A new route for the syntheses of coordination polymers using magnetic influence: syntheses, crystal structures and fluorescence properties

Guan, L.; Wang, Y.; Jin, H.; Yin, P.

doi:10.1107/S2052252523007650

research papers

IUCrJ

Volume 10| Part 6| November 2023| Pages 671-677

ISSN: 2052-2525

https://doi.org/10.1107/S2052252523007650

CHEMISTRY | CRYSTENG

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A new route for the syntheses of coordination polymers using magnetic influence: syntheses, crystal structures and fluorescence properties

Lei Guan,^a ^* Ying Wang,^a Hongzhe Jin ^a and Pengpeng Yin ^a

^aLiaoning Petrochemical University, Fushun, Liaoning 113001, People's Republic of China
^*Correspondence e-mail: guanlei@lnpu.edu.cn

Edited by M. Eddaoudi, King Abdullah University, Saudi Arabia (Received 18 October 2022; accepted 2 September 2023; online 18 September 2023)

Five coordination polymers [TM¹(absa)(H₂O)₄]_n and [TM²(absa)(bipy)(H₂O)]_n [TM¹ = Zn (1), Co (2); TM² = Zn (3), Co (4), Cu (5); Na₂absa = 5,5′-azobissalicylic acid disodium salt; bipy = 4,4′-bipyride] were synthesized by solvent evaporation under a magnetic field. It is evident that magnetic fields bring significant and noticeable changes to the absa²⁻ ligand orientation and the component movement behaviors to construct coordination polymers. The absa²⁻ ligands bind to the metal ions in bridging coordination mode through the carboxylate groups, in addition to the bipy molecules adopting bridging modes. Photoluminescence measurements indicate that the emissions of compounds 1–5 are at 626, 600, 632, 658 and 682 nm in the solid state, respectively.

Keywords: coordination polymers; fluorescence; synthetic approach; transition metals; crystallization and crystal growth.

CCDC references: 2210140; 2210141; 2210142; 2210143; 2210144; 2210145; 2210146

1. Introduction

The self-assembly of coordination compounds is induced by the coordination bonds between metal cations and ligands, as well as various weak intermolecular interactions, such as hydrogen bonding and π–π interactions etc. (Chen & Liu, 2015 ; Robson, 2000 ; Byrne et al., 2008 ; Leong & Vittal, 2011 ; Huang, 2003 ). The self-assembly of these components in solution can construct varied coordination polymers and form diverse topological networks with high dimensionalities (Erxleben, 2003 ; Ghosh & Bharadwaj, 2004 ; He et al., 2009 ). However, functional groups, coordination modes, charges and acidity have great effects on the final architectures, in addition to the ligands and metal cations (Kirillov, 2011 ; Zaworotko, 2010 ; Bitzer & Kleist, 2019 ). Therefore, the final structrual topologies induced by the weak interactions are not always unambiguously predictable and controllable. Recently, efforts have been focused on reliable synthetic strategies with the aim of obtaining predictable architectures with unusual topologies and physical properties (Lee et al., 2017 ; Williams et al., 2007 ). The magnetic field acts as a special driving force. The dynamical properties of the aqueous solution and colloidal system are changed under a magnetic field (Sheibani et al., 2003 ). Additionally, the phase equilibrium relationships between components are broken (Hermann et al., 2013 ; Gelfgat, 1999 ). Therefore, the use of magnetic influence has received considerable attention and has been applied in many fields, such as nanomaterials, biomedicine, environmental protection, metallurgy and semiconductors (Lin et al., 2014 ; Serantes et al., 2018 ; Cépas et al., 2002 ). It has been found that a magnetic field has unexpected effects on the crystallization behavior of drug molecules, preparation of nano-materials, growth of bulk single crystals and the processes of chemical reactions (Hermann et al., 2013; Ronco & Ferraudi, 1990 ). Consequently, our strategy – in order to gain control of and utilize the weak intermolecular interactions in solution – is to employ a controllable magnetic field as a driving force for constructing target products.

Herein, Na₂absa was employed as the ligand in the design and construction of various architectures. It has three distinctive characteristics: (1) four functional groups, which can present a diverse number of potential coordination modes, allowing for the formation of diverse topologies; (2) a rigid and long molecular structure, which can give rise to the formation of interpenetrating frameworks; and (3) a π-conjugate system, which can provide a π-surface for intermolecular interactions and can be easily affected by a magnetic field. When the Na₂absa ligand was used in combination with the rigid 4,4′-bipyridine (bipy) building block, five transition metal coordination polymers were synthesized via solvent evaporation under a magnetic field (see below).

2. Experimental

2.1. Materials and general measurements

The reagents and solvents employed were commercially available and used as received without further purification. Single-crystal X-ray diffraction data were collected with a Rigaku Saturn 70 CCD, a Bruker APEX-II diffractometer or a Bruker D8 VENTURE TXS PHOTON 100 equipped with graphite monochromated Mo Kα radiation (λ = 0.71073 Å) using either the ω or the φ–ω scan mode. Elemental analyses of carbon, hydrogen and nitrogen were performed with a Perkin Elmer 240C elemental analyzer. The infrared spectra were measured by a Magna-IR 750 spectrophotometer in the 4000–400 cm⁻¹ region (KBr pellet). Thermogravimetric analyses (TGA) were carried out on a NETZSCH STA 449C unit at a heating rate of 10°C min⁻¹ under a nitrogen atmosphere. Photoluminescence analyses were performed on a Perkin Elemer LS55 fluorescence spectrometer.

2.2. Syntheses of Na₂absa ligand

5,5′-azobissalicylic acid (H₂absa) was synthesized using procedures described in the literature (Kenawy et al., 2010 ). Sodium hydroxide solution (10%) was added dropwise to H₂absa (0.302 g, 1 mmol) with stirring to a pH value of 5, and the reaction mixture was further stirred for 1 h at room temperature. The product was recrystallized three times and colorless crystals were collected by filtration and dried under vacuum at room temperature.

2.3. Syntheses of compounds 1 and 2

The corresponding metal nitrates (0.1 mmol) and Na₂absa (0.1 mmol) were added to a vessel containing mixed solvent (5 ml of methanol and 10 ml of distilled water). The mixed solution was stirred and heated at 100°C for 3 h under a 1 T magnetic field. The solution obtained was kept in a small vial covered with parafilm at room temperature and left under a magnetic field. Block crystals were obtained after 10 days. For compound 1, IR (KBr, cm⁻¹): 3023, 1579, 1479, 1448, 1328, 1248, 1187, 1079, 828, 789, 720, 577, 473. Calculated for C₁₄H₁₆N₂O₁₀Zn (%): C, 38.39; H, 3.66; N, 6.40. Found (%): C, 38.42; H, 3.82; N, 6.46. For compound 2, IR (KBr, cm⁻¹): 3211, 1577, 1330, 1481, 1450, 1385, 1249, 1187, 1140, 1079, 853, 826, 792, 718, 677, 626, 575, 473. Calculated for C₁₄H₁₆N₂O₁₀Co (%): C, 38.96; H, 3.71; N, 6.49. Found (%): C, 38.90; H, 3.80; N, 6.55.

2.4. Syntheses of compounds 3–5

Compounds 3–5 were synthesized via a similar procedure used to produce compound 1 with the corresponding metal nitrates (0.1 mmol), Na₂absa (0.1 mmol) and bipy (0.1 mmol). For compound 3, IR (KBr, cm⁻¹): 3064, 1611, 1569, 1483, 1426, 1385, 1362, 1293, 1258, 1220, 1187, 1073, 832, 805, 783, 722, 642, 587, 457. Calculated for C₂₄H₁₈N₄O₇Zn (%): C, 53.35; H, 3.33; N, 10.37. Found (%): C, 53.41; H, 3.40; N, 10.35. For compound 4, IR (KBr, cm⁻¹): 3276, 1591, 1560, 1444, 1352, 1265, 1211, 1063, 807, 673, 630, 587, 465. Calculated for C₂₄H₁₈N₄O₇Co (%): C, 52.23; H, 3.63; N, 10.16. Found (%): C, 52.20; H, 3.65; N, 10.25. For compound 5, IR(KBr, cm⁻¹): 3066, 1569, 1477, 1436, 1379, 1328, 1254, 1185, 1071, 807, 681, 638, 587, 477. Calculated for C₂₄H₁₈N₄O₇Cu (%): C, 53.54; H, 3.35; N, 10.41. Found (%): C, 53.57; H, 3.46; N, 10.65.

2.5. Crystallographic data and structure refinements

For compounds 1, 6 and 7, the measurement device used was a Rigaku Saturn 70 CCD; scan mode: ω; data collection, cell refinement and data reduction were carried out using CrysAlisPro (Agilent, 2012 ). For compounds 2–4, the measurement device was a Bruker APEX-II CCD; scan mode: φ–ω; data collection was carried out using APEX2 (Bruker, 2019 ); cell refinement and data reduction were carried out using SAINT (Bruker, 2019). For compound 5, the measurement device was a Bruker D8 VENTURE TXS PHOTON 100; scan mode: φ–ω; data collection was carried out using APEX2 (Bruker, 2019); cell refinement and data reduction were carried out using SAINT (Bruker, 2019). For compounds 1–7, the program used to solve the structure by the dual-space method was SHELXT (Sheldrick, 2015a ) and the program used to refine the structure was SHELXL (Sheldrick, 2015b ).

Crystallographic data were deposited in the Cambridge Crystallographic Data Centre (CCDC 2210140–2210146). The data can be obtained free of charge from https://www.ccdc.cam.ac.uk/conts/retrieving.html or on request by contacting deposit@ccdc.cam.ac.uk.

3. Results and discussion

3.1. Structural characterization

Single-crystal X-ray analysis reveals that compounds 1 and 2 have similar structures, although their space groups and unit cells are different. Therefore, only the structure of compound 1 is described in detail. Compound 1 crystallizes in the space group P2₁/c with the monoclinic system (Table S1 of the supporting information). The asymmetric unit comprises one Zn atom, one absa²⁻ ligand and four coordinated water molecules [Fig. 1(a)]. Each Zn atom is in a distorted octahedron [Fig. 1(b)]. The absa²⁻ ligands bridge with the Zn ions to generate a chain structure through the carboxylate groups in a monodentate coordination fashion [Fig. 1(c)]. Note however that both phenol groups of the absa²⁻ ligand are not coordinated to Zn ions which, in the protonated state, balance the charges in compound 1.

Figure 1
(a) Molecular structure of compound 1 showing the atomic numbering schemes. All hydrogen atoms, with the exception of H3 and H6, have been omitted for clarity. (b) Coordination configuration of Zn1 ion. (c) One-dimensional chain structure.

The structures of compounds 3–5 are similar, hence only compound 3, as an example, is described in detail. Single-crystal X-ray analysis revealed that compound 3 crystallizes in the triclinic space group P1 (Table S3). Its asymmetric unit consists of one crystallographically independent Zn atom, one absa²⁻ ligand, one bipy molecule and one coordinated water molecule [Fig. 2(a)]. Each Zn atom adopts a distorted square-pyramidal coordination geometry [Fig. 2(b)]. The bipy molecule binds to the Zn ions, acting as a typical bridging ligand (Table S4). Each absa²⁻ ligand binds to Zn ions in bridging mode through both monodentate carboxylate groups, leaving both protonated phenol groups uncoordinated. Each bipy molecule bridges with Zn ions to form a wave-like one dimensional chain structure [Fig. 2(c)], and the absa²⁻ ligands link these one-dimensional chains to generate a two dimensional network through the coordination of carboxylate groups with Zn ions [Figs. 2(d) and 2(e)].

Figure 2
(a) Molecular structure of compound 3 showing the atomic numbering schemes. All hydrogen atoms, with the exception of H1 and H4, have been omitted for clarity. (b) Coordination configuration of the Zn1 ion. (c) Wave-like one-dimensional chain structure based on bipy molecules and Zn ions. (d) Bridging absa²⁻ ligand. (e) Two-dimensional network. (f) Four-connected framework.

To gain better insight into the framework structure, a topological analysis was carried out. Zn atoms bind to two absa²⁻ and two bipy ligands, and thus can be simplified as four-connected nodes, with the absa²⁻ and bipy ligands acting as connecting rods. The overall topology can be described as a four-connected framework [Fig. 2(f)]. From a topological point of view, it exhibits a two-dimensional layered net with the Schläfli symbol (4³·6³).

3.2. Comparison between compounds 1–5

Compounds 1–5 were synthesized by the application of a magnetic field. Compounds 1 and 2 have similar one-dimensional structures, which crystallize in the space group P2₁/c with the monoclinic system, and space group P4₃2₁2 with the tetragonal system, respectively. Compounds 3–5 have similar two-dimensional frameworks, which crystallize in the triclinic space group P1, and monoclinic space group P2₁/n. Note that their architectures are similar, but there is a slight difference in the lattice packing. Magnetic fields can cause the interesting phenomena observed in this work. Therefore, it is necessary to compare the magnetic field effects in the packings and framework geometries. As reported in the literature, on the one hand, the presence of a magnetic field has a significant influence on the intermolecular interactions of coordination polymers (Zubir et al., 2018 ). The molecules with π-conjugated systems lie parallel to the substrate for the sample grown under a magnetic field and slightly tilted for the sample without a magnetic field (Kolotovska et al., 2006 ); on the other hand, there are noticeable changes in the morphology of irregular agglomerates at zero field to regular crystals with smooth surfaces under a magnetic field (Zubir et al., 2016 ). Therefore, in contrast to zero magnetic field, a magnetic field can bring crystal orientation and morphology changes of coordination polymers, and increase the symmetry of crystal structures (Zubir et al., 2018). In addition, single-crystal X-ray analyses reveal that the average bond lengths of Zn—O and Co—O in compounds 1 and 2 are 2.091 and 2.179 Å (Table S2), and 2.012 Å (Zn—O) and 2.114 Å (Co—O) in compounds 3 and 4 (Table S4), respectively. Magnetic fields can strengthen the bonding interaction through induction interactions (Hong et al., 2019 ). As a consequence, Zn—O and Co—O bonds in compounds 3 and 4 are stronger than those in compounds 1 and 2. This phenomenon may be attributed to the different interactions of the magnetic field with paramagnetic centers and antimagnetic organic molecules (Hong et al., 2019), which provide an effective pathway for structural design of molecules, and even desired physical–chemical properties.

3.3. Influence of magnetic fields

Magnetic fields have been applied in materials research fields and achieved unexpected results (Gelfgat, 1999; Lin et al., 2014; Serantes et al., 2018). Introduction of a magnetic field can cause changes in magnetic orientation, mass-transport and concentration. In the preparation and self-assembly behavior, it can play an important role in increasing the directionality and collision probability of moving microparticles, and hence generate new materials (Xing et al., 2009 , 2007 ). Consequently, the morphologies, structures, sizes and properties of materials can be drastically modified, and the purity and crystallinity of materials have both shown marked improvement (Xing et al., 2007; Wu et al., 2005 ). The induction of the magnetic field is suggested to be a promising method for the preparation of novel structures. Therefore, we propose the introduction of a magnetic field into the crystal synthetic approach.

As is known, water is an important polar solvent for chemical reactions, in which electrolytes can be dissolved to form anions and cations (Li et al., 2008 ). In solution, ligand and metal cations are affected by the thermal movement of water molecules around them, and they move and collide irregularly. Therefore, the self-assembly of ligands and metal cations was induced by the intermolecular weak interactions and coordination bonds to construct the coordinaiton compounds (Lu et al., 2003 ). However, it is emphasized that the different structural characteristics of the coordination polymers can be mainly attributed to two main factors in this work. On the one hand, magnetic effect is essential for the well aligned orientation of aromatic ligand molecules (Morii et al., 2005 , 2004 ). In addition, a constant magnetic field influences both nucleation and growth of crystals of coordination polymers in a convection-free environment (Gavira & García-Ruiz, 2009 ). When the linear magnetic field is applied, the planes of the π-system in aromatic ligands are theoretically expected to orientate only perpendicular to the magnetic field in divergent directions, and the movement behaviors of metal cations and ligand anions are changed. The orientation and movement behaviors under a magnetic field can make the collision probability of the components in the specific direction much higher than other directions, which in turn affects the packing and coordination modes of the ligands with the metal cations (Li et al., 2017 ). It would be preferable to generate crystal nucleation to grow a specific structure (Gavira & García-Ruiz, 2009). With the evaporation of the solvent, crystal nucleii can gradually precipitate from solution and grow into block crystals suitable for single-crystal X-ray diffraction.

In order to better explain the result, we conducted comparative experiments. Under zero magnetic field, (H₂absa)·(bipy) (6) is separated from the solution, where the absa²⁻ ligand and bipy molecule are uncoordinated from the metal ions [Fig. 3(a) and Table S5]. This may be attributed to the fact that the carboxylate groups in the H₂absa ligand are protonated and bind to fewer metal centers.

Figure 3
Molecular structures of (a) compound 6 and (b) compound 7 (mononuclear N-donor coordination compound) showing the atomic numbering schemes.

With the increase of the magnetic field to 0.3 T, phen molecules, acting as chelated terminated ligands, prefer to coordinate with metal ions and occupy all coordination sites, in contrast to absa²⁻ ligands; thus a mononuclear coordination compound with N-donor ligands [Zn(phen)₃]·(absa)·7H₂O (7) was obtained [Fig. 3(b) and Table S5]. Under a 1 T magnetic field, the absa²⁻ ligands can resist irregular movement to a certain extent, and tend to be perpendicular to the magnetic field. Thus, they gain the opportunity to approach metal ions to form one-dimensional chains. When bipy is added under magnetic field, the absa²⁻ ligand is perpendicular to the magnetic field, which makes the ligand coordinate with metal ions in a certain direction, generating a two-dimensional net.

Very few block crystals of compounds 1–5 were isolated. Many attempts were made to obtain more crystals by improving the reaction conditions, but were unsuccessful. Because not enough samples were available, additional measurements were not performed, but thermogravimetric analyses and photoluminescence properties were studied. The effect of magnetic field on the types of structures are rather complicated and difficult to discuss. However, it is worth noting that the metal sources and the auxiliary ligands also play an important role. The orientation of the absa²⁻ ligand in a magnetic field will affect its coordination mode in compounds 1 and 2 relative to compounds 6 and 7. The presence of a high magnetic field and bipy facilitates the formation of high-dimensional coordination polymers such as compounds 3–5. However, much more systematic work is needed to further elucidate the magnetic field effect, which can influence and induce the formation of the resultant coordination compounds. It is also anticipated that further new types of coordination polymers can be designed by this synthetic method.

3.4. Thermogravimetric analyses

To investigate the thermal stability of compounds 1–5, TGA was performed under a nitrogen atmosphere at the heating rate of 10°C min⁻¹ between 25 and 900°C (Fig. 4). The TGA curves of compounds 1 and 2 exhibit the first weight losses of 16.7 and 16.6% in the temperature ranges 25–156°C and 25–189°C, which correspond to the release of coordinated water molecules (calculated 16.5 and 16.7%, respectively). The second weight losses in the temperature ranges 156–900°C and 189–900°C correspond to the pyrolysis of the absa²⁻ ligands. Up to 900°C, the thermogravimetric curves still show downward trends. The residues may be the metal oxide. For compounds 3–5, the weight losses in the temperature ranges 25–315°C, 25–220°C and 25–237°C amount to 3.4, 6.7 and 3.4%, which can be attributed to the removal of the coordinated water molecules (calculated 3.3, 6.5 and 3.3%, respectively). The weight losses of 29.0, 28.5 and 29.5% in the temperature ranges 315–371°C, 220–313°C and 237–280°C correspond to the loss of the bipy molecules (calculated 28.9, 28.3 and 29.0%, respectively). The weight losses in the temperature ranges 371–900°C, 313–900°C and 280–900°C correspond to the decomposing of the absa²⁻ ligands. Up to 900°C, the thermogravimetric curves still show downward trends. The residues may be the metal oxide.

Figure 4
TGA curves of compounds 1–5.

3.5. Photoluminescence properties

Luminescent coordination polymers are currently of great interest because of their applications in photochemistry, chemical sensors and luminescent displays (Allendorf et al., 2009 ). To establish the relationship between the crystal structures and their fluorescence properties, the solid fluorescence spectra of compounds 1–5 as well as the free Na₂absa ligand for comparison were measured at room temperature (Fig. 5). Compounds 1–5 exhibit photoluminescence emissions at 626, 600, 632, 658 and 682 nm, respectively, which are similar to those of the free Na₂absa ligand with an emission maximum at 612 nm. The observed emissions in compounds 1–5 are probably caused by π–π* intra-ligand transitions of the Na₂absa ligand (Cheng et al., 2012 ). The observed red and blue shifts of the emissions maximum between compounds 1–5 and the Na₂absa ligand were mainly attributed to the coordination of ligands with metal ions (Zhang et al., 2014 ). However, it is found that the emission intensity of compound 3 is much higher than those of compounds 1, 2, 4 and 5. This indicates that the zinc compound 3 shows better photoluminescence properties than the others. Whereas the emission intensities of compounds 1, 2, 4 and 5 are much lower than those of the free Na₂absa ligand, which indicates that the emission of the Na₂absa ligand was quenched to some extent.

Figure 5
Solid-state emission spectra of Na₂absa and compounds 1–5 at room temperature.

The magnetic field assisted self-assembly based on transition metal ions and the absa²⁻ ligand in the presence and absence of nitrogen donor molecules leads to the formation of coordination polymers with different characteristics. They feature one-dimensional and two-dimensional structures with different space groups, respectively. The progressive structural characteristics result from the distinct orientation of ligands and the movement behavior of components, leading to packing in certain directions as a consequence of the effects of magnetic fields. In addition, compounds 1–5 exhibit broad fluorescent emission bands at 626, 600, 632, 658 and 682 nm, respectively.

Supporting information

CCDC references: 2210140; 2210141; 2210142; 2210143; 2210144; 2210145; 2210146

Crystal structure: contains datablocks compound_1, compound_2, compound_3, compound_4, compound_5, compound_6, compound_7. DOI: https://doi.org/10.1107/S2052252523007650/ed5029sup1.cif

Supporting tables. DOI: https://doi.org/10.1107/S2052252523007650/ed5029sup2.pdf

Computing details top

Data collection: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for compound_1, compound_7; Bruker APEX2 for compound_2, compound_3, compound_4; Bruker BIS V6.2.1 for compound_6. Cell refinement: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for compound_1, compound_7; Bruker SAINT for compound_2, compound_3, compound_4; SAINT V8.40A (Bruker, 2019) for compound_5; SAINT V8.40B (Bruker, 2019) for compound_6. Data reduction: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for compound_1, compound_7; Bruker SAINT for compound_2, compound_3, compound_4; SAINT V8.40A (Bruker, 2019) for compound_5; SAINT V8.40B (Bruker, 2019) for compound_6. Program(s) used to solve structure: ShelXT (Sheldrick, 2015) for compound_1, compound_7; SHELXT 2014/5 (Sheldrick, 2014) for compound_2, compound_3, compound_4; SHELXT 2018/2 (Sheldrick, 2018) for compound_5, compound_6. Program(s) used to refine structure: SHELXL (Sheldrick, 2015) for compound_1, compound_7; SHELXL2018/3 (Sheldrick, 2018) for compound_2, compound_3, compound_4; SHELXL 2018/3 (Sheldrick, 2015) for compound_5, compound_6. Molecular graphics: Olex2 (Dolomanov et al., 2009) for compound_1, compound_7; Bruker SHELXTL for compound_2, compound_3, compound_4; Olex2 1.5 (Dolomanov et al., 2009) for compound_5, compound_6. Software used to prepare material for publication: Olex2 (Dolomanov et al., 2009) for compound_1, compound_7; Bruker SHELXTL for compound_2, compound_3, compound_4; Olex2 1.5 (Dolomanov et al., 2009) for compound_5, compound_6.

(compound_1) top

Crystal data top

C₁₄H₁₆N₂O₁₀Zn	F(000) = 896
M_r = 437.66	D_x = 1.754 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4322 (4) Å	Cell parameters from 9870 reflections
b = 11.3669 (4) Å	θ = 2.2–32.6°
c = 16.0822 (7) Å	µ = 1.54 mm⁻¹
β = 106.000 (4)°	T = 113 K
V = 1657.46 (12) Å³	Block
Z = 4	0.16 × 0.13 × 0.1 mm

Data collection top

Rigaku Saturn 70 CCD diffractometer	5723 independent reflections
Radiation source: rotating anode, Enhance (Mo) X-ray Source	4485 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.059
ω scans	θ_max = 32.9°, θ_min = 2.2°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)	h = −13→11
T_min = 0.884, T_max = 1.000	k = −17→16
20581 measured reflections	l = −16→24

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0358P)² + 3.7399P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
5723 reflections	Δρ_max = 0.75 e Å⁻³
249 parameters	Δρ_min = −0.72 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
Zn1	0.71670 (3)	0.85603 (3)	0.71303 (2)	0.01242 (9)
O1	−0.0455 (3)	0.0658 (2)	0.70155 (14)	0.0261 (5)
O2	−0.2294 (2)	−0.04024 (19)	0.61803 (13)	0.0192 (4)
O3	−0.3223 (3)	−0.0015 (2)	0.45694 (14)	0.0226 (5)
H3	−0.317622	−0.034433	0.504394	0.034*
O4	0.4711 (2)	0.63801 (19)	0.68015 (13)	0.0207 (4)
O5	0.5831 (2)	0.75968 (18)	0.60942 (13)	0.0154 (4)
O6	0.5262 (3)	0.7537 (2)	0.44596 (14)	0.0241 (5)
H6	0.562384	0.780280	0.496068	0.036*
O7	0.6684 (2)	0.74267 (19)	0.80659 (13)	0.0186 (4)
H7A	0.588450	0.699988	0.783558	0.028*
H7B	0.642001	0.782381	0.847627	0.028*
O8	0.5346 (2)	0.96219 (19)	0.70788 (14)	0.0204 (4)
H8A	0.491982	0.983181	0.654993	0.031*
H8B	0.562420	1.028529	0.734064	0.031*
O9	0.8400 (2)	0.95781 (18)	0.81462 (13)	0.0166 (4)
H9A	0.871936	0.914649	0.859530	0.025*
H9B	0.905686	0.999549	0.797660	0.025*
O10	0.8936 (2)	0.74928 (19)	0.71271 (13)	0.0193 (4)
H10A	0.874368	0.704833	0.666304	0.029*
H10B	0.909308	0.697622	0.754743	0.029*
N1	0.0917 (3)	0.3586 (2)	0.50390 (15)	0.0148 (4)
N2	0.1229 (3)	0.3948 (2)	0.43677 (15)	0.0132 (4)
C1	−0.1304 (3)	0.0405 (2)	0.62948 (18)	0.0171 (5)
C2	−0.1223 (3)	0.1075 (2)	0.55099 (18)	0.0147 (5)
C3	−0.2184 (3)	0.0837 (2)	0.46904 (18)	0.0155 (5)
C4	−0.2113 (3)	0.1511 (3)	0.39742 (18)	0.0175 (5)
H4	−0.275679	0.134038	0.342008	0.021*
C5	−0.1120 (3)	0.2417 (2)	0.40670 (18)	0.0157 (5)
H5	−0.109640	0.288127	0.357982	0.019*
C6	−0.0141 (3)	0.2661 (2)	0.48784 (18)	0.0138 (5)
C7	−0.0210 (3)	0.1988 (3)	0.55858 (18)	0.0167 (5)
H7	0.045013	0.215394	0.613598	0.020*
C8	0.2248 (3)	0.4888 (2)	0.44629 (17)	0.0138 (5)
C9	0.2452 (3)	0.5323 (3)	0.36895 (18)	0.0168 (5)
H9	0.190604	0.499436	0.315364	0.020*
C10	0.3437 (4)	0.6222 (3)	0.36961 (19)	0.0205 (6)
H10	0.355070	0.652101	0.316654	0.025*
C11	0.4266 (3)	0.6692 (2)	0.44810 (18)	0.0159 (5)
C12	0.4059 (3)	0.6271 (2)	0.52670 (17)	0.0119 (5)
C13	0.3058 (3)	0.5370 (2)	0.52482 (17)	0.0131 (5)
H13	0.292229	0.507926	0.577477	0.016*
C14	0.4918 (3)	0.6768 (2)	0.61184 (17)	0.0132 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01450 (16)	0.01217 (14)	0.00977 (15)	−0.00169 (12)	0.00196 (11)	−0.00064 (11)
O1	0.0312 (12)	0.0287 (12)	0.0135 (10)	−0.0177 (10)	−0.0023 (9)	0.0042 (9)
O2	0.0202 (10)	0.0199 (10)	0.0151 (10)	−0.0099 (8)	0.0008 (8)	0.0035 (8)
O3	0.0252 (11)	0.0234 (11)	0.0151 (10)	−0.0144 (9)	−0.0016 (9)	0.0043 (8)
O4	0.0285 (12)	0.0216 (10)	0.0107 (9)	−0.0101 (9)	0.0034 (8)	0.0018 (8)
O5	0.0177 (10)	0.0157 (9)	0.0126 (9)	−0.0082 (7)	0.0036 (7)	−0.0030 (7)
O6	0.0317 (12)	0.0290 (12)	0.0121 (10)	−0.0204 (10)	0.0069 (9)	−0.0029 (8)
O7	0.0224 (11)	0.0219 (10)	0.0122 (9)	−0.0065 (8)	0.0056 (8)	−0.0012 (8)
O8	0.0203 (11)	0.0207 (10)	0.0165 (10)	0.0026 (8)	−0.0014 (8)	−0.0060 (8)
O9	0.0186 (10)	0.0176 (9)	0.0126 (9)	−0.0021 (8)	0.0027 (8)	−0.0003 (7)
O10	0.0259 (11)	0.0187 (10)	0.0129 (9)	0.0056 (8)	0.0049 (8)	−0.0014 (8)
N1	0.0154 (11)	0.0156 (10)	0.0130 (10)	−0.0050 (9)	0.0034 (9)	0.0005 (8)
N2	0.0140 (11)	0.0148 (10)	0.0099 (10)	−0.0050 (8)	0.0019 (8)	−0.0002 (8)
C1	0.0200 (14)	0.0151 (12)	0.0147 (13)	−0.0046 (10)	0.0025 (11)	0.0044 (10)
C2	0.0153 (13)	0.0150 (12)	0.0124 (12)	−0.0038 (10)	0.0013 (10)	0.0022 (9)
C3	0.0153 (13)	0.0154 (12)	0.0142 (12)	−0.0051 (10)	0.0012 (10)	0.0002 (10)
C4	0.0179 (13)	0.0235 (14)	0.0089 (11)	−0.0063 (11)	−0.0001 (10)	−0.0002 (10)
C5	0.0183 (13)	0.0159 (12)	0.0120 (12)	−0.0043 (10)	0.0028 (10)	0.0020 (9)
C6	0.0151 (12)	0.0132 (11)	0.0130 (12)	−0.0040 (9)	0.0037 (10)	−0.0004 (9)
C7	0.0191 (14)	0.0194 (13)	0.0103 (12)	−0.0074 (11)	0.0018 (10)	0.0011 (10)
C8	0.0142 (12)	0.0146 (12)	0.0130 (12)	−0.0044 (9)	0.0044 (10)	−0.0020 (9)
C9	0.0207 (14)	0.0186 (13)	0.0108 (12)	−0.0073 (11)	0.0040 (10)	−0.0024 (10)
C10	0.0281 (16)	0.0226 (14)	0.0109 (13)	−0.0110 (12)	0.0057 (11)	−0.0001 (10)
C11	0.0184 (13)	0.0176 (13)	0.0124 (12)	−0.0062 (10)	0.0051 (10)	−0.0002 (10)
C12	0.0132 (12)	0.0111 (11)	0.0116 (11)	−0.0032 (9)	0.0038 (9)	−0.0015 (9)
C13	0.0152 (12)	0.0134 (11)	0.0108 (12)	−0.0033 (9)	0.0039 (10)	−0.0004 (9)
C14	0.0149 (12)	0.0119 (11)	0.0125 (12)	−0.0020 (9)	0.0029 (10)	−0.0004 (9)

Geometric parameters (Å, º) top

Zn1—O2ⁱ	2.100 (2)	N1—C6	1.422 (3)
Zn1—O5	2.0991 (19)	N2—C8	1.416 (3)
Zn1—O7	2.124 (2)	C1—C2	1.494 (4)
Zn1—O8	2.082 (2)	C2—C3	1.405 (4)
Zn1—O9	2.077 (2)	C2—C7	1.393 (4)
Zn1—O10	2.064 (2)	C3—C4	1.401 (4)
O1—C1	1.247 (4)	C4—H4	0.9500
O2—C1	1.286 (3)	C4—C5	1.372 (4)
O3—H3	0.8400	C5—H5	0.9500
O3—C3	1.353 (3)	C5—C6	1.403 (4)
O4—C14	1.248 (3)	C6—C7	1.388 (4)
O5—C14	1.284 (3)	C7—H7	0.9500
O6—H6	0.8400	C8—C9	1.400 (4)
O6—C11	1.350 (3)	C8—C13	1.396 (4)
O7—H7A	0.8871	C9—H9	0.9500
O7—H7B	0.8897	C9—C10	1.379 (4)
O8—H8A	0.8680	C10—H10	0.9500
O8—H8B	0.8683	C10—C11	1.395 (4)
O9—H9A	0.8562	C11—C12	1.414 (4)
O9—H9B	0.8809	C12—C13	1.388 (3)
O10—H10A	0.8777	C12—C14	1.496 (4)
O10—H10B	0.8766	C13—H13	0.9500
N1—N2	1.264 (3)

O2ⁱ—Zn1—O7	176.64 (9)	C7—C2—C3	118.4 (3)
O5—Zn1—O2ⁱ	85.87 (8)	O3—C3—C2	121.8 (2)
O5—Zn1—O7	92.68 (8)	O3—C3—C4	118.1 (2)
O8—Zn1—O2ⁱ	90.46 (9)	C4—C3—C2	120.1 (2)
O8—Zn1—O5	87.87 (8)	C3—C4—H4	119.8
O8—Zn1—O7	92.52 (9)	C5—C4—C3	120.5 (3)
O9—Zn1—O2ⁱ	93.68 (8)	C5—C4—H4	119.8
O9—Zn1—O5	177.00 (8)	C4—C5—H5	119.9
O9—Zn1—O7	87.92 (8)	C4—C5—C6	120.3 (3)
O9—Zn1—O8	89.17 (8)	C6—C5—H5	119.9
O10—Zn1—O2ⁱ	88.30 (9)	C5—C6—N1	124.3 (2)
O10—Zn1—O5	90.00 (8)	C7—C6—N1	116.6 (2)
O10—Zn1—O7	88.66 (9)	C7—C6—C5	119.0 (2)
O10—Zn1—O8	177.61 (8)	C2—C7—H7	119.2
O10—Zn1—O9	92.96 (8)	C6—C7—C2	121.7 (3)
C1—O2—Zn1ⁱⁱ	127.46 (18)	C6—C7—H7	119.2
C3—O3—H3	109.5	C9—C8—N2	115.2 (2)
C14—O5—Zn1	128.28 (17)	C13—C8—N2	125.5 (2)
C11—O6—H6	109.5	C13—C8—C9	119.3 (2)
Zn1—O7—H7A	111.1	C8—C9—H9	119.6
Zn1—O7—H7B	112.1	C10—C9—C8	120.8 (3)
H7A—O7—H7B	102.0	C10—C9—H9	119.6
Zn1—O8—H8A	110.6	C9—C10—H10	120.0
Zn1—O8—H8B	110.4	C9—C10—C11	119.9 (3)
H8A—O8—H8B	103.5	C11—C10—H10	120.0
Zn1—O9—H9A	109.6	O6—C11—C10	118.0 (2)
Zn1—O9—H9B	110.2	O6—C11—C12	122.1 (2)
H9A—O9—H9B	117.1	C10—C11—C12	119.9 (2)
Zn1—O10—H10A	111.3	C11—C12—C14	121.1 (2)
Zn1—O10—H10B	110.9	C13—C12—C11	119.4 (2)
H10A—O10—H10B	102.8	C13—C12—C14	119.5 (2)
N2—N1—C6	113.7 (2)	C8—C13—H13	119.7
N1—N2—C8	117.7 (2)	C12—C13—C8	120.6 (2)
O1—C1—O2	123.6 (3)	C12—C13—H13	119.7
O1—C1—C2	119.9 (3)	O4—C14—O5	123.7 (3)
O2—C1—C2	116.6 (2)	O4—C14—C12	119.7 (2)
C3—C2—C1	121.6 (2)	O5—C14—C12	116.6 (2)
C7—C2—C1	120.0 (2)

Zn1ⁱⁱ—O2—C1—O1	3.0 (5)	C3—C2—C7—C6	0.4 (5)
Zn1ⁱⁱ—O2—C1—C2	−175.53 (19)	C3—C4—C5—C6	1.5 (5)
Zn1—O5—C14—O4	−1.9 (4)	C4—C5—C6—N1	−179.5 (3)
Zn1—O5—C14—C12	177.40 (17)	C4—C5—C6—C7	−1.2 (4)
O1—C1—C2—C3	−178.3 (3)	C5—C6—C7—C2	0.2 (4)
O1—C1—C2—C7	−0.7 (5)	C6—N1—N2—C8	178.5 (2)
O2—C1—C2—C3	0.3 (4)	C7—C2—C3—O3	−178.2 (3)
O2—C1—C2—C7	178.0 (3)	C7—C2—C3—C4	−0.1 (4)
O3—C3—C4—C5	177.4 (3)	C8—C9—C10—C11	1.3 (5)
O6—C11—C12—C13	−177.6 (3)	C9—C8—C13—C12	−0.1 (4)
O6—C11—C12—C14	1.5 (4)	C9—C10—C11—O6	177.3 (3)
N1—N2—C8—C9	−174.5 (3)	C9—C10—C11—C12	−2.1 (5)
N1—N2—C8—C13	7.1 (4)	C10—C11—C12—C13	1.7 (4)
N1—C6—C7—C2	178.7 (3)	C10—C11—C12—C14	−179.2 (3)
N2—N1—C6—C5	−20.5 (4)	C11—C12—C13—C8	−0.6 (4)
N2—N1—C6—C7	161.1 (3)	C11—C12—C14—O4	180.0 (3)
N2—C8—C9—C10	−178.7 (3)	C11—C12—C14—O5	0.6 (4)
N2—C8—C13—C12	178.2 (3)	C13—C8—C9—C10	−0.3 (4)
C1—C2—C3—O3	−0.5 (5)	C13—C12—C14—O4	−1.0 (4)
C1—C2—C3—C4	177.6 (3)	C13—C12—C14—O5	179.7 (2)
C1—C2—C7—C6	−177.4 (3)	C14—C12—C13—C8	−179.7 (3)
C2—C3—C4—C5	−0.8 (5)

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

(compound_2) top

Crystal data top

C₁₄H₁₆CoN₂O₁₀	D_x = 1.792 Mg m⁻³
M_r = 431.22	Ga Kα radiation, λ = 1.34139 Å
Tetragonal, P4₃2₁2	Cell parameters from 9881 reflections
a = 10.2539 (5) Å	θ = 4.0–54.0°
c = 30.4058 (15) Å	µ = 6.27 mm⁻¹
V = 3196.9 (3) Å³	T = 193 K
Z = 8	Block
F(000) = 1768

Data collection top

Bruker APEX-II CCD diffractometer	R_int = 0.040
φ and ω scans	θ_max = 54.0°, θ_min = 4.0°
30178 measured reflections	h = −12→12
2881 independent reflections	k = −11→12
2787 reflections with I > 2σ(I)	l = −36→36

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.1P)² + 0.3162P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max = 0.001
S = 0.86	Δρ_max = 0.31 e Å⁻³
2881 reflections	Δρ_min = −0.54 e Å⁻³
255 parameters	Absolute structure: Refined as an inversion twin.
0 restraints	Absolute structure parameter: 0.104 (7)

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
C1	0.5005 (3)	0.2026 (3)	0.54785 (10)	0.0281 (7)
C2	0.5247 (3)	0.2754 (3)	0.50580 (10)	0.0270 (6)
C3	0.6211 (3)	0.3681 (3)	0.50400 (10)	0.0272 (7)
H3	0.670624	0.386167	0.529681	0.033*
C4	0.5764 (3)	0.4071 (4)	0.42769 (10)	0.0310 (7)
H4A	0.595684	0.450969	0.400950	0.037*
C5	0.4785 (4)	0.3160 (4)	0.42866 (10)	0.0330 (7)
H5	0.430169	0.297823	0.402727	0.040*
C6	0.4497 (3)	0.2501 (3)	0.46753 (11)	0.0285 (7)
C7	0.6480 (3)	0.4362 (3)	0.46549 (11)	0.0279 (7)
C8	1.0943 (3)	0.8511 (3)	0.48915 (11)	0.0292 (7)
C9	1.0760 (3)	0.7769 (3)	0.52726 (10)	0.0266 (7)
C10	1.0120 (4)	0.8317 (3)	0.45261 (11)	0.0314 (7)
H10	1.022620	0.884154	0.427100	0.038*
C11	0.9173 (3)	0.7385 (3)	0.45350 (11)	0.0285 (7)
H11	0.862353	0.726322	0.428684	0.034*
C12	0.9009 (3)	0.6605 (3)	0.49091 (10)	0.0281 (7)
C13	1.1526 (3)	0.8060 (3)	0.56813 (10)	0.0283 (7)
C14	0.9791 (3)	0.6820 (3)	0.52757 (11)	0.0287 (7)
H14	0.966142	0.630902	0.553270	0.034*
Co01	0.31615 (5)	0.03980 (5)	0.60770 (2)	0.03031 (18)
N1	0.7448 (3)	0.5336 (3)	0.46104 (9)	0.0285 (6)
N2	0.8033 (3)	0.5626 (3)	0.49590 (9)	0.0285 (6)
O1	0.3531 (3)	0.1613 (3)	0.46736 (8)	0.0370 (6)
H1	0.340553	0.134126	0.493079	0.056*
O2	0.3964 (2)	0.1338 (3)	0.54986 (7)	0.0315 (5)
O3	0.5804 (2)	0.2116 (2)	0.57861 (7)	0.0339 (6)
O4	1.1898 (3)	0.9402 (3)	0.48558 (8)	0.0378 (6)
H4	1.227383	0.948658	0.509971	0.057*
O5	1.1248 (3)	0.7516 (3)	0.60343 (7)	0.0357 (6)
O6	1.2428 (3)	0.8912 (2)	0.56407 (7)	0.0329 (5)
O7	0.5120 (2)	−0.0180 (3)	0.62459 (9)	0.0384 (6)
H7A	0.556435	−0.096582	0.632012	0.075 (18)*
H7B	0.559432	0.023494	0.602023	0.09 (2)*
O8	0.3354 (2)	0.2021 (2)	0.65554 (8)	0.0358 (5)
H8A	0.387814	0.210264	0.681011	0.065 (16)*
H8B	0.261378	0.255466	0.659714	0.064 (16)*
O9	0.2338 (3)	−0.0725 (3)	0.66017 (8)	0.0371 (6)
H9A	0.250376	−0.079057	0.690068	0.10 (2)*
H9B	0.164088	−0.127623	0.652062	0.044 (12)*
O10	0.1276 (3)	0.1425 (3)	0.59526 (8)	0.0387 (6)
H10A	0.102209	0.178212	0.567324	0.16 (4)*
H10B	0.095771	0.197669	0.617173	0.052 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0283 (17)	0.0232 (15)	0.0327 (16)	−0.0007 (13)	0.0023 (13)	0.0014 (12)
C2	0.0267 (16)	0.0284 (16)	0.0259 (14)	−0.0008 (12)	−0.0002 (12)	0.0005 (12)
C3	0.0267 (16)	0.0273 (16)	0.0277 (15)	−0.0003 (12)	−0.0010 (13)	−0.0002 (13)
C4	0.0337 (18)	0.0318 (18)	0.0274 (15)	−0.0024 (14)	0.0017 (14)	0.0027 (13)
C5	0.0376 (18)	0.0355 (19)	0.0260 (15)	−0.0062 (15)	−0.0026 (14)	−0.0008 (13)
C6	0.0274 (16)	0.0262 (16)	0.0318 (15)	−0.0039 (13)	−0.0008 (13)	0.0003 (13)
C7	0.0263 (16)	0.0268 (16)	0.0306 (16)	−0.0014 (12)	0.0013 (13)	−0.0008 (13)
C8	0.0294 (16)	0.0276 (17)	0.0305 (15)	−0.0032 (13)	0.0064 (13)	−0.0037 (12)
C9	0.0265 (15)	0.0240 (15)	0.0295 (15)	−0.0006 (12)	0.0024 (12)	−0.0019 (12)
C10	0.0344 (17)	0.0311 (18)	0.0286 (15)	−0.0032 (14)	0.0032 (13)	0.0027 (13)
C11	0.0275 (16)	0.0302 (17)	0.0279 (14)	−0.0004 (13)	−0.0001 (12)	0.0011 (13)
C12	0.0250 (15)	0.0272 (17)	0.0320 (16)	−0.0052 (12)	0.0022 (12)	0.0005 (13)
C13	0.0308 (17)	0.0245 (15)	0.0297 (15)	−0.0023 (13)	−0.0006 (13)	−0.0019 (13)
C14	0.0294 (16)	0.0269 (16)	0.0299 (15)	−0.0027 (13)	0.0004 (13)	0.0005 (12)
Co01	0.0310 (3)	0.0303 (3)	0.0297 (3)	−0.0025 (2)	−0.00013 (19)	0.00023 (19)
N1	0.0273 (14)	0.0266 (14)	0.0316 (13)	−0.0037 (11)	0.0016 (11)	0.0015 (11)
N2	0.0255 (14)	0.0298 (14)	0.0301 (13)	−0.0059 (11)	0.0001 (11)	0.0016 (11)
O1	0.0346 (13)	0.0426 (15)	0.0339 (11)	−0.0185 (11)	−0.0056 (10)	0.0068 (11)
O2	0.0288 (12)	0.0338 (13)	0.0320 (11)	−0.0065 (10)	0.0001 (10)	0.0056 (10)
O3	0.0355 (13)	0.0366 (14)	0.0295 (11)	−0.0091 (10)	−0.0049 (9)	0.0055 (10)
O4	0.0439 (15)	0.0368 (14)	0.0326 (12)	−0.0177 (12)	0.0006 (11)	0.0001 (10)
O5	0.0410 (14)	0.0357 (13)	0.0306 (11)	−0.0119 (11)	−0.0011 (10)	0.0012 (10)
O6	0.0332 (13)	0.0333 (13)	0.0321 (11)	−0.0103 (10)	0.0029 (10)	−0.0051 (9)
O7	0.0292 (12)	0.0386 (14)	0.0473 (12)	0.0048 (11)	0.0037 (11)	0.0121 (11)
O8	0.0346 (13)	0.0339 (13)	0.0390 (12)	−0.0008 (10)	−0.0008 (10)	−0.0080 (11)
O9	0.0428 (15)	0.0398 (14)	0.0288 (11)	−0.0125 (11)	−0.0015 (10)	0.0064 (10)
O10	0.0361 (14)	0.0460 (16)	0.0339 (12)	0.0102 (11)	−0.0009 (11)	0.0026 (11)

Geometric parameters (Å, º) top

C1—O3	1.247 (4)	C12—C14	1.391 (5)
C1—O2	1.281 (4)	C12—N2	1.425 (4)
C1—C2	1.501 (4)	C13—O5	1.243 (4)
C2—C3	1.372 (5)	C13—O6	1.278 (4)
C2—C6	1.419 (4)	C14—H14	0.9500
C3—C7	1.391 (5)	Co01—O9	2.141 (2)
C3—H3	0.9500	Co01—O6ⁱ	2.155 (2)
C4—C5	1.371 (5)	Co01—O7	2.156 (3)
C4—C7	1.396 (5)	Co01—O2	2.168 (2)
C4—H4A	0.9500	Co01—O8	2.219 (2)
C5—C6	1.394 (5)	Co01—O10	2.234 (3)
C5—H5	0.9500	N1—N2	1.254 (4)
C6—O1	1.345 (4)	O1—H1	0.8400
C7—N1	1.414 (4)	O4—H4	0.8400
C8—O4	1.343 (4)	O7—H7A	0.9524
C8—C9	1.399 (5)	O7—H7B	0.9428
C8—C10	1.410 (5)	O8—H8A	0.9464
C9—C14	1.391 (5)	O8—H8B	0.9438
C9—C13	1.500 (4)	O9—H9A	0.9272
C10—C11	1.363 (5)	O9—H9B	0.9443
C10—H10	0.9500	O10—H10A	0.9607
C11—C12	1.401 (5)	O10—H10B	0.9329
C11—H11	0.9500

O3—C1—O2	123.5 (3)	O6—C13—C9	115.8 (3)
O3—C1—C2	119.6 (3)	C12—C14—C9	121.1 (3)
O2—C1—C2	116.9 (3)	C12—C14—H14	119.4
C3—C2—C6	119.0 (3)	C9—C14—H14	119.4
C3—C2—C1	119.8 (3)	O9—Co01—O6ⁱ	86.63 (10)
C6—C2—C1	121.2 (3)	O9—Co01—O7	92.40 (10)
C2—C3—C7	121.6 (3)	O6ⁱ—Co01—O7	106.08 (11)
C2—C3—H3	119.2	O9—Co01—O2	173.41 (10)
C7—C3—H3	119.2	O6ⁱ—Co01—O2	86.98 (9)
C5—C4—C7	120.8 (3)	O7—Co01—O2	87.83 (10)
C5—C4—H4A	119.6	O9—Co01—O8	87.12 (10)
C7—C4—H4A	119.6	O6ⁱ—Co01—O8	164.68 (10)
C4—C5—C6	120.3 (3)	O7—Co01—O8	88.14 (10)
C4—C5—H5	119.9	O2—Co01—O8	99.47 (10)
C6—C5—H5	119.9	O9—Co01—O10	92.19 (10)
O1—C6—C5	118.8 (3)	O6ⁱ—Co01—O10	85.82 (10)
O1—C6—C2	121.8 (3)	O7—Co01—O10	167.47 (11)
C5—C6—C2	119.4 (3)	O2—Co01—O10	88.93 (10)
C3—C7—C4	118.8 (3)	O8—Co01—O10	80.46 (9)
C3—C7—N1	125.1 (3)	N2—N1—C7	115.0 (3)
C4—C7—N1	116.2 (3)	N1—N2—C12	114.4 (3)
O4—C8—C9	122.3 (3)	C6—O1—H1	109.5
O4—C8—C10	118.0 (3)	C1—O2—Co01	126.9 (2)
C9—C8—C10	119.7 (3)	C8—O4—H4	109.5
C14—C9—C8	118.8 (3)	C13—O6—Co01ⁱⁱ	132.5 (2)
C14—C9—C13	120.5 (3)	Co01—O7—H7A	137.3
C8—C9—C13	120.5 (3)	Co01—O7—H7B	100.5
C11—C10—C8	120.7 (3)	H7A—O7—H7B	107.9
C11—C10—H10	119.7	Co01—O8—H8A	130.8
C8—C10—H10	119.7	Co01—O8—H8B	116.8
C10—C11—C12	120.1 (3)	H8A—O8—H8B	107.2
C10—C11—H11	119.9	Co01—O9—H9A	134.2
C12—C11—H11	119.9	Co01—O9—H9B	115.2
C14—C12—C11	119.4 (3)	H9A—O9—H9B	110.6
C14—C12—N2	115.5 (3)	Co01—O10—H10A	124.3
C11—C12—N2	124.9 (3)	Co01—O10—H10B	117.9
O5—C13—O6	123.9 (3)	H10A—O10—H10B	107.8
O5—C13—C9	120.4 (3)

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

(compound_3) top

Crystal data top

C₂₄H₁₈N₄O₇Zn	Z = 2
M_r = 539.79	F(000) = 552
Triclinic, P1	D_x = 1.623 Mg m⁻³
a = 8.5332 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6081 (2) Å	Cell parameters from 6442 reflections
c = 14.1363 (3) Å	θ = 2.2–27.5°
α = 95.320 (1)°	µ = 1.17 mm⁻¹
β = 97.103 (1)°	T = 296 K
γ = 104.473 (1)°	Block
V = 1104.36 (4) Å³

Data collection top

Bruker APEX-II CCD diffractometer	R_int = 0.023
φ and ω scans	θ_max = 27.5°, θ_min = 2.2°
10598 measured reflections	h = −11→10
5032 independent reflections	k = −12→12
4595 reflections with I > 2σ(I)	l = −18→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.1P)² + 0.0429P] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max = 0.001
5032 reflections	Δρ_max = 0.37 e Å⁻³
329 parameters	Δρ_min = −0.34 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.5674 (2)	1.10974 (19)	0.82554 (14)	0.0254 (4)
C2	0.5129 (2)	0.97067 (18)	0.75871 (14)	0.0251 (4)
C3	0.5672 (2)	0.96144 (19)	0.67025 (14)	0.0268 (4)
H3	0.638724	1.041714	0.652842	0.032*
C4	0.4048 (2)	0.8486 (2)	0.78426 (14)	0.0291 (4)
C5	0.3471 (3)	0.7217 (2)	0.71925 (16)	0.0333 (4)
H5	0.270927	0.642698	0.734667	0.040*
C6	0.5150 (2)	0.8323 (2)	0.60731 (14)	0.0291 (4)
C7	0.4033 (3)	0.7142 (2)	0.63260 (16)	0.0335 (4)
H7	0.366365	0.628939	0.590055	0.040*
C8	0.6748 (2)	0.77068 (19)	0.34414 (14)	0.0264 (4)
H8	0.584348	0.698977	0.353592	0.032*
C9	0.8849 (2)	0.8633 (2)	0.24911 (14)	0.0284 (4)
C10	0.7461 (2)	0.75494 (19)	0.26219 (13)	0.0252 (4)
C11	0.7370 (2)	0.8925 (2)	0.41241 (14)	0.0289 (4)
C12	0.8692 (3)	1.0028 (2)	0.39558 (16)	0.0359 (5)
H12	0.907295	1.086854	0.439161	0.043*
C13	0.9429 (3)	0.9883 (2)	0.31582 (16)	0.0370 (5)
H13	1.031499	1.061599	0.306054	0.044*
C14	0.6786 (2)	0.6239 (2)	0.18901 (14)	0.0281 (4)
C15	0.0432 (2)	0.50909 (19)	0.45701 (13)	0.0243 (4)
C16	0.0376 (2)	0.6210 (2)	0.40246 (15)	0.0320 (4)
H16	−0.021433	0.686621	0.418912	0.038*
C17	0.1192 (3)	0.6358 (2)	0.32365 (15)	0.0315 (4)
H17	0.114919	0.712825	0.289030	0.038*
C18	0.1341 (3)	0.4153 (2)	0.42803 (17)	0.0366 (5)
H18	0.143604	0.339333	0.462614	0.044*
C19	0.2102 (3)	0.4358 (2)	0.34757 (17)	0.0366 (5)
H19	0.268760	0.370914	0.328945	0.044*
C20	0.0421 (2)	0.0743 (2)	0.02414 (14)	0.0311 (4)
C21	−0.0442 (3)	0.1765 (3)	0.0384 (2)	0.0560 (8)
H21	−0.156615	0.152728	0.017994	0.067*
C22	0.2823 (3)	0.2596 (2)	0.0950 (2)	0.0474 (6)
H22	0.395570	0.288065	0.112211	0.057*
C23	0.2091 (3)	0.1191 (2)	0.0521 (2)	0.0529 (7)
H23	0.272742	0.054868	0.042142	0.064*
C24	0.0370 (3)	0.3143 (3)	0.0832 (2)	0.0579 (8)
H24	−0.023393	0.381116	0.093178	0.069*
N1	0.5710 (2)	0.81029 (18)	0.51817 (13)	0.0329 (4)
N2	0.6770 (2)	0.91598 (18)	0.50026 (12)	0.0318 (4)
N3	0.20428 (19)	0.54373 (17)	0.29516 (12)	0.0276 (3)
N4	0.1985 (2)	0.35557 (17)	0.11265 (12)	0.0308 (4)
O1	0.3569 (2)	0.84804 (16)	0.87148 (12)	0.0417 (4)
H1	0.400594	0.926581	0.903988	0.063*
O2	0.52890 (19)	1.10987 (15)	0.90867 (11)	0.0362 (3)
O3	0.64975 (17)	1.21878 (13)	0.79361 (10)	0.0289 (3)
O4	0.96520 (19)	0.85050 (17)	0.17435 (11)	0.0381 (3)
H4	0.928711	0.769008	0.144508	0.057*
O5	0.7651 (2)	0.59960 (16)	0.12695 (11)	0.0412 (4)
O6	0.54004 (16)	0.54045 (14)	0.19438 (11)	0.0308 (3)
O7	0.3046 (2)	0.61047 (15)	0.02535 (11)	0.0416 (4)
H7A	0.303054	0.553627	−0.024493	0.043 (7)*
H7B	0.352322	0.695261	0.015146	0.058 (9)*
Zn1	0.31938 (2)	0.56970 (2)	0.16666 (2)	0.02466 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0276 (8)	0.0236 (8)	0.0240 (9)	0.0049 (6)	0.0067 (7)	−0.0011 (7)
C2	0.0304 (9)	0.0218 (8)	0.0223 (9)	0.0064 (6)	0.0041 (7)	−0.0005 (7)
C3	0.0330 (9)	0.0232 (8)	0.0233 (9)	0.0061 (7)	0.0065 (7)	−0.0007 (7)
C4	0.0337 (9)	0.0267 (8)	0.0257 (10)	0.0051 (7)	0.0075 (7)	0.0016 (7)
C5	0.0361 (10)	0.0232 (8)	0.0359 (11)	−0.0002 (7)	0.0053 (8)	0.0022 (8)
C6	0.0363 (9)	0.0268 (8)	0.0231 (9)	0.0092 (7)	0.0035 (7)	−0.0034 (7)
C7	0.0397 (11)	0.0243 (9)	0.0314 (11)	0.0046 (8)	0.0011 (8)	−0.0050 (8)
C8	0.0282 (8)	0.0265 (8)	0.0229 (9)	0.0061 (7)	0.0030 (7)	−0.0012 (7)
C9	0.0332 (9)	0.0281 (9)	0.0217 (9)	0.0045 (7)	0.0043 (7)	0.0016 (7)
C10	0.0276 (8)	0.0252 (8)	0.0208 (9)	0.0057 (7)	0.0013 (6)	−0.0010 (7)
C11	0.0334 (9)	0.0305 (9)	0.0214 (9)	0.0089 (7)	0.0030 (7)	−0.0038 (7)
C12	0.0428 (11)	0.0281 (9)	0.0296 (11)	0.0014 (8)	0.0031 (8)	−0.0080 (8)
C13	0.0397 (11)	0.0321 (10)	0.0304 (11)	−0.0044 (8)	0.0052 (8)	−0.0024 (8)
C14	0.0356 (9)	0.0264 (8)	0.0207 (9)	0.0072 (7)	0.0023 (7)	0.0005 (7)
C15	0.0259 (8)	0.0246 (8)	0.0205 (9)	0.0026 (6)	0.0066 (7)	0.0003 (6)
C16	0.0389 (10)	0.0349 (10)	0.0289 (10)	0.0168 (8)	0.0137 (8)	0.0076 (8)
C17	0.0411 (10)	0.0302 (9)	0.0284 (10)	0.0129 (8)	0.0135 (8)	0.0091 (7)
C18	0.0511 (12)	0.0299 (9)	0.0384 (12)	0.0173 (9)	0.0223 (10)	0.0134 (8)
C19	0.0500 (11)	0.0310 (10)	0.0375 (12)	0.0181 (8)	0.0225 (9)	0.0077 (8)
C20	0.0403 (10)	0.0235 (9)	0.0228 (10)	−0.0038 (8)	0.0072 (8)	−0.0003 (7)
C21	0.0316 (11)	0.0433 (13)	0.080 (2)	−0.0072 (9)	0.0231 (12)	−0.0298 (13)
C22	0.0399 (11)	0.0267 (10)	0.0640 (17)	0.0037 (8)	−0.0160 (10)	−0.0078 (10)
C23	0.0501 (14)	0.0261 (10)	0.0710 (19)	0.0116 (9)	−0.0242 (12)	−0.0121 (11)
C24	0.0324 (11)	0.0435 (13)	0.085 (2)	−0.0029 (9)	0.0190 (12)	−0.0344 (13)
N1	0.0429 (9)	0.0298 (8)	0.0242 (9)	0.0089 (7)	0.0066 (7)	−0.0048 (6)
N2	0.0388 (9)	0.0334 (8)	0.0209 (8)	0.0086 (7)	0.0040 (6)	−0.0043 (6)
N3	0.0323 (8)	0.0250 (7)	0.0252 (8)	0.0050 (6)	0.0094 (6)	0.0011 (6)
N4	0.0357 (8)	0.0254 (7)	0.0259 (9)	−0.0017 (6)	0.0091 (6)	−0.0035 (6)
O1	0.0533 (9)	0.0327 (7)	0.0326 (9)	−0.0050 (7)	0.0195 (7)	−0.0010 (6)
O2	0.0516 (9)	0.0283 (7)	0.0241 (7)	−0.0001 (6)	0.0154 (6)	−0.0035 (5)
O3	0.0393 (7)	0.0205 (6)	0.0255 (7)	0.0032 (5)	0.0128 (6)	−0.0017 (5)
O4	0.0423 (8)	0.0396 (8)	0.0263 (8)	−0.0011 (6)	0.0115 (6)	−0.0016 (6)
O5	0.0486 (9)	0.0376 (8)	0.0311 (8)	0.0001 (6)	0.0164 (7)	−0.0108 (6)
O6	0.0314 (7)	0.0234 (6)	0.0336 (8)	0.0042 (5)	0.0020 (5)	−0.0040 (5)
O7	0.0699 (11)	0.0238 (7)	0.0223 (7)	−0.0005 (7)	0.0048 (7)	−0.0031 (5)
Zn1	0.02956 (14)	0.02018 (14)	0.02160 (15)	0.00200 (9)	0.00729 (9)	−0.00268 (9)

Geometric parameters (Å, º) top

C1—O2	1.259 (2)	C15—C15ⁱ	1.499 (3)
C1—O3	1.262 (2)	C16—C17	1.385 (3)
C1—C2	1.497 (2)	C16—H16	0.9300
C2—C3	1.389 (3)	C17—N3	1.341 (2)
C2—C4	1.406 (2)	C17—H17	0.9300
C3—C6	1.396 (2)	C18—C19	1.384 (3)
C3—H3	0.9300	C18—H18	0.9300
C4—O1	1.346 (2)	C19—N3	1.337 (3)
C4—C5	1.398 (3)	C19—H19	0.9300
C5—C7	1.372 (3)	C20—C23	1.377 (3)
C5—H5	0.9300	C20—C21	1.382 (3)
C6—C7	1.394 (3)	C20—C20ⁱⁱ	1.486 (3)
C6—N1	1.418 (2)	C21—C24	1.382 (3)
C7—H7	0.9300	C21—H21	0.9300
C8—C10	1.387 (2)	C22—N4	1.325 (3)
C8—C11	1.392 (2)	C22—C23	1.384 (3)
C8—H8	0.9300	C22—H22	0.9300
C9—O4	1.341 (2)	C23—H23	0.9300
C9—C13	1.398 (3)	C24—N4	1.336 (3)
C9—C10	1.412 (2)	C24—H24	0.9300
C10—C14	1.495 (2)	N1—N2	1.248 (2)
C11—C12	1.402 (3)	N3—Zn1	2.1747 (16)
C11—N2	1.421 (2)	N4—Zn1	2.0816 (16)
C12—C13	1.370 (3)	O1—H1	0.8200
C12—H12	0.9300	O3—Zn1ⁱⁱⁱ	1.9998 (13)
C13—H13	0.9300	O4—H4	0.8200
C14—O5	1.256 (2)	O6—Zn1	1.9699 (14)
C14—O6	1.267 (2)	O7—Zn1	2.0658 (16)
C15—C16	1.387 (3)	O7—H7A	0.8471
C15—C18	1.393 (3)	O7—H7B	0.8489

O2—C1—O3	124.89 (16)	N3—C17—H17	118.6
O2—C1—C2	118.32 (16)	C16—C17—H17	118.6
O3—C1—C2	116.79 (16)	C19—C18—C15	119.72 (19)
C3—C2—C4	119.31 (17)	C19—C18—H18	120.1
C3—C2—C1	120.27 (16)	C15—C18—H18	120.1
C4—C2—C1	120.42 (17)	N3—C19—C18	123.57 (18)
C2—C3—C6	120.37 (18)	N3—C19—H19	118.2
C2—C3—H3	119.8	C18—C19—H19	118.2
C6—C3—H3	119.8	C23—C20—C21	116.96 (18)
O1—C4—C5	117.98 (17)	C23—C20—C20ⁱⁱ	122.1 (2)
O1—C4—C2	121.92 (17)	C21—C20—C20ⁱⁱ	120.8 (2)
C5—C4—C2	120.08 (18)	C24—C21—C20	119.8 (2)
C7—C5—C4	119.68 (18)	C24—C21—H21	120.1
C7—C5—H5	120.2	C20—C21—H21	120.1
C4—C5—H5	120.2	N4—C22—C23	123.0 (2)
C7—C6—C3	119.37 (18)	N4—C22—H22	118.5
C7—C6—N1	116.30 (17)	C23—C22—H22	118.5
C3—C6—N1	124.31 (18)	C20—C23—C22	120.0 (2)
C5—C7—C6	121.07 (18)	C20—C23—H23	120.0
C5—C7—H7	119.5	C22—C23—H23	120.0
C6—C7—H7	119.5	N4—C24—C21	122.9 (2)
C10—C8—C11	120.77 (17)	N4—C24—H24	118.6
C10—C8—H8	119.6	C21—C24—H24	118.6
C11—C8—H8	119.6	N2—N1—C6	114.43 (16)
O4—C9—C13	118.06 (17)	N1—N2—C11	114.53 (16)
O4—C9—C10	122.14 (17)	C19—N3—C17	116.99 (17)
C13—C9—C10	119.79 (18)	C19—N3—Zn1	122.77 (12)
C8—C10—C9	119.24 (16)	C17—N3—Zn1	120.21 (13)
C8—C10—C14	120.54 (16)	C22—N4—C24	117.36 (18)
C9—C10—C14	120.21 (16)	C22—N4—Zn1	120.55 (14)
C8—C11—C12	119.15 (18)	C24—N4—Zn1	121.55 (15)
C8—C11—N2	125.03 (17)	C4—O1—H1	109.5
C12—C11—N2	115.82 (16)	C1—O3—Zn1ⁱⁱⁱ	130.25 (11)
C13—C12—C11	120.90 (17)	C9—O4—H4	109.5
C13—C12—H12	119.5	C14—O6—Zn1	130.06 (13)
C11—C12—H12	119.5	Zn1—O7—H7A	128.5
C12—C13—C9	119.99 (18)	Zn1—O7—H7B	117.0
C12—C13—H13	120.0	H7A—O7—H7B	106.9
C9—C13—H13	120.0	O6—Zn1—O3ⁱⁱⁱ	104.64 (6)
O5—C14—O6	123.23 (17)	O6—Zn1—O7	103.04 (7)
O5—C14—C10	118.03 (16)	O3ⁱⁱⁱ—Zn1—O7	88.49 (6)
O6—C14—C10	118.71 (16)	O6—Zn1—N4	96.80 (6)
C16—C15—C18	116.47 (17)	O3ⁱⁱⁱ—Zn1—N4	158.56 (7)
C16—C15—C15ⁱ	121.6 (2)	O7—Zn1—N4	86.46 (6)
C18—C15—C15ⁱ	121.9 (2)	O6—Zn1—N3	108.20 (6)
C17—C16—C15	120.45 (17)	O3ⁱⁱⁱ—Zn1—N3	84.07 (5)
C17—C16—H16	119.8	O7—Zn1—N3	148.76 (7)
C15—C16—H16	119.8	N4—Zn1—N3	89.52 (6)
N3—C17—C16	122.78 (18)

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

(compound_4) top

Crystal data top

C₂₄H₂₀CoN₄O₈	Z = 2
M_r = 551.37	F(000) = 566
Triclinic, P1	D_x = 1.627 Mg m⁻³
a = 7.7901 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0895 (7) Å	Cell parameters from 6677 reflections
c = 15.5233 (8) Å	θ = 2.7–27.6°
α = 94.751 (2)°	µ = 0.82 mm⁻¹
β = 101.411 (2)°	T = 296 K
γ = 107.809 (2)°	Block, red
V = 1125.17 (11) Å³

Data collection top

Bruker APEX-II CCD diffractometer	R_int = 0.033
φ and ω scans	θ_max = 27.6°, θ_min = 2.2°
10738 measured reflections	h = −10→9
5141 independent reflections	k = −13→10
4509 reflections with I > 2σ(I)	l = −19→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.1P)² + 0.2935P] where P = (F_o² + 2F_c²)/3
S = 0.87	(Δ/σ)_max = 0.002
5141 reflections	Δρ_max = 0.54 e Å⁻³
336 parameters	Δρ_min = −0.58 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Co1	0.29366 (3)	0.43645 (3)	0.83093 (2)	0.01750 (11)
O1	0.23677 (19)	0.22458 (15)	0.78891 (9)	0.0223 (3)
O8	0.19363 (19)	0.38260 (15)	0.95166 (8)	0.0230 (3)
H8A	0.077468	0.398799	0.948327	0.034*
H8B	0.176950	0.285182	0.955574	0.034*
O7	0.5593 (2)	0.44591 (17)	0.89956 (9)	0.0280 (3)
H7A	0.606347	0.522998	0.947850	0.042*
H7B	0.640602	0.459982	0.859570	0.042*
O6	−0.02493 (19)	−0.42596 (15)	0.22787 (9)	0.0231 (3)
O2	0.1020 (2)	0.11573 (16)	0.88981 (9)	0.0291 (3)
O5	0.1721 (2)	−0.34399 (17)	0.14311 (9)	0.0288 (3)
O3	−0.0739 (2)	−0.14488 (17)	0.85770 (10)	0.0310 (3)
H3	−0.024274	−0.066210	0.887310	0.047*
O4	0.4039 (2)	−0.09281 (19)	0.18746 (10)	0.0343 (4)
H4	0.345339	−0.168280	0.155223	0.052*
N2	0.3587 (2)	0.65150 (18)	0.88238 (10)	0.0206 (3)
N1	0.3758 (2)	0.46708 (18)	0.70829 (10)	0.0202 (3)
N3	0.1102 (2)	−0.1710 (2)	0.53120 (11)	0.0274 (4)
N4	0.1937 (2)	−0.0574 (2)	0.50741 (11)	0.0273 (4)
C6	0.5887 (3)	0.8782 (2)	0.93560 (13)	0.0239 (4)
H6	0.708813	0.937148	0.939339	0.029*
C1	0.4728 (2)	0.4928 (2)	0.54335 (11)	0.0192 (4)
C12	0.0830 (3)	−0.0210 (2)	0.75482 (12)	0.0199 (4)
C11	0.1467 (3)	0.1166 (2)	0.81510 (12)	0.0206 (4)
C7	0.4706 (3)	0.9279 (2)	0.97573 (12)	0.0200 (4)
C18	0.2105 (3)	−0.2063 (2)	0.28124 (12)	0.0210 (4)
C19	0.1579 (3)	−0.1975 (2)	0.36182 (12)	0.0218 (4)
H19	0.069519	−0.274392	0.374333	0.026*
C8	0.2929 (3)	0.8324 (2)	0.96646 (13)	0.0234 (4)
H8	0.207770	0.858958	0.992040	0.028*
C20	0.3446 (3)	−0.0898 (2)	0.26314 (13)	0.0249 (4)
C13	0.1276 (3)	−0.0268 (2)	0.67263 (12)	0.0223 (4)
H13	0.197620	0.055004	0.655678	0.027*
C24	0.1133 (3)	−0.3348 (2)	0.21357 (12)	0.0216 (4)
C9	0.5297 (3)	0.7434 (2)	0.89063 (13)	0.0243 (4)
H9	0.612236	0.714118	0.864509	0.029*
C21	0.2359 (3)	−0.0756 (2)	0.42317 (13)	0.0252 (4)
C10	0.2430 (3)	0.6991 (2)	0.91971 (13)	0.0241 (4)
H10	0.122592	0.638789	0.913595	0.029*
C14	0.0683 (3)	−0.1541 (2)	0.61535 (13)	0.0244 (4)
C22	0.4175 (3)	0.0351 (2)	0.32361 (15)	0.0316 (5)
H22	0.502773	0.113583	0.310711	0.038*
C2	0.3289 (3)	0.5563 (2)	0.65654 (13)	0.0249 (4)
H2	0.264100	0.611280	0.676639	0.030*
C15	−0.0247 (3)	−0.1452 (2)	0.77917 (13)	0.0248 (4)
C3	0.4686 (3)	0.3896 (2)	0.67721 (12)	0.0243 (4)
H3A	0.500444	0.325383	0.711376	0.029*
C4	0.5200 (3)	0.3997 (2)	0.59679 (13)	0.0251 (4)
H4A	0.585998	0.344204	0.578693	0.030*
C23	0.3626 (3)	0.0417 (2)	0.40244 (14)	0.0307 (5)
H23	0.410445	0.125300	0.442411	0.037*
C16	−0.0834 (3)	−0.2727 (2)	0.72202 (15)	0.0308 (5)
H16	−0.153795	−0.354883	0.738441	0.037*
C5	0.3719 (3)	0.5711 (2)	0.57478 (13)	0.0250 (4)
H5	0.333587	0.633144	0.540817	0.030*
C17	−0.0365 (3)	−0.2763 (2)	0.64121 (15)	0.0303 (5)
H17	−0.075230	−0.361549	0.603235	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02176 (16)	0.01396 (16)	0.01565 (15)	0.00487 (11)	0.00524 (10)	−0.00198 (10)
O1	0.0280 (7)	0.0151 (7)	0.0221 (6)	0.0047 (6)	0.0078 (5)	−0.0017 (5)
O8	0.0282 (7)	0.0206 (7)	0.0191 (6)	0.0065 (6)	0.0068 (5)	−0.0004 (5)
O7	0.0261 (7)	0.0299 (8)	0.0244 (7)	0.0116 (6)	−0.0001 (5)	−0.0106 (6)
O6	0.0245 (7)	0.0195 (7)	0.0233 (6)	0.0069 (6)	0.0036 (5)	−0.0015 (5)
O2	0.0427 (9)	0.0221 (8)	0.0215 (7)	0.0074 (7)	0.0123 (6)	−0.0010 (6)
O5	0.0291 (7)	0.0346 (9)	0.0226 (7)	0.0110 (7)	0.0089 (6)	−0.0041 (6)
O3	0.0349 (8)	0.0249 (8)	0.0321 (8)	0.0032 (7)	0.0170 (6)	0.0022 (6)
O4	0.0366 (9)	0.0343 (10)	0.0311 (8)	0.0056 (7)	0.0156 (7)	0.0044 (7)
N2	0.0252 (8)	0.0161 (8)	0.0197 (7)	0.0065 (6)	0.0057 (6)	−0.0016 (6)
N1	0.0229 (8)	0.0196 (8)	0.0185 (7)	0.0067 (6)	0.0073 (6)	0.0006 (6)
N3	0.0317 (9)	0.0250 (10)	0.0221 (8)	0.0083 (7)	0.0036 (7)	−0.0054 (7)
N4	0.0309 (9)	0.0252 (10)	0.0216 (8)	0.0083 (8)	0.0024 (7)	−0.0060 (7)
C6	0.0231 (9)	0.0171 (10)	0.0308 (10)	0.0036 (8)	0.0111 (8)	−0.0002 (8)
C1	0.0216 (9)	0.0186 (10)	0.0170 (8)	0.0063 (7)	0.0048 (7)	0.0007 (7)
C12	0.0218 (9)	0.0163 (9)	0.0198 (8)	0.0062 (7)	0.0026 (7)	−0.0021 (7)
C11	0.0232 (9)	0.0201 (10)	0.0188 (8)	0.0088 (8)	0.0045 (7)	−0.0002 (7)
C7	0.0252 (9)	0.0168 (10)	0.0179 (8)	0.0075 (8)	0.0050 (7)	−0.0002 (7)
C18	0.0214 (9)	0.0217 (10)	0.0197 (8)	0.0092 (8)	0.0024 (7)	−0.0004 (7)
C19	0.0219 (9)	0.0220 (10)	0.0213 (9)	0.0083 (8)	0.0037 (7)	0.0003 (8)
C8	0.0227 (9)	0.0201 (10)	0.0263 (9)	0.0066 (8)	0.0069 (7)	−0.0037 (8)
C20	0.0232 (9)	0.0276 (11)	0.0242 (9)	0.0101 (8)	0.0041 (7)	0.0028 (8)
C13	0.0248 (9)	0.0172 (10)	0.0225 (9)	0.0057 (8)	0.0041 (7)	−0.0007 (7)
C24	0.0216 (9)	0.0251 (10)	0.0204 (8)	0.0123 (8)	0.0038 (7)	0.0006 (7)
C9	0.0279 (10)	0.0182 (10)	0.0280 (9)	0.0070 (8)	0.0125 (8)	−0.0008 (8)
C21	0.0254 (10)	0.0255 (11)	0.0214 (9)	0.0082 (8)	0.0012 (7)	−0.0027 (8)
C10	0.0236 (9)	0.0192 (10)	0.0279 (9)	0.0057 (8)	0.0074 (7)	−0.0030 (8)
C14	0.0261 (10)	0.0211 (10)	0.0230 (9)	0.0074 (8)	0.0032 (7)	−0.0050 (8)
C22	0.0282 (10)	0.0238 (11)	0.0348 (11)	0.0006 (8)	0.0031 (8)	0.0023 (9)
C2	0.0327 (10)	0.0228 (10)	0.0264 (9)	0.0143 (8)	0.0142 (8)	0.0060 (8)
C15	0.0241 (9)	0.0219 (10)	0.0279 (9)	0.0071 (8)	0.0074 (8)	0.0005 (8)
C3	0.0305 (10)	0.0274 (11)	0.0207 (9)	0.0156 (9)	0.0081 (7)	0.0063 (8)
C4	0.0310 (10)	0.0294 (11)	0.0224 (9)	0.0185 (9)	0.0094 (8)	0.0047 (8)
C23	0.0310 (11)	0.0221 (11)	0.0297 (10)	0.0032 (9)	−0.0011 (8)	−0.0051 (9)
C16	0.0322 (11)	0.0170 (10)	0.0385 (11)	0.0014 (8)	0.0100 (9)	0.0006 (9)
C5	0.0337 (10)	0.0243 (11)	0.0247 (9)	0.0153 (9)	0.0126 (8)	0.0099 (8)
C17	0.0318 (11)	0.0195 (11)	0.0331 (10)	0.0056 (9)	0.0027 (9)	−0.0084 (9)

Geometric parameters (Å, º) top

Co1—O1	2.0655 (14)	C12—C15	1.406 (3)
Co1—O6ⁱ	2.0783 (13)	C12—C11	1.493 (3)
Co1—O7	2.1016 (14)	C7—C8	1.396 (3)
Co1—N2	2.1173 (17)	C7—C7ⁱⁱⁱ	1.473 (4)
Co1—N1	2.1418 (15)	C18—C19	1.395 (3)
Co1—O8	2.2142 (13)	C18—C20	1.404 (3)
O1—C11	1.250 (2)	C18—C24	1.489 (3)
O8—H8A	0.9600	C19—C21	1.381 (3)
O8—H8B	0.9600	C19—H19	0.9300
O7—H7A	0.9600	C8—C10	1.375 (3)
O7—H7B	0.9600	C8—H8	0.9300
O6—C24	1.256 (2)	C20—C22	1.396 (3)
O2—C11	1.275 (2)	C13—C14	1.393 (3)
O5—C24	1.274 (2)	C13—H13	0.9300
O3—C15	1.348 (2)	C9—H9	0.9300
O3—H3	0.8200	C21—C23	1.397 (3)
O4—C20	1.346 (2)	C10—H10	0.9300
O4—H4	0.8200	C14—C17	1.394 (3)
N2—C10	1.344 (2)	C22—C23	1.377 (3)
N2—C9	1.345 (3)	C22—H22	0.9300
N1—C3	1.338 (2)	C2—C5	1.383 (3)
N1—C2	1.340 (3)	C2—H2	0.9300
N3—N4	1.258 (3)	C15—C16	1.394 (3)
N3—C14	1.417 (2)	C3—C4	1.387 (3)
N4—C21	1.421 (2)	C3—H3A	0.9300
C6—C9	1.372 (3)	C4—H4A	0.9300
C6—C7	1.393 (3)	C23—H23	0.9300
C6—H6	0.9300	C16—C17	1.375 (3)
C1—C4	1.387 (3)	C16—H16	0.9300
C1—C5	1.396 (3)	C5—H5	0.9300
C1—C1ⁱⁱ	1.494 (3)	C17—H17	0.9300
C12—C13	1.388 (3)

O1—Co1—O6ⁱ	92.02 (6)	C18—C19—H19	119.7
O1—Co1—O7	88.63 (6)	C10—C8—C7	120.37 (17)
O6ⁱ—Co1—O7	175.67 (5)	C10—C8—H8	119.8
O1—Co1—N2	176.31 (5)	C7—C8—H8	119.8
O6ⁱ—Co1—N2	90.26 (6)	O4—C20—C22	117.9 (2)
O7—Co1—N2	88.88 (6)	O4—C20—C18	122.06 (19)
O1—Co1—N1	85.42 (6)	C22—C20—C18	119.99 (19)
O6ⁱ—Co1—N1	91.05 (6)	C12—C13—C14	120.50 (19)
O7—Co1—N1	93.27 (6)	C12—C13—H13	119.8
N2—Co1—N1	97.44 (6)	C14—C13—H13	119.8
O1—Co1—O8	89.16 (5)	O6—C24—O5	123.70 (18)
O6ⁱ—Co1—O8	87.31 (5)	O6—C24—C18	118.35 (16)
O7—Co1—O8	88.41 (5)	O5—C24—C18	117.92 (18)
N2—Co1—O8	88.05 (6)	N2—C9—C6	123.38 (17)
N1—Co1—O8	174.28 (6)	N2—C9—H9	118.3
C11—O1—Co1	131.94 (12)	C6—C9—H9	118.3
Co1—O8—H8A	109.5	C19—C21—C23	119.47 (19)
Co1—O8—H8B	109.4	C19—C21—N4	124.73 (19)
H8A—O8—H8B	109.5	C23—C21—N4	115.78 (19)
Co1—O7—H7A	109.4	N2—C10—C8	123.53 (18)
Co1—O7—H7B	109.3	N2—C10—H10	118.2
H7A—O7—H7B	109.5	C8—C10—H10	118.2
C24—O6—Co1ⁱ	121.29 (12)	C13—C14—C17	119.45 (18)
C15—O3—H3	109.5	C13—C14—N3	124.56 (19)
C20—O4—H4	109.5	C17—C14—N3	115.98 (18)
C10—N2—C9	116.30 (17)	C23—C22—C20	119.7 (2)
C10—N2—Co1	122.33 (14)	C23—C22—H22	120.2
C9—N2—Co1	120.71 (13)	C20—C22—H22	120.2
C3—N1—C2	116.63 (16)	N1—C2—C5	123.50 (18)
C3—N1—Co1	120.32 (13)	N1—C2—H2	118.3
C2—N1—Co1	122.92 (13)	C5—C2—H2	118.3
N4—N3—C14	114.18 (18)	O3—C15—C16	118.18 (19)
N3—N4—C21	113.69 (18)	O3—C15—C12	121.46 (18)
C9—C6—C7	120.73 (18)	C16—C15—C12	120.36 (18)
C9—C6—H6	119.6	N1—C3—C4	123.51 (17)
C7—C6—H6	119.6	N1—C3—H3A	118.2
C4—C1—C5	116.48 (16)	C4—C3—H3A	118.2
C4—C1—C1ⁱⁱ	121.4 (2)	C3—C4—C1	119.98 (17)
C5—C1—C1ⁱⁱ	122.2 (2)	C3—C4—H4A	120.0
C13—C12—C15	119.14 (18)	C1—C4—H4A	120.0
C13—C12—C11	119.77 (18)	C22—C23—C21	120.9 (2)
C15—C12—C11	121.08 (16)	C22—C23—H23	119.6
O1—C11—O2	124.45 (18)	C21—C23—H23	119.6
O1—C11—C12	118.43 (16)	C17—C16—C15	119.6 (2)
O2—C11—C12	117.10 (17)	C17—C16—H16	120.2
C6—C7—C8	115.66 (17)	C15—C16—H16	120.2
C6—C7—C7ⁱⁱⁱ	122.1 (2)	C2—C5—C1	119.87 (17)
C8—C7—C7ⁱⁱⁱ	122.2 (2)	C2—C5—H5	120.1
C19—C18—C20	119.25 (18)	C1—C5—H5	120.1
C19—C18—C24	119.29 (18)	C16—C17—C14	121.0 (2)
C20—C18—C24	121.30 (17)	C16—C17—H17	119.5
C21—C19—C18	120.61 (19)	C14—C17—H17	119.5
C21—C19—H19	119.7

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

(compound_5) top

Crystal data top

C₂₄H₁₈CuN₄O₇	F(000) = 1100
M_r = 537.96	D_x = 1.628 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2074 (4) Å	Cell parameters from 7226 reflections
b = 16.8579 (7) Å	θ = 2.3–27.3°
c = 18.3599 (7) Å	µ = 1.05 mm⁻¹
β = 100.371 (2)°	T = 193 K
V = 2194.31 (17) Å³	Block
Z = 4	0.12 × 0.1 × 0.1 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 diffractometer	5029 independent reflections
φ and ω scans	3908 reflections with I > 2σ(I)
Absorption correction: multi-scan TWINABS-2012/1 (Bruker,2012) was used for absorption correction. For component 1: wR2(int) was 0.0959 before and 0.0602 after correction. For component 2: wR2(int) was 0.1292 before and 0.0614 after correction. The Ratio of minimum to maximum transmission is 0.91. Final HKLF 4 output contains 37521 reflections, Rint = 0.0700 (18065 with I > 3sig(I), Rint = 0.0528)	R_int = 0.070
T_min = 0.677, T_max = 0.746	θ_max = 27.5°, θ_min = 2.3°
5029 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0294P)² + 3.8358P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5029 reflections	Δρ_max = 0.46 e Å⁻³
330 parameters	Δρ_min = −0.40 e Å⁻³
1 restraint

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.31864 (6)	0.13366 (2)	0.56014 (2)	0.01895 (11)
O1	0.1531 (4)	0.80474 (12)	0.59486 (12)	0.0314 (6)
H1	0.162990	0.849279	0.575413	0.047*
O2	0.2185 (4)	0.90228 (12)	0.49903 (12)	0.0300 (5)
O3	0.3640 (3)	0.86371 (11)	0.40781 (11)	0.0235 (5)
O4	0.4051 (4)	0.23068 (12)	0.26640 (12)	0.0337 (6)
H4	0.407268	0.189769	0.292663	0.051*
O5	0.3408 (4)	0.14754 (11)	0.37808 (11)	0.0274 (5)
O6	0.2953 (3)	0.21160 (11)	0.48056 (10)	0.0225 (5)
O7	0.2913 (5)	0.05100 (12)	0.48581 (12)	0.0422 (7)
H7A	0.296116	−0.000139	0.492279	0.063*
H7B	0.314579	0.057859	0.441350	0.063*
N1	0.2867 (4)	0.05079 (13)	0.63624 (13)	0.0202 (5)
N2	0.2011 (4)	−0.27376 (13)	0.87150 (13)	0.0203 (5)
N3	0.2905 (4)	0.49503 (14)	0.43245 (14)	0.0271 (6)
N4	0.3065 (4)	0.56390 (14)	0.40765 (14)	0.0248 (6)
C1	0.2108 (5)	0.60767 (17)	0.52548 (17)	0.0249 (7)
H1A	0.196063	0.554220	0.539814	0.030*
C2	0.1742 (5)	0.66830 (17)	0.57055 (17)	0.0263 (7)
H2	0.135024	0.656829	0.616137	0.032*
C3	0.1945 (5)	0.74732 (16)	0.54935 (16)	0.0219 (6)
C4	0.2556 (4)	0.76464 (16)	0.48269 (15)	0.0187 (6)
C5	0.2825 (5)	0.84879 (16)	0.46076 (16)	0.0206 (6)
C6	0.2918 (5)	0.70206 (16)	0.43742 (16)	0.0202 (6)
H6	0.331733	0.713038	0.391895	0.024*
C7	0.2699 (5)	0.62406 (16)	0.45825 (16)	0.0211 (6)
C8	0.3221 (5)	0.43178 (16)	0.38594 (16)	0.0223 (6)
C9	0.3695 (5)	0.43772 (17)	0.31509 (17)	0.0275 (7)
H9	0.384122	0.488378	0.294180	0.033*
C10	0.3946 (5)	0.37009 (18)	0.27617 (17)	0.0286 (7)
H10	0.423984	0.374395	0.227919	0.034*
C11	0.3773 (5)	0.29488 (16)	0.30674 (16)	0.0225 (6)
C12	0.3342 (4)	0.28837 (16)	0.37813 (15)	0.0191 (6)
C13	0.3081 (5)	0.35729 (16)	0.41634 (16)	0.0208 (6)
H13	0.279798	0.353271	0.464779	0.025*
C14	0.3229 (4)	0.20963 (16)	0.41438 (16)	0.0194 (6)
C15	0.4322 (5)	0.02308 (17)	0.68509 (16)	0.0233 (6)
H15	0.553167	0.045958	0.686159	0.028*
C16	0.4145 (5)	−0.03747 (17)	0.73418 (17)	0.0247 (7)
H16	0.520554	−0.054474	0.769157	0.030*
C17	0.2387 (5)	−0.07336 (16)	0.73176 (15)	0.0194 (6)
C18	0.0875 (5)	−0.04497 (16)	0.68016 (15)	0.0210 (6)
H18	−0.034229	−0.067804	0.676717	0.025*
C19	0.1170 (5)	0.01695 (16)	0.63391 (16)	0.0208 (6)
H19	0.012951	0.036251	0.599167	0.025*
C20	0.2181 (4)	−0.14158 (16)	0.78110 (15)	0.0200 (6)
C21	0.3230 (5)	−0.14507 (17)	0.85224 (16)	0.0242 (6)
H21	0.402704	−0.102161	0.871255	0.029*
C22	0.3106 (5)	−0.21167 (17)	0.89526 (16)	0.0226 (6)
H22	0.383211	−0.213282	0.943853	0.027*
C23	0.0956 (5)	−0.26939 (17)	0.80348 (16)	0.0248 (7)
H23	0.014651	−0.312526	0.786256	0.030*
C24	0.0996 (5)	−0.20466 (17)	0.75735 (16)	0.0238 (7)
H24	0.021693	−0.203559	0.709762	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0332 (2)	0.00974 (15)	0.01522 (17)	−0.00102 (15)	0.00776 (14)	0.00005 (13)
O1	0.0544 (17)	0.0172 (10)	0.0270 (12)	−0.0021 (11)	0.0192 (12)	−0.0036 (9)
O2	0.0509 (16)	0.0120 (9)	0.0308 (12)	0.0009 (10)	0.0176 (11)	−0.0013 (8)
O3	0.0322 (13)	0.0172 (9)	0.0223 (10)	−0.0001 (9)	0.0087 (9)	0.0041 (8)
O4	0.0617 (18)	0.0191 (10)	0.0249 (12)	0.0049 (11)	0.0201 (12)	−0.0006 (9)
O5	0.0475 (15)	0.0145 (10)	0.0223 (11)	0.0025 (9)	0.0122 (10)	−0.0013 (8)
O6	0.0418 (14)	0.0137 (9)	0.0144 (10)	0.0002 (9)	0.0111 (9)	0.0006 (7)
O7	0.097 (2)	0.0130 (10)	0.0205 (11)	−0.0106 (13)	0.0210 (13)	−0.0030 (8)
N1	0.0311 (16)	0.0136 (11)	0.0168 (12)	−0.0004 (10)	0.0069 (11)	0.0011 (9)
N2	0.0312 (16)	0.0142 (11)	0.0179 (12)	0.0000 (10)	0.0111 (11)	−0.0002 (9)
N3	0.0411 (18)	0.0114 (11)	0.0304 (14)	0.0003 (11)	0.0108 (13)	−0.0007 (10)
N4	0.0338 (17)	0.0132 (11)	0.0284 (13)	0.0014 (11)	0.0079 (12)	0.0013 (10)
C1	0.0320 (19)	0.0159 (13)	0.0276 (16)	−0.0038 (13)	0.0075 (14)	0.0061 (11)
C2	0.036 (2)	0.0206 (14)	0.0239 (15)	−0.0007 (14)	0.0100 (14)	0.0053 (12)
C3	0.0278 (18)	0.0169 (13)	0.0219 (14)	−0.0003 (12)	0.0065 (13)	0.0004 (11)
C4	0.0240 (16)	0.0147 (12)	0.0182 (13)	−0.0001 (11)	0.0058 (12)	0.0029 (10)
C5	0.0270 (17)	0.0142 (13)	0.0201 (14)	0.0003 (12)	0.0031 (12)	−0.0003 (10)
C6	0.0244 (17)	0.0152 (13)	0.0211 (14)	0.0004 (12)	0.0047 (13)	0.0018 (10)
C7	0.0268 (17)	0.0131 (12)	0.0234 (14)	−0.0002 (12)	0.0046 (12)	−0.0005 (11)
C8	0.0298 (18)	0.0128 (12)	0.0251 (15)	0.0005 (12)	0.0070 (13)	0.0005 (11)
C9	0.037 (2)	0.0182 (14)	0.0278 (16)	0.0012 (13)	0.0082 (15)	0.0081 (12)
C10	0.044 (2)	0.0235 (15)	0.0219 (15)	0.0043 (15)	0.0143 (14)	0.0067 (12)
C11	0.0299 (19)	0.0171 (13)	0.0218 (14)	0.0025 (12)	0.0080 (13)	0.0004 (11)
C12	0.0258 (17)	0.0138 (12)	0.0186 (14)	0.0003 (12)	0.0061 (12)	0.0020 (10)
C13	0.0292 (17)	0.0157 (13)	0.0188 (13)	0.0004 (12)	0.0074 (12)	0.0023 (10)
C14	0.0239 (17)	0.0145 (12)	0.0204 (14)	0.0002 (12)	0.0054 (12)	0.0006 (10)
C15	0.0265 (18)	0.0196 (13)	0.0239 (15)	−0.0039 (13)	0.0047 (13)	0.0034 (11)
C16	0.0281 (19)	0.0222 (14)	0.0235 (15)	−0.0002 (13)	0.0039 (13)	0.0078 (12)
C17	0.0291 (18)	0.0148 (12)	0.0158 (13)	−0.0002 (12)	0.0077 (12)	0.0006 (10)
C18	0.0266 (17)	0.0170 (13)	0.0195 (14)	−0.0021 (12)	0.0046 (13)	0.0010 (11)
C19	0.0265 (17)	0.0162 (13)	0.0190 (14)	−0.0007 (12)	0.0021 (12)	0.0010 (10)
C20	0.0228 (16)	0.0187 (13)	0.0193 (13)	−0.0004 (12)	0.0058 (12)	0.0040 (11)
C21	0.0283 (18)	0.0208 (14)	0.0230 (15)	−0.0047 (13)	0.0033 (13)	0.0019 (11)
C22	0.0256 (18)	0.0227 (14)	0.0194 (14)	−0.0029 (13)	0.0034 (13)	0.0044 (11)
C23	0.039 (2)	0.0178 (13)	0.0171 (14)	−0.0062 (13)	0.0045 (13)	0.0005 (11)
C24	0.0337 (19)	0.0228 (14)	0.0148 (13)	−0.0050 (13)	0.0040 (13)	0.0011 (11)

Geometric parameters (Å, º) top

Cu1—O3ⁱ	2.257 (2)	C6—H6	0.9500
Cu1—O6	1.9496 (19)	C6—C7	1.386 (4)
Cu1—O7	1.935 (2)	C8—C9	1.407 (4)
Cu1—N1	2.018 (2)	C8—C13	1.385 (4)
Cu1—N2ⁱⁱ	2.024 (2)	C9—H9	0.9500
O1—H1	0.8400	C9—C10	1.375 (4)
O1—C3	1.347 (3)	C10—H10	0.9500
O2—C5	1.279 (3)	C10—C11	1.401 (4)
O3—C5	1.249 (3)	C11—C12	1.405 (4)
O4—H4	0.8400	C12—C13	1.387 (4)
O4—C11	1.347 (3)	C12—C14	1.494 (4)
O5—C14	1.260 (3)	C13—H13	0.9500
O6—C14	1.267 (3)	C15—H15	0.9500
O7—H7A	0.8701	C15—C16	1.383 (4)
O7—H7B	0.8701	C16—H16	0.9500
N1—C15	1.336 (4)	C16—C17	1.397 (4)
N1—C19	1.343 (4)	C17—C18	1.394 (4)
N2—C22	1.336 (4)	C17—C20	1.488 (4)
N2—C23	1.342 (4)	C18—H18	0.9500
N3—N4	1.260 (3)	C18—C19	1.386 (4)
N3—C8	1.410 (4)	C19—H19	0.9500
N4—C7	1.432 (3)	C20—C21	1.388 (4)
C1—H1A	0.9500	C20—C24	1.384 (4)
C1—C2	1.370 (4)	C21—H21	0.9500
C1—C7	1.404 (4)	C21—C22	1.385 (4)
C2—H2	0.9500	C22—H22	0.9500
C2—C3	1.403 (4)	C23—H23	0.9500
C3—C4	1.404 (4)	C23—C24	1.385 (4)
C4—C5	1.497 (4)	C24—H24	0.9500
C4—C6	1.396 (4)

O6—Cu1—O3ⁱ	97.40 (9)	C8—C9—H9	120.1
O6—Cu1—N1	168.57 (11)	C10—C9—C8	119.9 (3)
O6—Cu1—N2ⁱⁱ	86.49 (8)	C10—C9—H9	120.1
O7—Cu1—O3ⁱ	99.65 (11)	C9—C10—H10	119.6
O7—Cu1—O6	88.43 (8)	C9—C10—C11	120.8 (3)
O7—Cu1—N1	88.86 (9)	C11—C10—H10	119.6
O7—Cu1—N2ⁱⁱ	169.39 (12)	O4—C11—C10	118.3 (2)
N1—Cu1—O3ⁱ	94.00 (9)	O4—C11—C12	122.0 (2)
N1—Cu1—N2ⁱⁱ	94.30 (9)	C10—C11—C12	119.7 (3)
N2ⁱⁱ—Cu1—O3ⁱ	90.24 (9)	C11—C12—C14	121.6 (2)
C3—O1—H1	109.5	C13—C12—C11	118.6 (2)
C5—O3—Cu1ⁱ	113.4 (2)	C13—C12—C14	119.7 (2)
C11—O4—H4	109.5	C8—C13—C12	122.0 (3)
C14—O6—Cu1	133.95 (18)	C8—C13—H13	119.0
Cu1—O7—H7A	128.4	C12—C13—H13	119.0
Cu1—O7—H7B	123.6	O5—C14—O6	125.3 (2)
H7A—O7—H7B	104.5	O5—C14—C12	118.9 (2)
C15—N1—Cu1	122.2 (2)	O6—C14—C12	115.8 (2)
C15—N1—C19	118.3 (2)	N1—C15—H15	118.6
C19—N1—Cu1	119.2 (2)	N1—C15—C16	122.8 (3)
C22—N2—Cu1ⁱⁱⁱ	120.3 (2)	C16—C15—H15	118.6
C22—N2—C23	117.6 (2)	C15—C16—H16	120.4
C23—N2—Cu1ⁱⁱⁱ	121.9 (2)	C15—C16—C17	119.3 (3)
N4—N3—C8	116.3 (2)	C17—C16—H16	120.4
N3—N4—C7	112.2 (2)	C16—C17—C20	120.3 (3)
C2—C1—H1A	119.8	C18—C17—C16	117.8 (3)
C2—C1—C7	120.4 (3)	C18—C17—C20	121.9 (3)
C7—C1—H1A	119.8	C17—C18—H18	120.4
C1—C2—H2	120.0	C19—C18—C17	119.2 (3)
C1—C2—C3	120.0 (3)	C19—C18—H18	120.4
C3—C2—H2	120.0	N1—C19—C18	122.6 (3)
O1—C3—C2	117.7 (2)	N1—C19—H19	118.7
O1—C3—C4	122.1 (2)	C18—C19—H19	118.7
C2—C3—C4	120.3 (3)	C21—C20—C17	120.6 (3)
C3—C4—C5	120.5 (2)	C24—C20—C17	121.7 (3)
C6—C4—C3	118.9 (2)	C24—C20—C21	117.7 (3)
C6—C4—C5	120.6 (2)	C20—C21—H21	120.3
O2—C5—C4	116.3 (2)	C22—C21—C20	119.4 (3)
O3—C5—O2	123.5 (3)	C22—C21—H21	120.3
O3—C5—C4	120.1 (2)	N2—C22—C21	123.0 (3)
C4—C6—H6	119.7	N2—C22—H22	118.5
C7—C6—C4	120.6 (3)	C21—C22—H22	118.5
C7—C6—H6	119.7	N2—C23—H23	118.6
C1—C7—N4	123.5 (2)	N2—C23—C24	122.8 (3)
C6—C7—N4	116.7 (2)	C24—C23—H23	118.6
C6—C7—C1	119.8 (3)	C20—C24—C23	119.5 (3)
C9—C8—N3	126.8 (3)	C20—C24—H24	120.3
C13—C8—N3	114.2 (2)	C23—C24—H24	120.3
C13—C8—C9	119.0 (3)

Cu1ⁱ—O3—C5—O2	95.4 (3)	C7—C1—C2—C3	0.4 (5)
Cu1ⁱ—O3—C5—C4	−84.4 (3)	C8—N3—N4—C7	179.3 (3)
Cu1—O6—C14—O5	14.9 (5)	C8—C9—C10—C11	−1.3 (5)
Cu1—O6—C14—C12	−165.2 (2)	C9—C8—C13—C12	−1.9 (5)
Cu1—N1—C15—C16	−175.5 (2)	C9—C10—C11—O4	−179.4 (3)
Cu1—N1—C19—C18	174.4 (2)	C9—C10—C11—C12	−0.1 (5)
Cu1ⁱⁱⁱ—N2—C22—C21	−176.9 (2)	C10—C11—C12—C13	0.6 (5)
Cu1ⁱⁱⁱ—N2—C23—C24	176.5 (2)	C10—C11—C12—C14	−177.2 (3)
O1—C3—C4—C5	1.8 (5)	C11—C12—C13—C8	0.4 (5)
O1—C3—C4—C6	−178.5 (3)	C11—C12—C14—O5	−4.5 (5)
O4—C11—C12—C13	179.8 (3)	C11—C12—C14—O6	175.5 (3)
O4—C11—C12—C14	2.0 (5)	C13—C8—C9—C10	2.3 (5)
N1—C15—C16—C17	1.9 (4)	C13—C12—C14—O5	177.7 (3)
N2—C23—C24—C20	0.7 (5)	C13—C12—C14—O6	−2.3 (5)
N3—N4—C7—C1	−4.0 (5)	C14—C12—C13—C8	178.3 (3)
N3—N4—C7—C6	177.3 (3)	C15—N1—C19—C18	0.2 (4)
N3—C8—C9—C10	−179.6 (3)	C15—C16—C17—C18	−1.1 (4)
N3—C8—C13—C12	179.8 (3)	C15—C16—C17—C20	176.6 (3)
N4—N3—C8—C9	0.1 (5)	C16—C17—C18—C19	−0.1 (4)
N4—N3—C8—C13	178.3 (3)	C16—C17—C20—C21	35.4 (4)
C1—C2—C3—O1	178.7 (3)	C16—C17—C20—C24	−142.4 (3)
C1—C2—C3—C4	−1.2 (5)	C17—C18—C19—N1	0.5 (4)
C2—C1—C7—N4	−178.5 (3)	C17—C20—C21—C22	−175.7 (3)
C2—C1—C7—C6	0.2 (5)	C17—C20—C24—C23	175.3 (3)
C2—C3—C4—C5	−178.4 (3)	C18—C17—C20—C21	−147.0 (3)
C2—C3—C4—C6	1.3 (5)	C18—C17—C20—C24	35.2 (4)
C3—C4—C5—O2	−10.9 (5)	C19—N1—C15—C16	−1.5 (4)
C3—C4—C5—O3	168.9 (3)	C20—C17—C18—C19	−177.7 (3)
C3—C4—C6—C7	−0.7 (5)	C20—C21—C22—N2	0.0 (5)
C4—C6—C7—N4	178.8 (3)	C21—C20—C24—C23	−2.5 (5)
C4—C6—C7—C1	0.0 (5)	C22—N2—C23—C24	1.5 (4)
C5—C4—C6—C7	179.0 (3)	C23—N2—C22—C21	−1.9 (4)
C6—C4—C5—O2	169.4 (3)	C24—C20—C21—C22	2.2 (4)
C6—C4—C5—O3	−10.8 (5)

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

(compound_6) top

Crystal data top

C₁₄H₁₀N₂O₆·C₁₀H₈N₂	F(000) = 952
M_r = 458.42	D_x = 1.535 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.020 (2) Å	Cell parameters from 5123 reflections
b = 11.953 (2) Å	θ = 2.6–27.5°
c = 14.174 (3) Å	µ = 0.11 mm⁻¹
β = 103.163 (7)°	T = 173 K
V = 1983.1 (7) Å³	Block, yellow
Z = 4	0.13 × 0.12 × 0.1 mm

Data collection top

Bruker D8 VENTURE TXS PHOTON 100 diffractometer	2265 independent reflections
Radiation source: TXS, Rotaing Anode	2018 reflections with I > 2σ(I)
Helios Multi-layer Optic monochromator	R_int = 0.044
Detector resolution: 7.41 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
ω and φ shutterless scans	h = −15→15
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1143 before and 0.0755 after correction. The Ratio of minimum to maximum transmission is 0.8020. The λ/2 correction factor is Not present.	k = −13→15
T_min = 0.598, T_max = 0.746	l = −18→17
8494 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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.0574P)² + 2.5838P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2265 reflections	Δρ_max = 0.46 e Å⁻³
156 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
O3	0.36324 (10)	0.81196 (9)	0.63879 (8)	0.0248 (3)
H3	0.374463	0.826648	0.583747	0.037*
O1	0.36932 (11)	0.47222 (10)	0.69729 (9)	0.0267 (3)
H1	0.376617	0.505912	0.647040	0.040*
O2	0.37628 (11)	0.63667 (10)	0.58761 (8)	0.0271 (3)
N2	0.26505 (12)	0.77148 (11)	0.96418 (10)	0.0212 (3)
N1	0.08896 (11)	0.64280 (11)	0.52963 (10)	0.0211 (3)
C006	0.34105 (12)	0.66265 (12)	0.74344 (10)	0.0179 (3)
C3	0.01783 (12)	0.63359 (12)	0.70325 (10)	0.0175 (3)
C9	0.29295 (13)	0.69211 (13)	0.89863 (11)	0.0196 (3)
C2	0.06464 (13)	0.53973 (13)	0.66828 (11)	0.0201 (3)
H2	0.072155	0.471169	0.703059	0.024*
C1	0.10004 (13)	0.54805 (13)	0.58194 (11)	0.0215 (3)
H1A	0.133310	0.484466	0.558997	0.026*
C10	0.31330 (13)	0.73399 (13)	0.81278 (11)	0.0188 (3)
H10	0.308290	0.812271	0.800983	0.023*
C11	0.36153 (13)	0.70458 (13)	0.65015 (11)	0.0197 (3)
C6	0.34743 (13)	0.54658 (13)	0.76164 (11)	0.0203 (3)
C4	0.00581 (13)	0.73082 (13)	0.64804 (12)	0.0210 (3)
H4	−0.026980	0.795805	0.669197	0.025*
C5	0.04180 (14)	0.73231 (13)	0.56234 (12)	0.0220 (3)
H5	0.032881	0.799142	0.525111	0.026*
C7	0.32848 (14)	0.50520 (13)	0.84912 (12)	0.0244 (4)
H7	0.334070	0.427108	0.861770	0.029*
C8	0.30197 (14)	0.57621 (14)	0.91657 (12)	0.0235 (3)
H8	0.289617	0.547172	0.975735	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0397 (7)	0.0206 (6)	0.0188 (6)	0.0011 (5)	0.0165 (5)	0.0019 (4)
O1	0.0376 (7)	0.0198 (6)	0.0251 (6)	0.0029 (5)	0.0121 (5)	−0.0028 (4)
O2	0.0423 (7)	0.0230 (6)	0.0202 (6)	−0.0010 (5)	0.0161 (5)	−0.0036 (4)
N2	0.0271 (7)	0.0231 (7)	0.0153 (6)	−0.0006 (5)	0.0087 (5)	0.0014 (5)
N1	0.0232 (6)	0.0241 (7)	0.0175 (6)	−0.0022 (5)	0.0080 (5)	−0.0022 (5)
C006	0.0205 (7)	0.0191 (7)	0.0151 (7)	−0.0014 (5)	0.0059 (5)	0.0003 (6)
C3	0.0181 (7)	0.0205 (7)	0.0154 (7)	−0.0016 (5)	0.0067 (5)	−0.0011 (5)
C9	0.0230 (7)	0.0213 (7)	0.0159 (7)	−0.0012 (6)	0.0073 (6)	0.0005 (6)
C2	0.0223 (7)	0.0197 (7)	0.0194 (7)	−0.0009 (6)	0.0072 (6)	−0.0015 (6)
C1	0.0241 (7)	0.0214 (7)	0.0208 (8)	0.0001 (6)	0.0091 (6)	−0.0037 (6)
C10	0.0236 (7)	0.0188 (7)	0.0154 (7)	−0.0021 (5)	0.0072 (6)	0.0010 (5)
C11	0.0230 (7)	0.0219 (7)	0.0156 (7)	0.0009 (6)	0.0073 (6)	−0.0009 (6)
C6	0.0211 (7)	0.0201 (7)	0.0203 (7)	0.0006 (6)	0.0061 (6)	−0.0014 (6)
C4	0.0256 (8)	0.0200 (7)	0.0198 (8)	0.0020 (6)	0.0104 (6)	0.0000 (6)
C5	0.0276 (8)	0.0225 (8)	0.0180 (8)	0.0004 (6)	0.0091 (6)	0.0020 (6)
C7	0.0304 (8)	0.0178 (7)	0.0265 (9)	0.0014 (6)	0.0099 (7)	0.0048 (6)
C8	0.0282 (8)	0.0243 (8)	0.0198 (7)	0.0000 (6)	0.0095 (6)	0.0060 (6)

Geometric parameters (Å, º) top

O3—H3	0.8400	C3—C4	1.390 (2)
O3—C11	1.294 (2)	C9—C10	1.388 (2)
O1—H1	0.8400	C9—C8	1.408 (2)
O1—C6	1.3418 (18)	C2—H2	0.9500
O2—C11	1.2440 (19)	C2—C1	1.388 (2)
N2—N2ⁱ	1.262 (3)	C1—H1A	0.9500
N2—C9	1.421 (2)	C10—H10	0.9500
N1—C1	1.344 (2)	C6—C7	1.401 (2)
N1—C5	1.342 (2)	C4—H4	0.9500
C006—C10	1.398 (2)	C4—C5	1.379 (2)
C006—C11	1.486 (2)	C5—H5	0.9500
C006—C6	1.410 (2)	C7—H7	0.9500
C3—C3ⁱⁱ	1.483 (3)	C7—C8	1.369 (2)
C3—C2	1.396 (2)	C8—H8	0.9500

C11—O3—H3	109.5	C9—C10—C006	120.95 (14)
C6—O1—H1	109.5	C9—C10—H10	119.5
N2ⁱ—N2—C9	114.08 (16)	O3—C11—C006	117.11 (13)
C5—N1—C1	118.56 (13)	O2—C11—O3	123.33 (14)
C10—C006—C11	122.29 (13)	O2—C11—C006	119.56 (14)
C10—C006—C6	118.91 (13)	O1—C6—C006	122.57 (14)
C6—C006—C11	118.78 (13)	O1—C6—C7	117.67 (14)
C2—C3—C3ⁱⁱ	122.64 (10)	C7—C6—C006	119.75 (14)
C4—C3—C3ⁱⁱ	119.27 (9)	C3—C4—H4	120.2
C4—C3—C2	118.08 (13)	C5—C4—C3	119.56 (14)
C10—C9—N2	116.58 (13)	C5—C4—H4	120.2
C10—C9—C8	119.44 (14)	N1—C5—C4	122.41 (15)
C8—C9—N2	123.98 (14)	N1—C5—H5	118.8
C3—C2—H2	120.5	C4—C5—H5	118.8
C1—C2—C3	119.01 (14)	C6—C7—H7	119.7
C1—C2—H2	120.5	C8—C7—C6	120.64 (14)
N1—C1—C2	122.36 (14)	C8—C7—H7	119.7
N1—C1—H1A	118.8	C9—C8—H8	119.9
C2—C1—H1A	118.8	C7—C8—C9	120.29 (14)
C006—C10—H10	119.5	C7—C8—H8	119.9

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

(compound_7) top

Crystal data top

2(C₁₈H₁₂N₃Zn_0.5)·C₁₄H₈N₂O₆·8(H₂O)	F(000) = 2184
M_r = 1050.33	D_x = 1.481 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.1895 (10) Å	Cell parameters from 8395 reflections
b = 14.8309 (9) Å	θ = 2.0–31.5°
c = 22.4020 (15) Å	µ = 0.60 mm⁻¹
β = 92.676 (6)°	T = 113 K
V = 4709.2 (5) Å³	Block
Z = 4	0.12 × 0.1 × 0.07 mm

Data collection top

Rigaku Saturn 70 CCD diffractometer	9636 independent reflections
Radiation source: rotating anode, Enhance (Mo) X-ray Source	5147 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.141
ω scans	θ_max = 26.4°, θ_min = 2.0°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)	h = −17→17
T_min = 0.719, T_max = 1.000	k = −18→18
41394 measured reflections	l = −28→25

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.065	w = 1/[σ²(F_o²) + (0.0302P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.131	(Δ/σ)_max = 0.001
S = 1.00	Δρ_max = 0.54 e Å⁻³
9636 reflections	Δρ_min = −0.53 e Å⁻³
692 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
11 restraints	Extinction coefficient: 0.00074 (8)
Primary atom site location: dual

Special details top

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

	x	y	z	U_iso*/U_eq
Zn1	0.500000	0.65366 (4)	0.750000	0.01980 (19)
N1	0.3549 (2)	0.6747 (2)	0.71688 (14)	0.0200 (8)
N2	0.4446 (2)	0.7491 (2)	0.81368 (14)	0.0189 (8)
N3	0.5294 (2)	0.5410 (2)	0.69362 (14)	0.0185 (8)
C1	0.3122 (3)	0.6399 (3)	0.66819 (18)	0.0251 (11)
H1	0.348425	0.604642	0.642298	0.030*
C2	0.2161 (3)	0.6528 (3)	0.65316 (19)	0.0278 (11)
H2	0.187738	0.626064	0.618226	0.033*
C3	0.1642 (3)	0.7047 (3)	0.68988 (19)	0.0288 (11)
H3	0.099308	0.715136	0.680044	0.035*
C4	0.2062 (3)	0.7426 (3)	0.74207 (19)	0.0232 (10)
C5	0.1571 (3)	0.7969 (3)	0.7832 (2)	0.0327 (12)
H5	0.091763	0.808356	0.775475	0.039*
C6	0.2008 (3)	0.8324 (3)	0.8327 (2)	0.0310 (12)
H6	0.165752	0.867164	0.859507	0.037*
C7	0.2995 (3)	0.8179 (3)	0.84490 (18)	0.0225 (10)
C8	0.3492 (3)	0.8542 (3)	0.89495 (19)	0.0294 (11)
H8	0.317568	0.889853	0.923016	0.035*
C9	0.4433 (3)	0.8378 (3)	0.90276 (19)	0.0293 (11)
H9	0.477737	0.862333	0.936337	0.035*
C10	0.4894 (3)	0.7850 (3)	0.86164 (18)	0.0247 (10)
H10	0.555143	0.774246	0.868030	0.030*
C11	0.3503 (3)	0.7658 (3)	0.80533 (18)	0.0214 (10)
C12	0.3021 (3)	0.7256 (3)	0.75328 (17)	0.0182 (9)
C13	0.5584 (3)	0.5412 (3)	0.63822 (18)	0.0252 (11)
H13	0.569923	0.597725	0.620006	0.030*
C14	0.5728 (3)	0.4634 (3)	0.60524 (19)	0.0293 (11)
H14	0.592615	0.467041	0.565390	0.035*
C15	0.5580 (3)	0.3818 (3)	0.63119 (19)	0.0287 (11)
H15	0.567543	0.327896	0.609341	0.034*
C16	0.5285 (3)	0.3771 (3)	0.69043 (19)	0.0254 (11)
C17	0.5152 (3)	0.4590 (3)	0.71977 (16)	0.0189 (10)
C18	0.5138 (3)	0.2951 (3)	0.72166 (18)	0.0333 (12)
H18	0.523754	0.239246	0.702126	0.040*
Zn2	0.000000	1.12863 (4)	0.750000	0.02063 (19)
N4	0.0560 (2)	1.0307 (2)	0.68826 (14)	0.0211 (8)
N5	0.1448 (2)	1.1066 (2)	0.78459 (15)	0.0201 (8)
N6	−0.0281 (2)	1.2412 (2)	0.80654 (14)	0.0197 (8)
C19	0.0125 (3)	0.9942 (3)	0.64081 (18)	0.0273 (11)
H19	−0.052576	1.007141	0.633305	0.033*
C20	0.0568 (3)	0.9379 (3)	0.6012 (2)	0.0364 (12)
H20	0.022668	0.913660	0.567463	0.044*
C21	0.1498 (4)	0.9179 (3)	0.6115 (2)	0.0380 (13)
H21	0.180876	0.879279	0.584871	0.046*
C22	0.1996 (3)	0.9543 (3)	0.6614 (2)	0.0307 (12)
C23	0.2967 (3)	0.9371 (3)	0.6760 (2)	0.0373 (13)
H23	0.331134	0.899154	0.650648	0.045*
C24	0.3410 (3)	0.9734 (3)	0.7250 (2)	0.0388 (13)
H24	0.405722	0.960189	0.733622	0.047*
C25	0.2920 (3)	1.0313 (3)	0.7640 (2)	0.0268 (11)
C26	0.3336 (3)	1.0711 (3)	0.8159 (2)	0.0343 (12)
H26	0.397889	1.059410	0.827066	0.041*
C27	0.2817 (3)	1.1261 (3)	0.8497 (2)	0.0343 (12)
H27	0.309284	1.152653	0.884961	0.041*
C28	0.1872 (3)	1.1436 (3)	0.83263 (18)	0.0254 (11)
H28	0.152203	1.183430	0.856326	0.031*
C29	0.1965 (3)	1.0509 (3)	0.75021 (19)	0.0220 (10)
C30	0.1489 (3)	1.0111 (3)	0.69906 (19)	0.0220 (10)
C31	−0.0557 (3)	1.2407 (3)	0.86244 (17)	0.0218 (10)
H31	−0.066828	1.184148	0.880778	0.026*
C32	−0.0691 (3)	1.3190 (3)	0.89557 (19)	0.0272 (11)
H32	−0.087870	1.315455	0.935659	0.033*
C33	−0.0548 (3)	1.4011 (3)	0.86937 (19)	0.0240 (10)
H33	−0.063714	1.455230	0.891048	0.029*
C34	−0.0268 (3)	1.4042 (3)	0.80995 (18)	0.0207 (10)
C35	−0.0142 (3)	1.3227 (3)	0.78021 (17)	0.0187 (10)
C36	−0.0124 (3)	1.4876 (3)	0.77886 (17)	0.0278 (11)
H36	−0.020463	1.543298	0.798989	0.033*
O1	0.3508 (2)	0.4803 (2)	0.53204 (13)	0.0377 (9)
O2	0.3809 (2)	0.3466 (2)	0.48989 (13)	0.0334 (8)
O3	0.3550 (2)	0.20452 (19)	0.54282 (13)	0.0365 (8)
H3A	0.366000	0.239758	0.514626	0.055*
O4	0.1468 (2)	0.30910 (18)	0.99840 (13)	0.0290 (8)
O5	0.1148 (2)	0.44528 (19)	1.03344 (13)	0.0350 (8)
O6	0.1408 (2)	0.58456 (18)	0.97470 (12)	0.0308 (8)
H6A	0.124962	0.552504	1.003476	0.046*
N7	0.2337 (2)	0.3660 (2)	0.78496 (16)	0.0251 (9)
N8	0.2527 (2)	0.4073 (2)	0.73763 (15)	0.0238 (9)
C37	0.3517 (3)	0.3967 (3)	0.5330 (2)	0.0301 (11)
C38	0.3224 (3)	0.3467 (3)	0.58730 (18)	0.0202 (10)
C39	0.3266 (3)	0.2524 (3)	0.58994 (19)	0.0251 (10)
C40	0.3036 (3)	0.2077 (3)	0.64203 (18)	0.0265 (11)
H40	0.304507	0.143636	0.643466	0.032*
C41	0.2797 (3)	0.2565 (3)	0.69145 (18)	0.0238 (10)
H41	0.266006	0.225737	0.727238	0.029*
C42	0.2753 (3)	0.3500 (3)	0.68960 (18)	0.0216 (10)
C43	0.2961 (3)	0.3938 (3)	0.63740 (18)	0.0220 (10)
H43	0.292349	0.457739	0.635768	0.026*
C44	0.2126 (3)	0.4256 (3)	0.83285 (18)	0.0203 (10)
C45	0.1924 (3)	0.3859 (3)	0.88614 (18)	0.0228 (10)
H45	0.194925	0.322083	0.889480	0.027*
C46	0.1684 (3)	0.4366 (3)	0.93528 (18)	0.0213 (10)
C47	0.1662 (3)	0.5309 (3)	0.92937 (18)	0.0219 (10)
C48	0.1887 (3)	0.5716 (3)	0.87565 (18)	0.0252 (10)
H48	0.188792	0.635473	0.872481	0.030*
C49	0.2107 (3)	0.5197 (3)	0.82723 (18)	0.0245 (10)
H49	0.224362	0.547456	0.790402	0.029*
C50	0.1417 (3)	0.3939 (3)	0.99285 (19)	0.0259 (11)
O7	0.3122 (2)	0.7821 (2)	0.5323 (2)	0.0644 (12)
H7A	0.359 (2)	0.745 (3)	0.531 (2)	0.097*
H7B	0.2613 (18)	0.762 (3)	0.514 (2)	0.097*
O8	0.4321 (2)	0.6445 (2)	0.53618 (16)	0.0373 (9)
H8A	0.488947	0.642508	0.528343	0.056*
H8B	0.408232	0.596579	0.533942	0.056*
O9	0.1910 (2)	0.99113 (19)	0.95939 (12)	0.0403 (9)
H9A	0.241206	1.013066	0.972715	0.060*
H9B	0.155726	1.029316	0.955505	0.060*
O10	0.1001 (2)	0.8498 (2)	1.01039 (14)	0.0491 (10)
H10A	0.137272	0.890869	0.996921	0.074*
H10B	0.090982	0.805649	0.986051	0.074*
O11	0.4726 (2)	1.0599 (2)	0.57585 (17)	0.0444 (10)
H11A	0.519369	1.059963	0.562480	0.067*
H11B	0.436650	1.102823	0.567502	0.067*
O12	0.37175 (19)	0.9449 (2)	0.49660 (13)	0.0410 (9)
H12A	0.397164	0.968780	0.527907	0.061*
H12B	0.357744	0.890320	0.503977	0.061*
O13	0.0852 (2)	0.8564 (2)	0.45740 (16)	0.0412 (9)
H13A	0.111 (2)	0.8055 (16)	0.467 (2)	0.062*
H13B	0.0257 (10)	0.859 (3)	0.464 (2)	0.062*
O14	−0.0146 (2)	0.7224 (2)	0.57162 (16)	0.0432 (9)
H14A	−0.053 (2)	0.679 (2)	0.565 (2)	0.065*
H14B	0.0393 (15)	0.717 (3)	0.556 (2)	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0216 (4)	0.0188 (4)	0.0190 (4)	0.000	0.0018 (3)	0.000
N1	0.022 (2)	0.0185 (19)	0.020 (2)	−0.0025 (16)	0.0012 (16)	0.0025 (15)
N2	0.020 (2)	0.0146 (19)	0.022 (2)	−0.0014 (15)	0.0007 (16)	0.0009 (15)
N3	0.015 (2)	0.022 (2)	0.019 (2)	0.0038 (15)	0.0004 (15)	−0.0028 (15)
C1	0.034 (3)	0.020 (2)	0.022 (3)	−0.006 (2)	0.004 (2)	−0.0010 (19)
C2	0.029 (3)	0.028 (3)	0.026 (3)	−0.009 (2)	−0.009 (2)	0.004 (2)
C3	0.026 (3)	0.025 (3)	0.034 (3)	−0.006 (2)	−0.005 (2)	0.007 (2)
C4	0.018 (3)	0.022 (2)	0.029 (3)	−0.0027 (19)	0.001 (2)	0.006 (2)
C5	0.024 (3)	0.032 (3)	0.042 (3)	0.002 (2)	0.003 (2)	0.001 (2)
C6	0.025 (3)	0.029 (3)	0.040 (3)	0.009 (2)	0.008 (2)	0.000 (2)
C7	0.028 (3)	0.017 (2)	0.023 (3)	0.0030 (19)	0.005 (2)	0.0019 (18)
C8	0.036 (3)	0.027 (3)	0.026 (3)	0.003 (2)	0.005 (2)	−0.004 (2)
C9	0.040 (3)	0.019 (2)	0.030 (3)	−0.003 (2)	0.003 (2)	−0.008 (2)
C10	0.030 (3)	0.017 (2)	0.027 (3)	−0.001 (2)	0.000 (2)	0.0004 (19)
C11	0.024 (3)	0.014 (2)	0.026 (3)	0.0001 (18)	0.000 (2)	0.0062 (18)
C12	0.024 (3)	0.014 (2)	0.017 (2)	−0.0035 (18)	0.0043 (19)	0.0057 (17)
C13	0.027 (3)	0.027 (3)	0.022 (3)	0.002 (2)	0.002 (2)	0.0000 (19)
C14	0.027 (3)	0.039 (3)	0.023 (3)	0.007 (2)	0.004 (2)	−0.006 (2)
C15	0.021 (3)	0.032 (3)	0.032 (3)	0.009 (2)	−0.004 (2)	−0.015 (2)
C16	0.016 (3)	0.028 (3)	0.032 (3)	0.005 (2)	−0.005 (2)	−0.006 (2)
C17	0.015 (2)	0.021 (2)	0.020 (2)	0.0043 (18)	−0.0070 (19)	−0.0021 (17)
C18	0.030 (3)	0.018 (2)	0.051 (3)	0.004 (2)	−0.005 (3)	−0.005 (2)
Zn2	0.0221 (4)	0.0168 (4)	0.0233 (4)	0.000	0.0038 (3)	0.000
N4	0.022 (2)	0.0182 (19)	0.023 (2)	−0.0014 (16)	0.0042 (17)	−0.0011 (15)
N5	0.020 (2)	0.0158 (18)	0.026 (2)	−0.0037 (15)	0.0053 (17)	0.0013 (15)
N6	0.020 (2)	0.0196 (19)	0.019 (2)	−0.0004 (15)	0.0028 (16)	−0.0001 (15)
C19	0.034 (3)	0.022 (2)	0.026 (3)	0.002 (2)	0.001 (2)	−0.007 (2)
C20	0.044 (3)	0.028 (3)	0.037 (3)	0.002 (2)	0.001 (3)	−0.007 (2)
C21	0.057 (4)	0.021 (3)	0.038 (3)	0.006 (2)	0.018 (3)	−0.009 (2)
C22	0.035 (3)	0.020 (2)	0.038 (3)	0.007 (2)	0.011 (2)	0.004 (2)
C23	0.035 (3)	0.025 (3)	0.053 (4)	0.011 (2)	0.011 (3)	0.005 (2)
C24	0.022 (3)	0.031 (3)	0.064 (4)	0.009 (2)	0.010 (3)	0.013 (3)
C25	0.020 (3)	0.020 (2)	0.040 (3)	−0.0011 (19)	−0.001 (2)	0.013 (2)
C26	0.022 (3)	0.036 (3)	0.045 (3)	−0.003 (2)	−0.001 (2)	0.018 (2)
C27	0.033 (3)	0.035 (3)	0.034 (3)	−0.010 (2)	−0.004 (2)	0.011 (2)
C28	0.030 (3)	0.025 (3)	0.021 (3)	−0.005 (2)	0.000 (2)	0.002 (2)
C29	0.023 (3)	0.014 (2)	0.029 (3)	−0.0013 (19)	0.007 (2)	0.0111 (19)
C30	0.024 (3)	0.012 (2)	0.030 (3)	−0.0011 (19)	0.007 (2)	0.0036 (18)
C31	0.020 (3)	0.025 (2)	0.021 (3)	0.0041 (19)	0.004 (2)	0.0007 (19)
C32	0.027 (3)	0.035 (3)	0.020 (3)	0.007 (2)	0.003 (2)	−0.001 (2)
C33	0.020 (3)	0.021 (2)	0.031 (3)	0.0051 (19)	−0.004 (2)	−0.009 (2)
C34	0.018 (3)	0.017 (2)	0.027 (3)	0.0008 (18)	−0.005 (2)	−0.0020 (19)
C35	0.014 (2)	0.018 (2)	0.024 (2)	−0.0005 (18)	−0.0024 (19)	0.0026 (17)
C36	0.027 (3)	0.020 (2)	0.036 (3)	0.003 (2)	−0.006 (2)	−0.0080 (19)
O1	0.040 (2)	0.033 (2)	0.040 (2)	−0.0072 (16)	0.0048 (16)	0.0126 (16)
O2	0.036 (2)	0.041 (2)	0.0245 (19)	0.0049 (16)	0.0139 (15)	0.0042 (15)
O3	0.054 (2)	0.0284 (19)	0.028 (2)	0.0069 (17)	0.0167 (17)	−0.0008 (14)
O4	0.0335 (19)	0.0150 (16)	0.038 (2)	0.0014 (14)	0.0000 (15)	0.0022 (13)
O5	0.054 (2)	0.0273 (18)	0.0249 (19)	0.0049 (16)	0.0100 (16)	−0.0004 (14)
O6	0.046 (2)	0.0264 (18)	0.0207 (18)	0.0080 (16)	0.0053 (15)	−0.0035 (14)
N7	0.020 (2)	0.029 (2)	0.026 (2)	−0.0029 (16)	0.0000 (17)	−0.0035 (17)
N8	0.016 (2)	0.029 (2)	0.027 (2)	0.0004 (16)	0.0012 (17)	−0.0019 (17)
C37	0.018 (3)	0.038 (3)	0.033 (3)	0.000 (2)	−0.002 (2)	0.009 (2)
C38	0.014 (2)	0.023 (2)	0.025 (3)	−0.0007 (18)	0.0015 (19)	0.0072 (19)
C39	0.025 (3)	0.024 (2)	0.027 (3)	0.003 (2)	0.007 (2)	0.002 (2)
C40	0.039 (3)	0.016 (2)	0.024 (3)	−0.001 (2)	0.000 (2)	0.0024 (19)
C41	0.025 (3)	0.025 (3)	0.022 (3)	−0.003 (2)	0.005 (2)	0.0062 (19)
C42	0.020 (3)	0.022 (2)	0.022 (3)	0.0012 (19)	0.0006 (19)	−0.0061 (19)
C43	0.018 (3)	0.016 (2)	0.031 (3)	0.0009 (18)	−0.004 (2)	0.0003 (19)
C44	0.012 (2)	0.023 (2)	0.026 (3)	0.0017 (18)	−0.0012 (19)	−0.0053 (19)
C45	0.015 (2)	0.024 (2)	0.029 (3)	0.0029 (19)	−0.001 (2)	−0.004 (2)
C46	0.018 (2)	0.023 (2)	0.023 (3)	0.0035 (19)	−0.0001 (19)	−0.0031 (19)
C47	0.021 (3)	0.026 (2)	0.019 (3)	0.0010 (19)	0.0012 (19)	−0.0026 (19)
C48	0.029 (3)	0.018 (2)	0.029 (3)	0.001 (2)	0.003 (2)	−0.0004 (19)
C49	0.021 (3)	0.028 (3)	0.025 (3)	−0.001 (2)	0.003 (2)	0.001 (2)
C50	0.020 (3)	0.028 (3)	0.028 (3)	−0.001 (2)	−0.009 (2)	0.001 (2)
O7	0.024 (2)	0.027 (2)	0.141 (4)	−0.0029 (17)	−0.005 (2)	−0.001 (2)
O8	0.032 (2)	0.029 (2)	0.051 (2)	0.0007 (16)	0.0048 (18)	−0.0122 (17)
O9	0.035 (2)	0.034 (2)	0.052 (2)	−0.0050 (16)	0.0077 (17)	−0.0090 (16)
O10	0.059 (3)	0.040 (2)	0.049 (2)	−0.0076 (18)	0.0053 (19)	0.0126 (17)
O11	0.036 (2)	0.049 (2)	0.049 (3)	0.0118 (19)	0.0051 (19)	−0.0004 (19)
O12	0.035 (2)	0.032 (2)	0.056 (2)	−0.0045 (15)	−0.0023 (17)	−0.0033 (16)
O13	0.042 (2)	0.035 (2)	0.046 (2)	0.0018 (17)	−0.0022 (19)	0.0023 (17)
O14	0.042 (2)	0.035 (2)	0.055 (2)	−0.0125 (17)	0.0193 (19)	−0.0137 (17)

Geometric parameters (Å, º) top

Zn1—N1	2.178 (3)	C25—C26	1.409 (6)
Zn1—N1ⁱ	2.178 (3)	C25—C29	1.407 (5)
Zn1—N2	2.182 (3)	C26—H26	0.9500
Zn1—N2ⁱ	2.182 (3)	C26—C27	1.355 (6)
Zn1—N3ⁱ	2.148 (3)	C27—H27	0.9500
Zn1—N3	2.148 (3)	C27—C28	1.402 (6)
N1—C1	1.327 (5)	C28—H28	0.9500
N1—C12	1.361 (5)	C29—C30	1.430 (5)
N2—C10	1.334 (5)	C31—H31	0.9500
N2—C11	1.366 (5)	C31—C32	1.396 (5)
N3—C13	1.326 (4)	C32—H32	0.9500
N3—C17	1.368 (5)	C32—C33	1.371 (5)
C1—H1	0.9500	C33—H33	0.9500
C1—C2	1.402 (5)	C33—C34	1.407 (5)
C2—H2	0.9500	C34—C35	1.395 (5)
C2—C3	1.366 (5)	C34—C36	1.439 (5)
C3—H3	0.9500	C35—C35ⁱⁱ	1.430 (7)
C3—C4	1.405 (5)	C36—C36ⁱⁱ	1.356 (7)
C4—C5	1.429 (5)	C36—H36	0.9500
C4—C12	1.395 (5)	O1—C37	1.241 (5)
C5—H5	0.9500	O2—C37	1.301 (5)
C5—C6	1.352 (6)	O3—H3A	0.8400
C6—H6	0.9500	O3—C39	1.349 (5)
C6—C7	1.431 (6)	O4—C50	1.265 (5)
C7—C8	1.404 (6)	O5—C50	1.260 (5)
C7—C11	1.401 (5)	O6—H6A	0.8400
C8—H8	0.9500	O6—C47	1.352 (4)
C8—C9	1.360 (6)	N7—N8	1.264 (4)
C9—H9	0.9500	N7—C44	1.432 (5)
C9—C10	1.395 (5)	N8—C42	1.419 (5)
C10—H10	0.9500	C37—C38	1.500 (5)
C11—C12	1.452 (5)	C38—C39	1.401 (5)
C13—H13	0.9500	C38—C43	1.388 (5)
C13—C14	1.390 (5)	C39—C40	1.394 (5)
C14—H14	0.9500	C40—H40	0.9500
C14—C15	1.363 (6)	C40—C41	1.379 (5)
C15—H15	0.9500	C41—H41	0.9500
C15—C16	1.412 (5)	C41—C42	1.390 (5)
C16—C17	1.398 (5)	C42—C43	1.382 (5)
C16—C18	1.424 (5)	C43—H43	0.9500
C17—C17ⁱ	1.441 (7)	C44—C45	1.373 (5)
C18—C18ⁱ	1.347 (8)	C44—C49	1.402 (5)
C18—H18	0.9500	C45—H45	0.9500
Zn2—N4	2.181 (3)	C45—C46	1.389 (5)
Zn2—N4ⁱⁱ	2.181 (3)	C46—C47	1.404 (5)
Zn2—N5	2.187 (3)	C46—C50	1.502 (5)
Zn2—N5ⁱⁱ	2.187 (3)	C47—C48	1.397 (5)
Zn2—N6	2.145 (3)	C48—H48	0.9500
Zn2—N6ⁱⁱ	2.145 (3)	C48—C49	1.377 (5)
N4—C19	1.320 (5)	C49—H49	0.9500
N4—C30	1.361 (5)	O7—H7A	0.862 (10)
N5—C28	1.327 (5)	O7—H7B	0.864 (10)
N5—C29	1.365 (5)	O8—H8A	0.83 (4)
N6—C31	1.329 (4)	O8—H8B	0.7881
N6—C35	1.364 (4)	O9—H9A	0.8267
C19—H19	0.9500	O9—H9B	0.7578
C19—C20	1.390 (5)	O10—H10A	0.8696
C20—H20	0.9500	O10—H10B	0.8576
C20—C21	1.361 (6)	O11—H11A	0.74 (4)
C21—H21	0.9500	O11—H11B	0.8317
C21—C22	1.402 (6)	O12—H12A	0.8511
C22—C23	1.424 (6)	O12—H12B	0.8509
C22—C30	1.413 (5)	O13—H13A	0.864 (10)
C23—H23	0.9500	O13—H13B	0.864 (10)
C23—C24	1.351 (6)	O14—H14A	0.851 (10)
C24—H24	0.9500	O14—H14B	0.857 (10)
C24—C25	1.428 (6)

N1—Zn1—N1ⁱ	163.54 (16)	C19—C20—H20	120.4
N1ⁱ—Zn1—N2ⁱ	76.49 (12)	C21—C20—C19	119.2 (4)
N1—Zn1—N2	76.49 (12)	C21—C20—H20	120.4
N1ⁱ—Zn1—N2	92.75 (12)	C20—C21—H21	120.0
N1—Zn1—N2ⁱ	92.75 (12)	C20—C21—C22	119.9 (4)
N2ⁱ—Zn1—N2	99.11 (16)	C22—C21—H21	120.0
N3—Zn1—N1ⁱ	96.04 (12)	C21—C22—C23	124.1 (4)
N3ⁱ—Zn1—N1	96.04 (12)	C21—C22—C30	117.0 (4)
N3—Zn1—N1	96.75 (12)	C30—C22—C23	118.9 (4)
N3ⁱ—Zn1—N1ⁱ	96.75 (12)	C22—C23—H23	119.2
N3—Zn1—N2ⁱ	91.98 (12)	C24—C23—C22	121.6 (4)
N3—Zn1—N2	167.21 (12)	C24—C23—H23	119.2
N3ⁱ—Zn1—N2ⁱ	167.21 (12)	C23—C24—H24	119.5
N3ⁱ—Zn1—N2	91.98 (12)	C23—C24—C25	121.0 (4)
N3—Zn1—N3ⁱ	77.79 (17)	C25—C24—H24	119.5
C1—N1—Zn1	127.8 (3)	C26—C25—C24	124.0 (4)
C1—N1—C12	117.7 (4)	C29—C25—C24	118.8 (4)
C12—N1—Zn1	114.4 (3)	C29—C25—C26	117.2 (4)
C10—N2—Zn1	127.8 (3)	C25—C26—H26	120.1
C10—N2—C11	117.7 (4)	C27—C26—C25	119.8 (4)
C11—N2—Zn1	114.1 (3)	C27—C26—H26	120.1
C13—N3—Zn1	128.7 (3)	C26—C27—H27	120.1
C13—N3—C17	117.5 (3)	C26—C27—C28	119.8 (5)
C17—N3—Zn1	113.8 (2)	C28—C27—H27	120.1
N1—C1—H1	118.5	N5—C28—C27	122.5 (4)
N1—C1—C2	123.1 (4)	N5—C28—H28	118.8
C2—C1—H1	118.5	C27—C28—H28	118.8
C1—C2—H2	120.7	N5—C29—C25	122.6 (4)
C3—C2—C1	118.5 (4)	N5—C29—C30	117.2 (4)
C3—C2—H2	120.7	C25—C29—C30	120.2 (4)
C2—C3—H3	119.8	N4—C30—C22	122.5 (4)
C2—C3—C4	120.5 (4)	N4—C30—C29	118.1 (4)
C4—C3—H3	119.8	C22—C30—C29	119.4 (4)
C3—C4—C5	124.1 (4)	N6—C31—H31	118.4
C12—C4—C3	116.7 (4)	N6—C31—C32	123.3 (4)
C12—C4—C5	119.1 (4)	C32—C31—H31	118.4
C4—C5—H5	119.0	C31—C32—H32	120.5
C6—C5—C4	121.9 (4)	C33—C32—C31	119.0 (4)
C6—C5—H5	119.0	C33—C32—H32	120.5
C5—C6—H6	119.8	C32—C33—H33	120.4
C5—C6—C7	120.4 (4)	C32—C33—C34	119.2 (4)
C7—C6—H6	119.8	C34—C33—H33	120.4
C8—C7—C6	123.1 (4)	C33—C34—C36	122.6 (4)
C11—C7—C6	119.3 (4)	C35—C34—C33	118.1 (4)
C11—C7—C8	117.6 (4)	C35—C34—C36	119.3 (4)
C7—C8—H8	120.4	N6—C35—C34	122.4 (4)
C9—C8—C7	119.2 (4)	N6—C35—C35ⁱⁱ	117.5 (2)
C9—C8—H8	120.4	C34—C35—C35ⁱⁱ	120.0 (2)
C8—C9—H9	119.9	C34—C36—H36	119.7
C8—C9—C10	120.2 (4)	C36ⁱⁱ—C36—C34	120.7 (2)
C10—C9—H9	119.9	C36ⁱⁱ—C36—H36	119.7
N2—C10—C9	122.4 (4)	C39—O3—H3A	109.5
N2—C10—H10	118.8	C47—O6—H6A	109.5
C9—C10—H10	118.8	N8—N7—C44	112.9 (3)
N2—C11—C7	122.9 (4)	N7—N8—C42	114.2 (3)
N2—C11—C12	117.2 (4)	O1—C37—O2	124.2 (4)
C7—C11—C12	119.9 (4)	O1—C37—C38	120.3 (4)
N1—C12—C4	123.5 (4)	O2—C37—C38	115.5 (4)
N1—C12—C11	117.2 (4)	C39—C38—C37	121.0 (4)
C4—C12—C11	119.3 (4)	C43—C38—C37	120.2 (4)
N3—C13—H13	118.1	C43—C38—C39	118.7 (4)
N3—C13—C14	123.7 (4)	O3—C39—C38	120.4 (4)
C14—C13—H13	118.1	O3—C39—C40	119.6 (4)
C13—C14—H14	120.6	C40—C39—C38	120.0 (4)
C15—C14—C13	118.7 (4)	C39—C40—H40	120.1
C15—C14—H14	120.6	C41—C40—C39	119.9 (4)
C14—C15—H15	119.9	C41—C40—H40	120.1
C14—C15—C16	120.2 (4)	C40—C41—H41	119.6
C16—C15—H15	119.9	C40—C41—C42	120.9 (4)
C15—C16—C18	124.1 (4)	C42—C41—H41	119.6
C17—C16—C15	116.9 (4)	C41—C42—N8	125.9 (4)
C17—C16—C18	119.0 (4)	C43—C42—N8	115.2 (4)
N3—C17—C16	123.0 (4)	C43—C42—C41	118.9 (4)
N3—C17—C17ⁱ	117.3 (2)	C38—C43—H43	119.2
C16—C17—C17ⁱ	119.7 (2)	C42—C43—C38	121.6 (4)
C16—C18—H18	119.4	C42—C43—H43	119.2
C18ⁱ—C18—C16	121.3 (2)	C45—C44—N7	116.5 (4)
C18ⁱ—C18—H18	119.4	C45—C44—C49	120.1 (4)
N4ⁱⁱ—Zn2—N4	96.46 (17)	C49—C44—N7	123.4 (4)
N4—Zn2—N5	76.19 (12)	C44—C45—H45	119.1
N4ⁱⁱ—Zn2—N5	92.27 (12)	C44—C45—C46	121.7 (4)
N4ⁱⁱ—Zn2—N5ⁱⁱ	76.19 (13)	C46—C45—H45	119.1
N4—Zn2—N5ⁱⁱ	92.27 (12)	C45—C46—C47	118.0 (4)
N5ⁱⁱ—Zn2—N5	162.80 (16)	C45—C46—C50	122.2 (4)
N6ⁱⁱ—Zn2—N4	93.48 (12)	C47—C46—C50	119.7 (4)
N6—Zn2—N4ⁱⁱ	93.49 (12)	O6—C47—C46	121.4 (4)
N6ⁱⁱ—Zn2—N4ⁱⁱ	167.56 (12)	O6—C47—C48	118.2 (4)
N6—Zn2—N4	167.56 (12)	C48—C47—C46	120.4 (4)
N6ⁱⁱ—Zn2—N5ⁱⁱ	96.01 (12)	C47—C48—H48	119.8
N6ⁱⁱ—Zn2—N5	97.36 (12)	C49—C48—C47	120.4 (4)
N6—Zn2—N5ⁱⁱ	97.36 (12)	C49—C48—H48	119.8
N6—Zn2—N5	96.02 (12)	C44—C49—H49	120.3
N6ⁱⁱ—Zn2—N6	77.73 (17)	C48—C49—C44	119.3 (4)
C19—N4—Zn2	127.8 (3)	C48—C49—H49	120.3
C19—N4—C30	117.9 (4)	O4—C50—C46	119.2 (4)
C30—N4—Zn2	114.1 (3)	O5—C50—O4	123.3 (4)
C28—N5—Zn2	127.5 (3)	O5—C50—C46	117.5 (4)
C28—N5—C29	118.2 (4)	H7A—O7—H7B	112.7 (18)
C29—N5—Zn2	114.2 (3)	H8A—O8—H8B	111.8
C31—N6—Zn2	128.5 (3)	H9A—O9—H9B	107.5
C31—N6—C35	117.9 (3)	H10A—O10—H10B	112.9
C35—N6—Zn2	113.6 (2)	H11A—O11—H11B	117.3
N4—C19—H19	118.3	H12A—O12—H12B	109.3
N4—C19—C20	123.5 (4)	H13A—O13—H13B	113.4 (18)
C20—C19—H19	118.3	H14A—O14—H14B	115.6 (18)

Zn1—N1—C1—C2	175.3 (3)	C21—C22—C30—C29	−179.3 (4)
Zn1—N1—C12—C4	−176.1 (3)	C22—C23—C24—C25	−0.5 (7)
Zn1—N1—C12—C11	5.7 (4)	C23—C22—C30—N4	−179.9 (4)
Zn1—N2—C10—C9	−172.8 (3)	C23—C22—C30—C29	1.0 (6)
Zn1—N2—C11—C7	173.5 (3)	C23—C24—C25—C26	179.7 (4)
Zn1—N2—C11—C12	−5.4 (4)	C23—C24—C25—C29	−0.7 (6)
Zn1—N3—C13—C14	−178.2 (3)	C24—C25—C26—C27	179.2 (4)
Zn1—N3—C17—C16	178.8 (3)	C24—C25—C29—N5	−179.1 (4)
Zn1—N3—C17—C17ⁱ	−1.0 (6)	C24—C25—C29—C30	2.0 (6)
N1—C1—C2—C3	1.0 (6)	C25—C26—C27—C28	−0.6 (6)
N2—C11—C12—N1	−0.2 (5)	C25—C29—C30—N4	178.7 (3)
N2—C11—C12—C4	−178.4 (3)	C25—C29—C30—C22	−2.1 (6)
N3—C13—C14—C15	−1.1 (7)	C26—C25—C29—N5	0.5 (6)
C1—N1—C12—C4	0.2 (6)	C26—C25—C29—C30	−178.4 (4)
C1—N1—C12—C11	−178.0 (3)	C26—C27—C28—N5	1.5 (6)
C1—C2—C3—C4	−1.2 (6)	C28—N5—C29—C25	0.3 (6)
C2—C3—C4—C5	−179.4 (4)	C28—N5—C29—C30	179.3 (3)
C2—C3—C4—C12	1.0 (6)	C29—N5—C28—C27	−1.4 (6)
C3—C4—C5—C6	−179.6 (4)	C29—C25—C26—C27	−0.4 (6)
C3—C4—C12—N1	−0.4 (6)	C30—N4—C19—C20	−0.7 (6)
C3—C4—C12—C11	177.7 (3)	C30—C22—C23—C24	0.3 (7)
C4—C5—C6—C7	1.3 (7)	C31—N6—C35—C34	0.7 (6)
C5—C4—C12—N1	179.9 (4)	C31—N6—C35—C35ⁱⁱ	−179.1 (4)
C5—C4—C12—C11	−2.0 (6)	C31—C32—C33—C34	−0.2 (6)
C5—C6—C7—C8	178.9 (4)	C32—C33—C34—C35	−0.4 (6)
C5—C6—C7—C11	−0.6 (6)	C32—C33—C34—C36	178.6 (4)
C6—C7—C8—C9	−179.3 (4)	C33—C34—C35—N6	0.1 (6)
C6—C7—C11—N2	179.8 (4)	C33—C34—C35—C35ⁱⁱ	180.0 (4)
C6—C7—C11—C12	−1.3 (6)	C33—C34—C36—C36ⁱⁱ	−178.5 (5)
C7—C8—C9—C10	−0.4 (6)	C35—N6—C31—C32	−1.3 (6)
C7—C11—C12—N1	−179.2 (4)	C35—C34—C36—C36ⁱⁱ	0.5 (7)
C7—C11—C12—C4	2.6 (6)	C36—C34—C35—N6	−178.9 (4)
C8—C7—C11—N2	0.3 (6)	C36—C34—C35—C35ⁱⁱ	1.0 (7)
C8—C7—C11—C12	179.2 (4)	O1—C37—C38—C39	−177.5 (4)
C8—C9—C10—N2	0.2 (6)	O1—C37—C38—C43	−1.5 (6)
C10—N2—C11—C7	−0.5 (6)	O2—C37—C38—C39	−0.3 (6)
C10—N2—C11—C12	−179.4 (3)	O2—C37—C38—C43	175.7 (4)
C11—N2—C10—C9	0.3 (6)	O3—C39—C40—C41	176.4 (4)
C11—C7—C8—C9	0.2 (6)	O6—C47—C48—C49	−177.0 (4)
C12—N1—C1—C2	−0.5 (6)	N7—N8—C42—C41	−1.5 (6)
C12—C4—C5—C6	0.0 (6)	N7—N8—C42—C43	179.9 (4)
C13—N3—C17—C16	−1.0 (6)	N7—C44—C45—C46	−178.3 (4)
C13—N3—C17—C17ⁱ	179.3 (4)	N7—C44—C49—C48	179.4 (4)
C13—C14—C15—C16	0.0 (6)	N8—N7—C44—C45	−179.1 (3)
C14—C15—C16—C17	0.4 (6)	N8—N7—C44—C49	1.7 (6)
C14—C15—C16—C18	−178.2 (4)	N8—C42—C43—C38	177.9 (3)
C15—C16—C17—N3	0.0 (6)	C37—C38—C39—O3	−1.6 (6)
C15—C16—C17—C17ⁱ	179.8 (4)	C37—C38—C39—C40	176.7 (4)
C15—C16—C18—C18ⁱ	179.6 (5)	C37—C38—C43—C42	−175.3 (4)
C17—N3—C13—C14	1.5 (6)	C38—C39—C40—C41	−2.0 (7)
C17—C16—C18—C18ⁱ	1.0 (8)	C39—C38—C43—C42	0.8 (6)
C18—C16—C17—N3	178.8 (4)	C39—C40—C41—C42	2.0 (7)
C18—C16—C17—C17ⁱ	−1.5 (7)	C40—C41—C42—N8	−179.1 (4)
Zn2—N4—C19—C20	174.4 (3)	C40—C41—C42—C43	−0.5 (6)
Zn2—N4—C30—C22	−175.3 (3)	C41—C42—C43—C38	−0.9 (6)
Zn2—N4—C30—C29	3.9 (4)	C43—C38—C39—O3	−177.7 (4)
Zn2—N5—C28—C27	−178.3 (3)	C43—C38—C39—C40	0.6 (6)
Zn2—N5—C29—C25	177.7 (3)	C44—N7—N8—C42	179.2 (3)
Zn2—N5—C29—C30	−3.4 (4)	C44—C45—C46—C47	−0.7 (6)
Zn2—N6—C31—C32	178.0 (3)	C44—C45—C46—C50	177.0 (4)
Zn2—N6—C35—C34	−178.7 (3)	C45—C44—C49—C48	0.2 (6)
Zn2—N6—C35—C35ⁱⁱ	1.5 (6)	C45—C46—C47—O6	178.1 (4)
N4—C19—C20—C21	0.6 (7)	C45—C46—C47—C48	−0.7 (6)
N5—C29—C30—N4	−0.3 (5)	C45—C46—C50—O4	4.6 (6)
N5—C29—C30—C22	178.9 (4)	C45—C46—C50—O5	−175.2 (4)
N6—C31—C32—C33	1.1 (6)	C46—C47—C48—C49	1.9 (6)
C19—N4—C30—C22	0.4 (6)	C47—C46—C50—O4	−177.8 (4)
C19—N4—C30—C29	179.6 (3)	C47—C46—C50—O5	2.4 (6)
C19—C20—C21—C22	−0.2 (7)	C47—C48—C49—C44	−1.6 (6)
C20—C21—C22—C23	179.8 (4)	C49—C44—C45—C46	0.9 (6)
C20—C21—C22—C30	0.0 (7)	C50—C46—C47—O6	0.3 (6)
C21—C22—C23—C24	−179.4 (4)	C50—C46—C47—C48	−178.5 (4)
C21—C22—C30—N4	−0.1 (6)

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

Funding information

Funding was provided by the Basic Scientific Research Project of the Universities from the Department of Education of Liaoning Province (grant Nos. LJKZ0371; LJKMZ20220738).

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IUCrJ

Volume 10| Part 6| November 2023| Pages 671-677

ISSN: 2052-2525

https://doi.org/10.1107/S2052252523007650

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