Crystal structure of (N,N′-ethyl­enebis{3-[2-(3-nitro­phen­yl)hydrazin-1-yl­idene]-4-oxo­pentan-2-iminato})copper(II)–3-[2-(3-nitro­phen­yl)hydrazin-1-yl­idene]pentane-2,4-dione (1/1)

Marten, J.; Seichter, W.; Weber, E.

doi:10.1107/S2056989019005838

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ISSN: 2056-9890

Volume 75| Part 6| June 2019| Pages 834-837

https://doi.org/10.1107/S2056989019005838

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Crystal structure of (N,N′-ethylenebis{3-[2-(3-nitrophenyl)hydrazin-1-ylidene]-4-oxopentan-2-iminato})copper(II)–3-[2-(3-nitrophenyl)hydrazin-1-ylidene]pentane-2,4-dione (1/1)

Jan Marten,^a Wilhelm Seichter ^a and Edwin Weber ^a ^*

^aTU Bergakademie Freiberg, Leipziger Str. 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 22 March 2019; accepted 28 April 2019; online 21 May 2019)

In the title 1:1 co-crystal, [Cu(C₂₄H₂₄N₈O₆)]·C₁₁H₁₁N₃O₄, each of the crystal components forms undulating layers which stack alternately along the b-axis direction. Molecules of the Cu^II complex are connected via C—H⋯O hydrogen bonds involving the nitro and keto oxygen atoms, thus forming supramolecular networks. Molecules of the arylhydrazone component are linked by C—H⋯O interactions into zigzag strands showing no interstrand association.

Keywords: crystal structure; arylhydrazone; Cu^II chelate; two-component crystal; molecular layer formation; C—H⋯O hydrogen bonding.

CCDC reference: 1912679

1. Chemical context

Hydrazone imines derived from β-diketones and aryldiazonium salts using a Japp–Klingemann route (Phillips, 1959 ) have attracted considerable interest as precursors of potential antidiabetic drugs (Garg & Prakash, 1971 ; Küçükgüzel et al., 1999 ) as well as regarding their particular property of hydrogen bonding (Marten et al., 2007 ; Sethukumar & Arul Prakasam, 2010 ) and their remarkable behavior in the formation of metal complexes. Transition-metal chelates of the respective hydrazine imines have been described in great numbers (Albert et al., 1997 ; Mishra et al., 2000 ; Marten et al., 2005 ). Preferentially, the chelates with Cu^II, Co^II and Ni^II show a tetrahedrally distorted square N₂O₂ coordination environment. In the presence of a diamine and Ni^II, related bis(hydrazonoimine) complexes are formed displaying an unusual behavior of the effective magnetic moment at low temperature (Khudina et al., 2007 ). A corresponding chelate complex, formed of 3-[2-(3-nitrophenyl)hydrazin-1-ylidene]pentane-2,4-dione (Marten et al., 2018 ) and bis(ethylenediamine)copper(II) chloride yielded a co-crystal consisting of N,N′-ethylenebis{3-[2-(3-nitrophenyl)hydrazine-1-ylidene]-4-oxopentane-2-iminato}copper(II) and 3-[2-(3-nitrophenyl)hydrazine-1-ylidene]pentane-2,4-dione in a 1:1 stoichiometric composition (the title compound), whose crystal structure is reported on herein.

2. Structural commentary

The title co-crystal possesses orthorhombic symmetry (space group Pbca) with one molecule of the Cu^II complex and one molecule of the arylhydrazone in the asymmetric unit. A perspective view is shown in Fig. 1. The metal center of the complex adopts a tetrahedrally distorted square coordination environment formed by four nitrogen atoms (N2, N4, N7, N8) of the ligand. As a result of the tetradentate coordination mode and the steric interaction between the terminal aromatic rings of the ligand, the complex molecule adopts a helical geometry with a distance of 3.384 (4) Å between the benzene ring centroids and a dihedral angle of 10.43 (4)° between the benzene ring planes. The Cu—N distances are 1.940 (2), 1.943 (2), 1.953 (2) and 1.957 (2) Å, the bond angles N7—Cu—N8, N7—Cu—N2, N8—Cu—N5 and N2—Cu—N5 are 86.3 (1), 88.4 (1), 89.1 (1) and 100.4 (1)°, respectively. The nitro groups deviate slightly from the planes of the respective benzene rings, with plane N3/O2/O3 being inclined to benzene ring C6–C11 of 3.8 (1)° and plane N6/O5/O6 being inclined to benzene ring C17–C22 by 5.1 (2)° between the nitro groups and the respective benzene rings. The conformation of the arylhydrazone component is nearly identical with that found in the reported structure of this compound (Marten et al., 2018). The molecule features an intramolecular N—H⋯O=C interaction that yields a six-membered hydrogen-bonded ring. The dihedral angle between the mean plane of this ring and the aromatic ring is 7.8 (2)°. The nitro group is tilted at an angle of 5.8 (2)° with respect to the benzene ring.

Figure 1
Perspective view of an asymmetric unit of the title co-crystal with atom labeling. Displacement ellipsoids of non-H atoms are shown at the 40% probability level.

3. Supramolecular features

In the crystal, the Cu^II complexes as well as the arylhydrazone molecules form undulating layers extending parallel to the ac plane and arranged in an alternating order along the b-axis direction (Fig. 2). Within a layer of complexes, one carbonyl oxygen and one nitro group per molecule interact via C_arene—H⋯O hydrogen bonding (Desiraju & Steiner, 1999 ), thus generating a supramolecular network (Table 1, Fig. 3). The arylhydrazone molecules are connected by means of C_aryl—H⋯O_nitro interactions to form zigzag-like strands that run along the a-axis direction (Table 1, Fig. 4). No directed non-covalent bonds are observed between the supramolecular strands. In the stacking direction, the molecules are linked by C—H⋯O interactions involving a nitro oxygen atom of the arylhydrazone molecule and a methyl hydrogen of the coordinated ligand.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11A—H11A⋯O4Aⁱ	0.95	2.43	3.320 (3)	156
N2A—H2A⋯O1A	0.90 (1)	1.81 (2)	2.531 (3)	135 (3)
C22—H22⋯O1ⁱⁱ	0.95	2.27	3.207 (3)	169
C16—H16A⋯O5ⁱⁱⁱ	0.98	2.63	3.532 (3)	154
C12—H12B⋯O3A^iv	0.98	2.53	3.413 (3)	151
C11—H11⋯O3^v	0.95	2.50	3.350 (3)	150
C5—H5C⋯O3^v	0.98	2.65	3.426 (3)	137
C1—H1B⋯O3A^vi	0.98	2.58	3.490 (3)	154
C1—H1B⋯O1	0.98	2.34	2.842 (3)	111
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (ii) -x, -y, -z+1; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (vi) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Packing structure of the of the title co-crystal viewed down the crystallographic c axis. Dashed lines represent hydrogen bonds.

Figure 3
Structure of the Cu^II complex layer viewed along the b axis. The C—H⋯O interactions (Table 1

) are shown as dashed lines.

Figure 4
Layer structure of the arylhydrazone viewed along the b axis. Dashed lines represent the C—H⋯O interactions (Table 1

4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.38, update February 2017; Groom et al., 2016 ) revealed one hit for a crystal structure of a transition-metal complex containing a structurally related ligand species. The complex N,N′-ethylene-bis[3-(4-methylphenyl)hydrazono-4-oxo-5,5,6,6,7,7,8,8-octafluorooctane-2-iminato]nickel(II) (JIXQAJ; Khudina et al., 2007) adopts a helical geometry that resembles that of the title complex. As a result of the presence of two extended fluoroalkyl moieties, the pattern of intermolecular non-covalent bonding is dominated by C—H⋯F and F⋯F interactions (Reichenbächer et al., 2005 ), creating a three-dimensional supramolecular architecture. Unlike the title structure, in the reported crystal structure of 3-[2-(3-nitrophenyl)hydrazine-1-ylidene]pentane-2,4-dione (Marten et al., 2018) the molecules are connected via C_arene—H⋯O_nitro and C_arene—H⋯O_keto interactions giving rise to supramolecular sheets.

5. Synthesis and crystallization

A solution containing 3-[2-(3-nitrophenyl)hydrazine-1-ylidene]pentane-2,4-dione and bis(ethylenediamine)copper(II) chloride in n-butanol was heated for several hours. After cooling and storing the reaction solution, blue-colored crystals could be isolated which turned out to consist of the title compound.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH H atom of 3-[2-(3-nitrophenyl)-hydrazine-1-ylidene]pentane-2,4-dione was located in a difference-Fourier map and freely refined. The C-bound and N-bound H atoms were included in the model in calculated positions and refined as riding atoms: C—H = 0.95–0.99 Å with U_iso(H) = 1.5U_eq(C) for methyl and U_iso(H) = 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₂₄H₂₄N₈O₆)]·C₁₁H₁₁N₃O₄
M_r	833.28
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	153
a, b, c (Å)	15.5820 (5), 20.0517 (7), 23.3082 (8)
V (Å³)	7282.5 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.68
Crystal size (mm)	0.54 × 0.44 × 0.07

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.712, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	86372, 9862, 6112
R_int	0.106
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.130, 0.96
No. of reflections	9862
No. of parameters	524
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.68
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC reference: 1912679

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005838/yk2120sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005838/yk2120Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(N,N'-Ethylenebis{3-[2-(3-nitrophenyl)hydrazin-1-ylidene]-4-oxopentan-2-iminato})copper(II)–3-[2-(3-nitrophenyl)hydrazine-1-ylidene]pentane-2,4-dione (1/1) top

Crystal data top

[Cu(C₂₄H₂₄N₈O₆)]·C₁₁H₁₁N₃O₄	D_x = 1.520 Mg m⁻³
M_r = 833.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 8051 reflections
a = 15.5820 (5) Å	θ = 2.2–28.2°
b = 20.0517 (7) Å	µ = 0.68 mm⁻¹
c = 23.3082 (8) Å	T = 153 K
V = 7282.5 (4) Å³	Plate, blue
Z = 8	0.54 × 0.44 × 0.07 mm
F(000) = 3448

Data collection top

Bruker SMART APEXII diffractometer	6112 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.106
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 29.3°, θ_min = 2.2°
T_min = 0.712, T_max = 0.954	h = −20→21
86372 measured reflections	k = −27→25
9862 independent reflections	l = −31→28

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: mixed
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ²(F_o²) + (0.0736P)² + 0.2354P] where P = (F_o² + 2F_c²)/3
9862 reflections	(Δ/σ)_max = 0.001
524 parameters	Δρ_max = 1.00 e Å⁻³
1 restraint	Δρ_min = −0.67 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	0.23540 (2)	0.01555 (2)	0.46535 (2)	0.01874 (9)
O1	−0.07371 (10)	−0.09037 (9)	0.50519 (7)	0.0288 (4)
O2	0.46419 (12)	−0.03799 (13)	0.31472 (9)	0.0542 (6)
O3	0.43989 (13)	−0.02538 (13)	0.22515 (9)	0.0543 (6)
O4	0.56630 (10)	0.08866 (10)	0.47203 (8)	0.0357 (4)
O5	0.23463 (12)	0.16123 (9)	0.16939 (7)	0.0348 (4)
O6	0.35277 (12)	0.13307 (11)	0.21053 (8)	0.0419 (5)
N1	0.10026 (11)	−0.06399 (9)	0.41500 (7)	0.0171 (4)
N2	0.17823 (11)	−0.04081 (9)	0.40872 (7)	0.0181 (4)
N3	0.41581 (13)	−0.03341 (11)	0.27448 (9)	0.0293 (5)
N4	0.36211 (11)	0.10044 (9)	0.41302 (8)	0.0197 (4)
N5	0.27979 (11)	0.08627 (9)	0.41566 (7)	0.0180 (4)
N6	0.27544 (13)	0.14372 (10)	0.21161 (8)	0.0244 (4)
N7	0.18147 (11)	−0.03715 (10)	0.52509 (7)	0.0200 (4)
N8	0.31978 (12)	0.04022 (10)	0.52296 (8)	0.0208 (4)
C1	0.07728 (15)	−0.11055 (13)	0.57134 (10)	0.0282 (5)
H1A	0.1254	−0.1339	0.5895	0.042*
H1B	0.0352	−0.1432	0.5576	0.042*
H1C	0.0500	−0.0809	0.5994	0.042*
C2	0.10993 (14)	−0.06983 (11)	0.52124 (9)	0.0188 (4)
C3	0.06458 (13)	−0.07253 (11)	0.46652 (9)	0.0176 (4)
C4	−0.02728 (13)	−0.09027 (11)	0.46301 (10)	0.0203 (5)
C5	−0.06491 (15)	−0.10480 (14)	0.40497 (10)	0.0315 (6)
H5A	−0.1214	−0.1256	0.4096	0.047*
H5B	−0.0269	−0.1352	0.3840	0.047*
H5C	−0.0710	−0.0631	0.3834	0.047*
C6	0.20627 (13)	−0.04200 (11)	0.35057 (9)	0.0175 (4)
C7	0.29434 (13)	−0.04252 (11)	0.34078 (9)	0.0191 (4)
H7	0.3338	−0.0463	0.3717	0.023*
C8	0.32268 (14)	−0.03731 (12)	0.28491 (10)	0.0214 (5)
C9	0.26778 (15)	−0.03286 (11)	0.23830 (10)	0.0224 (5)
H9	0.2895	−0.0283	0.2004	0.027*
C10	0.18059 (15)	−0.03522 (11)	0.24867 (10)	0.0227 (5)
H10	0.1415	−0.0339	0.2174	0.027*
C11	0.14957 (14)	−0.03950 (11)	0.30421 (9)	0.0204 (5)
H11	0.0894	−0.0407	0.3108	0.025*
C12	0.44975 (16)	0.08755 (14)	0.56354 (11)	0.0351 (6)
H12A	0.4146	0.1030	0.5958	0.053*
H12B	0.4891	0.1232	0.5518	0.053*
H12C	0.4829	0.0483	0.5753	0.053*
C13	0.39251 (14)	0.06942 (11)	0.51413 (10)	0.0213 (5)
C14	0.41621 (13)	0.08968 (11)	0.45596 (9)	0.0204 (5)
C15	0.50662 (15)	0.10235 (12)	0.43992 (11)	0.0257 (5)
C16	0.52487 (15)	0.12956 (15)	0.38115 (11)	0.0377 (7)
H16A	0.5842	0.1457	0.3795	0.057*
H16B	0.4856	0.1665	0.3730	0.057*
H16C	0.5168	0.0943	0.3526	0.057*
C17	0.23544 (13)	0.10738 (10)	0.36559 (9)	0.0172 (4)
C18	0.27775 (13)	0.11919 (11)	0.31372 (9)	0.0191 (4)
H18	0.3385	0.1164	0.3114	0.023*
C19	0.22975 (14)	0.13491 (11)	0.26627 (9)	0.0200 (5)
C20	0.14114 (14)	0.14071 (11)	0.26706 (10)	0.0228 (5)
H20	0.1098	0.1516	0.2334	0.027*
C21	0.10001 (14)	0.12994 (11)	0.31900 (10)	0.0238 (5)
H21	0.0393	0.1339	0.3212	0.029*
C22	0.14640 (13)	0.11353 (11)	0.36762 (9)	0.0204 (5)
H22	0.1172	0.1064	0.4029	0.025*
C23	0.23529 (15)	−0.04049 (13)	0.57677 (10)	0.0249 (5)
H23A	0.2720	−0.0808	0.5752	0.030*
H23B	0.1984	−0.0437	0.6112	0.030*
C24	0.29118 (15)	0.02124 (13)	0.58082 (10)	0.0260 (5)
H24A	0.2582	0.0583	0.5982	0.031*
H24B	0.3416	0.0120	0.6055	0.031*
O1A	0.46165 (13)	0.22072 (15)	0.78627 (10)	0.0664 (7)
O2A	0.28475 (13)	0.17207 (10)	0.66034 (9)	0.0457 (5)
O3A	0.04080 (11)	0.24229 (10)	0.94118 (10)	0.0469 (5)
O4A	0.06525 (13)	0.25224 (11)	1.03186 (10)	0.0499 (6)
N1A	0.28478 (13)	0.20901 (10)	0.80646 (10)	0.0296 (5)
N2A	0.33228 (13)	0.21815 (11)	0.85192 (10)	0.0332 (5)
H2A	0.3888 (7)	0.2245 (15)	0.8469 (13)	0.051 (9)*
N3A	0.08951 (14)	0.24565 (11)	0.98228 (12)	0.0370 (6)
C1A	0.45036 (19)	0.21587 (17)	0.68630 (13)	0.0501 (8)
H1A1	0.5084	0.2346	0.6880	0.075*
H1A2	0.4142	0.2441	0.6619	0.075*
H1A3	0.4527	0.1707	0.6703	0.075*
C2A	0.41369 (17)	0.21322 (14)	0.74488 (13)	0.0386 (7)
C3A	0.32060 (16)	0.20372 (12)	0.75493 (11)	0.0295 (6)
C4A	0.25922 (17)	0.18854 (13)	0.70795 (13)	0.0341 (6)
C5A	0.16462 (17)	0.19307 (15)	0.71948 (13)	0.0423 (7)
H5A1	0.1413	0.2328	0.7006	0.063*
H5A2	0.1548	0.1962	0.7609	0.063*
H5A3	0.1360	0.1532	0.7045	0.063*
C6A	0.29704 (16)	0.22805 (12)	0.90680 (11)	0.0277 (5)
C7A	0.20906 (16)	0.22976 (12)	0.91655 (12)	0.0291 (6)
H7A	0.1691	0.2227	0.8864	0.035*
C8A	0.18222 (15)	0.24215 (12)	0.97171 (12)	0.0310 (6)
C9A	0.23753 (18)	0.25281 (14)	1.01735 (14)	0.0367 (6)
H9A	0.2164	0.2613	1.0549	0.044*
C10A	0.32440 (17)	0.25058 (13)	1.00628 (13)	0.0369 (6)
H10A	0.3642	0.2577	1.0366	0.044*
C11A	0.35401 (16)	0.23805 (13)	0.95142 (12)	0.0330 (6)
H11A	0.4140	0.2363	0.9443	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01805 (14)	0.02554 (15)	0.01264 (15)	−0.00435 (10)	−0.00054 (11)	0.00152 (11)
O1	0.0193 (8)	0.0433 (10)	0.0237 (10)	−0.0008 (7)	0.0055 (7)	0.0031 (8)
O2	0.0194 (10)	0.1091 (19)	0.0342 (12)	0.0037 (10)	−0.0026 (9)	0.0060 (12)
O3	0.0299 (11)	0.1047 (19)	0.0285 (12)	−0.0084 (11)	0.0138 (9)	−0.0071 (11)
O4	0.0180 (8)	0.0470 (11)	0.0420 (12)	−0.0009 (7)	−0.0038 (8)	0.0096 (9)
O5	0.0451 (11)	0.0437 (11)	0.0155 (9)	0.0029 (8)	−0.0008 (8)	0.0026 (8)
O6	0.0291 (10)	0.0713 (14)	0.0254 (11)	0.0017 (9)	0.0110 (8)	0.0074 (9)
N1	0.0152 (9)	0.0209 (9)	0.0152 (10)	−0.0009 (7)	0.0019 (7)	0.0002 (7)
N2	0.0149 (9)	0.0263 (10)	0.0132 (10)	−0.0015 (7)	0.0019 (7)	−0.0010 (7)
N3	0.0193 (10)	0.0425 (13)	0.0261 (12)	0.0009 (8)	0.0057 (9)	−0.0055 (9)
N4	0.0166 (9)	0.0229 (10)	0.0197 (10)	−0.0026 (7)	0.0023 (7)	−0.0014 (7)
N5	0.0160 (9)	0.0259 (10)	0.0122 (9)	−0.0009 (7)	0.0000 (7)	−0.0001 (7)
N6	0.0328 (12)	0.0263 (10)	0.0140 (11)	−0.0034 (8)	0.0029 (9)	−0.0022 (8)
N7	0.0187 (9)	0.0287 (10)	0.0125 (10)	−0.0021 (7)	−0.0001 (7)	0.0017 (7)
N8	0.0201 (9)	0.0283 (10)	0.0139 (10)	−0.0030 (8)	−0.0017 (7)	0.0000 (8)
C1	0.0287 (13)	0.0370 (14)	0.0189 (13)	−0.0090 (10)	0.0002 (10)	0.0064 (10)
C2	0.0189 (11)	0.0234 (11)	0.0142 (11)	0.0018 (8)	0.0021 (8)	0.0008 (8)
C3	0.0165 (10)	0.0212 (11)	0.0151 (11)	−0.0001 (8)	0.0018 (9)	0.0005 (9)
C4	0.0176 (11)	0.0249 (12)	0.0184 (12)	−0.0002 (8)	0.0006 (9)	0.0036 (9)
C5	0.0186 (12)	0.0507 (16)	0.0251 (14)	−0.0082 (11)	−0.0044 (10)	0.0038 (11)
C6	0.0196 (10)	0.0191 (10)	0.0138 (11)	−0.0022 (8)	0.0021 (9)	−0.0005 (8)
C7	0.0177 (10)	0.0251 (11)	0.0144 (11)	0.0009 (9)	−0.0019 (9)	−0.0019 (9)
C8	0.0162 (10)	0.0283 (12)	0.0196 (12)	−0.0002 (9)	0.0032 (9)	−0.0038 (9)
C9	0.0269 (12)	0.0280 (12)	0.0124 (11)	−0.0011 (9)	0.0047 (9)	−0.0022 (9)
C10	0.0253 (12)	0.0276 (12)	0.0150 (12)	0.0004 (9)	−0.0023 (9)	−0.0012 (9)
C11	0.0170 (11)	0.0245 (11)	0.0197 (12)	−0.0009 (8)	−0.0009 (9)	−0.0009 (9)
C12	0.0307 (14)	0.0470 (16)	0.0275 (15)	−0.0145 (12)	−0.0082 (11)	0.0006 (12)
C13	0.0202 (11)	0.0237 (12)	0.0200 (12)	−0.0013 (8)	−0.0007 (9)	0.0009 (9)
C14	0.0166 (10)	0.0246 (12)	0.0201 (13)	−0.0016 (8)	−0.0011 (9)	−0.0011 (9)
C15	0.0211 (12)	0.0276 (13)	0.0284 (14)	−0.0041 (9)	0.0002 (10)	−0.0010 (10)
C16	0.0212 (12)	0.0599 (19)	0.0320 (16)	−0.0085 (12)	0.0048 (11)	0.0052 (13)
C17	0.0181 (10)	0.0183 (10)	0.0152 (11)	−0.0027 (8)	−0.0004 (9)	−0.0016 (8)
C18	0.0179 (11)	0.0203 (11)	0.0191 (12)	−0.0031 (8)	0.0020 (9)	−0.0006 (9)
C19	0.0273 (12)	0.0196 (11)	0.0132 (11)	−0.0037 (9)	0.0043 (9)	0.0001 (8)
C20	0.0242 (12)	0.0240 (11)	0.0202 (13)	0.0011 (9)	−0.0042 (9)	0.0025 (9)
C21	0.0189 (11)	0.0285 (13)	0.0240 (13)	0.0024 (9)	0.0014 (9)	0.0015 (10)
C22	0.0200 (11)	0.0245 (11)	0.0168 (12)	−0.0001 (8)	0.0051 (9)	0.0020 (9)
C23	0.0241 (11)	0.0348 (13)	0.0157 (12)	−0.0046 (10)	−0.0034 (10)	0.0058 (10)
C24	0.0232 (11)	0.0399 (14)	0.0148 (12)	−0.0082 (10)	−0.0012 (10)	−0.0009 (10)
O1A	0.0253 (11)	0.125 (2)	0.0487 (15)	−0.0036 (13)	0.0007 (10)	−0.0065 (14)
O2A	0.0480 (12)	0.0499 (13)	0.0391 (13)	−0.0020 (9)	−0.0019 (10)	−0.0082 (10)
O3A	0.0217 (10)	0.0523 (13)	0.0666 (16)	0.0003 (8)	−0.0052 (10)	−0.0050 (11)
O4A	0.0394 (12)	0.0507 (13)	0.0598 (16)	−0.0008 (9)	0.0198 (11)	−0.0019 (10)
N1A	0.0268 (11)	0.0212 (10)	0.0408 (14)	0.0010 (8)	−0.0017 (10)	0.0022 (9)
N2A	0.0194 (11)	0.0390 (13)	0.0413 (15)	0.0025 (9)	−0.0025 (10)	0.0045 (10)
N3A	0.0273 (12)	0.0277 (12)	0.0561 (17)	−0.0010 (9)	0.0066 (12)	−0.0004 (11)
C1A	0.0426 (17)	0.058 (2)	0.050 (2)	−0.0103 (14)	0.0105 (15)	−0.0140 (15)
C2A	0.0309 (15)	0.0421 (16)	0.0430 (18)	0.0001 (12)	0.0060 (13)	−0.0037 (13)
C3A	0.0293 (13)	0.0230 (12)	0.0363 (16)	0.0030 (9)	0.0015 (11)	−0.0006 (10)
C4A	0.0338 (15)	0.0234 (13)	0.0451 (18)	0.0008 (10)	−0.0033 (13)	0.0007 (11)
C5A	0.0324 (15)	0.0404 (16)	0.054 (2)	−0.0016 (11)	−0.0050 (13)	−0.0117 (14)
C6A	0.0250 (12)	0.0260 (13)	0.0321 (15)	0.0032 (9)	0.0007 (11)	0.0049 (10)
C7A	0.0235 (12)	0.0246 (12)	0.0392 (16)	0.0001 (9)	−0.0047 (11)	0.0025 (10)
C8A	0.0193 (12)	0.0253 (13)	0.0483 (18)	0.0015 (9)	0.0018 (12)	0.0050 (11)
C9A	0.0367 (15)	0.0365 (15)	0.0369 (16)	0.0031 (11)	0.0011 (12)	0.0034 (12)
C10A	0.0309 (14)	0.0410 (15)	0.0388 (17)	0.0013 (11)	−0.0111 (13)	0.0055 (12)
C11A	0.0218 (12)	0.0347 (14)	0.0426 (18)	0.0023 (10)	−0.0012 (11)	0.0072 (11)

Geometric parameters (Å, º) top

Cu1—N7	1.9395 (18)	C15—C16	1.502 (3)
Cu1—N8	1.9434 (18)	C16—H16A	0.9800
Cu1—N2	1.9527 (18)	C16—H16B	0.9800
Cu1—N5	1.9573 (18)	C16—H16C	0.9800
O1—C4	1.221 (3)	C17—C22	1.394 (3)
O2—N3	1.207 (3)	C17—C18	1.397 (3)
O3—N3	1.220 (3)	C18—C19	1.372 (3)
O4—C15	1.225 (3)	C18—H18	0.9500
O5—N6	1.223 (2)	C19—C20	1.386 (3)
O6—N6	1.224 (3)	C20—C21	1.387 (3)
N1—N2	1.309 (2)	C20—H20	0.9500
N1—C3	1.334 (3)	C21—C22	1.384 (3)
N2—C6	1.424 (3)	C21—H21	0.9500
N3—C8	1.473 (3)	C22—H22	0.9500
N4—N5	1.315 (2)	C23—C24	1.516 (3)
N4—C14	1.326 (3)	C23—H23A	0.9900
N5—C17	1.421 (3)	C23—H23B	0.9900
N6—C19	1.470 (3)	C24—H24A	0.9900
N7—C2	1.296 (3)	C24—H24B	0.9900
N7—C23	1.469 (3)	O1A—C2A	1.230 (3)
N8—C13	1.292 (3)	O2A—C4A	1.224 (3)
N8—C24	1.471 (3)	O3A—N3A	1.224 (3)
C1—C2	1.513 (3)	O4A—N3A	1.223 (3)
C1—H1A	0.9800	N1A—N2A	1.305 (3)
C1—H1B	0.9800	N1A—C3A	1.329 (3)
C1—H1C	0.9800	N2A—C6A	1.406 (3)
C2—C3	1.459 (3)	N2A—H2A	0.898 (10)
C3—C4	1.477 (3)	N3A—C8A	1.467 (3)
C4—C5	1.503 (3)	C1A—C2A	1.481 (4)
C5—H5A	0.9800	C1A—H1A1	0.9800
C5—H5B	0.9800	C1A—H1A2	0.9800
C5—H5C	0.9800	C1A—H1A3	0.9800
C6—C7	1.391 (3)	C2A—C3A	1.482 (4)
C6—C11	1.397 (3)	C3A—C4A	1.485 (4)
C7—C8	1.379 (3)	C4A—C5A	1.501 (4)
C7—H7	0.9500	C5A—H5A1	0.9800
C8—C9	1.386 (3)	C5A—H5A2	0.9800
C9—C10	1.381 (3)	C5A—H5A3	0.9800
C9—H9	0.9500	C6A—C11A	1.382 (4)
C10—C11	1.385 (3)	C6A—C7A	1.390 (4)
C10—H10	0.9500	C7A—C8A	1.375 (4)
C11—H11	0.9500	C7A—H7A	0.9500
C12—C13	1.501 (3)	C8A—C9A	1.386 (4)
C12—H12A	0.9800	C9A—C10A	1.379 (4)
C12—H12B	0.9800	C9A—H9A	0.9500
C12—H12C	0.9800	C10A—C11A	1.382 (4)
C13—C14	1.463 (3)	C10A—H10A	0.9500
C14—C15	1.479 (3)	C11A—H11A	0.9500

N7—Cu1—N8	86.32 (8)	C15—C16—H16B	109.5
N7—Cu1—N2	88.42 (8)	H16A—C16—H16B	109.5
N8—Cu1—N2	157.38 (8)	C15—C16—H16C	109.5
N7—Cu1—N5	166.59 (8)	H16A—C16—H16C	109.5
N8—Cu1—N5	89.16 (7)	H16B—C16—H16C	109.5
N2—Cu1—N5	100.40 (7)	C22—C17—C18	119.0 (2)
N2—N1—C3	122.21 (18)	C22—C17—N5	118.85 (18)
N1—N2—C6	112.66 (17)	C18—C17—N5	122.12 (18)
N1—N2—Cu1	123.59 (14)	C19—C18—C17	118.63 (19)
C6—N2—Cu1	120.87 (13)	C19—C18—H18	120.7
O2—N3—O3	123.4 (2)	C17—C18—H18	120.7
O2—N3—C8	118.9 (2)	C18—C19—C20	123.5 (2)
O3—N3—C8	117.7 (2)	C18—C19—N6	117.53 (19)
N5—N4—C14	123.34 (18)	C20—C19—N6	118.9 (2)
N4—N5—C17	111.82 (17)	C19—C20—C21	117.3 (2)
N4—N5—Cu1	121.92 (14)	C19—C20—H20	121.3
C17—N5—Cu1	122.01 (13)	C21—C20—H20	121.3
O5—N6—O6	123.0 (2)	C22—C21—C20	120.7 (2)
O5—N6—C19	118.68 (19)	C22—C21—H21	119.6
O6—N6—C19	118.27 (19)	C20—C21—H21	119.6
C2—N7—C23	121.64 (18)	C21—C22—C17	120.9 (2)
C2—N7—Cu1	126.75 (15)	C21—C22—H22	119.6
C23—N7—Cu1	111.48 (13)	C17—C22—H22	119.6
C13—N8—C24	121.95 (19)	N7—C23—C24	109.98 (19)
C13—N8—Cu1	126.78 (16)	N7—C23—H23A	109.7
C24—N8—Cu1	111.27 (13)	C24—C23—H23A	109.7
C2—C1—H1A	109.5	N7—C23—H23B	109.7
C2—C1—H1B	109.5	C24—C23—H23B	109.7
H1A—C1—H1B	109.5	H23A—C23—H23B	108.2
C2—C1—H1C	109.5	N8—C24—C23	109.15 (18)
H1A—C1—H1C	109.5	N8—C24—H24A	109.8
H1B—C1—H1C	109.5	C23—C24—H24A	109.8
N7—C2—C3	119.72 (19)	N8—C24—H24B	109.8
N7—C2—C1	120.57 (19)	C23—C24—H24B	109.8
C3—C2—C1	119.46 (19)	H24A—C24—H24B	108.3
N1—C3—C2	125.46 (19)	N2A—N1A—C3A	120.5 (2)
N1—C3—C4	112.64 (18)	N1A—N2A—C6A	122.5 (2)
C2—C3—C4	121.77 (19)	N1A—N2A—H2A	118 (2)
O1—C4—C3	122.0 (2)	C6A—N2A—H2A	119 (2)
O1—C4—C5	119.6 (2)	O4A—N3A—O3A	123.6 (2)
C3—C4—C5	118.32 (19)	O4A—N3A—C8A	117.9 (2)
C4—C5—H5A	109.5	O3A—N3A—C8A	118.5 (2)
C4—C5—H5B	109.5	C2A—C1A—H1A1	109.5
H5A—C5—H5B	109.5	C2A—C1A—H1A2	109.5
C4—C5—H5C	109.5	H1A1—C1A—H1A2	109.5
H5A—C5—H5C	109.5	C2A—C1A—H1A3	109.5
H5B—C5—H5C	109.5	H1A1—C1A—H1A3	109.5
C7—C6—C11	119.83 (19)	H1A2—C1A—H1A3	109.5
C7—C6—N2	117.31 (18)	O1A—C2A—C1A	119.0 (3)
C11—C6—N2	122.79 (19)	O1A—C2A—C3A	119.1 (3)
C8—C7—C6	118.0 (2)	C1A—C2A—C3A	121.9 (3)
C8—C7—H7	121.0	N1A—C3A—C2A	122.9 (2)
C6—C7—H7	121.0	N1A—C3A—C4A	114.4 (2)
C7—C8—C9	123.2 (2)	C2A—C3A—C4A	122.7 (2)
C7—C8—N3	118.4 (2)	O2A—C4A—C3A	121.0 (2)
C9—C8—N3	118.4 (2)	O2A—C4A—C5A	119.8 (2)
C10—C9—C8	117.9 (2)	C3A—C4A—C5A	119.2 (2)
C10—C9—H9	121.0	C4A—C5A—H5A1	109.5
C8—C9—H9	121.0	C4A—C5A—H5A2	109.5
C9—C10—C11	120.6 (2)	H5A1—C5A—H5A2	109.5
C9—C10—H10	119.7	C4A—C5A—H5A3	109.5
C11—C10—H10	119.7	H5A1—C5A—H5A3	109.5
C10—C11—C6	120.3 (2)	H5A2—C5A—H5A3	109.5
C10—C11—H11	119.8	C11A—C6A—C7A	120.5 (2)
C6—C11—H11	119.8	C11A—C6A—N2A	117.0 (2)
C13—C12—H12A	109.5	C7A—C6A—N2A	122.5 (2)
C13—C12—H12B	109.5	C8A—C7A—C6A	117.2 (2)
H12A—C12—H12B	109.5	C8A—C7A—H7A	121.4
C13—C12—H12C	109.5	C6A—C7A—H7A	121.4
H12A—C12—H12C	109.5	C7A—C8A—C9A	123.8 (2)
H12B—C12—H12C	109.5	C7A—C8A—N3A	117.7 (2)
N8—C13—C14	119.7 (2)	C9A—C8A—N3A	118.4 (2)
N8—C13—C12	120.6 (2)	C10A—C9A—C8A	117.5 (3)
C14—C13—C12	119.6 (2)	C10A—C9A—H9A	121.2
N4—C14—C13	125.75 (19)	C8A—C9A—H9A	121.2
N4—C14—C15	112.74 (19)	C9A—C10A—C11A	120.4 (3)
C13—C14—C15	121.5 (2)	C9A—C10A—H10A	119.8
O4—C15—C14	122.0 (2)	C11A—C10A—H10A	119.8
O4—C15—C16	119.7 (2)	C6A—C11A—C10A	120.5 (2)
C14—C15—C16	118.2 (2)	C6A—C11A—H11A	119.7
C15—C16—H16A	109.5	C10A—C11A—H11A	119.7

C3—N1—N2—C6	174.16 (18)	N4—N5—C17—C22	−162.16 (19)
C3—N1—N2—Cu1	−25.0 (3)	Cu1—N5—C17—C22	40.6 (3)
C14—N4—N5—C17	175.52 (19)	N4—N5—C17—C18	20.8 (3)
C14—N4—N5—Cu1	−27.2 (3)	Cu1—N5—C17—C18	−136.36 (17)
C23—N7—C2—C3	−171.5 (2)	C22—C17—C18—C19	−1.5 (3)
Cu1—N7—C2—C3	4.0 (3)	N5—C17—C18—C19	175.48 (19)
C23—N7—C2—C1	2.7 (3)	C17—C18—C19—C20	1.0 (3)
Cu1—N7—C2—C1	178.17 (17)	C17—C18—C19—N6	−176.94 (18)
N2—N1—C3—C2	−12.0 (3)	O5—N6—C19—C18	−176.2 (2)
N2—N1—C3—C4	172.09 (19)	O6—N6—C19—C18	3.9 (3)
N7—C2—C3—N1	23.5 (3)	O5—N6—C19—C20	5.9 (3)
C1—C2—C3—N1	−150.7 (2)	O6—N6—C19—C20	−174.1 (2)
N7—C2—C3—C4	−161.0 (2)	C18—C19—C20—C21	0.1 (3)
C1—C2—C3—C4	24.8 (3)	N6—C19—C20—C21	177.9 (2)
N1—C3—C4—O1	−168.9 (2)	C19—C20—C21—C22	−0.5 (3)
C2—C3—C4—O1	15.1 (3)	C20—C21—C22—C17	0.0 (3)
N1—C3—C4—C5	7.6 (3)	C18—C17—C22—C21	1.1 (3)
C2—C3—C4—C5	−168.4 (2)	N5—C17—C22—C21	−176.0 (2)
N1—N2—C6—C7	−156.94 (19)	C2—N7—C23—C24	−156.1 (2)
Cu1—N2—C6—C7	41.6 (2)	Cu1—N7—C23—C24	27.8 (2)
N1—N2—C6—C11	26.1 (3)	C13—N8—C24—C23	−149.4 (2)
Cu1—N2—C6—C11	−135.30 (18)	Cu1—N8—C24—C23	30.5 (2)
C11—C6—C7—C8	3.0 (3)	N7—C23—C24—N8	−37.7 (3)
N2—C6—C7—C8	−173.99 (19)	C3A—N1A—N2A—C6A	176.1 (2)
C6—C7—C8—C9	−1.2 (3)	N2A—N1A—C3A—C2A	−5.2 (4)
C6—C7—C8—N3	176.08 (19)	N2A—N1A—C3A—C4A	175.8 (2)
O2—N3—C8—C7	3.4 (3)	O1A—C2A—C3A—N1A	6.4 (4)
O3—N3—C8—C7	−176.3 (2)	C1A—C2A—C3A—N1A	−171.8 (2)
O2—N3—C8—C9	−179.2 (2)	O1A—C2A—C3A—C4A	−174.6 (3)
O3—N3—C8—C9	1.1 (3)	C1A—C2A—C3A—C4A	7.2 (4)
C7—C8—C9—C10	−1.4 (3)	N1A—C3A—C4A—O2A	−168.4 (2)
N3—C8—C9—C10	−178.7 (2)	C2A—C3A—C4A—O2A	12.5 (4)
C8—C9—C10—C11	2.3 (3)	N1A—C3A—C4A—C5A	11.1 (3)
C9—C10—C11—C6	−0.5 (3)	C2A—C3A—C4A—C5A	−167.9 (2)
C7—C6—C11—C10	−2.2 (3)	N1A—N2A—C6A—C11A	−179.2 (2)
N2—C6—C11—C10	174.6 (2)	N1A—N2A—C6A—C7A	−0.9 (4)
C24—N8—C13—C14	−177.5 (2)	C11A—C6A—C7A—C8A	0.5 (3)
Cu1—N8—C13—C14	2.6 (3)	N2A—C6A—C7A—C8A	−177.7 (2)
C24—N8—C13—C12	−2.3 (3)	C6A—C7A—C8A—C9A	0.0 (4)
Cu1—N8—C13—C12	177.78 (18)	C6A—C7A—C8A—N3A	178.6 (2)
N5—N4—C14—C13	−8.6 (3)	O4A—N3A—C8A—C7A	175.2 (2)
N5—N4—C14—C15	173.19 (19)	O3A—N3A—C8A—C7A	−5.2 (3)
N8—C13—C14—N4	22.3 (4)	O4A—N3A—C8A—C9A	−6.1 (3)
C12—C13—C14—N4	−153.0 (2)	O3A—N3A—C8A—C9A	173.5 (2)
N8—C13—C14—C15	−159.6 (2)	C7A—C8A—C9A—C10A	−0.2 (4)
C12—C13—C14—C15	25.1 (3)	N3A—C8A—C9A—C10A	−178.8 (2)
N4—C14—C15—O4	−172.4 (2)	C8A—C9A—C10A—C11A	−0.1 (4)
C13—C14—C15—O4	9.2 (4)	C7A—C6A—C11A—C10A	−0.7 (4)
N4—C14—C15—C16	4.4 (3)	N2A—C6A—C11A—C10A	177.6 (2)
C13—C14—C15—C16	−174.0 (2)	C9A—C10A—C11A—C6A	0.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11A—H11A···O4Aⁱ	0.95	2.43	3.320 (3)	156
N2A—H2A···O1A	0.90 (1)	1.81 (2)	2.531 (3)	135 (3)
C22—H22···O1ⁱⁱ	0.95	2.27	3.207 (3)	169
C16—H16A···O5ⁱⁱⁱ	0.98	2.63	3.532 (3)	154
C12—H12B···O3A^iv	0.98	2.53	3.413 (3)	151
C11—H11···O3^v	0.95	2.50	3.350 (3)	150
C5—H5C···O3^v	0.98	2.65	3.426 (3)	137
C1—H1B···O3A^vi	0.98	2.58	3.490 (3)	154
C1—H1B···O1	0.98	2.34	2.842 (3)	111

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

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