ClO₄)₂ complex (PyDHA = pyridine-2,6-dihydroxamic acid) by Gumienna-Kontecka et al. (2013 ). Similar geometric parameters have also been reported for {[Cu(succ)(deed)]·4H₂O}_n [Cu—O: 2.123 (8)–2.142 (8) Å deed = N,N-diethylethylenediamine; Şen et al., 2017 ] and [Cu₂(C₄H₄O₄)₂(C₁₂H₁₂N₂)]_n, [Cu—O: 1.955 (4)–1.983 (5) Å; González Garmendia et al., 2009 ]. Selected bond lengths and angles are given in Table 1. The succinate ligands bridge the Cu^II centres, forming one-dimensional polymeric chains.

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.9639 (17)	O1—C7	1.275 (3)
Cu1—O3ⁱ	1.9958 (16)	O2—C7	1.236 (3)
Cu1—O4ⁱ	2.4315 (17)	O3—C10	1.273 (3)
Cu1—N1	2.024 (2)	O4—C10	1.239 (3)
Cu1—N2	2.038 (2)	N1—C1	1.459 (5)

O1—Cu1—O3ⁱ	89.80 (7)	O1—Cu1—N2	92.40 (8)
O1—Cu1—O4ⁱ	91.00 (7)	O3ⁱ—Cu1—N1	94.20 (8)
O1—Cu1—N1	167.77 (9)	O3ⁱ—Cu1—N2	165.06 (8)
Symmetry code: (i) x-1, y, z.

Figure 1
Perspective view of {[Cu(succ)(tmeda)]·4H₂O}_n, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (i) −1 + x, y, z; (ii) 1 + x, y, z].

Figure 2
Ellipsoid plot (50%) of a section of the polymeric chain of {[Cu(succ)(tmeda)]·4H₂O}_n.

Figure 3
The two-dimensional layered structure of {[Cu(succ)(tmeda)]·4H₂O}_n. For clarity, the TMEDA ligands are shown only by their N atoms.

3. Supramolecular features

In the asymmetric unit of the title complex, there are O5—H5H⋯O4, O6—H6G⋯O5, O7—H7A⋯O2, O8—H8C⋯O3 and O8—H8D⋯O7 hydrogen-bonding interactions, which act to stabilize the crystal packing. The crystal packing (Fig. 3) also features symmetry-related intermolecular hydrogen bonds (O7—H7B⋯O6ⁱⁱ, O5—H5G⋯O1ⁱⁱⁱ and O6—H6H⋯O8^iv; symmetry codes as in Table 2), linking the one-dimensional polymeric chains into sheets that lie parallel to the ac plane.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5H⋯O4	0.79 (2)	1.98 (2)	2.763 (3)	169 (6)
O6—H6G⋯O5	0.82 (2)	1.88 (2)	2.694 (3)	175 (5)
O7—H7A⋯O2	0.82 (2)	1.96 (2)	2.774 (3)	172 (6)
O8—H8C⋯O3	0.83 (2)	2.04 (2)	2.869 (3)	173 (5)
O8—H8D⋯O7	0.83 (2)	1.93 (2)	2.733 (4)	165 (5)
O7—H7B⋯O6ⁱⁱ	0.81 (1)	1.97 (2)	2.763 (4)	167 (6)
O5—H5G⋯O1ⁱⁱⁱ	0.80 (2)	2.00 (2)	2.799 (3)	176 (6)
O6—H6H⋯O8^iv	0.84 (2)	2.01 (2)	2.803 (4)	157 (5)
Symmetry codes: (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.40, update of February 2019; Groom et al., 2016 ) for the title complex gave four hits: aqua(cyclobutane-1,1-dicarboxylato)(N,N,N′,N′-tetramethylethylenediamine)copper(II) monohydrate (CBXECU; Pajunen & Pajunen, 1979a ), bis(μ₂-glutarato)bis[(N,N,N′,N′-tetraethylethylenediamine)copper(II)] (GLUECU; Pajunen & Pajunen, 1979b ), [N-(2-oxybenzylidene)valinato](N,N,N′,N′-tetramethylethane-1,2-diamine)copper(II) (UZAPES; Lakshmi et al., 2016 ) and (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine)(L-valinato)copper(II) perchlorate (VEGRUU; Murakami & Kita, 1998 ). The Cu—N bond lengths range from 1.941 to 2.415 Å. When these bond lengths are compared with the title complex, the Cu—N bond lengths [2.024 (2)–2.038 (2) Å] fall within these limits.

5. Hirshfeld surface analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots were performed with CrystalExplorer17 (Turner et al., 2017 ). Hirshfeld surface analysis enables the visualization of intermolecular interactions by different colours and colour intensity, representing short or long contacts and indicating the relative strength of the interactions. Fig. 4 shows the Hirshfeld surface mapped over d_norm (–0.629 to 1.578 a.u.). The overall two-dimensional fingerprint plot for the title complex and those delineated into H⋯H, O⋯H/H⋯O and Cu⋯O/O⋯Cu contacts are illustrated in Fig. 5. The percentage contributions from the different inter-atomic contacts to the Hirshfeld surface are as follows: H⋯H (63.2%), O⋯H/H⋯O (29.5%) and Cu⋯O/O⋯Cu (3.8%). The percentage contributions for other intermolecular contacts amount to less than 3% of the Hirshfeld surface mapping.

Figure 4
Hirshfeld surface mapped over d_norm for {[Cu(succ)(tmeda)]·4H₂O}_n.

Figure 5
The two-dimensional fingerprint plots for {[Cu(succ)(tmeda)]·4H₂O}_n showing the main interactions and their percentage contributions (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 succinate (10 mmol, 1.6 g) was added to an aqueous solution of Cu(NO₃)₂·3H₂O (10 mmol, 2.4 g) under stirring. A light-blue precipitate was formed. The precipitate was filtered and washed with water. The precipitate was dispersed in water and tetramethylethylenediamine (10 mmol, 1.2 g) was added giving a dark-blue solution. The solution was filtered. Single crystals were obtained on slow evaporation of the solution after one week.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Carbon-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93, 0.96 and 0.97 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) otherwise. The methyl groups were modelled as disordered over two torsional orientations. Water hydrogen-atom coordinates were refined, but U_iso(H) was set to 1.5U_eq(water O).

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(C₄H₄O₄)(C₆H₁₆N₂)]·4H₂O
M_r	367.88
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.1195 (4), 12.3172 (6), 19.8590 (12)
β (°)	91.160 (5)
V (Å³)	1741.12 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.29
Crystal size (mm)	0.61 × 0.33 × 0.17

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 )
T_min, T_max	0.645, 0.810
No. of measured, independent and observed [I > 2σ(I)] reflections	12278, 3427, 2864
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.04
No. of reflections	3427
No. of parameters	233
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.26
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002), SHELXT2017/1 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2006634

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007227/pk2626sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020007227/pk2626Isup3.hkl

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2017/1 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[[(N,N,N',N'-tetramethylethylenediamine-κ²N,N')copper(II)]-µ-succinato-κ²O¹:O⁴] tetrahydrate] top

Crystal data top

[Cu(C₄H₄O₄)(C₆H₁₆N₂)]·4H₂O	F(000) = 780
M_r = 367.88	D_x = 1.403 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.1195 (4) Å	Cell parameters from 19036 reflections
b = 12.3172 (6) Å	θ = 1.7–29.9°
c = 19.8590 (12) Å	µ = 1.29 mm⁻¹
β = 91.160 (5)°	T = 296 K
V = 1741.12 (17) Å³	Stick, blue
Z = 4	0.61 × 0.33 × 0.17 mm

Data collection top

Stoe IPDS 2 diffractometer	2864 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.033
rotation method scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −8→8
T_min = 0.645, T_max = 0.810	k = −14→15
12278 measured reflections	l = −24→24
3427 independent reflections

Refinement top

Refinement on F²	10 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.056P)² + 0.2662P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3427 reflections	Δρ_max = 0.28 e Å⁻³
233 parameters	Δρ_min = −0.26 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	Occ. (<1)
Cu1	0.21554 (4)	0.28617 (2)	0.62467 (2)	0.03940 (11)
O1	0.3640 (2)	0.41083 (14)	0.59461 (8)	0.0471 (4)
O2	0.5331 (3)	0.34615 (16)	0.67869 (10)	0.0581 (5)
O3	1.0718 (2)	0.38395 (14)	0.68503 (8)	0.0457 (4)
O4	0.9260 (3)	0.37395 (14)	0.58714 (8)	0.0512 (4)
O7	0.6289 (4)	0.3189 (3)	0.81373 (13)	0.1013 (10)
H7A	0.604 (7)	0.321 (5)	0.7735 (10)	0.152*
H7B	0.535 (4)	0.302 (4)	0.834 (2)	0.152*
O8	0.9959 (4)	0.3821 (3)	0.82634 (12)	0.0839 (7)
H8C	1.023 (7)	0.387 (4)	0.7861 (12)	0.126*
H8D	0.892 (4)	0.353 (4)	0.826 (3)	0.126*
N1	0.1142 (4)	0.14824 (18)	0.66575 (12)	0.0592 (6)
N2	0.3026 (3)	0.19183 (18)	0.54703 (11)	0.0545 (5)
C1	0.2261 (7)	0.1220 (4)	0.7259 (2)	0.1078 (15)
H1A	0.356188	0.117338	0.714512	0.129*	0.495 (18)
H1B	0.210105	0.177807	0.759095	0.129*	0.495 (18)
H1C	0.185516	0.053701	0.743793	0.129*	0.495 (18)
H1D	0.145018	0.115226	0.763755	0.129*	0.505 (18)
H1E	0.291101	0.054757	0.719171	0.129*	0.505 (18)
H1F	0.315690	0.178863	0.734474	0.129*	0.505 (18)
C2	−0.0839 (5)	0.1548 (3)	0.6849 (3)	0.1029 (15)
H2A	−0.160188	0.172027	0.645981	0.124*	0.505 (18)
H2B	−0.122672	0.086297	0.703029	0.124*	0.505 (18)
H2C	−0.098082	0.210404	0.718331	0.124*	0.505 (18)
H2D	−0.093773	0.140458	0.732246	0.124*	0.495 (18)
H2E	−0.131289	0.226188	0.675199	0.124*	0.495 (18)
H2F	−0.155879	0.102082	0.659896	0.124*	0.495 (18)
C3	0.086 (3)	0.0712 (12)	0.6087 (8)	0.085 (4)	0.495 (18)
H3A	−0.018047	0.093743	0.579712	0.102*	0.495 (18)
H3B	0.062106	−0.001667	0.624964	0.102*	0.495 (18)
C3A	0.179 (2)	0.0582 (10)	0.6193 (8)	0.077 (3)	0.505 (18)
H3AA	0.302001	0.033292	0.633975	0.093*	0.505 (18)
H3AB	0.092507	−0.002668	0.622077	0.093*	0.505 (18)
C4	0.276 (3)	0.0761 (8)	0.5704 (6)	0.079 (3)	0.495 (18)
H4A	0.378964	0.054535	0.600078	0.095*	0.495 (18)
H4B	0.271645	0.027282	0.532075	0.095*	0.495 (18)
C4A	0.187 (2)	0.0950 (11)	0.5496 (7)	0.087 (4)	0.505 (18)
H4AA	0.239477	0.038474	0.521768	0.105*	0.505 (18)
H4AB	0.060916	0.111090	0.532601	0.105*	0.505 (18)
C5	0.2202 (9)	0.2343 (5)	0.4859 (2)	0.144 (3)
H5A	0.086425	0.238681	0.490305	0.173*	0.495 (18)
H5B	0.269870	0.305336	0.477526	0.173*	0.495 (18)
H5C	0.249344	0.187114	0.449077	0.173*	0.495 (18)
H5D	0.317334	0.248739	0.454300	0.173*	0.505 (18)
H5E	0.133889	0.182085	0.467080	0.173*	0.505 (18)
H5F	0.154415	0.300307	0.495528	0.173*	0.505 (18)
C6	0.5040 (6)	0.1852 (4)	0.5403 (3)	0.1154 (17)
H6A	0.559369	0.156878	0.581131	0.138*	0.505 (18)
H6B	0.533023	0.138122	0.503435	0.138*	0.505 (18)
H6C	0.553549	0.256345	0.531883	0.138*	0.505 (18)
H6D	0.537925	0.210685	0.496501	0.138*	0.495 (18)
H6E	0.564271	0.229441	0.574198	0.138*	0.495 (18)
H6F	0.543745	0.111219	0.545750	0.138*	0.495 (18)
C7	0.5046 (3)	0.41647 (19)	0.63531 (12)	0.0424 (5)
C8	0.6324 (4)	0.51218 (19)	0.62714 (14)	0.0484 (6)
H8A	0.566631	0.577064	0.641138	0.058*
H8B	0.659682	0.520189	0.579733	0.058*
C9	0.8161 (4)	0.5050 (2)	0.66639 (14)	0.0510 (6)
H9A	0.882166	0.573443	0.662250	0.061*
H9B	0.789224	0.494519	0.713636	0.061*
C10	0.9432 (3)	0.41491 (19)	0.64394 (12)	0.0409 (5)
O5	0.7915 (5)	0.3966 (2)	0.45643 (13)	0.1012 (10)
H5G	0.751 (8)	0.454 (3)	0.443 (3)	0.152*
H5H	0.827 (8)	0.399 (5)	0.4946 (13)	0.152*
O6	0.8144 (4)	0.2050 (2)	0.39169 (17)	0.0906 (8)
H6G	0.801 (7)	0.263 (3)	0.411 (2)	0.136*
H6H	0.715 (5)	0.197 (4)	0.369 (2)	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03491 (16)	0.04272 (17)	0.04064 (16)	0.00251 (12)	0.00232 (10)	0.00379 (11)
O1	0.0359 (9)	0.0524 (9)	0.0529 (9)	0.0013 (7)	−0.0021 (7)	0.0085 (7)
O2	0.0532 (11)	0.0621 (11)	0.0589 (11)	−0.0009 (9)	−0.0042 (8)	0.0186 (9)
O3	0.0373 (9)	0.0555 (10)	0.0443 (9)	0.0048 (7)	−0.0012 (7)	−0.0012 (7)
O4	0.0481 (10)	0.0573 (10)	0.0482 (9)	0.0097 (8)	−0.0044 (7)	−0.0052 (8)
O7	0.0633 (15)	0.182 (3)	0.0581 (14)	−0.0182 (18)	−0.0042 (11)	0.0190 (17)
O8	0.0686 (15)	0.124 (2)	0.0586 (12)	−0.0156 (14)	−0.0081 (11)	0.0052 (14)
N1	0.0668 (15)	0.0447 (11)	0.0665 (14)	0.0005 (11)	0.0140 (11)	0.0083 (10)
N2	0.0558 (13)	0.0586 (13)	0.0494 (12)	0.0057 (10)	0.0066 (10)	−0.0055 (10)
C1	0.115 (3)	0.107 (3)	0.101 (3)	0.013 (3)	−0.002 (2)	0.059 (3)
C2	0.068 (2)	0.078 (2)	0.164 (4)	−0.0142 (19)	0.028 (2)	0.037 (3)
C3	0.101 (10)	0.061 (6)	0.095 (7)	−0.012 (7)	0.034 (8)	−0.005 (5)
C3A	0.076 (7)	0.045 (4)	0.112 (8)	0.000 (5)	0.020 (7)	0.004 (4)
C4	0.116 (10)	0.055 (4)	0.069 (6)	0.017 (5)	0.026 (6)	−0.002 (4)
C4A	0.096 (8)	0.066 (6)	0.100 (8)	−0.023 (5)	0.011 (6)	−0.031 (6)
C5	0.208 (6)	0.169 (5)	0.055 (2)	0.100 (5)	−0.035 (3)	−0.033 (3)
C6	0.067 (2)	0.148 (4)	0.132 (4)	0.014 (3)	0.026 (2)	−0.067 (3)
C7	0.0361 (12)	0.0459 (12)	0.0453 (12)	0.0079 (10)	0.0072 (9)	0.0023 (10)
C8	0.0395 (13)	0.0412 (12)	0.0646 (15)	0.0047 (10)	0.0023 (11)	0.0016 (11)
C9	0.0414 (13)	0.0450 (13)	0.0664 (16)	0.0019 (11)	−0.0021 (11)	−0.0103 (11)
C10	0.0337 (12)	0.0433 (11)	0.0459 (12)	−0.0035 (9)	0.0034 (9)	0.0006 (10)
O5	0.170 (3)	0.0614 (13)	0.0705 (15)	0.0345 (16)	−0.0484 (17)	−0.0091 (12)
O6	0.0686 (16)	0.0971 (19)	0.106 (2)	0.0074 (14)	0.0017 (13)	−0.0434 (15)

Geometric parameters (Å, º) top

Cu1—O1	1.9639 (17)	C3—H3A	0.9700
Cu1—O3ⁱ	1.9958 (16)	C3—H3B	0.9700
Cu1—O4ⁱ	2.4315 (17)	C3—C4	1.56 (2)
Cu1—N1	2.024 (2)	C3A—H3AA	0.9700
Cu1—N2	2.038 (2)	C3A—H3AB	0.9700
Cu1—C10ⁱ	2.540 (2)	C3A—C4A	1.46 (2)
O1—C7	1.275 (3)	C4—H4A	0.9700
O2—C7	1.236 (3)	C4—H4B	0.9700
O3—C10	1.273 (3)	C4A—H4AA	0.9700
O4—C10	1.239 (3)	C4A—H4AB	0.9700
O7—H7A	0.815 (19)	C5—H5A	0.9600
O7—H7B	0.812 (10)	C5—H5B	0.9600
O8—H8C	0.828 (19)	C5—H5C	0.9600
O8—H8D	0.827 (19)	C5—H5D	0.9600
N1—C1	1.459 (5)	C5—H5E	0.9600
N1—C2	1.470 (4)	C5—H5F	0.9600
N1—C3	1.489 (14)	C6—H6A	0.9600
N1—C3A	1.520 (14)	C6—H6B	0.9600
N2—C4	1.513 (10)	C6—H6C	0.9600
N2—C4A	1.453 (11)	C6—H6D	0.9600
N2—C5	1.436 (5)	C6—H6E	0.9600
N2—C6	1.445 (4)	C6—H6F	0.9600
C1—H1A	0.9600	C7—C8	1.500 (3)
C1—H1B	0.9600	C8—H8A	0.9700
C1—H1C	0.9600	C8—H8B	0.9700
C1—H1D	0.9600	C8—C9	1.512 (3)
C1—H1E	0.9600	C9—H9A	0.9700
C1—H1F	0.9600	C9—H9B	0.9700
C2—H2A	0.9600	C9—C10	1.504 (3)
C2—H2B	0.9600	O5—H5G	0.80 (2)
C2—H2C	0.9600	O5—H5H	0.794 (19)
C2—H2D	0.9600	O6—H6G	0.821 (19)
C2—H2E	0.9600	O6—H6H	0.835 (19)
C2—H2F	0.9600

O1—Cu1—O3ⁱ	89.80 (7)	C4—C3—H3B	111.0
O1—Cu1—O4ⁱ	91.00 (7)	N1—C3A—H3AA	109.3
O1—Cu1—N1	167.77 (9)	N1—C3A—H3AB	109.3
O1—Cu1—N2	92.40 (8)	H3AA—C3A—H3AB	108.0
O1—Cu1—C10ⁱ	88.56 (7)	C4A—C3A—N1	111.5 (11)
O3ⁱ—Cu1—O4ⁱ	58.26 (6)	C4A—C3A—H3AA	109.3
O3ⁱ—Cu1—N1	94.20 (8)	C4A—C3A—H3AB	109.3
O3ⁱ—Cu1—N2	165.06 (8)	N2—C4—C3	107.6 (10)
O3ⁱ—Cu1—C10ⁱ	29.61 (7)	N2—C4—H4A	110.2
O4ⁱ—Cu1—C10ⁱ	28.77 (6)	N2—C4—H4B	110.2
N1—Cu1—O4ⁱ	100.93 (8)	C3—C4—H4A	110.2
N1—Cu1—N2	86.72 (9)	C3—C4—H4B	110.2
N1—Cu1—C10ⁱ	100.59 (9)	H4A—C4—H4B	108.5
N2—Cu1—O4ⁱ	106.90 (8)	N2—C4A—C3A	108.8 (11)
N2—Cu1—C10ⁱ	135.64 (9)	N2—C4A—H4AA	109.9
C7—O1—Cu1	105.67 (14)	N2—C4A—H4AB	109.9
C10—O3—Cu1ⁱⁱ	99.60 (14)	C3A—C4A—H4AA	109.9
C10—O4—Cu1ⁱⁱ	80.46 (14)	C3A—C4A—H4AB	109.9
H7A—O7—H7B	109 (2)	H4AA—C4A—H4AB	108.3
H8C—O8—H8D	105 (5)	N2—C5—H5A	109.5
C1—N1—Cu1	108.8 (2)	N2—C5—H5B	109.5
C1—N1—C2	108.1 (3)	N2—C5—H5C	109.5
C1—N1—C3	123.0 (8)	H5A—C5—H5B	109.5
C1—N1—C3A	99.7 (6)	H5A—C5—H5C	109.5
C2—N1—Cu1	114.2 (2)	H5B—C5—H5C	109.5
C2—N1—C3	96.8 (7)	H5D—C5—H5E	109.5
C2—N1—C3A	120.0 (6)	H5D—C5—H5F	109.5
C3—N1—Cu1	105.8 (5)	H5E—C5—H5F	109.5
C3A—N1—Cu1	104.7 (5)	N2—C6—H6A	109.5
C4—N2—Cu1	105.2 (4)	N2—C6—H6B	109.5
C4A—N2—Cu1	105.0 (5)	N2—C6—H6C	109.5
C5—N2—Cu1	107.9 (2)	H6A—C6—H6B	109.5
C5—N2—C4	123.4 (8)	H6A—C6—H6C	109.5
C5—N2—C4A	96.1 (8)	H6B—C6—H6C	109.5
C5—N2—C6	109.4 (4)	H6D—C6—H6E	109.5
C6—N2—Cu1	114.8 (2)	H6D—C6—H6F	109.5
C6—N2—C4	96.2 (7)	H6E—C6—H6F	109.5
C6—N2—C4A	121.6 (7)	O1—C7—C8	116.4 (2)
N1—C1—H1A	109.5	O2—C7—O1	121.3 (2)
N1—C1—H1B	109.5	O2—C7—C8	122.3 (2)
N1—C1—H1C	109.5	C7—C8—H8A	108.6
H1A—C1—H1B	109.5	C7—C8—H8B	108.6
H1A—C1—H1C	109.5	C7—C8—C9	114.7 (2)
H1B—C1—H1C	109.5	H8A—C8—H8B	107.6
H1D—C1—H1E	109.5	C9—C8—H8A	108.6
H1D—C1—H1F	109.5	C9—C8—H8B	108.6
H1E—C1—H1F	109.5	C8—C9—H9A	108.7
N1—C2—H2A	109.5	C8—C9—H9B	108.7
N1—C2—H2B	109.5	H9A—C9—H9B	107.6
N1—C2—H2C	109.5	C10—C9—C8	114.2 (2)
H2A—C2—H2B	109.5	C10—C9—H9A	108.7
H2A—C2—H2C	109.5	C10—C9—H9B	108.7
H2B—C2—H2C	109.5	O3—C10—Cu1ⁱⁱ	50.79 (11)
H2D—C2—H2E	109.5	O3—C10—C9	117.4 (2)
H2D—C2—H2F	109.5	O4—C10—Cu1ⁱⁱ	70.77 (13)
H2E—C2—H2F	109.5	O4—C10—O3	121.2 (2)
N1—C3—H3A	111.0	O4—C10—C9	121.4 (2)
N1—C3—H3B	111.0	C9—C10—Cu1ⁱⁱ	166.01 (17)
N1—C3—C4	104.0 (13)	H5G—O5—H5H	113 (5)
H3A—C3—H3B	109.0	H6G—O6—H6H	105 (3)
C4—C3—H3A	111.0

Cu1—O1—C7—O2	5.8 (3)	N1—C3A—C4A—N2	54.0 (19)
Cu1—O1—C7—C8	−174.58 (16)	C1—N1—C3—C4	−76.7 (11)
Cu1ⁱⁱ—O3—C10—O4	7.5 (3)	C1—N1—C3A—C4A	−145.2 (12)
Cu1ⁱⁱ—O3—C10—C9	−171.00 (18)	C2—N1—C3—C4	166.6 (11)
Cu1ⁱⁱ—O4—C10—O3	−6.2 (2)	C2—N1—C3A—C4A	97.2 (12)
Cu1ⁱⁱ—O4—C10—C9	172.3 (2)	C5—N2—C4—C3	−84.0 (12)
Cu1—N1—C3—C4	49.0 (13)	C5—N2—C4A—C3A	−155.7 (13)
Cu1—N1—C3A—C4A	−32.7 (14)	C6—N2—C4—C3	157.9 (13)
Cu1—N2—C4—C3	40.1 (15)	C6—N2—C4A—C3A	87.1 (12)
Cu1—N2—C4A—C3A	−45.4 (15)	C7—C8—C9—C10	65.1 (3)
O1—C7—C8—C9	−168.5 (2)	C8—C9—C10—Cu1ⁱⁱ	169.4 (6)
O2—C7—C8—C9	11.1 (3)	C8—C9—C10—O3	−160.5 (2)
N1—C3—C4—N2	−60.5 (18)	C8—C9—C10—O4	20.9 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5H···O4	0.79 (2)	1.98 (2)	2.763 (3)	169 (6)
O6—H6G···O5	0.82 (2)	1.88 (2)	2.694 (3)	175 (5)
O7—H7A···O2	0.82 (2)	1.96 (2)	2.774 (3)	172 (6)
O8—H8C···O3	0.83 (2)	2.04 (2)	2.869 (3)	173 (5)
O8—H8D···O7	0.83 (2)	1.93 (2)	2.733 (4)	165 (5)
O7—H7B···O6ⁱⁱⁱ	0.81 (1)	1.97 (2)	2.763 (4)	167 (6)
O5—H5G···O1^iv	0.80 (2)	2.00 (2)	2.799 (3)	176 (6)
O6—H6H···O8^v	0.84 (2)	2.01 (2)	2.803 (4)	157 (5)

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

Funding information

This study was supported by Ondokuz Mayıs University under project No. PYO·FEN.1906.19.001.

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