Syntheses and crystal structures of a new pyrazine dicarboxamide ligand, N2,N3-bis­(quinolin-8-yl)pyrazine-2,3-dicarboxamide, and of a copper perchlorate binuclear complex

Cati, D.S.; Stoeckli-Evans, H.

doi:10.1107/S2056989020001838

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Volume 76| Part 3| March 2020| Pages 332-338

https://doi.org/10.1107/S2056989020001838

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Syntheses and crystal structures of a new pyrazine dicarboxamide ligand, N²,N³-bis(quinolin-8-yl)pyrazine-2,3-dicarboxamide, and of a copper perchlorate binuclear complex

Dilovan S. Cati ^a and Helen Stoeckli-Evans ^b ^*

^aDebiopharm International S.A., Chemin Messidor 5-7, CH-1002 Lausanne, Switzerland, and ^bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

Edited by M. Zeller, Purdue University, USA (Received 7 February 2020; accepted 9 February 2020; online 14 February 2020)

The title pyrazine dicarboxamide ligand, N²,N³-bis(quinolin-8-yl)pyrazine-2,3-dicarboxamide (H₂L1), C₂₄H₁₆N₆O₂, has a twisted conformation with the outer quinoline groups being inclined to the central pyrazine ring by 9.00 (6) and 78.67 (5)°, and by 79.94 (4)° to each other. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming layers parallel to the (10 $[\overline{1}]$ ) plane, which are in turn linked by offset π–π interactions [intercentroid distances 3.4779 (9) and 3.6526 (8) Å], forming a supramolecular three-dimensional structure. Reaction of the ligand H₂L1 with Cu(ClO₄)₂ in acetonitrile leads to the formation of the binuclear complex, [μ-(3-{hydroxy[(quinolin-8-yl)imino]methyl}pyrazin-2-yl)[(quinolin-8-yl)imino]methanolato]bis[diacetonitrilecopper(II)] tris(perchlorate) acetonitrile disolvate, [Cu₂(C₂₄H₁₅N₆O₂)(CH₃CN)₄](ClO₄)₃·2CH₃CN or [Cu₂(HL1⁻)(CH₃CN)₄](ClO₄)₃·2CH₃CN (I). In the cation of complex I, the ligand coordinates to the copper(II) atoms in a bis-tridentate fashion. A resonance-assisted O—H⋯O hydrogen bond is present in the ligand; the position of this H atom was located in a difference-Fourier map. Both copper(II) atoms are fivefold coordinate, being ligated by three N atoms of the ligand and by the N atoms of two acetonitrile molecules. The first copper atom has a perfect square-pyramidal geometry while the second copper atom has a distorted shape. In the crystal, the cation and perchlorate anions are linked by a number of C—H⋯O hydrogen bonds, forming a supramolecular three-dimensional structure.

Keywords: crystal structure; pyrazine; dicarboxamide; quinoline; copper(II); bis-tridentate coordination; hydrogen bonding; offset π–π interactions; Hirshfeld surface analysis.

CCDC references: 1982863; 1982862

1. Chemical context

The title ligand, N²,N³-bis(quinolin-8-yl)pyrazine-2,3-dicarboxamide (H₂L1), is very similar to ligand N²-[(2,3-dihydropyridin-2-yl)methyl]-N³-(pyridin-2-ylmethyl)pyrazine-2,3-dicarboxamide (H₂L2), for which two polymorphs have been reported (Cati et al., 2004 ; Cati & Stoeckli-Evans, 2004 ). These and other pyrazine-carboxamide ligands were synthesized to explore their coordination behaviour with first-row transition metals and to study the magnetic exchange behaviour of the complexes (Cati, 2002 ). With ligand H₂L2, grid [2 × 2] complexes have been synthesized using Cu(BF₄)₂ (Hausmann et al., 2003 ), and with Cu(ClO₄)₂ and NiCl₂ (Cati et al., 2004). The latter complexes were shown to exhibit multiple anion encapsulation and antiferromagnetic exchange behaviour. In all of these complexes, the ligand is monodeprotonated and the bis-tridentate coordinated ligands have relatively planar conformations. Herein, we report on the syntheses and crystal structures of the title pyrazine dicarboxamide ligand (H₂L1), and of a binuclear copper complex, I, which was synthesized by the reaction of H₂L1 with copper perchlorate using acetonitrile as solvent. The various intermolecular contacts in the crystal of H₂L1 have been studied by Hirshfeld surface analysis.

2. Structural commentary

The molecular structure of ligand H₂L1 is illustrated in Fig. 1. The quinoline ring (N4/C6–C14, r.m.s. deviation 0.008 Å) is inclined to the pyrazine ring (N1/N2/C1–C4) by 9.00 (6)°. The NH hydrogen atom H3N is involved in two intramolecular N—H⋯N contacts (Fig. 1, Table 1). On the opposite side of the molecule, the quinoline ring system (N6/C16–C124, r.m.s. deviation 0.009 Å) is inclined to the pyrazine ring by 78.67 (5)°, with a single intramolecular N—H⋯N contact (Fig. 1, Table 1). Both carboxamide O atoms, O1 and O2, are involved in short C—H⋯O intramolecular contacts, enclosing S(6) ring motifs (Fig. 1, Table 1). Hence, the molecule is L-shaped with the two quinoline ring systems being inclined to each other by 79.94 (4)°.

Table 1
Hydrogen-bond geometry (Å, °) for H₂L1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N1	0.88 (2)	2.256 (16)	2.6791 (18)	109 (1)
N3—H3N⋯N4	0.88 (2)	2.218 (16)	2.6657 (16)	111 (1)
N5—H5N⋯N6	0.85 (2)	2.233 (16)	2.6759 (17)	113 (1)
C7—H7⋯O1	0.94	2.31	2.9136 (19)	122
C17—H17⋯O2	0.94	2.28	2.8818 (18)	122
C4—H4⋯O1ⁱ	0.94	2.57	3.4249 (18)	151
C12—H12⋯O2ⁱⁱ	0.94	2.60	3.3589 (19)	138
C18—H18⋯O2ⁱⁱⁱ	0.94	2.48	3.3289 (19)	151
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+2, -z+1; (iii) -x, -y+1, -z.

Figure 1
Molecular structure of ligand H₂L1, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular contacts are shown as dashed lines (see Table 1

In the binuclear copper complex I (Fig. 2), which was formed by the reaction of H₂L1 with Cu(ClO₄)₂·2H₂O, the bond lengths and angles involving the two amide moieties (Table 2; notably the bond lengths involving atoms C5 and C15) indicate that the situation in the crystal resembles that shown in the scheme for HL1⁻. On coordinating to two metal ions the ligand H₂L1 becomes negatively charged, and is stabilized by a hydrogen bond to the adjacent neutral amide tautomer. In order to locate the H atom of this resonance-assisted O—H⋯O hydrogen bond (Table 4), and as recommended by Fábry (Fábry, 2018 ) and Spek (Spek, 2020 ), a difference-Fourier map (Fig. 3) was examined and the position of the H atom was located closest to atom O2.

Table 2
A comparison of bond lengths and angles (Å, °) in the carboxamide units of H₂L1 and I

	H₂L1	I
O1—C5	1.222 (2)	1.289 (5)
N3—C5	1.347 (2)	1.319 (6)
C1—C5	1.506 (2)	1.477 (7)
O2—C15	1.219 (2)	1.267 (5)
N5—C15	1.348 (2)	1.310 (6)
C2—C15	1.508 (2)	1.518 (5)

N3—C5—O1	125.78 (13)	123.9 (4)
N3—C5—C1	113.91 (12)	114.4 (4)
O1—C5—C1	120.32 (12)	121.7 (4)
N5—C15—O2	125.13 (13)	125.7 (4)
N5—C15—C2	115.76 (12)	112.1 (4)
O2—C15—C2	118.87 (12)	122.1 (4)

Table 4
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O1	1.12 (6)	1.29 (6)	2.397 (4)	169 (6)
C7—H7⋯O1	0.95	2.35	2.920 (6)	118
C17—H17⋯O2	0.95	2.32	2.897 (5)	119
C17—H17⋯O32ⁱ	0.95	2.36	3.175 (7)	144
C22—H22⋯O12ⁱⁱ	0.95	2.50	3.108 (6)	122
C23—H23⋯O34ⁱⁱ	0.95	2.41	3.255 (7)	148
C34—H34A⋯O24	0.98	2.31	3.130 (10)	140
C34—H34C⋯O11ⁱⁱⁱ	0.98	2.56	3.272 (9)	130
C36—H36A⋯O21^iv	0.98	2.46	3.429 (8)	168
C38—H38B⋯N31^iv	0.98	2.57	3.454 (10)	150
C40—H40C⋯O32^v	0.98	2.57	3.516 (8)	162
Symmetry codes: (i) x+1, y-1, z; (ii) x, y-1, z; (iii) x, y, z-1; (iv) -x, -y, -z+1; (v) -x, -y+1, -z+1.

Figure 2
Molecular structure of the cation of complex I, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. For clarity, the perchlorate anions and the solvate acetonitrile molecules have been omitted.

Figure 3
A difference-Fourier map showing the position (X) of the hydroxyl H atom, H2O, in complex I.

The asymmetric unit of compound I is composed of the binuclear 3⁺ cation, three perchlorate anions and two acetonitrile solvate molecules. In the cation (Fig. 2), the ligand coordinates to the copper(II) atoms in a bis-tridentate fashion. Selected bond lengths and angles involving atoms Cu1 and Cu2 are given in Table 3. Atom Cu1 has a perfect square-pyramidal fivefold CuN₅ coordination sphere with a τ₅ value of 0.0 (τ₅ = 0 for an ideal square-pyramidal coordination sphere, and = 1 for an ideal trigonal–pyramidal coordination sphere; Addison et al., 1984 ). The Cu—N bond lengths in the equatorial plane vary from 1.936 (3) to 2.013 (4) Å, while the apical Cu—N12 bond length is 2.266 (4) Å. Atom Cu2 also has a fivefold CuN₅ coordination sphere but the value of τ₅ is 0.38, indicating a distorted shape. The Cu—N bond lengths in the approximate equatorial plane vary from 1.943 (4) to 2.054 (4) Å, while the apical Cu—N21 bond length is 2.137 (4) Å. The ligand is essentially planar with the quinoline ring systems (involving atoms N4 and N6) being inclined to the central pyrazine ring by 1.78 (17) and 1.80 (17)°, respectively, and by 2.65 (13)° to each other.

Table 3
Selected geometric parameters (Å, °) for I

Cu1—N1	2.013 (4)	Cu2—N2	1.996 (4)
Cu1—N3	1.936 (3)	Cu2—N5	1.943 (4)
Cu1—N4	1.952 (4)	Cu2—N6	1.961 (3)
Cu1—N11	1.982 (4)	Cu2—N21	2.137 (4)
Cu1—N12	2.266 (4)	Cu2—N22	2.054 (4)

N4—Cu1—N1	163.76 (14)	N6—Cu2—N2	163.51 (16)
N3—Cu1—N11	163.66 (16)	N5—Cu2—N22	140.74 (16)

3. Supramolecular features

In the crystal of H₂L1, molecules are linked by two pairs of C—H⋯O hydrogen bonds (C12—H12⋯O2ⁱⁱ and C18—H18⋯O2ⁱⁱⁱ), each involving inversion-related molecules, forming chains of loops propagating along the [10 $[\overline{1}]$ ] direction. The loops enclose R₂²(14) and R₂²(24) ring motifs (see Fig. 4, Table 1). A third C—H⋯O hydrogen bond (C4—H4⋯O1ⁱ) links the chains in the b-axis direction (Table 1), so forming layers lying parallel to the (10 $[\overline{1}]$ ) plane. Finally the layers are linked by offset π–π interactions involving the pyrazine ring and an inversion-related quinoline ring system, and by inversion-related quinoline ring systems, so forming a supramolecular three-dimensional structure (Fig. 5). The first offset π–π interaction involves pyrazine ring N1/N2/C1–C4 (centroid Cg1) and quinoline ring system N4/C6–C14 (centroid Cg2) with Cg1⋯Cg2ⁱ = 3.4779 (9) Å, α = 9.00 (6)°, β = 17.5 °, γ = 11.3°; the interplanar distances are 3.4106 (6) and 3.3162 (5) Å, with an offset of 1.048 Å [symmetry code: (i) −x, −y + 2, −z + 1]. The second offset π–π interaction involves inversion-related N6/C16–C24 (centroid Cg3) quinoline ring systems with Cg3⋯Cg3ⁱⁱ = 3.6526 (8) Å, α = 0.00 (4)°, β = 24.1°, γ = 24.1°, interplanar distance = 3.3333 (4) Å, with an offset of 1.494 Å [symmetry code: (ii) −x − 1, −y + 1, −z].

Figure 4
A partial view along the b axis of the crystal packing of ligand H₂L1. Hydrogen bonds are shown as dashed lines (see Table 1

). For clarity, in this and subsequent crystal packing figures, only the H atoms involved in these interactions have been included.

Figure 5
The crystal packing of ligand H₂L1, viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1

In the crystal of complex I, the cations are arranged in layers parallel to the (012) plane. They are linked via the perchlorate anions by a number of C—H⋯O hydrogen bonds (Table 4), so forming a supramolecular three-dimensional structure (Figs. 6 and 7). There is only one significant C—H⋯N hydrogen bond present involving the solvate acetonitrile N atom, N31, linking it to the CH₃ group of a coordinated acetonitrile molecule on atom Cu2 (Table 4).

Figure 6
The crystal packing of complex I, viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 4

Figure 7
The crystal packing of complex I, viewed along the c axis. Hydrogen bonds are shown as dashed lines (see Table 4

4. Hirshfeld surface analysis of ligand HL1

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were performed with CrystalExplorer17 (Turner et al., 2017 ). A view of the Hirshfeld surface of H₂L1 mapped over d_norm is shown in Fig. 8a, where short interatomic contacts are indicated by the faint red spots. The π–π stacking in the crystal is confirmed by the small blue regions surrounding bright-red spots in the various aromatic rings in Fig. 8b, the Hirshfeld surface mapped over the shape-index. The π–π stacking is also confirmed by the flat regions around the aromatic units in Fig. 8c, the Hirshfeld surface mapped over the curvedness.

Figure 8
(a) A view of the Hirshfeld surface for H₂L1 mapped over d_norm, with colour code −0.1884 to 1.1906 a.u., (b) a view of the Hirshfeld surface mapped over the shape-index for H₂L1, (c) a view of the Hirshfeld surface mapped over the curvedness for H₂L1.

The two-dimensional fingerprint plots for H₂L1 are given in Fig. 9. The principal intermolecular contact types are delineated into H⋯H at 36.4% (Fig. 9b), C⋯H/H⋯C at 24.1% (Fig. 9c), O⋯H/H⋯O at 12.2% (Fig. 9d) and N⋯H/H⋯N at 11.8% (Fig. 9e) contacts. The contributions of the C⋯N (Fig. 9f) and C⋯C (Fig. 9g) contacts are 7.7 and 6.7%, respectively.

Figure 9
(a) The full two-dimensional fingerprint plot for H₂L1 and the fingerprint plots delineated into (b) H⋯H, (c) C⋯H/H⋯C, (d) O⋯H/H⋯O, (e) N⋯H/H⋯N, (f) C⋯N, (g) C⋯C contacts.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.41, update November 2019; Groom et al., 2016 ) for pyrazine carboxamides including a quinoline group yielded 28 hits. Many of these structures concern the ligand N-(quinolin-8-yl)pyrazine-2-carboxamide (CSD refcode EFODIP; Cati & Stoeckli-Evans, 2019 ) and metal complexes of this ligand, such as (acetato)[N-(quinolin-8-yl)pyrazine-2-carboxamidato]copper(II) monohydrate (AYIFOF; Meghdadi et al., 2013 ) and hexakis(μ-acetato)bis(methanol)bis[N-(quniolin-8-yl)pyrazine-2-carboxamide]tetracopper(II) methanol solvate (EFODOV; Cati & Stoeckli-Evans, 2019). However, the majority of the structures are hetero bimetallic iron–manganese cyano complexes that exhibit super-exchange magnetic properties (see file S1 in the supporting information).

6. Synthesis and crystallization

Synthesis of the ligand N²,N³-di(quinolin-8-yl)pyrazine-2,3-dicarboxamide (H₂L1): 8-aminoquinoline (3.18g, 22 mmol) was added to a solution of pyrazine-2,3-dicarboxylic acid (1.68g, 10 mmol) and 1,1′-carbonyldiimidazole (4.20g, 26 mmol) in 180 ml of DMF (anhydride) in a two-necked flask (500 ml). The solution was mixed for 15 min at room temperature and then heated gradually for 1 h and then refluxed for 7 h. The reaction mixture was then cooled and added directly to a column (10 g of SiO₂, diameter of the column 1 cm), and eluted with DMF. After evaporation of the solvent the solid obtained was refluxed in 80 ml of ethanol for 10 min and then filtered. The brown–yellow solid obtained was recrystallized from DMF and on slow evaporation of the solvent pale-yellow rod-like crystals of H₂L1 were obtained (yield 22%; m.p. 569 K). ¹H NMR (400 MHz, DMSO-d₆): 11.47 (s, 1H, HN₃); 9.04 (s, 1H, H3 = H4); 8.95 (dd, 1H, J_13,12 = 4.2, J_13,11 = 1.7, H13); 8.82 (dd, 1H, J_7,8 = 7.7, J_7,9 = 1.2, H7); 8.47 (dd, 1H, J_11,12 = 8.3, J_11,13 = 1.7, H11); 7.77 (dd, 1H, J_9,8 = 8.3, J_9,7 = 1.2, H9); 7.66 (m, 2H, H12 & H8). IR (KBr pellet, cm⁻¹): 3350 (s), 3300 (s), 1678 (vs), 1560 (vs), 1530 (vs), 1520 (vs), 1488 (vs), 1465 (s), 1427 (vs), 1385 (s), 1326 (s), 1151 (s), 1109 (s), 919 (s), 829 (vs), 792 (vs), 752 (s), 652 (s), 607 (s). Analysis. for C₂₄H₁₆N₆O₂ (Mr = 420.43 g mol⁻¹) calculated (%) C: 68.56, H: 3.84, N: 19.99; found (%) C: 68.70, H: 3.92, N: 20.40.

Synthesis of complex [Cu₂(HL⁻)(CH₃CN)₄]·3(ClO₄)·2(CH₃CN) (I): Cu(ClO₄)₂·6H₂O (28 mg, 0.075 mmol) and H₂L (15 mg, 0.036 mmol) were added to 10 ml of acetonitrile. The green solution obtained was stirred at room temperature for 10 min, then left at ambient temperature. After slow evaporation of the solvent green plate-like crystals of I were obtained (yield: 15 mg, 40%). IR (KBr pellet, cm⁻¹): 1660 (vs), 1645 (vs), 1615 (vs), 1581 (s), 1566 (s), 1389 (s), 1147 (s), 1089 (vs), 625 (s).

During this experiment, two types of crystals were obtained on slow evaporation of the filtrate of the reaction mixture; green plate-like crystals of the binuclear complex I and thin colourless crystals of a second binuclear complex, [(H₂O)Cu₂(HL1⁻)(ClO₄)₂(CH₃CN)]·(ClO₄)·2(CH₃CN) (II). The data set for II, measured at 153 K, has only 20% observed data; the crystal did not diffract beyond 20° in θ. While the structure is perfectly clear (Fig. 10), the analysis is probably at the limit of being acceptable: R_int = 0.36 and GoF = 0.43, with the s.u.s. of the Cu—O/N bond lengths varying between 0.008 and 0.014 Å. The final values of R[F² > 2σ(F²)] and wR(F²) are 0.0558 and 0.1328. The CIF, including the HKL file, has been deposited with the Cambridge Structural Database (refcode XUFZAC; CCDC 1981495; Groom et al., 2016). It is supplied here as supporting information file S2.

Figure 10
The structure of complex [(H₂O)Cu₂(HL1⁻)(ClO₄)₂(CH₃CN)]·(ClO₄)·2(CH₃CN) (II).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. For ligand H₂L1, the NH H atoms were located in a difference-Fourier map and freely refined. For both H₂L1 and complex I, the C-bound H atoms were included in calculated positions and refined as riding: C—H = 0.94–0.98 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms. For complex I, a resonance assisted O2—H2O⋯O1 hydrogen bond (Table 4) is present in the ligand; the position of the H atom, H2O, was located closest to atom O2 in a difference-Fourier map (Fig. 3) and was freely refined.

Table 5
Experimental details

	H₂L1	I
Crystal data
Chemical formula	C₂₄H₁₆N₆O₂	[Cu₂(C₂₄H₁₅N₆O₂)(C₂H₃N)₄](ClO₄)₃·2C₂H₃N
M_r	420.43	1091.17
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	223	153
a, b, c (Å)	7.9633 (11), 8.0043 (12), 15.615 (2)	12.6281 (10), 13.4938 (11), 14.7884 (14)
α, β, γ (°)	97.629 (14), 98.349 (11), 100.407 (17)	74.678 (10), 89.115 (10), 65.170 (9)
V (Å³)	955.6 (2)	2192.5 (4)
Z	2	2
Radiation type	Cu Kα	Mo Kα
μ (mm⁻¹)	0.80	1.23
Crystal size (mm)	0.46 × 0.23 × 0.15	0.30 × 0.30 × 0.15

Data collection
Diffractometer	STOE-Siemens AED2, 4-circle	STOE IPDS 1
Absorption correction	Multi-scan (MULABS; Spek, 2020)	Multi-scan (MULABS; Spek, 2020)
T_min, T_max	0.984, 1.000	0.857, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5536, 2791, 2596	17344, 7942, 4757
R_int	0.017	0.077
θ_max (°)	59.6	25.9
(sin θ/λ)_max (Å⁻¹)	0.560	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.092, 1.04	0.053, 0.138, 0.86
No. of reflections	2791	7942
No. of parameters	298	615
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17	0.91, −0.93
Computer programs: STADI4 (Stoe & Cie, 1997 ), EXPOSE, CELL and INTEGRATE in IPDS1 (Stoe & Cie, 2004 ), X-RED (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 2008 ), SHELXL2014/6 and SHELXL2016/6 (Sheldrick, 2015 ), PLATON (Spek, 2020), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

With the STOE IPDS I, a one-circle diffractometer, for the triclinic system often only 93% of the Ewald sphere is accessible. Hence, for complex I the `diffrn_reflns_Laue_measured_fraction_full' of 0.941 is below the required minimum of 0.95.

Supporting information

CCDC references: 1982863; 1982862

Crystal structure: contains datablocks H2L1, I, Global. DOI: https://doi.org/10.1107/S2056989020001838/zl2771sup1.cif

Structure factors: contains datablock H2L1. DOI: https://doi.org/10.1107/S2056989020001838/zl2771H2L1sup2.hkl

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020001838/zl2771Isup3.hkl

CSD search. DOI: https://doi.org/10.1107/S2056989020001838/zl2771sup4.pdf

CIF for compound II. DOI: https://doi.org/10.1107/S2056989020001838/zl2771sup5.cif

checkCIF report

Computing details top

Data collection: STADI4 (Stoe & Cie, 1997) for H2L1; EXPOSE in IPDS1 (Stoe & Cie, 2004) for (I). Cell refinement: STADI4 (Stoe & Cie, 1997) for H2L1; CELL in IPDS1 (Stoe & Cie, 2004) for (I). Data reduction: X-RED (Stoe & Cie, 1997) for H2L1; INTEGRATE in IPDS1 (Stoe & Cie, 2004) for (I). For both structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020) and Mercury (Macrae et al., 2020). Software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010) for H2L1; SHELXL2016/6 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010) for (I).

N²,N³-Bis(quinolin-8-yl)pyrazine-2,3-dicarboxamide (H2L1) top

Crystal data top

C₂₄H₁₆N₆O₂	Z = 2
M_r = 420.43	F(000) = 436
Triclinic, P1	D_x = 1.461 Mg m⁻³
a = 7.9633 (11) Å	Cu Kα radiation, λ = 1.54186 Å
b = 8.0043 (12) Å	Cell parameters from 21 reflections
c = 15.615 (2) Å	θ = 15.5–27.3°
α = 97.629 (14)°	µ = 0.80 mm⁻¹
β = 98.349 (11)°	T = 223 K
γ = 100.407 (17)°	Rod, pale_yellow
V = 955.6 (2) Å³	0.46 × 0.23 × 0.15 mm

Data collection top

STOE-Siemens AED2, 4-circle diffractometer	2596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Plane graphite monochromator	θ_max = 59.6°, θ_min = 2.9°
ω/2θ scans	h = −8→8
Absorption correction: multi-scan (MULABS; Spek, 2009)	k = −8→8
T_min = 0.984, T_max = 1.000	l = −17→17
5536 measured reflections	2 standard reflections every 60 min
2791 independent reflections	intensity decay: 2%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0602P)² + 0.1623P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2791 reflections	Δρ_max = 0.20 e Å⁻³
298 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: (SHELXL-2016/6; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0083 (8)

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
N1	0.03840 (15)	1.12688 (15)	0.36884 (8)	0.0351 (3)
N2	−0.16596 (15)	1.03169 (15)	0.20236 (8)	0.0365 (3)
N3	0.17902 (15)	0.89849 (16)	0.45078 (7)	0.0334 (3)
H3N	0.200 (2)	1.011 (2)	0.4667 (10)	0.038 (4)*
N4	0.38594 (14)	1.09265 (14)	0.59206 (7)	0.0317 (3)
N5	−0.26526 (15)	0.64169 (15)	0.16840 (7)	0.0298 (3)
H5N	−0.343 (2)	0.668 (2)	0.1963 (11)	0.039 (4)*
N6	−0.59109 (14)	0.47298 (14)	0.15991 (7)	0.0307 (3)
O1	0.02271 (14)	0.67866 (12)	0.34455 (7)	0.0449 (3)
O2	0.01629 (13)	0.72082 (14)	0.15181 (7)	0.0454 (3)
C1	0.00279 (16)	0.96459 (17)	0.32722 (8)	0.0291 (3)
C2	−0.09398 (16)	0.91763 (17)	0.24276 (9)	0.0295 (3)
C3	−0.13458 (19)	1.19183 (19)	0.24608 (10)	0.0389 (4)
H3	−0.185777	1.274605	0.220628	0.047*
C4	−0.03009 (19)	1.24052 (18)	0.32706 (10)	0.0385 (4)
H4	−0.006243	1.356654	0.353677	0.046*
C5	0.06931 (17)	0.83168 (17)	0.37497 (9)	0.0314 (3)
C6	0.26615 (18)	0.81207 (17)	0.50976 (9)	0.0321 (3)
C7	0.2510 (2)	0.63717 (19)	0.50045 (10)	0.0446 (4)
H7	0.177771	0.566095	0.451485	0.054*
C8	0.3440 (2)	0.5635 (2)	0.56341 (11)	0.0529 (5)
H8	0.331749	0.443146	0.556124	0.063*
C9	0.4514 (2)	0.6625 (2)	0.63477 (11)	0.0486 (4)
H9	0.512816	0.610421	0.676168	0.058*
C10	0.47108 (19)	0.84334 (18)	0.64690 (9)	0.0347 (3)
C11	0.57800 (19)	0.95486 (19)	0.71977 (9)	0.0372 (4)
H11	0.642381	0.909866	0.763226	0.045*
C12	0.58759 (18)	1.12744 (19)	0.72692 (9)	0.0364 (3)
H12	0.658863	1.203331	0.774906	0.044*
C13	0.48898 (19)	1.18985 (18)	0.66126 (9)	0.0354 (3)
H13	0.496900	1.309536	0.666969	0.043*
C14	0.37686 (17)	0.91962 (17)	0.58438 (8)	0.0294 (3)
C15	−0.10800 (17)	0.74740 (18)	0.18488 (8)	0.0304 (3)
C16	−0.32246 (17)	0.49008 (16)	0.10646 (8)	0.0270 (3)
C17	−0.22451 (18)	0.42460 (17)	0.04976 (9)	0.0311 (3)
H17	−0.107818	0.478027	0.053540	0.037*
C18	−0.29793 (19)	0.27840 (18)	−0.01373 (9)	0.0339 (3)
H18	−0.229132	0.235331	−0.051940	0.041*
C19	−0.46653 (19)	0.19748 (18)	−0.02128 (9)	0.0341 (3)
H19	−0.513986	0.101611	−0.065281	0.041*
C20	−0.56981 (17)	0.25848 (16)	0.03745 (8)	0.0297 (3)
C21	−0.74570 (18)	0.18132 (18)	0.03417 (9)	0.0360 (4)
H21	−0.798983	0.083571	−0.007714	0.043*
C22	−0.83701 (19)	0.24976 (19)	0.09212 (10)	0.0374 (4)
H22	−0.953714	0.199482	0.090878	0.045*
C23	−0.75489 (18)	0.39644 (18)	0.15383 (9)	0.0350 (3)
H23	−0.820165	0.442744	0.193010	0.042*
C24	−0.49857 (17)	0.40505 (16)	0.10189 (8)	0.0262 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0356 (6)	0.0310 (7)	0.0333 (6)	0.0009 (5)	−0.0001 (5)	0.0007 (5)
N2	0.0365 (7)	0.0386 (7)	0.0330 (6)	0.0065 (5)	0.0003 (5)	0.0081 (5)
N3	0.0414 (7)	0.0272 (7)	0.0266 (6)	0.0034 (5)	−0.0045 (5)	0.0022 (5)
N4	0.0353 (7)	0.0290 (6)	0.0277 (6)	0.0045 (5)	0.0006 (5)	0.0022 (5)
N5	0.0260 (6)	0.0329 (6)	0.0275 (6)	0.0042 (5)	0.0027 (5)	−0.0012 (5)
N6	0.0311 (6)	0.0322 (6)	0.0288 (6)	0.0073 (5)	0.0036 (5)	0.0058 (5)
O1	0.0560 (7)	0.0293 (6)	0.0385 (6)	−0.0005 (5)	−0.0121 (5)	0.0013 (5)
O2	0.0286 (6)	0.0562 (7)	0.0446 (6)	0.0027 (5)	0.0065 (5)	−0.0079 (5)
C1	0.0264 (7)	0.0301 (7)	0.0268 (7)	−0.0012 (5)	0.0024 (5)	0.0022 (6)
C2	0.0237 (7)	0.0343 (7)	0.0287 (7)	0.0010 (5)	0.0035 (5)	0.0070 (6)
C3	0.0418 (8)	0.0353 (8)	0.0397 (8)	0.0077 (6)	0.0032 (7)	0.0110 (7)
C4	0.0419 (8)	0.0283 (8)	0.0421 (8)	0.0035 (6)	0.0031 (7)	0.0039 (6)
C5	0.0327 (7)	0.0301 (8)	0.0271 (7)	−0.0001 (6)	0.0011 (6)	0.0022 (6)
C6	0.0374 (8)	0.0311 (8)	0.0250 (7)	0.0043 (6)	0.0004 (6)	0.0036 (6)
C7	0.0574 (10)	0.0325 (8)	0.0350 (8)	0.0033 (7)	−0.0095 (7)	0.0011 (6)
C8	0.0745 (12)	0.0291 (8)	0.0466 (9)	0.0086 (8)	−0.0125 (9)	0.0038 (7)
C9	0.0643 (11)	0.0352 (8)	0.0417 (9)	0.0136 (8)	−0.0116 (8)	0.0079 (7)
C10	0.0377 (8)	0.0355 (8)	0.0290 (7)	0.0072 (6)	0.0006 (6)	0.0050 (6)
C11	0.0371 (8)	0.0424 (9)	0.0298 (8)	0.0095 (6)	−0.0032 (6)	0.0054 (6)
C12	0.0335 (8)	0.0401 (8)	0.0292 (7)	0.0022 (6)	−0.0019 (6)	−0.0026 (6)
C13	0.0391 (8)	0.0309 (8)	0.0320 (8)	0.0034 (6)	0.0021 (6)	−0.0005 (6)
C14	0.0309 (7)	0.0303 (7)	0.0258 (7)	0.0043 (6)	0.0046 (6)	0.0032 (5)
C15	0.0265 (7)	0.0378 (8)	0.0241 (7)	0.0045 (6)	−0.0014 (5)	0.0045 (6)
C16	0.0294 (7)	0.0281 (7)	0.0225 (6)	0.0069 (5)	−0.0007 (5)	0.0047 (5)
C17	0.0304 (7)	0.0343 (7)	0.0301 (7)	0.0099 (6)	0.0036 (6)	0.0071 (6)
C18	0.0432 (8)	0.0334 (8)	0.0283 (7)	0.0150 (6)	0.0078 (6)	0.0047 (6)
C19	0.0454 (9)	0.0278 (7)	0.0283 (7)	0.0101 (6)	0.0018 (6)	0.0031 (6)
C20	0.0358 (8)	0.0256 (7)	0.0270 (7)	0.0076 (6)	−0.0014 (6)	0.0070 (5)
C21	0.0379 (8)	0.0282 (7)	0.0364 (8)	0.0015 (6)	−0.0041 (6)	0.0050 (6)
C22	0.0299 (7)	0.0372 (8)	0.0426 (8)	0.0017 (6)	0.0008 (6)	0.0107 (7)
C23	0.0304 (8)	0.0377 (8)	0.0384 (8)	0.0073 (6)	0.0066 (6)	0.0099 (6)
C24	0.0293 (7)	0.0257 (7)	0.0239 (7)	0.0080 (5)	0.0002 (5)	0.0068 (5)

Geometric parameters (Å, º) top

N1—C1	1.3339 (18)	C8—C9	1.359 (2)
N1—C4	1.3358 (19)	C8—H8	0.9400
N2—C3	1.3319 (19)	C9—C10	1.412 (2)
N2—C2	1.3406 (18)	C9—H9	0.9400
N3—C5	1.3466 (18)	C10—C11	1.411 (2)
N3—C6	1.4018 (18)	C10—C14	1.414 (2)
N3—H3N	0.880 (17)	C11—C12	1.358 (2)
N4—C13	1.3171 (18)	C11—H11	0.9400
N4—C14	1.3620 (18)	C12—C13	1.401 (2)
N5—C15	1.3477 (18)	C12—H12	0.9400
N5—C16	1.4058 (17)	C13—H13	0.9400
N5—H5N	0.846 (17)	C16—C17	1.3756 (19)
N6—C23	1.3212 (18)	C16—C24	1.4312 (19)
N6—C24	1.3663 (18)	C17—C18	1.404 (2)
O1—C5	1.2222 (17)	C17—H17	0.9400
O2—C15	1.2193 (16)	C18—C19	1.362 (2)
C1—C2	1.3940 (19)	C18—H18	0.9400
C1—C5	1.506 (2)	C19—C20	1.415 (2)
C2—C15	1.5082 (19)	C19—H19	0.9400
C3—C4	1.375 (2)	C20—C24	1.4111 (19)
C3—H3	0.9400	C20—C21	1.416 (2)
C4—H4	0.9400	C21—C22	1.360 (2)
C6—C7	1.369 (2)	C21—H21	0.9400
C6—C14	1.4273 (19)	C22—C23	1.405 (2)
C7—C8	1.401 (2)	C22—H22	0.9400
C7—H7	0.9400	C23—H23	0.9400

C1—N1—C4	116.56 (12)	C12—C11—H11	120.1
C3—N2—C2	116.33 (12)	C10—C11—H11	120.1
C5—N3—C6	128.53 (12)	C11—C12—C13	118.55 (13)
C5—N3—H3N	117.3 (10)	C11—C12—H12	120.7
C6—N3—H3N	114.2 (10)	C13—C12—H12	120.7
C13—N4—C14	116.99 (12)	N4—C13—C12	124.61 (13)
C15—N5—C16	127.71 (12)	N4—C13—H13	117.7
C15—N5—H5N	118.6 (11)	C12—C13—H13	117.7
C16—N5—H5N	113.7 (11)	N4—C14—C10	122.93 (12)
C23—N6—C24	117.39 (12)	N4—C14—C6	117.86 (12)
N1—C1—C2	121.70 (13)	C10—C14—C6	119.21 (12)
N1—C1—C5	117.72 (12)	O2—C15—N5	125.13 (13)
C2—C1—C5	120.58 (12)	O2—C15—C2	118.87 (12)
N2—C2—C1	121.15 (13)	N5—C15—C2	115.76 (12)
N2—C2—C15	114.00 (11)	C17—C16—N5	124.89 (12)
C1—C2—C15	124.37 (12)	C17—C16—C24	119.45 (12)
N2—C3—C4	122.43 (14)	N5—C16—C24	115.61 (12)
N2—C3—H3	118.8	C16—C17—C18	120.33 (13)
C4—C3—H3	118.8	C16—C17—H17	119.8
N1—C4—C3	121.62 (14)	C18—C17—H17	119.8
N1—C4—H4	119.2	C19—C18—C17	121.56 (13)
C3—C4—H4	119.2	C19—C18—H18	119.2
O1—C5—N3	125.78 (13)	C17—C18—H18	119.2
O1—C5—C1	120.32 (12)	C18—C19—C20	119.65 (13)
N3—C5—C1	113.91 (12)	C18—C19—H19	120.2
C7—C6—N3	124.96 (13)	C20—C19—H19	120.2
C7—C6—C14	119.65 (13)	C24—C20—C21	117.14 (13)
N3—C6—C14	115.39 (12)	C24—C20—C19	119.73 (12)
C6—C7—C8	120.45 (14)	C21—C20—C19	123.12 (13)
C6—C7—H7	119.8	C22—C21—C20	119.48 (13)
C8—C7—H7	119.8	C22—C21—H21	120.3
C9—C8—C7	121.29 (15)	C20—C21—H21	120.3
C9—C8—H8	119.4	C21—C22—C23	119.24 (13)
C7—C8—H8	119.4	C21—C22—H22	120.4
C8—C9—C10	120.14 (14)	C23—C22—H22	120.4
C8—C9—H9	119.9	N6—C23—C22	123.70 (13)
C10—C9—H9	119.9	N6—C23—H23	118.1
C11—C10—C9	123.61 (13)	C22—C23—H23	118.1
C11—C10—C14	117.12 (13)	N6—C24—C20	123.04 (12)
C9—C10—C14	119.26 (13)	N6—C24—C16	117.72 (12)
C12—C11—C10	119.79 (13)	C20—C24—C16	119.23 (12)

C4—N1—C1—C2	3.0 (2)	C9—C10—C14—C6	−1.0 (2)
C4—N1—C1—C5	−176.41 (12)	C7—C6—C14—N4	−178.83 (13)
C3—N2—C2—C1	2.27 (19)	N3—C6—C14—N4	0.86 (19)
C3—N2—C2—C15	−170.17 (12)	C7—C6—C14—C10	0.9 (2)
N1—C1—C2—N2	−4.9 (2)	N3—C6—C14—C10	−179.42 (12)
C5—C1—C2—N2	174.45 (12)	C16—N5—C15—O2	−5.5 (2)
N1—C1—C2—C15	166.71 (12)	C16—N5—C15—C2	168.88 (12)
C5—C1—C2—C15	−13.9 (2)	N2—C2—C15—O2	99.14 (15)
C2—N2—C3—C4	1.9 (2)	C1—C2—C15—O2	−73.02 (18)
C1—N1—C4—C3	1.2 (2)	N2—C2—C15—N5	−75.58 (15)
N2—C3—C4—N1	−3.8 (2)	C1—C2—C15—N5	112.26 (14)
C6—N3—C5—O1	1.6 (2)	C15—N5—C16—C17	−1.2 (2)
C6—N3—C5—C1	−178.64 (13)	C15—N5—C16—C24	−178.69 (12)
N1—C1—C5—O1	170.92 (13)	N5—C16—C17—C18	−175.64 (12)
C2—C1—C5—O1	−8.5 (2)	C24—C16—C17—C18	1.78 (19)
N1—C1—C5—N3	−8.81 (18)	C16—C17—C18—C19	0.0 (2)
C2—C1—C5—N3	171.79 (12)	C17—C18—C19—C20	−1.7 (2)
C5—N3—C6—C7	−1.3 (2)	C18—C19—C20—C24	1.56 (19)
C5—N3—C6—C14	179.02 (13)	C18—C19—C20—C21	−179.78 (12)
N3—C6—C7—C8	−179.94 (15)	C24—C20—C21—C22	−0.14 (19)
C14—C6—C7—C8	−0.3 (2)	C19—C20—C21—C22	−178.84 (12)
C6—C7—C8—C9	−0.2 (3)	C20—C21—C22—C23	0.3 (2)
C7—C8—C9—C10	0.1 (3)	C24—N6—C23—C22	0.6 (2)
C8—C9—C10—C11	179.05 (16)	C21—C22—C23—N6	−0.6 (2)
C8—C9—C10—C14	0.5 (3)	C23—N6—C24—C20	−0.43 (18)
C9—C10—C11—C12	−179.09 (15)	C23—N6—C24—C16	178.29 (11)
C14—C10—C11—C12	−0.5 (2)	C21—C20—C24—N6	0.19 (18)
C10—C11—C12—C13	0.4 (2)	C19—C20—C24—N6	178.93 (11)
C14—N4—C13—C12	−0.5 (2)	C21—C20—C24—C16	−178.51 (11)
C11—C12—C13—N4	0.1 (2)	C19—C20—C24—C16	0.23 (18)
C13—N4—C14—C10	0.4 (2)	C17—C16—C24—N6	179.34 (11)
C13—N4—C14—C6	−179.89 (12)	N5—C16—C24—N6	−3.01 (17)
C11—C10—C14—N4	0.1 (2)	C17—C16—C24—C20	−1.88 (18)
C9—C10—C14—N4	178.73 (14)	N5—C16—C24—C20	175.77 (11)
C11—C10—C14—C6	−179.65 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1	0.88 (2)	2.256 (16)	2.6791 (18)	109 (1)
N3—H3N···N4	0.88 (2)	2.218 (16)	2.6657 (16)	111 (1)
N5—H5N···N6	0.85 (2)	2.233 (16)	2.6759 (17)	113 (1)
C7—H7···O1	0.94	2.31	2.9136 (19)	122
C17—H17···O2	0.94	2.28	2.8818 (18)	122
C4—H4···O1ⁱ	0.94	2.57	3.4249 (18)	151
C12—H12···O2ⁱⁱ	0.94	2.60	3.3589 (19)	138
C18—H18···O2ⁱⁱⁱ	0.94	2.48	3.3289 (19)	151

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

[µ-(3-{Hydroxy[(quinolin-8-yl)imino]methyl}pyrazin-2-yl)[(quinolin-8-yl)imino]methanolato]bis[diacetonitrilecopper(II)] tris(perchlorate) acetonitrile disolvate (I) top

Crystal data top

[Cu₂(C₂₄H₁₅N₆O₂)(C₂H₃N)₄](ClO₄)₃·2C₂H₃N	Z = 2
M_r = 1091.17	F(000) = 1108
Triclinic, P1	D_x = 1.653 Mg m⁻³
a = 12.6281 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.4938 (11) Å	Cell parameters from 8000 reflections
c = 14.7884 (14) Å	θ = 1.9–25.9°
α = 74.678 (10)°	µ = 1.23 mm⁻¹
β = 89.115 (10)°	T = 153 K
γ = 65.170 (9)°	Plate, green
V = 2192.5 (4) Å³	0.30 × 0.30 × 0.15 mm

Data collection top

STOE IPDS 1 diffractometer	7942 independent reflections
Radiation source: fine-focus sealed tube	4757 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.077
φ rotation scans	θ_max = 25.9°, θ_min = 1.9°
Absorption correction: multi-scan (MULABS; Spek, 2009)	h = −15→15
T_min = 0.857, T_max = 1.000	k = −16→16
17344 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.138	w = 1/[σ²(F_o²) + (0.0806P)²] where P = (F_o² + 2F_c²)/3
S = 0.86	(Δ/σ)_max < 0.001
7942 reflections	Δρ_max = 0.91 e Å⁻³
615 parameters	Δρ_min = −0.93 e Å⁻³
0 restraints	Extinction correction: (SHELXL-2016/6; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0021 (6)

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.31089 (4)	0.36323 (4)	0.17677 (4)	0.02595 (17)
Cu2	0.33585 (5)	−0.14019 (4)	0.43021 (4)	0.02764 (17)
N1	0.3033 (3)	0.2198 (3)	0.2544 (2)	0.0240 (8)
N2	0.3161 (3)	0.0140 (3)	0.3545 (2)	0.0266 (9)
N3	0.4715 (3)	0.2794 (3)	0.2351 (2)	0.0260 (9)
N4	0.3613 (3)	0.4827 (3)	0.1225 (2)	0.0262 (9)
N5	0.4906 (3)	−0.1517 (3)	0.4603 (2)	0.0234 (8)
N6	0.4004 (3)	−0.2963 (3)	0.5139 (2)	0.0256 (9)
O1	0.6081 (3)	0.1110 (3)	0.3337 (2)	0.0307 (8)
H2O	0.622 (5)	0.012 (5)	0.386 (4)	0.059 (17)*
O2	0.6151 (3)	−0.0656 (3)	0.4298 (2)	0.0281 (7)
C1	0.4089 (4)	0.1378 (3)	0.3039 (3)	0.0225 (10)
C2	0.4127 (4)	0.0330 (4)	0.3559 (3)	0.0239 (10)
C3	0.2154 (4)	0.0958 (4)	0.3057 (3)	0.0288 (11)
H3	0.147651	0.081917	0.305320	0.035*
C4	0.2096 (4)	0.2002 (4)	0.2561 (3)	0.0257 (10)
H4	0.137294	0.258614	0.222702	0.031*
C5	0.5038 (4)	0.1753 (4)	0.2911 (3)	0.0250 (10)
C6	0.5416 (4)	0.3376 (4)	0.2101 (3)	0.0247 (10)
C7	0.6599 (4)	0.3015 (4)	0.2368 (3)	0.0290 (11)
H7	0.704730	0.226789	0.276687	0.035*
C8	0.7137 (4)	0.3756 (4)	0.2047 (3)	0.0323 (12)
H8	0.794450	0.350005	0.224037	0.039*
C9	0.6518 (4)	0.4835 (4)	0.1464 (3)	0.0309 (11)
H9	0.689483	0.532160	0.125900	0.037*
C10	0.5319 (4)	0.5223 (4)	0.1169 (3)	0.0269 (11)
C11	0.4626 (4)	0.6320 (4)	0.0526 (3)	0.0323 (11)
H11	0.496049	0.683626	0.028325	0.039*
C12	0.3481 (4)	0.6609 (4)	0.0269 (3)	0.0318 (12)
H12	0.301292	0.733390	−0.015634	0.038*
C13	0.2994 (4)	0.5859 (4)	0.0622 (3)	0.0278 (11)
H13	0.219212	0.608312	0.043100	0.033*
C14	0.4778 (4)	0.4509 (4)	0.1486 (3)	0.0229 (10)
C15	0.5170 (4)	−0.0680 (4)	0.4180 (3)	0.0225 (10)
C16	0.5693 (4)	−0.2589 (4)	0.5187 (3)	0.0257 (11)
C17	0.6844 (4)	−0.2951 (4)	0.5505 (3)	0.0270 (10)
H17	0.721286	−0.245362	0.532594	0.032*
C18	0.7484 (4)	−0.4074 (4)	0.6102 (3)	0.0331 (12)
H18	0.828775	−0.432457	0.630637	0.040*
C19	0.6979 (4)	−0.4800 (4)	0.6390 (3)	0.0321 (12)
H19	0.742703	−0.554228	0.679823	0.038*
C20	0.5791 (4)	−0.4457 (4)	0.6086 (3)	0.0284 (11)
C21	0.5187 (4)	−0.5154 (4)	0.6354 (3)	0.0330 (12)
H21	0.557824	−0.590133	0.676896	0.040*
C22	0.4040 (4)	−0.4741 (4)	0.6009 (3)	0.0333 (12)
H22	0.362917	−0.520124	0.617845	0.040*
C23	0.3473 (4)	−0.3628 (4)	0.5402 (3)	0.0318 (12)
H23	0.267137	−0.334616	0.517247	0.038*
C24	0.5152 (4)	−0.3350 (3)	0.5481 (3)	0.0237 (10)
N11	0.1393 (3)	0.4596 (3)	0.1516 (3)	0.0312 (10)
N12	0.3124 (4)	0.2964 (4)	0.0511 (3)	0.0339 (10)
N21	0.1935 (4)	−0.0653 (3)	0.5072 (3)	0.0350 (10)
N22	0.2413 (4)	−0.1562 (3)	0.3276 (3)	0.0340 (10)
N31	−0.0216 (5)	0.3087 (5)	0.7312 (4)	0.0761 (19)
N41	0.6128 (5)	0.1094 (4)	0.1045 (4)	0.0633 (15)
C31	0.0403 (4)	0.5107 (4)	0.1374 (3)	0.0338 (12)
C32	−0.0859 (4)	0.5739 (5)	0.1177 (4)	0.0529 (17)
H32A	−0.106839	0.655648	0.097208	0.079*
H32B	−0.122554	0.556263	0.174940	0.079*
H32C	−0.113802	0.552464	0.067735	0.079*
C33	0.3372 (4)	0.2123 (5)	0.0361 (3)	0.0352 (12)
C34	0.3688 (6)	0.1031 (5)	0.0199 (5)	0.067 (2)
H34A	0.300051	0.086608	0.022887	0.101*
H34B	0.431395	0.043918	0.068279	0.101*
H34C	0.396348	0.104566	−0.042546	0.101*
C35	0.1362 (4)	−0.0221 (4)	0.5572 (3)	0.0361 (13)
C36	0.0637 (5)	0.0322 (5)	0.6241 (4)	0.0548 (16)
H36A	0.061187	−0.026485	0.678574	0.082*
H36B	−0.016047	0.082587	0.593230	0.082*
H36C	0.097525	0.076747	0.645207	0.082*
C37	0.2107 (4)	−0.1557 (4)	0.2554 (3)	0.0329 (12)
C38	0.1728 (6)	−0.1549 (5)	0.1627 (4)	0.0549 (17)
H38A	0.118838	−0.076994	0.127438	0.082*
H38B	0.132646	−0.204398	0.169850	0.082*
H38C	0.241295	−0.182614	0.128469	0.082*
C39	0.0411 (6)	0.3305 (5)	0.6832 (4)	0.0534 (16)
C40	0.1219 (6)	0.3564 (6)	0.6225 (5)	0.0639 (18)
H40A	0.201931	0.312437	0.654576	0.096*
H40B	0.101443	0.437947	0.607678	0.096*
H40C	0.117327	0.336521	0.564073	0.096*
C41	0.7059 (6)	0.0440 (5)	0.1161 (4)	0.0468 (15)
C42	0.8281 (8)	−0.0358 (9)	0.1254 (7)	0.134 (5)
H42A	0.846983	−0.055433	0.066062	0.202*
H42B	0.842543	−0.104882	0.176330	0.202*
H42C	0.877582	−0.001087	0.140095	0.202*
Cl1	0.45230 (12)	0.20687 (10)	0.77805 (8)	0.0413 (3)
O11	0.3457 (5)	0.2730 (5)	0.8096 (3)	0.0921 (19)
O12	0.4683 (5)	0.2688 (3)	0.6886 (3)	0.0808 (17)
O13	0.5461 (5)	0.1804 (5)	0.8468 (3)	0.0925 (18)
O14	0.4542 (5)	0.1041 (4)	0.7714 (3)	0.0713 (14)
Cl2	0.00354 (11)	0.19052 (11)	0.08660 (8)	0.0419 (3)
O21	−0.0275 (6)	0.1401 (5)	0.1734 (4)	0.102 (2)
O22	−0.0253 (4)	0.3067 (3)	0.0811 (3)	0.0647 (12)
O23	−0.0508 (5)	0.1810 (5)	0.0102 (4)	0.103 (2)
O24	0.1275 (4)	0.1280 (5)	0.0930 (4)	0.098 (2)
Cl3	0.01801 (11)	0.70326 (11)	0.59390 (8)	0.0390 (3)
O31	0.0200 (4)	0.6207 (3)	0.6788 (3)	0.0688 (14)
O32	−0.1024 (3)	0.7712 (4)	0.5514 (3)	0.0599 (12)
O33	0.0616 (4)	0.7765 (3)	0.6140 (3)	0.0602 (12)
O34	0.0865 (4)	0.6450 (4)	0.5308 (3)	0.0665 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0182 (3)	0.0212 (3)	0.0263 (3)	−0.0047 (2)	−0.0075 (2)	0.0066 (2)
Cu2	0.0211 (3)	0.0211 (3)	0.0300 (3)	−0.0063 (2)	−0.0075 (2)	0.0056 (2)
N1	0.0194 (18)	0.0234 (18)	0.0213 (18)	−0.0075 (16)	−0.0068 (14)	0.0039 (14)
N2	0.0217 (19)	0.0214 (19)	0.0269 (19)	−0.0057 (16)	−0.0065 (15)	0.0028 (15)
N3	0.0241 (19)	0.0215 (19)	0.0194 (17)	−0.0047 (17)	−0.0066 (14)	0.0065 (14)
N4	0.0212 (19)	0.0223 (19)	0.0246 (18)	−0.0040 (16)	−0.0066 (15)	0.0015 (15)
N5	0.0202 (18)	0.0188 (18)	0.0224 (18)	−0.0048 (16)	−0.0067 (14)	0.0024 (14)
N6	0.0238 (19)	0.0208 (18)	0.0249 (18)	−0.0078 (17)	−0.0027 (15)	0.0024 (15)
O1	0.0190 (15)	0.0286 (17)	0.0311 (16)	−0.0083 (14)	−0.0107 (13)	0.0102 (13)
O2	0.0196 (16)	0.0237 (16)	0.0296 (16)	−0.0069 (14)	−0.0111 (13)	0.0070 (13)
C1	0.018 (2)	0.020 (2)	0.020 (2)	−0.0019 (18)	−0.0079 (16)	−0.0026 (17)
C2	0.023 (2)	0.021 (2)	0.022 (2)	−0.0066 (19)	−0.0043 (17)	−0.0011 (17)
C3	0.016 (2)	0.027 (2)	0.034 (2)	−0.0056 (19)	−0.0082 (18)	0.0013 (19)
C4	0.021 (2)	0.023 (2)	0.024 (2)	−0.0072 (19)	−0.0062 (17)	0.0040 (18)
C5	0.021 (2)	0.027 (2)	0.022 (2)	−0.008 (2)	−0.0026 (17)	−0.0036 (18)
C6	0.022 (2)	0.021 (2)	0.022 (2)	−0.0059 (19)	−0.0049 (17)	0.0013 (17)
C7	0.026 (2)	0.029 (2)	0.025 (2)	−0.010 (2)	−0.0063 (18)	0.0007 (19)
C8	0.025 (2)	0.031 (3)	0.031 (2)	−0.011 (2)	−0.0079 (19)	0.005 (2)
C9	0.030 (3)	0.030 (2)	0.032 (2)	−0.016 (2)	0.000 (2)	−0.002 (2)
C10	0.028 (2)	0.022 (2)	0.022 (2)	−0.006 (2)	−0.0031 (18)	0.0007 (17)
C11	0.038 (3)	0.022 (2)	0.032 (2)	−0.013 (2)	0.003 (2)	0.0006 (19)
C12	0.030 (3)	0.020 (2)	0.031 (2)	−0.003 (2)	−0.005 (2)	0.0037 (19)
C13	0.021 (2)	0.022 (2)	0.029 (2)	−0.0048 (19)	−0.0066 (18)	0.0034 (18)
C14	0.023 (2)	0.022 (2)	0.018 (2)	−0.0070 (19)	−0.0030 (17)	−0.0014 (17)
C15	0.019 (2)	0.022 (2)	0.020 (2)	−0.0066 (19)	−0.0054 (17)	0.0003 (17)
C16	0.024 (2)	0.024 (2)	0.018 (2)	−0.0016 (19)	−0.0036 (17)	−0.0017 (17)
C17	0.026 (2)	0.025 (2)	0.022 (2)	−0.009 (2)	−0.0028 (18)	0.0015 (18)
C18	0.028 (2)	0.029 (2)	0.026 (2)	−0.002 (2)	−0.0086 (19)	0.0031 (19)
C19	0.031 (3)	0.026 (2)	0.024 (2)	−0.006 (2)	−0.0081 (19)	0.0067 (19)
C20	0.031 (2)	0.022 (2)	0.023 (2)	−0.006 (2)	−0.0026 (18)	0.0008 (18)
C21	0.034 (3)	0.020 (2)	0.032 (2)	−0.006 (2)	−0.004 (2)	0.0022 (19)
C22	0.038 (3)	0.026 (2)	0.032 (2)	−0.015 (2)	0.003 (2)	0.0009 (19)
C23	0.025 (2)	0.026 (2)	0.037 (3)	−0.007 (2)	−0.003 (2)	−0.002 (2)
C24	0.024 (2)	0.018 (2)	0.022 (2)	−0.0053 (19)	−0.0020 (17)	0.0007 (17)
N11	0.025 (2)	0.024 (2)	0.031 (2)	−0.0047 (18)	−0.0053 (16)	0.0042 (16)
N12	0.034 (2)	0.034 (2)	0.028 (2)	−0.015 (2)	−0.0069 (17)	0.0001 (18)
N21	0.027 (2)	0.030 (2)	0.032 (2)	−0.0031 (18)	−0.0054 (18)	0.0013 (18)
N22	0.033 (2)	0.027 (2)	0.035 (2)	−0.0111 (18)	−0.0042 (18)	0.0000 (17)
N31	0.062 (4)	0.070 (4)	0.063 (4)	−0.013 (3)	−0.006 (3)	0.009 (3)
N41	0.063 (4)	0.045 (3)	0.070 (4)	−0.016 (3)	0.003 (3)	−0.011 (3)
C31	0.026 (3)	0.031 (3)	0.029 (2)	−0.007 (2)	−0.0054 (19)	0.006 (2)
C32	0.021 (3)	0.059 (4)	0.051 (3)	−0.002 (3)	−0.011 (2)	0.004 (3)
C33	0.029 (3)	0.035 (3)	0.029 (2)	−0.009 (2)	−0.004 (2)	0.006 (2)
C34	0.072 (5)	0.045 (4)	0.079 (5)	−0.016 (3)	0.011 (4)	−0.024 (3)
C35	0.029 (3)	0.034 (3)	0.031 (3)	−0.009 (2)	−0.007 (2)	0.004 (2)
C36	0.051 (4)	0.059 (4)	0.046 (3)	−0.015 (3)	0.010 (3)	−0.017 (3)
C37	0.024 (2)	0.032 (3)	0.034 (3)	−0.007 (2)	−0.003 (2)	−0.005 (2)
C38	0.060 (4)	0.056 (4)	0.037 (3)	−0.013 (3)	−0.010 (3)	−0.014 (3)
C39	0.049 (4)	0.047 (3)	0.049 (4)	−0.012 (3)	−0.006 (3)	−0.005 (3)
C40	0.068 (4)	0.074 (4)	0.059 (4)	−0.036 (4)	0.010 (3)	−0.025 (3)
C41	0.056 (4)	0.035 (3)	0.038 (3)	−0.013 (3)	−0.008 (3)	−0.003 (2)
C42	0.075 (6)	0.122 (8)	0.155 (9)	0.027 (6)	−0.056 (6)	−0.072 (7)
Cl1	0.0529 (8)	0.0322 (6)	0.0319 (6)	−0.0135 (6)	0.0035 (5)	−0.0061 (5)
O11	0.072 (3)	0.086 (4)	0.071 (3)	0.012 (3)	0.012 (3)	−0.025 (3)
O12	0.160 (5)	0.043 (2)	0.042 (2)	−0.051 (3)	0.030 (3)	−0.0075 (19)
O13	0.084 (4)	0.131 (5)	0.067 (3)	−0.048 (4)	−0.012 (3)	−0.031 (3)
O14	0.130 (4)	0.054 (3)	0.050 (2)	−0.056 (3)	0.023 (3)	−0.019 (2)
Cl2	0.0319 (6)	0.0409 (7)	0.0377 (7)	−0.0044 (6)	−0.0097 (5)	−0.0054 (5)
O21	0.130 (5)	0.091 (4)	0.081 (4)	−0.055 (4)	0.039 (3)	−0.007 (3)
O22	0.062 (3)	0.040 (2)	0.078 (3)	−0.014 (2)	−0.007 (2)	−0.008 (2)
O23	0.087 (4)	0.102 (4)	0.084 (3)	0.005 (3)	−0.053 (3)	−0.043 (3)
O24	0.033 (2)	0.091 (4)	0.147 (5)	0.009 (3)	−0.023 (3)	−0.058 (4)
Cl3	0.0301 (6)	0.0420 (7)	0.0404 (7)	−0.0161 (6)	−0.0015 (5)	−0.0034 (5)
O31	0.083 (3)	0.045 (2)	0.061 (3)	−0.026 (2)	0.017 (2)	0.009 (2)
O32	0.0272 (19)	0.068 (3)	0.076 (3)	−0.013 (2)	−0.0099 (18)	−0.018 (2)
O33	0.058 (3)	0.051 (2)	0.071 (3)	−0.030 (2)	−0.025 (2)	−0.003 (2)
O34	0.044 (2)	0.094 (4)	0.063 (3)	−0.024 (2)	0.017 (2)	−0.036 (3)

Geometric parameters (Å, º) top

Cu1—N1	2.013 (4)	C18—H18	0.9500
Cu1—N3	1.936 (3)	C19—C20	1.412 (7)
Cu1—N4	1.952 (4)	C19—H19	0.9500
Cu1—N11	1.982 (4)	C20—C24	1.409 (6)
Cu1—N12	2.266 (4)	C20—C21	1.422 (7)
Cu2—N2	1.996 (4)	C21—C22	1.364 (7)
Cu2—N5	1.943 (4)	C21—H21	0.9500
Cu2—N6	1.961 (3)	C22—C23	1.407 (6)
Cu2—N21	2.137 (4)	C22—H22	0.9500
Cu2—N22	2.054 (4)	C23—H23	0.9500
N1—C4	1.315 (6)	N11—C31	1.136 (6)
N1—C1	1.378 (5)	N12—C33	1.126 (6)
N2—C3	1.336 (5)	N21—C35	1.126 (6)
N2—C2	1.349 (6)	N22—C37	1.138 (6)
N3—C5	1.319 (6)	N31—C39	1.133 (8)
N3—C6	1.400 (6)	N41—C41	1.116 (7)
N4—C13	1.341 (5)	C31—C32	1.447 (6)
N4—C14	1.378 (6)	C32—H32A	0.9800
N5—C15	1.310 (6)	C32—H32B	0.9800
N5—C16	1.409 (5)	C32—H32C	0.9800
N6—C23	1.311 (6)	C33—C34	1.441 (9)
N6—C24	1.370 (6)	C34—H34A	0.9800
O1—C5	1.289 (5)	C34—H34B	0.9800
O1—H2O	1.29 (6)	C34—H34C	0.9800
O2—C15	1.267 (5)	C35—C36	1.464 (8)
O2—H2O	1.12 (6)	C36—H36A	0.9800
C1—C2	1.401 (6)	C36—H36B	0.9800
C1—C5	1.477 (7)	C36—H36C	0.9800
C2—C15	1.518 (5)	C37—C38	1.455 (7)
C3—C4	1.379 (6)	C38—H38A	0.9800
C3—H3	0.9500	C38—H38B	0.9800
C4—H4	0.9500	C38—H38C	0.9800
C6—C7	1.389 (6)	C39—C40	1.440 (10)
C6—C14	1.438 (5)	C40—H40A	0.9800
C7—C8	1.412 (7)	C40—H40B	0.9800
C7—H7	0.9500	C40—H40C	0.9800
C8—C9	1.370 (6)	C41—C42	1.447 (10)
C8—H8	0.9500	C42—H42A	0.9800
C9—C10	1.411 (6)	C42—H42B	0.9800
C9—H9	0.9500	C42—H42C	0.9800
C10—C14	1.384 (7)	Cl1—O14	1.407 (4)
C10—C11	1.434 (6)	Cl1—O11	1.420 (5)
C11—C12	1.360 (7)	Cl1—O12	1.428 (4)
C11—H11	0.9500	Cl1—O13	1.433 (5)
C12—C13	1.382 (7)	Cl2—O23	1.392 (5)
C12—H12	0.9500	Cl2—O21	1.417 (5)
C13—H13	0.9500	Cl2—O24	1.423 (5)
C16—C17	1.370 (6)	Cl2—O22	1.432 (4)
C16—C24	1.433 (7)	Cl3—O33	1.408 (4)
C17—C18	1.420 (6)	Cl3—O34	1.424 (4)
C17—H17	0.9500	Cl3—O31	1.434 (4)
C18—C19	1.357 (7)	Cl3—O32	1.450 (4)

N3—Cu1—N4	83.36 (15)	C16—C17—C18	119.7 (5)
N4—Cu1—N1	163.76 (14)	C16—C17—H17	120.2
N3—Cu1—N11	163.66 (16)	C18—C17—H17	120.2
N4—Cu1—N11	97.64 (15)	C19—C18—C17	121.8 (4)
N3—Cu1—N1	80.64 (15)	C19—C18—H18	119.1
N11—Cu1—N1	96.94 (15)	C17—C18—H18	119.1
N3—Cu1—N12	103.58 (15)	C18—C19—C20	120.3 (4)
N4—Cu1—N12	100.38 (15)	C18—C19—H19	119.8
N11—Cu1—N12	92.32 (16)	C20—C19—H19	119.8
N1—Cu1—N12	86.12 (15)	C24—C20—C19	118.4 (5)
N5—Cu2—N6	83.48 (15)	C24—C20—C21	117.3 (4)
N5—Cu2—N2	80.04 (15)	C19—C20—C21	124.3 (4)
N6—Cu2—N2	163.51 (16)	C22—C21—C20	119.5 (4)
N5—Cu2—N22	140.74 (16)	C22—C21—H21	120.2
N6—Cu2—N22	99.75 (16)	C20—C21—H21	120.2
N2—Cu2—N22	93.02 (15)	C21—C22—C23	119.4 (5)
N5—Cu2—N21	120.72 (16)	C21—C22—H22	120.3
N6—Cu2—N21	97.88 (15)	C23—C22—H22	120.3
N2—Cu2—N21	90.62 (15)	N6—C23—C22	122.7 (4)
N22—Cu2—N21	97.77 (16)	N6—C23—H23	118.7
C4—N1—C1	121.1 (4)	C22—C23—H23	118.7
C4—N1—Cu1	124.8 (3)	N6—C24—C20	121.9 (4)
C1—N1—Cu1	114.0 (3)	N6—C24—C16	117.3 (3)
C3—N2—C2	120.4 (4)	C20—C24—C16	120.8 (4)
C3—N2—Cu2	124.1 (3)	C31—N11—Cu1	177.0 (5)
C2—N2—Cu2	115.5 (3)	C33—N12—Cu1	138.6 (4)
C5—N3—C6	127.3 (4)	C35—N21—Cu2	165.0 (4)
C5—N3—Cu1	118.1 (3)	C37—N22—Cu2	160.1 (4)
C6—N3—Cu1	114.6 (2)	N11—C31—C32	178.5 (6)
C13—N4—C14	118.2 (4)	C31—C32—H32A	109.5
C13—N4—Cu1	128.6 (3)	C31—C32—H32B	109.5
C14—N4—Cu1	113.2 (3)	H32A—C32—H32B	109.5
C15—N5—C16	125.9 (4)	C31—C32—H32C	109.5
C15—N5—Cu2	119.3 (3)	H32A—C32—H32C	109.5
C16—N5—Cu2	114.2 (3)	H32B—C32—H32C	109.5
C23—N6—C24	119.2 (4)	N12—C33—C34	178.3 (6)
C23—N6—Cu2	128.3 (3)	C33—C34—H34A	109.5
C24—N6—Cu2	112.5 (3)	C33—C34—H34B	109.5
C5—O1—H2O	115 (3)	H34A—C34—H34B	109.5
C15—O2—H2O	116 (3)	C33—C34—H34C	109.5
N1—C1—C2	117.6 (4)	H34A—C34—H34C	109.5
N1—C1—C5	112.8 (4)	H34B—C34—H34C	109.5
C2—C1—C5	129.5 (4)	N21—C35—C36	178.7 (5)
N2—C2—C1	120.1 (3)	C35—C36—H36A	109.5
N2—C2—C15	112.8 (4)	C35—C36—H36B	109.5
C1—C2—C15	127.1 (4)	H36A—C36—H36B	109.5
N2—C3—C4	120.1 (4)	C35—C36—H36C	109.5
N2—C3—H3	119.9	H36A—C36—H36C	109.5
C4—C3—H3	119.9	H36B—C36—H36C	109.5
N1—C4—C3	120.6 (4)	N22—C37—C38	179.3 (6)
N1—C4—H4	119.7	C37—C38—H38A	109.5
C3—C4—H4	119.7	C37—C38—H38B	109.5
O1—C5—N3	123.9 (4)	H38A—C38—H38B	109.5
O1—C5—C1	121.7 (4)	C37—C38—H38C	109.5
N3—C5—C1	114.4 (4)	H38A—C38—H38C	109.5
C7—C6—N3	129.3 (4)	H38B—C38—H38C	109.5
C7—C6—C14	117.8 (4)	N31—C39—C40	179.1 (7)
N3—C6—C14	112.8 (4)	C39—C40—H40A	109.5
C6—C7—C8	120.2 (4)	C39—C40—H40B	109.5
C6—C7—H7	119.9	H40A—C40—H40B	109.5
C8—C7—H7	119.9	C39—C40—H40C	109.5
C9—C8—C7	121.4 (4)	H40A—C40—H40C	109.5
C9—C8—H8	119.3	H40B—C40—H40C	109.5
C7—C8—H8	119.3	N41—C41—C42	176.0 (8)
C8—C9—C10	119.8 (5)	C41—C42—H42A	109.5
C8—C9—H9	120.1	C41—C42—H42B	109.5
C10—C9—H9	120.1	H42A—C42—H42B	109.5
C14—C10—C9	119.3 (4)	C41—C42—H42C	109.5
C14—C10—C11	117.5 (4)	H42A—C42—H42C	109.5
C9—C10—C11	123.1 (5)	H42B—C42—H42C	109.5
C12—C11—C10	118.8 (5)	O14—Cl1—O11	110.9 (4)
C12—C11—H11	120.6	O14—Cl1—O12	109.5 (3)
C10—C11—H11	120.6	O11—Cl1—O12	110.8 (3)
C11—C12—C13	120.6 (4)	O14—Cl1—O13	108.4 (3)
C11—C12—H12	119.7	O11—Cl1—O13	107.4 (3)
C13—C12—H12	119.7	O12—Cl1—O13	109.7 (4)
N4—C13—C12	122.2 (4)	O23—Cl2—O21	111.5 (4)
N4—C13—H13	118.9	O23—Cl2—O24	110.5 (3)
C12—C13—H13	118.9	O21—Cl2—O24	104.3 (4)
N4—C14—C10	122.6 (4)	O23—Cl2—O22	112.1 (3)
N4—C14—C6	116.0 (4)	O21—Cl2—O22	108.4 (3)
C10—C14—C6	121.4 (4)	O24—Cl2—O22	109.7 (3)
O2—C15—N5	125.7 (4)	O33—Cl3—O34	110.8 (3)
O2—C15—C2	122.1 (4)	O33—Cl3—O31	110.6 (3)
N5—C15—C2	112.1 (4)	O34—Cl3—O31	108.7 (3)
C17—C16—N5	128.6 (5)	O33—Cl3—O32	108.3 (3)
C17—C16—C24	119.0 (4)	O34—Cl3—O32	109.7 (3)
N5—C16—C24	112.3 (4)	O31—Cl3—O32	108.8 (3)

C4—N1—C1—C2	0.0 (6)	C9—C10—C14—N4	−179.7 (4)
Cu1—N1—C1—C2	−176.7 (3)	C11—C10—C14—N4	−1.6 (7)
C4—N1—C1—C5	178.6 (4)	C9—C10—C14—C6	−0.8 (7)
Cu1—N1—C1—C5	1.8 (4)	C11—C10—C14—C6	177.4 (4)
C3—N2—C2—C1	−1.9 (6)	C7—C6—C14—N4	178.9 (4)
Cu2—N2—C2—C1	179.0 (3)	N3—C6—C14—N4	−1.6 (6)
C3—N2—C2—C15	177.7 (4)	C7—C6—C14—C10	−0.1 (6)
Cu2—N2—C2—C15	−1.4 (5)	N3—C6—C14—C10	179.3 (4)
N1—C1—C2—N2	1.7 (6)	C16—N5—C15—O2	−7.2 (7)
C5—C1—C2—N2	−176.6 (4)	Cu2—N5—C15—O2	−178.6 (3)
N1—C1—C2—C15	−177.8 (4)	C16—N5—C15—C2	176.7 (4)
C5—C1—C2—C15	3.9 (7)	Cu2—N5—C15—C2	5.2 (5)
C2—N2—C3—C4	0.3 (7)	N2—C2—C15—O2	−178.6 (4)
Cu2—N2—C3—C4	179.4 (3)	C1—C2—C15—O2	0.9 (7)
C1—N1—C4—C3	−1.6 (7)	N2—C2—C15—N5	−2.3 (5)
Cu1—N1—C4—C3	174.8 (3)	C1—C2—C15—N5	177.2 (4)
N2—C3—C4—N1	1.4 (7)	C15—N5—C16—C17	6.4 (7)
C6—N3—C5—O1	1.5 (7)	Cu2—N5—C16—C17	178.2 (4)
Cu1—N3—C5—O1	179.8 (3)	C15—N5—C16—C24	−175.3 (4)
C6—N3—C5—C1	179.9 (4)	Cu2—N5—C16—C24	−3.5 (5)
Cu1—N3—C5—C1	−1.8 (5)	N5—C16—C17—C18	179.3 (4)
N1—C1—C5—O1	178.3 (4)	C24—C16—C17—C18	1.1 (6)
C2—C1—C5—O1	−3.3 (7)	C16—C17—C18—C19	−1.6 (7)
N1—C1—C5—N3	−0.1 (5)	C17—C18—C19—C20	1.0 (7)
C2—C1—C5—N3	178.3 (4)	C18—C19—C20—C24	0.0 (7)
C5—N3—C6—C7	0.3 (8)	C18—C19—C20—C21	−179.7 (5)
Cu1—N3—C6—C7	−178.1 (4)	C24—C20—C21—C22	1.1 (7)
C5—N3—C6—C14	−179.1 (4)	C19—C20—C21—C22	−179.2 (5)
Cu1—N3—C6—C14	2.5 (5)	C20—C21—C22—C23	−0.6 (7)
N3—C6—C7—C8	−178.6 (4)	C24—N6—C23—C22	−1.5 (7)
C14—C6—C7—C8	0.8 (7)	Cu2—N6—C23—C22	179.9 (3)
C6—C7—C8—C9	−0.6 (7)	C21—C22—C23—N6	0.8 (8)
C7—C8—C9—C10	−0.3 (7)	C23—N6—C24—C20	2.0 (7)
C8—C9—C10—C14	1.0 (7)	Cu2—N6—C24—C20	−179.2 (3)
C8—C9—C10—C11	−177.1 (5)	C23—N6—C24—C16	−179.1 (4)
C14—C10—C11—C12	0.7 (7)	Cu2—N6—C24—C16	−0.2 (5)
C9—C10—C11—C12	178.8 (4)	C19—C20—C24—N6	178.5 (4)
C10—C11—C12—C13	0.0 (7)	C21—C20—C24—N6	−1.8 (7)
C14—N4—C13—C12	−0.8 (7)	C19—C20—C24—C16	−0.4 (7)
Cu1—N4—C13—C12	−177.8 (3)	C21—C20—C24—C16	179.3 (4)
C11—C12—C13—N4	0.0 (7)	C17—C16—C24—N6	−179.1 (4)
C13—N4—C14—C10	1.6 (6)	N5—C16—C24—N6	2.4 (6)
Cu1—N4—C14—C10	179.0 (3)	C17—C16—C24—C20	−0.2 (7)
C13—N4—C14—C6	−177.4 (4)	N5—C16—C24—C20	−178.6 (4)
Cu1—N4—C14—C6	0.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1	1.12 (6)	1.29 (6)	2.397 (4)	169 (6)
C7—H7···O1	0.95	2.35	2.920 (6)	118
C17—H17···O2	0.95	2.32	2.897 (5)	119
C17—H17···O32ⁱ	0.95	2.36	3.175 (7)	144
C22—H22···O12ⁱⁱ	0.95	2.50	3.108 (6)	122
C23—H23···O34ⁱⁱ	0.95	2.41	3.255 (7)	148
C34—H34A···O24	0.98	2.31	3.130 (10)	140
C34—H34C···O11ⁱⁱⁱ	0.98	2.56	3.272 (9)	130
C36—H36A···O21^iv	0.98	2.46	3.429 (8)	168
C38—H38B···N31^iv	0.98	2.57	3.454 (10)	150
C40—H40C···O32^v	0.98	2.57	3.516 (8)	162

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

A comparison of bond lengths and angles (Å, °) in the carboxamide units of H₂L1 and I top

	H₂L1	I
O1—C5	1.222 (2)	1.289 (5)
N3—C5	1.347 (2)	1.319 (6)
C1—C5	1.506 (2)	1.477 (7)
O2—C15	1.219 (2)	1.267 (5)
N5—C15	1.348 (2)	1.310 (6)
C2—C15	1.508 (2)	1.518 (5)

N3—C5—O1	125.78 (13)	123.9 (4)
N3—C5—C1	113.91 (12)	114.4 (4)
O1—C5—C1	120.32 (12)	121.7 (4)
N5—C15—O2	125.13 (13)	125.7 (4)
N5—C15—C2	115.76 (12)	112.1 (4)
O2—C15—C2	118.87 (12)	122.1 (4)

Acknowledgements

HSE is grateful to the University of Neuchâtel for support over the years.

Funding information

Funding for this research was provided by: Swiss National Science Foundation; University of Neuchâtel.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Cati, D. S. (2002). PhD Thesis, University of Neuchâtel, Switzerland. Google Scholar
Cati, D. S., Ribas, J., Ribas-Ariño, J. & Stoeckli-Evans, H. (2004). Inorg. Chem. 43, 1021–1030. Web of Science CSD CrossRef PubMed CAS Google Scholar
Cati, D. S. & Stoeckli-Evans, H. (2004). Acta Cryst. E60, o210–o212. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cati, D. S. & Stoeckli-Evans, H. (2019). Acta Cryst. E75, 755–761. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fábry, J. (2018). Acta Cryst. E74, 1344–1357. Web of Science CSD CrossRef IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hausmann, J., Jameson, G. B. & Brooker, S. (2003). Chem. Commun. pp. 2992–2993. Web of Science CSD CrossRef Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814. Google Scholar
Meghdadi, S., Amirnasr, M., Azarkamanzad, Z., Schenk Joss, K., Fadaee, F., Amiri, A. & Abbasi, S. (2013). J. Coord. Chem. 66, 4330–4343. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (1997). STADI4 and X-RED Software. Stoe & Cie GmbH, Damstadt, Germany. Google Scholar
Stoe & Cie (2004). IPDS1 Bedienungshandbuch. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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