The crystal structures of the ligand N-(quinolin-8-yl)pyrazine-2-carboxamide and of a tetra­nuclear copper(II) complex

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

doi:10.1107/S2056989019005450

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ISSN: 2056-9890

Volume 75| Part 6| June 2019| Pages 755-761

https://doi.org/10.1107/S2056989019005450

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The crystal structures of the ligand N-(quinolin-8-yl)pyrazine-2-carboxamide and of a tetranuclear copper(II) complex

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

^aDebiopharm International S.A., Chemin Messidor 5-7, CP 5911, 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 17 April 2019; accepted 21 April 2019; online 10 May 2019)

The title tridentate ligand, C₁₄H₁₀N₄O, N-(quinolin-8-yl)pyrazine-2-carboxamide (HL1), crystallizes with three independent molecules (A, B and C) in the asymmetric unit. All three molecules are relatively planar (r.m.s. deviations are 0.068, 0.055 and 0.06 Å, respectively), with the NH H atom forming three-centered (bifurcated) intramolecular N—H⋯N hydrogen bonds in each molecule. There is also an intramolecular C—H⋯O contact present in each molecule, involving the benzene ring of the quinoline unit and the amide carboxamide O atom. In the crystal, the three molecules stack in columns with the various molecules being linked by offset π-π interactions [intercentroid distances vary from 3.367 (5) to 3.589 (5) Å], forming layers parallel to the ab plane. The title complex, [Cu₄(C₄₂H₄₄N₈O₁₆)]·2CH₃OH, {hexa-μ-acetato-1:2κ²O:O′;2:3κ⁸O:O′;3:4κ²O:O′-dimethanol-1κO,2κO-bis[N-(quinolin-8-yl)pyrazine-2-carboxamide]-1κ³N,N′,N′′;4κ³N,N′,N′′-tetracopper(II) methanol disolvate} (I), was obtained by the reaction of HL1 with Cu(CH₃CO₂)₂. It consists of a tetranuclear complex with a central tetrakis(μ-acetato)dicopper paddle-wheel moiety linked on either side via bridging acetato ions to a mononuclear copper(II)–(L1) complex; it crystallizes as a methanol disolvate. The complex possesses inversion symmetry, being located about a center of symmetry situated at the mid-point of the Cu⋯Cu bond of the paddle-wheel moiety. In the crystal, the complex molecules are linked by O—H⋯O hydrogen bonds, forming chains along the [01 $[\overline{1}]$ ] direction, which are linked by offset π–π interactions [intercentroid distance = 3.7367 (11) Å] and C—H⋯O hydrogen bonds, leading to the formation of a supramolecular framework.

Keywords: crystal structure; pyrazine; quinoline; carboxamide; copper(II); tetranuclear complex; paddle-wheel; hydrogen bonding; offset π–π interactions; Hirshfeld surface analysis; supramolecular framework.

CCDC references: 1911375; 1911374

1. Chemical context

The crystal structures of a number of hetero bimetallic iron–manganese cyano complexes of the ligand HL1 have been synthesized in order to explore their super-exchange magnetic properties (Kim et al., 2007 ; Zhou et al., 2014 ). To the best of our knowledge (Cambridge Structural Database; Groom et al., 2016 ), the crystal structure of the ligand itself has never been described, although the structure of the pyridine analogue, N-(8-quinolyl)pyridine-2-carboxamide, has been reported (Zhang et al., 2001 ). There is only one previous report of a copper(II) complex of ligand HL1, viz. (acetato)[N-(quinolin-8-yl)pyrazine-2-carboxamidato]copper(II) monohydrate, a mononuclear complex with the ligand coordinating in a tridentate fashion (Meghdadi et al., 2013 ). It has been shown previously that pyrazine carboxamide ligands are useful for the synthesis of transition-metal complexes that exhibit magnetic super-exchange and anion encapsulation (Hausmann et al., 2003 ; Cati et al., 2004 ; Klingele et al., 2007 ). During further work in this area (Cati, 2002 ), the title copper(II) complex, I, of ligand HL1 was synthesized, and we report herein on the crystal structures of ligand HL1 and complex I. The various intermolecular interactions in the crystal of HL1 have been studied by Hirshfeld surface analysis.

2. Structural commentary

The ligand HL1 crystallized with three independent molecules (A, B and C) in the asymmetric unit, and their molecular structures are illustrated in Fig. 1. In each molecule the carboxamide NH H atom forms three-centered (bifurcated) intramolecular N—H⋯N hydrogen bonds involving the quinoline and the adjacent pyrazine N atoms (Fig. 1 and Table 1). This arrangement is similar to that observed in 1,3-bis(2-pyridylimino)isoindoline (Schilf, 2004 ) and its pyrazine analogue, bis(pyridin-2-yl)-6,7-dihydro-pyrrolo[3,4-b]pyrazine-5,7-diimine (Posel & Stoeckli-Evans, 2018 ). There is also a short C—H⋯O contact present in each molecule (Fig. 1 and Table 1). Hence, the three molecules have similar conformations, with the pyrazine ring being inclined to the quinoline ring by 4.5 (4)° in molecule A, 3.1 (4)° in B and 4.1 (4)° in C. For the three molecules, the r.m.s. deviations for the mean planes of the non-H atoms are 0.068, 0.055 and 0.06 Å, respectively. Inverted molecule A on molecule B has an r.m.s. deviation of 0.054 Å for the 19 non-H atoms, while inverted molecule B on molecule C has an r.m.s. deviation of 0.054 Å, and molecule A and molecule C have an r.m.s. deviation of 0.057 Å.

Table 1
Hydrogen-bond geometry (Å, °) for HL1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N1	0.87	2.21	2.661 (10)	112
N3—H3N⋯N4	0.87	2.23	2.667 (10)	111
C7—H7⋯O1	0.94	2.36	2.967 (13)	122
N23—H23N⋯N21	0.87	2.22	2.662 (10)	112
N23—H23N⋯N24	0.87	2.24	2.675 (11)	110
C27—H27⋯O2	0.94	2.34	2.912 (13)	119
N33—H33N⋯N31	0.87	2.21	2.667 (10)	113
N33—H33N⋯N34	0.87	2.26	2.674 (11)	109
C47—H47⋯O3	0.94	2.27	2.893 (12)	123

Figure 1
A view of the molecular structure of the three independent molecules (A, B and C) of ligand HL1, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Intramolecular N—H⋯O and C—H⋯O contacts (see Table 1

) are shown as dashed lines.

Reaction of HL1 with Cu(CH₃CO₂)₂ produced a tetranuclear complex, I, with a central tetrakis(μ-acetato)-dicopper paddle-wheel moiety linked on either side via a bridging acetate anion to a mononuclear copper(II)–(L1) complex, illustrated in Fig. 2. Selected geometrical parameters are given in Table 2. The complex possesses inversion symmetry, being located about a center of symmetry situated at the mid-point of the Cu2⋯Cu2ⁱ bond [2.6202 (6) Å; symmetry code: (i) −x + 1, −y, −z + 1)] of the paddle-wheel moiety (Table 2). Both copper atoms are fivefold coordinate; CuN₃O₂ for Cu1 and CuO₅ for Cu2. Atom Cu1 is ligated in the equatorial plane by the three N atoms of the ligand and an O atom, O3, of the bridging acetate ion, and with a coordinated methanol O atom, O2, in the apical position. It has an irregular coordination sphere with a τ₅ factor of 0.17 (τ₅ = 0 for an ideal square-pyramidal coordination sphere, and = 1 for an ideal trigonal–pyramidal coordination sphere; Addison et al., 1984 ). Atom Cu2 is ligated by four acetate O atoms (O5, O6, O7 and O8) of the paddle-wheel moiety in the equatorial plane and by atom O4 of the bridging acetate ion in the apical position. It has a perfect square-pyramidal coordination sphere with a τ₅ factor of 0.01. There are two intramolecular C—H⋯O contacts present involving the quinoline unit and oxygen atoms O1 of the carboxymide group and O4 of the bridging acetate ion (Fig. 2 and Table 3).

Table 2
Selected geometric parameters (Å, °) for I

Cu1—N1	2.037 (2)	Cu2—O4	2.1255 (16)
Cu1—N3	1.9457 (18)	Cu2—O5	1.9703 (17)
Cu1—N4	1.998 (2)	Cu2—O6	1.9793 (15)
Cu1—O2	2.3541 (16)	Cu2—O7	1.9692 (18)
Cu1—O3	1.9401 (15)	Cu2—O8	1.9671 (16)
Cu2—Cu2ⁱ	2.6202 (6)

O3—Cu1—N3	172.66 (8)	O7—Cu2—O5	169.04 (7)
N4—Cu1—N1	162.67 (8)	O8—Cu2—O6	168.74 (7)
Symmetry code: (i) -x+1, -y, -z+1.

Table 3
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O1ⁱⁱ	0.86 (3)	1.84 (3)	2.689 (3)	178 (3)
O9—H9O⋯O4	0.84	2.33	2.955 (3)	132
O9—H9O⋯O6	0.84	2.30	3.000 (3)	141
C3—H3⋯O8ⁱⁱⁱ	0.95	2.56	3.508 (3)	174
C7—H7⋯O1	0.95	2.36	2.943 (3)	119
C9—H9⋯O9^iv	0.95	2.57	3.415 (3)	149
C13—H13⋯O4	0.95	2.54	3.175 (3)	124
C21—H21C⋯O8^v	0.98	2.59	3.563 (3)	170
Symmetry codes: (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y, -z; (v) x+1, y, z.

Figure 2
A view of the molecular structure of complex I, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The unlabelled atoms are related to labelled atoms by inversion symmetry [symmetry code: (i) −x + 1, −y, −z + 1]. The intramolecular C-H...O contacts are shown as dashed lines (Table 3

). For clarity, the methanol solvate molecules have been omitted.

3. Supramolecular features

In the crystal of ligand HL1, and as can be seen from Fig. 1, molecule B is closely related to molecules A and C by non-crystallographic inversion symmetry, while molecules A and C are closely related by non-space group translation. An analysis with PLATON/ADDSYM (Spek, 2009 ), however, concluded that no obvious extra crystallographic symmetry was present and no change in the space group (Cc) was required. In the crystal, packets of the three molecules stack in the order (ABC), (ABC) etc (Fig. 3; A blue, B red, C green). They are linked by offset π–π interactions, so forming layers lying parallel to the ab plane (Fig. 4 and Table 4).

Table 4
π–π interactions (Å, °) in the crystal of ligand HL1

Cg1, Cg5 and Cg9 are the centroids of the pyrazine rings (N1/N2/C1–C4) in molecule A, (N22/N23/C21–C24) in molecule B and (N31/N32/C41–C44) in molecule C, respectively. Cg4, Cg8 and Cg12 are the centroids of the quinoline ring systems (N4/C6–C14)in molecule A, (N24/C26–C34) in molecule B and (N34/C46–C54) in molecule C, respectively.

Ring_pz	ring_quin	centroid–centroid	α	β	γ	interplanar_1	interplanar_2	offset
Cg1	Cg8ⁱ	3.589 (5)	2.9 (4)	9.2	8.2	3.552 (4)	3.543 (4)	0.572
Cg1	Cg12ⁱ	3.493 (5)	4.1 (4)	12.2	8.6	3.453 (4)	3.414 (3)	0.737
Cg5	Cg4ⁱⁱ	3.367 (5)	3.8 (4)	4.7	2.3	3.364 (4)	3.355 (4)	0.275
Cg5	Cg12ⁱⁱⁱ	3.492 (5)	4.1 (4)	2.7	6.7	3.468 (4)	3.488 (3)	0.163
Cg9	Cg4^iv	3.455 (6)	4.2 (4)	11.0	8.0	3.420 (4)	3.390 (4)	0.662
Cg9	Cg8^v	3.532 (6)	2.9 (4)	3.4	5.7	3.515 (4)	3.526 (4)	0.211
Symmetry codes: (i) x, y + 1, z − $[{1\over 2}]$ ; (ii) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iii) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z; (iv) x, −y + 1, z + $[{1\over 2}]$ ; (v) x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , z.

Figure 3
A view along the c axis of the crystal packing of ligand HL1. The π–π interactions, represented here by dashed lines, are given in Table 4

. Colour code: A molecules are blue, B are red and C are green.

Figure 4
A view normal to plane (110) of the crystal packing of ligand HL1 (colour code: A molecules are blue, B are red and C are green).

In the crystal of I, molecules are linked by pairs of O—H⋯O hydrogen bonds involving the coordinated methanol molecule and the carboxamide O atom, O1, forming chains propagating along [01 $[\overline{1}]$ ]; see Table 3 and Fig. 5. The chains thus formed enclose R₂²(12) ring motifs, as illustrated in Fig. 5. The methanol solvent molecule is linked to the chain via bifurcated O—H⋯O/O hydrogen bonds, which enclose an R₁²(4) ring motif (Fig. 5 and Table 3). Inversion-related chains are linked by offset π–π interactions involving the quinoline ring systems [Figs. 5 and 6; Cg⋯Cg^vi = 3.7367 (11) Å, Cg is the centroid of the N4/C6–C14 ring, α = 0.04 (7)°, β = 25.7°, interplanar distance = 3.3684 (8) Å, offset 1.618 Å; symmetry code: (vi) −x + 1, −y, −z]. The chains are also linked by C—H⋯O hydrogen bonds, resulting in the formation of a supramolecular framework (Table 3 and Fig. 6).

Figure 5
A partial view along the a axis of the crystal packing of complex I. The hydrogen bonds (see Table 3

) are shown as dashed lines and C-bound H atoms have been omitted.

Figure 6
A view along the a axis of the crystal pack of complex I. The hydrogen bonds (see Table 3

) are shown as dashed lines and only the H atoms involved in these intermolecular interactions have been included (the two methanol hydroxyl H atoms are shown as grey balls).

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 recent article by Tiekink and collaborators (Tan et al., 2019 ) `outlines the various procedures and what can be learned by using CrystalExplorer'.

The Hirshfeld surface of HL1 mapped over d_norm is given in Fig. 7a, where short interatomic contacts are indicated by the faint red spots. The π–π stacking is confirmed by the small blue regions surrounding bright red spots in the various aromatic rings in Fig. 7b, the Hirshfeld surface mapped over the shape-index, and by the flat regions around the aromatic regions in Fig. 7c, the Hirshfeld surface mapped over the curvedness.

Figure 7
Hirshfeld surfaces for HL1 (molecules A, B and C) mapped over (a) d_norm, −0.164 to 1.208 arbitrary units, (b) shape-index and (c) curvedness.

The full two-dimensional fingerprint plots for HL1 and for the individual molecules are given in Fig. 8a. The principal intermolecular interactions for HL1 (Fig. 8b), are delineated into H⋯H at 43.0%, N⋯H/H⋯N at 14.5%, followed by C⋯H/H⋯C interactions at 11.8%. The contributions of the C⋯C and C⋯N interactions, which are 10.8 and 10.7%, respectively, are superior to the contribution of the O⋯H/H⋯O interactions at 8.1%. The relative percentage contributions of close contacts to the Hirshfeld surface for HL1 and for the individual molecules are similar, as indicated in Table 5.

Table 5
Relative percentage contributions of close contacts to the Hirshfeld surface of ligand HL1, and for the individual molecules

Contact	HL1	Molecule A	Molecule B	Molecule C
H⋯H	43.0	44.5	41.7	43.0
N⋯H/H⋯N	14.5	13.5	14.6	14.3
C⋯H/H⋯C	11.8	10.5	11.7	11.1
O⋯H/H⋯O	8.1	9.2	10.2	9.4
C⋯C	10.8	10.6	10.6	10.5
C⋯N	10.7	10.5	10.1	10.7

Figure 8
(a) The overall fingerprint plot for HL1 (all three molecules), and for the individual molecules (A, B and C). (b) Fingerprint plots for HL1 (all three molecules) delineated into H⋯H, N⋯H/H⋯N, C⋯H/H⋯C, C⋯C, C⋯N, and O⋯H/H⋯O contacts.

5. Database survey

A search of the Cambridge Structural Database (Version 5.40, update February 2019; Groom et al., 2016) of ligand HL1 yielded nine hits. The majority of these compounds are hetero bimetallic iron–manganese cyano complexes that exhibit super-exchange magnetic properties [e.g. CSD refcodes JIVGIF and JIVGOL (Kim et al., 2007) and BOLJOD, BOLJUJ and BOLKIY (Zhou et al., 2014)]. Only one hit concerns a copper(II) complex, namely (acetato)(N-(quinolin-8-yl)pyrazine-2-carboxamidato)copper(II) monohydrate, with the ligand coordinating in a tridentate fashion (AYIFOF; Meghdadi et al., 2013). The copper ion is ligated by the three N atoms of the ligand, and the two O atoms of the acetate anion, hence the copper atom is CuN₃O₂ five-coordinate with an irregular coordination sphere; τ₅ = 0.17. This value is similar to that for atom Cu1 in the title complex I (τ₅ factor of 0.17).

A search for complexes of the pyridine analogue of HL1 yielded 16 hits, including the analogue itself, N-(8-quinolyl)pyridine-2-carboxamide (WOVYAH; Zhang et al., 2001). A number of hits involve again hetero bimetallic (Fe–Mn) cyano complexes (e.g. BARTUL and BARVUN; Senapati et al., 2012 ), and trimetallic (Fe–Mn–Fe) cyano complexes (CEBYIS, CEBYOY and CEBYUE; Ni et al., 2005 ); they all exhibit super-exchange magnetic properties. The structure of a copper(II) acetate complex, (acetato-O)-aqua-[N-(8-quinolyl)pyridine-2-carboxamide-N,N′,N′′]copper(II) has also been reported (XAFKUL; Zhang et al., 2007 ). In this mononuclear copper(II) complex, the copper ion is ligated by the three N atoms of the ligand, an O atom of the acetate anion and a water O atom, hence the copper atom is CuN₃O₂ five-coordinate with an irregular coordination sphere; τ₅ = 0.13. This geometry is similar to that of atom Cu1 in the title complex I (τ₅ factor of 0.17), and that in compound AYIFOF mentioned above.

A search for the tetrakis(μ-acetato)dicopper paddle-wheel moiety gave 356 hits. Limiting the search for a tetrakis(μ-acetato)-dicopper paddle-wheel moiety bridged on either side by an acetato group to a second copper atom gave 15 hits for 14 structures (see supporting information file S1). Eight of these compounds are polymeric structures, for example, the network structure catena-[octakis(μ₂-acetato-O,O′)[μ₂-2,5-bis(2-pyridyl)pyrazine-N,N′,N′′,N′′′]tetracopper(II)] [YOMTUP; Neels et al., 1995 ]. Only six are tetranuclear compounds similar to compound I; for example, hexakis(μ₂-acetato)-bis[1-(5-bromosalicylaldimino)-3-(2-methylpiperidino)propane]tetracopper(II) (PIBXOU; Chiari et al., 1993 ), hexakis(μ₂-acetato)bis(2-{[(2,2,6,6-tetramethylpiperidin-4-yl)imino] methyl}phenolato)tetracopper(II) [UJOWEX; Huang & Liu, 2016 ], and tetrakis(μ₂-acetato-O,O′)bis(μ₂-acetato-O,O,O′)tetrakis(triphenylphosphine-P)dicopper(I)dicopper(II) [CERTOI; Koman et al., 1984 : CERTOI10; Valigura et al., 1986 ]. The Cu⋯Cu distance in the paddle-wheel unit varies from ca 2.604 to 2.669 Å; in I this distance, Cu2⋯Cu2ⁱ, is 2.6201 (6) Å. The Cu⋯Cu distance involving the two copper atoms bridged by a single acetato group varies from ca 3.772 to 5.441 Å. The longer distance is observed when only one O atom bridges the two copper atoms as in compound I, where distance Cu2⋯Cu1 is ca 5.147 Å, close to the distance of ca 5.392 Å observed in UJOWEX. A shorter distance is observed when one O atom bridges the two copper atoms and the second O atom coordinates to the second copper atom, in a (μ²-acetato-O,O,O′) manner, as in CERTOI/CERTOI10 where this Cu⋯Cu distance is ca 3.772 Å.

6. Synthesis and crystallization

Synthesis of N-(quinolin-8-yl)pyrazine-2-carboxamide (HL1):

A suspension of pyrazine-2-carboxylic acid (1.49 g, 12 mmol) and 8-aminoquinoline (1.15 g, 8 mmol) in 80 ml of 1,2-dichloroethane was distilled to azeotropically remove any solvated H₂O (vapour temperature 355 K). The mixture was allowed to cool, and then 1,1′-carbonyldiimidazole (1.95 g, 12 mmol) was added. After gas evolution had diminished, the solution was heated at reflux for 16 h. The reaction mixture was allowed to cool to RT and then added directly to a column (R = 1.2 cm, 30 g of SiO₂) and eluted with CHCl₃. On evaporation of the solvent the residue obtained was recrystallized from ethanol giving block-like colourless crystals of HL1 (yield 75%, m.p. 461 K).

Spectroscopic data for HL1 (for the numbering scheme see molecule A in Fig. 1): ¹H NMR (400 MHz, DMSO-d₆): 11.95 (s, 1H, HN3); 9.41 (d, J_2,3 = 1.4, 1H, H2); 9.02 (m, 2H, H3 & H4); 8.93 (m, 1H, H13); 8.89 (dd, 1H, J_7,8 = 7.6, J_7,9 = 1.2, H7); 8.48 (dd, 1H, J_11,12 = 8.3, J_11,13 = 1.6, H11); 7.78 (dd, 1H, J_9,8 = 8.3, J_9,7 = 1.2, H9); 7.69 (m, 2H, H12 & H8). ¹³C NMR (400 MHz, DMSO-d₆): 161.7 (C5), 150.3 (C13), 149.2 (C4), 144.9 (C1), 144.6 (C2), 144.5 (C3), 139.0 (C14), 137.7 (C11), 134.2 (C6), 128.8 (C10), 128.0 (C8), 123.7 (C12), 123.4 (C7), 117.0 C(9). IR (KBr pellet, cm⁻¹): 1686 (vs), 1559 (s), 1533 (vs), 1485 (vs), 1471 (s), 1460 (s), 1425 (s), 1403 (s), 1384 (s), 1325 (s), 1129 (s), 1058 (s), 1020 (s), 830 (s), 796 (s), 763 (s), 741 (s), 710 (s), 599 (s). Analysis for C₁₄H₁₀N₄O (M_r = 250.26 g mol⁻¹); calculated (%) C 67.19, H 4.03, N 22.39; found (%) C 67.00, H 4.04, N 22.37.

Synthesis of compound I:

Cu(Ac)₂·H₂O (74.9 mg; 0.375 mmol) was added to a solution of HL1 (37.5 mg; 0.150 mmol) dissolved in 15 ml of methanol. The green solution was stirred at room temperature for 30 min. It was then left to allow slow evaporation of the solvent giving finally green block-like crystals of I. The crystals were filtered off and washed with diethyl ether (yield 61 mg, 67%). IR (KBr pellet, cm⁻¹): 3422 (s), 1624 (vs), 1581 (vs), 1430 (s), 1396 (vs).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6. Intensity data for ligand HL1 were measured at 223 K on a four-circle diffractometer assuming a C-centered unit cell and only one equivalent of data were measured; hence R_int = 0 and the h,k,l reflections for which h + k = 2n + 1 were not measured. For compound I, data were measured at 173 K on a Stoe IPDS1, a one-circle image-plate diffractometer. For compound I a small cusp of data is missing. This is common with data measured using the IPDS1 for monoclinic and triclinic crystal systems.

Table 6
Experimental details

	HL1	I
Crystal data
Chemical formula	C₁₄H₁₀N₄O	[Cu₄(C₄₂H₄₄N₈O₁₆)]·2CH₄O
M_r	250.26	1235.09
Crystal system, space group	Monoclinic, Cc	Triclinic, P $[\overline{1}]$
Temperature (K)	223	153
a, b, c (Å)	11.5047 (9), 23.410 (3), 13.4115 (11)	8.1485 (7), 11.2132 (9), 14.2662 (12)
α, β, γ (°)	90, 104.305 (8), 90	98.352 (9), 93.668 (10), 103.578 (9)
V (Å³)	3500.0 (6)	1247.11 (19)
Z	12	1
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.10	1.76
Crystal size (mm)	0.50 × 0.40 × 0.30	0.50 × 0.30 × 0.25

Data collection
Diffractometer	STOE–Siemens AED2, 4-circle	STOE IPDS 1
Absorption correction	–	Multi-scan (MULABS; Spek, 2009)
T_min, T_max	–	0.564, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4090, 4090, 2851	9825, 4499, 3906
R_int	0.0	0.050
(sin θ/λ)_max (Å⁻¹)	0.605	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.134, 1.17	0.031, 0.083, 0.98
No. of reflections	4090	4499
No. of parameters	515	344
No. of restraints	2	0
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21	0.66, −0.66
Computer programs: STADI4, EXPOSE, CELL and INTEGRATE in IPDS-I (Stoe & Cie, 2004 ), X-RED (Stoe & Cie, 1997 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), PLATON (Spek, 2009), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009) and publCIF (Westrip, 2010 ).

For ligand HL1 the NH H atoms could be located in a difference-Fourier map, but during refinement they were included in calculated positions and treated as riding: N—H = 0.87 Å with U_iso(H) = 1.2U_eq(N). The OH H atom of the coordinated methanol molecule in complex I was located in a difference-Fourier map and freely refined. The OH H atom of the solvent methanol molecule in I was included in a calculated position and treated as riding: O—H = 0.84 Å with U_iso(H) = 1.5U_eq(O). For HL1 and complex I the C-bound H atoms were included in calculated positions and treated as riding: C—H = 0.95–0.99 Å with U_iso(H) = 1.2U_eq(C).

Supporting information

CCDC references: 1911375; 1911374

Crystal structure: contains datablocks HL1, I, Global. DOI: https://doi.org/10.1107/S2056989019005450/zl2755sup1.cif

Structure factors: contains datablock HL1. DOI: https://doi.org/10.1107/S2056989019005450/zl2755HL1sup2.hkl

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019005450/zl2755Isup3.hkl

CSD search S1. DOI: https://doi.org/10.1107/S2056989019005450/zl2755sup4.pdf

checkCIF report

Computing details top

Data collection: STADI4 (Stoe & Cie, 1997) for HL1; EXPOSE in IPDS-I (Stoe & Cie, 2004) for (I). Cell refinement: STADI4 (Stoe & Cie, 1997) for HL1; CELL in IPDS-I (Stoe & Cie, 2004) for (I). Data reduction: X-RED (Stoe & Cie, 1997) for HL1; INTEGRATE in IPDS-I (Stoe & Cie, 2004) for (I). For both structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

N-(quinolin-8-yl)pyrazine-2-carboxamide (HL1) top

Crystal data top

C₁₄H₁₀N₄O	F(000) = 1560
M_r = 250.26	D_x = 1.425 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 11.5047 (9) Å	Cell parameters from 38 reflections
b = 23.410 (3) Å	θ = 10.1–19.2°
c = 13.4115 (11) Å	µ = 0.10 mm⁻¹
β = 104.305 (8)°	T = 223 K
V = 3500.0 (6) Å³	Block, colourless
Z = 12	0.50 × 0.40 × 0.30 mm

Data collection top

STOE-Siemens AED2, 4-circle diffractometer	R_int = 0.0
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.0°
Plane graphite monochromator	h = −13→13
ω/\2q scans	k = 0→28
4090 measured reflections	l = −15→16
4090 independent reflections	2 standard reflections every 60 min
2851 reflections with I > 2σ(I)	intensity decay: 1.5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.059	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0283P)² + 4.6085P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.003
4090 reflections	Δρ_max = 0.19 e Å⁻³
515 parameters	Δρ_min = −0.21 e Å⁻³
2 restraints	Extinction correction: (SHELXL-2018/3; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0021 (2)

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
O1	0.7337 (5)	0.0790 (3)	0.8655 (4)	0.0463 (14)
N1	0.7597 (7)	0.1224 (4)	1.1248 (6)	0.0382 (19)
N2	0.6261 (8)	0.2143 (4)	1.0247 (7)	0.044 (2)
N3	0.8141 (6)	0.0339 (3)	1.0201 (5)	0.0360 (15)
H3N	0.822207	0.037888	1.085969	0.043*
N4	0.9191 (8)	−0.0366 (3)	1.1719 (7)	0.0331 (17)
C1	0.7234 (8)	0.1270 (4)	1.0203 (8)	0.034 (2)
C2	0.6608 (8)	0.1720 (4)	0.9717 (8)	0.037 (2)
H2	0.641206	0.173510	0.899409	0.044*
C3	0.6545 (8)	0.2114 (4)	1.1237 (8)	0.042 (2)
H3	0.627584	0.239705	1.162515	0.050*
C4	0.7270 (10)	0.1651 (5)	1.1748 (9)	0.045 (2)
H4	0.752016	0.165464	1.247046	0.055*
C5	0.7573 (6)	0.0775 (3)	0.9596 (6)	0.0320 (17)
C6	0.8616 (9)	−0.0171 (4)	0.9887 (7)	0.031 (2)
C7	0.8578 (10)	−0.0331 (5)	0.8907 (8)	0.042 (2)
H7	0.818655	−0.009305	0.836235	0.050*
C8	0.9096 (10)	−0.0833 (5)	0.8681 (9)	0.046 (3)
H8	0.906182	−0.092985	0.799415	0.055*
C9	0.9658 (10)	−0.1189 (5)	0.9464 (9)	0.046 (3)
H9	1.000005	−0.153289	0.931312	0.055*
C10	0.9724 (10)	−0.1040 (5)	1.0502 (9)	0.037 (2)
C11	1.0315 (11)	−0.1379 (5)	1.1327 (10)	0.056 (3)
H11	1.069668	−0.171833	1.120905	0.067*
C12	1.0335 (10)	−0.1216 (5)	1.2294 (9)	0.046 (3)
H12	1.073731	−0.143839	1.285804	0.055*
C13	0.9749 (9)	−0.0713 (5)	1.2449 (8)	0.038 (2)
H13	0.975561	−0.061557	1.313068	0.046*
C14	0.9177 (9)	−0.0536 (4)	1.0716 (8)	0.029 (2)
O2	1.1664 (6)	0.0867 (3)	1.2537 (5)	0.0469 (17)
N21	1.1428 (7)	0.0431 (3)	0.9977 (6)	0.0334 (19)
N22	1.2741 (9)	−0.0505 (4)	1.0996 (7)	0.047 (2)
N23	1.0843 (6)	0.1305 (3)	1.1025 (5)	0.0311 (16)
H23N	1.074944	0.126707	1.036416	0.037*
N24	0.9780 (7)	0.2026 (4)	0.9528 (6)	0.0359 (19)
C21	1.1773 (11)	0.0001 (5)	0.9463 (8)	0.041 (2)
H21	1.158817	0.001603	0.874010	0.049*
C22	1.2378 (11)	−0.0452 (5)	0.9946 (9)	0.049 (3)
H22	1.256284	−0.074972	0.954083	0.058*
C23	1.2382 (11)	−0.0062 (5)	1.1504 (9)	0.046 (3)
H23	1.256952	−0.006842	1.222691	0.055*
C24	1.1760 (8)	0.0391 (4)	1.1000 (7)	0.030 (2)
C25	1.1415 (7)	0.0869 (4)	1.1595 (6)	0.035 (2)
C26	1.0377 (8)	0.1811 (4)	1.1325 (7)	0.0267 (19)
C27	1.0415 (9)	0.1959 (4)	1.2346 (7)	0.033 (2)
H27	1.080413	0.172461	1.289764	0.040*
C28	0.9845 (10)	0.2474 (5)	1.2516 (9)	0.045 (3)
H28	0.987051	0.258236	1.319558	0.054*
C29	0.9267 (11)	0.2815 (4)	1.1738 (10)	0.046 (3)
H29	0.887722	0.314476	1.188833	0.056*
C30	0.9238 (10)	0.2689 (5)	1.0723 (10)	0.043 (3)
C31	0.8637 (10)	0.3020 (5)	0.9884 (9)	0.046 (3)
H31	0.822150	0.334769	1.000800	0.056*
C32	0.8633 (10)	0.2884 (5)	0.8881 (9)	0.051 (3)
H32	0.824502	0.311252	0.832158	0.061*
C33	0.9265 (10)	0.2366 (5)	0.8750 (9)	0.041 (3)
H33	0.931273	0.226477	0.808338	0.050*
C34	0.9778 (8)	0.2169 (4)	1.0483 (8)	0.030 (2)
O3	1.2338 (5)	0.2464 (3)	0.8676 (4)	0.0499 (15)
N31	1.2533 (7)	0.2882 (4)	1.1263 (6)	0.0357 (18)
N32	1.1316 (9)	0.3839 (4)	1.0267 (8)	0.056 (2)
N33	1.3101 (5)	0.2002 (3)	1.0212 (5)	0.0343 (14)
H33N	1.315150	0.203851	1.086711	0.041*
N34	1.4154 (7)	0.1285 (4)	1.1717 (6)	0.0351 (19)
C41	1.2238 (8)	0.2920 (4)	1.0237 (7)	0.032 (2)
C42	1.1626 (9)	0.3411 (4)	0.9757 (7)	0.040 (2)
H42	1.143118	0.343064	0.903457	0.048*
C43	1.1578 (10)	0.3785 (5)	1.1267 (9)	0.055 (3)
H43	1.132327	0.406954	1.165939	0.066*
C44	1.2214 (9)	0.3326 (4)	1.1769 (8)	0.041 (2)
H44	1.243254	0.332380	1.249264	0.050*
C45	1.2556 (6)	0.2439 (3)	0.9620 (6)	0.0337 (17)
C46	1.3596 (9)	0.1501 (4)	0.9928 (8)	0.035 (2)
C47	1.3526 (9)	0.1366 (4)	0.8925 (7)	0.036 (2)
H47	1.310731	0.160484	0.839348	0.043*
C48	1.4091 (10)	0.0861 (5)	0.8688 (9)	0.043 (3)
H48	1.406998	0.077855	0.799766	0.052*
C49	1.4661 (11)	0.0493 (5)	0.9437 (10)	0.048 (3)
H49	1.499598	0.015108	0.926739	0.057*
C50	1.4738 (9)	0.0637 (4)	1.0481 (9)	0.034 (2)
C51	1.5356 (10)	0.0298 (5)	1.1340 (10)	0.052 (3)
H51	1.576831	−0.003515	1.123746	0.062*
C52	1.5333 (10)	0.0465 (4)	1.2297 (10)	0.048 (3)
H52	1.573714	0.024722	1.286647	0.058*
C53	1.4737 (10)	0.0941 (5)	1.2445 (9)	0.044 (3)
H53	1.473984	0.103532	1.312724	0.053*
C54	1.4176 (9)	0.1133 (5)	1.0717 (8)	0.034 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.062 (4)	0.052 (4)	0.024 (3)	0.008 (3)	0.009 (3)	0.003 (2)
N1	0.038 (4)	0.041 (5)	0.033 (4)	0.001 (3)	0.004 (3)	−0.002 (3)
N2	0.047 (5)	0.031 (4)	0.052 (6)	0.005 (3)	0.011 (4)	0.010 (4)
N3	0.044 (4)	0.039 (4)	0.026 (3)	0.003 (3)	0.009 (3)	0.000 (3)
N4	0.037 (4)	0.032 (4)	0.028 (4)	0.004 (3)	0.004 (3)	0.001 (3)
C1	0.025 (4)	0.040 (5)	0.039 (5)	0.001 (3)	0.010 (4)	−0.002 (4)
C2	0.032 (5)	0.040 (5)	0.033 (5)	0.005 (4)	−0.002 (4)	0.014 (4)
C3	0.031 (5)	0.033 (5)	0.059 (7)	0.007 (4)	0.008 (4)	0.001 (4)
C4	0.043 (5)	0.037 (5)	0.048 (6)	0.005 (4)	−0.004 (4)	0.002 (4)
C5	0.030 (4)	0.028 (4)	0.040 (5)	0.001 (3)	0.013 (3)	0.000 (3)
C6	0.033 (5)	0.026 (4)	0.032 (5)	−0.007 (3)	0.004 (4)	0.001 (3)
C7	0.041 (5)	0.060 (6)	0.024 (5)	−0.007 (4)	0.008 (4)	0.010 (4)
C8	0.050 (6)	0.051 (6)	0.037 (5)	−0.008 (5)	0.015 (5)	−0.015 (5)
C9	0.057 (6)	0.042 (5)	0.043 (6)	−0.002 (5)	0.020 (5)	−0.015 (5)
C10	0.036 (5)	0.033 (5)	0.041 (6)	0.006 (4)	0.011 (4)	0.005 (4)
C11	0.058 (7)	0.043 (6)	0.075 (8)	0.017 (5)	0.031 (6)	0.013 (5)
C12	0.042 (5)	0.040 (6)	0.053 (7)	0.001 (5)	0.007 (5)	0.024 (5)
C13	0.035 (5)	0.057 (6)	0.021 (4)	−0.005 (4)	0.004 (4)	0.002 (4)
C14	0.031 (5)	0.031 (4)	0.027 (5)	−0.009 (4)	0.011 (4)	0.001 (4)
O2	0.055 (4)	0.052 (4)	0.034 (4)	0.009 (3)	0.011 (3)	0.010 (3)
N21	0.039 (4)	0.025 (4)	0.035 (5)	0.005 (3)	0.007 (4)	0.004 (3)
N22	0.059 (6)	0.038 (5)	0.043 (5)	0.009 (4)	0.011 (4)	0.010 (4)
N23	0.038 (4)	0.033 (4)	0.021 (4)	0.007 (3)	0.005 (3)	0.000 (3)
N24	0.032 (4)	0.043 (5)	0.031 (4)	−0.006 (4)	0.005 (3)	0.000 (4)
C21	0.059 (6)	0.034 (5)	0.032 (5)	−0.005 (5)	0.015 (5)	−0.005 (4)
C22	0.074 (8)	0.032 (6)	0.042 (6)	−0.005 (5)	0.019 (6)	−0.003 (5)
C23	0.054 (6)	0.042 (6)	0.045 (7)	−0.005 (5)	0.020 (5)	0.010 (5)
C24	0.033 (5)	0.027 (5)	0.029 (5)	−0.008 (4)	0.006 (4)	0.004 (4)
C25	0.025 (4)	0.055 (6)	0.022 (4)	−0.004 (4)	−0.001 (3)	0.016 (4)
C26	0.020 (4)	0.033 (5)	0.027 (5)	−0.002 (4)	0.004 (3)	0.004 (4)
C27	0.039 (5)	0.029 (5)	0.031 (5)	−0.014 (4)	0.010 (4)	−0.009 (4)
C28	0.053 (7)	0.044 (6)	0.046 (6)	−0.015 (5)	0.025 (5)	−0.009 (5)
C29	0.054 (6)	0.025 (5)	0.068 (8)	−0.004 (4)	0.031 (6)	−0.008 (5)
C30	0.038 (6)	0.041 (6)	0.054 (7)	−0.005 (5)	0.019 (5)	−0.006 (5)
C31	0.050 (6)	0.034 (5)	0.055 (7)	−0.002 (5)	0.015 (5)	0.002 (5)
C32	0.043 (6)	0.058 (8)	0.049 (7)	−0.001 (6)	0.006 (5)	−0.005 (5)
C33	0.043 (6)	0.036 (6)	0.042 (6)	0.001 (4)	0.006 (5)	0.013 (5)
C34	0.022 (4)	0.025 (4)	0.038 (5)	−0.003 (3)	0.001 (4)	−0.009 (4)
O3	0.062 (4)	0.064 (4)	0.024 (3)	0.007 (3)	0.011 (3)	0.009 (3)
N31	0.036 (4)	0.038 (4)	0.032 (4)	−0.001 (3)	0.005 (3)	0.002 (3)
N32	0.061 (5)	0.046 (5)	0.061 (6)	0.009 (4)	0.015 (5)	0.010 (5)
N33	0.035 (3)	0.043 (4)	0.026 (3)	0.000 (3)	0.008 (3)	0.002 (3)
N34	0.038 (4)	0.039 (4)	0.028 (4)	−0.007 (3)	0.008 (3)	0.000 (3)
C41	0.026 (4)	0.035 (5)	0.036 (5)	−0.002 (3)	0.008 (4)	0.009 (4)
C42	0.041 (5)	0.043 (6)	0.033 (5)	0.007 (4)	0.006 (4)	0.008 (4)
C43	0.054 (6)	0.053 (7)	0.056 (7)	0.012 (5)	0.009 (5)	0.009 (5)
C44	0.047 (5)	0.040 (5)	0.038 (5)	0.012 (4)	0.013 (4)	−0.001 (4)
C45	0.038 (4)	0.026 (4)	0.036 (4)	0.001 (3)	0.007 (3)	0.003 (3)
C46	0.039 (5)	0.033 (5)	0.038 (5)	−0.006 (4)	0.018 (4)	−0.013 (4)
C47	0.039 (5)	0.042 (5)	0.030 (5)	−0.005 (4)	0.014 (4)	−0.003 (4)
C48	0.045 (6)	0.047 (6)	0.045 (6)	−0.017 (5)	0.024 (5)	−0.021 (5)
C49	0.050 (6)	0.043 (6)	0.056 (7)	−0.008 (5)	0.024 (5)	−0.023 (5)
C50	0.036 (5)	0.024 (5)	0.045 (6)	−0.008 (4)	0.015 (4)	0.000 (4)
C51	0.044 (5)	0.037 (5)	0.082 (9)	0.005 (4)	0.032 (6)	0.013 (5)
C52	0.039 (5)	0.042 (6)	0.063 (7)	0.010 (4)	0.012 (5)	0.036 (5)
C53	0.037 (5)	0.056 (6)	0.035 (5)	−0.009 (4)	0.002 (4)	0.001 (4)
C54	0.035 (5)	0.040 (5)	0.027 (5)	−0.007 (4)	0.013 (4)	−0.001 (4)

Geometric parameters (Å, º) top

O1—C5	1.224 (9)	C26—C27	1.403 (13)
N1—C4	1.311 (14)	C26—C34	1.439 (14)
N1—C1	1.364 (12)	C27—C28	1.418 (15)
N2—C3	1.289 (13)	C27—H27	0.9400
N2—C2	1.337 (13)	C28—C29	1.351 (17)
N3—C5	1.366 (10)	C28—H28	0.9400
N3—C6	1.419 (11)	C29—C30	1.385 (17)
N3—H3N	0.8700	C29—H29	0.9400
N4—C13	1.312 (14)	C30—C31	1.400 (16)
N4—C14	1.398 (13)	C30—C34	1.438 (15)
C1—C2	1.349 (14)	C31—C32	1.380 (16)
C1—C5	1.521 (11)	C31—H31	0.9400
C2—H2	0.9400	C32—C33	1.447 (16)
C3—C4	1.435 (15)	C32—H32	0.9400
C3—H3	0.9400	C33—H33	0.9400
C4—H4	0.9400	O3—C45	1.230 (9)
C6—C7	1.358 (13)	N31—C41	1.337 (12)
C6—C14	1.424 (14)	N31—C44	1.340 (12)
C7—C8	1.385 (15)	N32—C43	1.306 (14)
C7—H7	0.9400	N32—C42	1.312 (13)
C8—C9	1.371 (17)	N33—C45	1.350 (10)
C8—H8	0.9400	N33—C46	1.399 (11)
C9—C10	1.419 (16)	N33—H33N	0.8700
C9—H9	0.9400	N34—C53	1.314 (14)
C10—C11	1.395 (16)	N34—C54	1.395 (13)
C10—C14	1.400 (11)	C41—C42	1.417 (14)
C11—C12	1.347 (17)	C41—C45	1.494 (12)
C11—H11	0.9400	C42—H42	0.9400
C12—C13	1.398 (15)	C43—C44	1.378 (16)
C12—H12	0.9400	C43—H43	0.9400
C13—H13	0.9400	C44—H44	0.9400
O2—C25	1.224 (11)	C46—C47	1.366 (13)
N21—C24	1.333 (12)	C46—C54	1.398 (15)
N21—C21	1.334 (13)	C47—C48	1.422 (13)
N22—C23	1.360 (15)	C47—H47	0.9400
N22—C22	1.372 (15)	C48—C49	1.362 (17)
N23—C25	1.347 (11)	C48—H48	0.9400
N23—C26	1.399 (11)	C49—C50	1.421 (16)
N23—H23N	0.8700	C49—H49	0.9400
N24—C34	1.324 (13)	C50—C54	1.403 (11)
N24—C33	1.329 (13)	C50—C51	1.435 (16)
C21—C22	1.344 (17)	C51—C52	1.348 (16)
C21—H21	0.9400	C51—H51	0.9400
C22—H22	0.9400	C52—C53	1.350 (15)
C23—C24	1.362 (16)	C52—H52	0.9400
C23—H23	0.9400	C53—H53	0.9400
C24—C25	1.484 (13)

C4—N1—C1	114.3 (10)	C26—C27—C28	117.5 (10)
C3—N2—C2	118.4 (9)	C26—C27—H27	121.2
C5—N3—C6	128.0 (7)	C28—C27—H27	121.2
C5—N3—H3N	116.0	C29—C28—C27	122.5 (11)
C6—N3—H3N	116.0	C29—C28—H28	118.7
C13—N4—C14	115.5 (8)	C27—C28—H28	118.7
C2—C1—N1	123.4 (9)	C28—C29—C30	121.4 (10)
C2—C1—C5	120.8 (9)	C28—C29—H29	119.3
N1—C1—C5	115.8 (9)	C30—C29—H29	119.3
N2—C2—C1	121.0 (9)	C29—C30—C31	124.0 (11)
N2—C2—H2	119.5	C29—C30—C34	119.5 (12)
C1—C2—H2	119.5	C31—C30—C34	116.3 (11)
N2—C3—C4	120.1 (9)	C32—C31—C30	122.5 (11)
N2—C3—H3	120.0	C32—C31—H31	118.8
C4—C3—H3	120.0	C30—C31—H31	118.8
N1—C4—C3	122.6 (10)	C31—C32—C33	115.5 (11)
N1—C4—H4	118.7	C31—C32—H32	122.2
C3—C4—H4	118.7	C33—C32—H32	122.2
O1—C5—N3	125.8 (7)	N24—C33—C32	123.1 (11)
O1—C5—C1	120.6 (8)	N24—C33—H33	118.4
N3—C5—C1	113.5 (7)	C32—C33—H33	118.4
C7—C6—N3	126.7 (9)	N24—C34—C30	122.3 (11)
C7—C6—C14	119.3 (9)	N24—C34—C26	119.8 (8)
N3—C6—C14	114.0 (8)	C30—C34—C26	117.9 (10)
C6—C7—C8	122.3 (10)	C41—N31—C44	116.1 (9)
C6—C7—H7	118.9	C43—N32—C42	116.0 (10)
C8—C7—H7	118.9	C45—N33—C46	129.6 (7)
C9—C8—C7	119.7 (10)	C45—N33—H33N	115.2
C9—C8—H8	120.2	C46—N33—H33N	115.2
C7—C8—H8	120.2	C53—N34—C54	115.5 (9)
C8—C9—C10	120.2 (10)	N31—C41—C42	119.5 (9)
C8—C9—H9	119.9	N31—C41—C45	119.1 (8)
C10—C9—H9	119.9	C42—C41—C45	121.4 (8)
C11—C10—C14	118.2 (9)	N32—C42—C41	123.5 (9)
C11—C10—C9	122.4 (10)	N32—C42—H42	118.3
C14—C10—C9	119.4 (9)	C41—C42—H42	118.3
C12—C11—C10	119.5 (10)	N32—C43—C44	122.5 (11)
C12—C11—H11	120.3	N32—C43—H43	118.7
C10—C11—H11	120.3	C44—C43—H43	118.7
C11—C12—C13	119.2 (10)	N31—C44—C43	122.3 (10)
C11—C12—H12	120.4	N31—C44—H44	118.8
C13—C12—H12	120.4	C43—C44—H44	118.8
N4—C13—C12	125.1 (10)	O3—C45—N33	126.1 (7)
N4—C13—H13	117.4	O3—C45—C41	121.2 (8)
C12—C13—H13	117.4	N33—C45—C41	112.7 (7)
N4—C14—C10	122.5 (8)	C47—C46—C54	120.3 (9)
N4—C14—C6	118.4 (9)	C47—C46—N33	122.3 (9)
C10—C14—C6	119.1 (8)	C54—C46—N33	117.5 (8)
C24—N21—C21	115.7 (9)	C46—C47—C48	119.6 (10)
C23—N22—C22	113.1 (10)	C46—C47—H47	120.2
C25—N23—C26	130.3 (8)	C48—C47—H47	120.2
C25—N23—H23N	114.9	C49—C48—C47	121.6 (10)
C26—N23—H23N	114.9	C49—C48—H48	119.2
C34—N24—C33	120.0 (9)	C47—C48—H48	119.2
N21—C21—C22	122.0 (11)	C48—C49—C50	118.6 (10)
N21—C21—H21	119.0	C48—C49—H49	120.7
C22—C21—H21	119.0	C50—C49—H49	120.7
C21—C22—N22	123.8 (11)	C54—C50—C49	119.9 (9)
C21—C22—H22	118.1	C54—C50—C51	116.2 (8)
N22—C22—H22	118.1	C49—C50—C51	123.9 (10)
N22—C23—C24	122.1 (11)	C52—C51—C50	118.8 (10)
N22—C23—H23	118.9	C52—C51—H51	120.6
C24—C23—H23	118.9	C50—C51—H51	120.6
N21—C24—C23	123.2 (9)	C51—C52—C53	120.7 (10)
N21—C24—C25	117.0 (8)	C51—C52—H52	119.7
C23—C24—C25	119.8 (9)	C53—C52—H52	119.7
O2—C25—N23	123.1 (9)	N34—C53—C52	125.5 (11)
O2—C25—C24	121.8 (9)	N34—C53—H53	117.2
N23—C25—C24	115.1 (8)	C52—C53—H53	117.2
N23—C26—C27	124.6 (9)	N34—C54—C46	116.9 (9)
N23—C26—C34	114.2 (8)	N34—C54—C50	123.2 (8)
C27—C26—C34	121.1 (9)	C46—C54—C50	120.0 (7)

C4—N1—C1—C2	1.0 (13)	C27—C28—C29—C30	−2.4 (17)
C4—N1—C1—C5	−178.7 (8)	C28—C29—C30—C31	178.9 (11)
C3—N2—C2—C1	0.3 (14)	C28—C29—C30—C34	3.3 (17)
N1—C1—C2—N2	−2.7 (14)	C29—C30—C31—C32	179.5 (11)
C5—C1—C2—N2	177.0 (8)	C34—C30—C31—C32	−4.8 (16)
C2—N2—C3—C4	3.3 (14)	C30—C31—C32—C33	1.6 (16)
C1—N1—C4—C3	2.7 (14)	C34—N24—C33—C32	−3.1 (16)
N2—C3—C4—N1	−5.1 (16)	C31—C32—C33—N24	2.6 (16)
C6—N3—C5—O1	2.7 (13)	C33—N24—C34—C30	−0.4 (15)
C6—N3—C5—C1	−177.2 (8)	C33—N24—C34—C26	−177.6 (9)
C2—C1—C5—O1	3.8 (12)	C29—C30—C34—N24	−179.8 (8)
N1—C1—C5—O1	−176.5 (8)	C31—C30—C34—N24	4.3 (16)
C2—C1—C5—N3	−176.2 (8)	C29—C30—C34—C26	−2.6 (16)
N1—C1—C5—N3	3.4 (10)	C31—C30—C34—C26	−178.5 (7)
C5—N3—C6—C7	−1.3 (14)	N23—C26—C34—N24	−4.6 (12)
C5—N3—C6—C14	178.9 (7)	C27—C26—C34—N24	178.4 (9)
N3—C6—C7—C8	178.4 (9)	N23—C26—C34—C30	178.1 (9)
C14—C6—C7—C8	−1.8 (15)	C27—C26—C34—C30	1.1 (14)
C6—C7—C8—C9	0.8 (17)	C44—N31—C41—C42	0.0 (12)
C7—C8—C9—C10	−0.9 (17)	C44—N31—C41—C45	−179.6 (8)
C8—C9—C10—C11	−178.2 (11)	C43—N32—C42—C41	−1.7 (15)
C8—C9—C10—C14	2.1 (15)	N31—C41—C42—N32	−0.5 (14)
C14—C10—C11—C12	0.5 (15)	C45—C41—C42—N32	179.1 (9)
C9—C10—C11—C12	−179.3 (11)	C42—N32—C43—C44	4.3 (17)
C10—C11—C12—C13	0.7 (17)	C41—N31—C44—C43	2.5 (14)
C14—N4—C13—C12	1.7 (15)	N32—C43—C44—N31	−5.0 (18)
C11—C12—C13—N4	−1.9 (18)	C46—N33—C45—O3	3.7 (13)
C13—N4—C14—C10	−0.3 (12)	C46—N33—C45—C41	−175.4 (8)
C13—N4—C14—C6	−178.2 (9)	N31—C41—C45—O3	−177.5 (8)
C11—C10—C14—N4	−0.7 (12)	C42—C41—C45—O3	2.9 (12)
C9—C10—C14—N4	179.0 (11)	N31—C41—C45—N33	1.6 (10)
C11—C10—C14—C6	177.2 (11)	C42—C41—C45—N33	−178.0 (8)
C9—C10—C14—C6	−3.1 (12)	C45—N33—C46—C47	−3.9 (14)
C7—C6—C14—N4	−179.1 (9)	C45—N33—C46—C54	176.2 (7)
N3—C6—C14—N4	0.8 (12)	C54—C46—C47—C48	−2.6 (14)
C7—C6—C14—C10	2.9 (12)	N33—C46—C47—C48	177.4 (9)
N3—C6—C14—C10	−177.2 (7)	C46—C47—C48—C49	2.8 (15)
C24—N21—C21—C22	2.4 (16)	C47—C48—C49—C50	−3.2 (16)
N21—C21—C22—N22	−3.1 (19)	C48—C49—C50—C54	3.5 (14)
C23—N22—C22—C21	2.7 (17)	C48—C49—C50—C51	−177.4 (10)
C22—N22—C23—C24	−2.0 (16)	C54—C50—C51—C52	1.6 (13)
C21—N21—C24—C23	−1.8 (15)	C49—C50—C51—C52	−177.6 (10)
C21—N21—C24—C25	178.6 (9)	C50—C51—C52—C53	0.3 (16)
N22—C23—C24—N21	1.8 (16)	C54—N34—C53—C52	−0.3 (15)
N22—C23—C24—C25	−178.6 (9)	C51—C52—C53—N34	−1.0 (18)
C26—N23—C25—O2	−3.2 (15)	C53—N34—C54—C46	−178.0 (9)
C26—N23—C25—C24	178.6 (8)	C53—N34—C54—C50	2.4 (12)
N21—C24—C25—O2	178.9 (9)	C47—C46—C54—N34	−176.6 (9)
C23—C24—C25—O2	−0.7 (13)	N33—C46—C54—N34	3.4 (13)
N21—C24—C25—N23	−2.8 (11)	C47—C46—C54—C50	3.0 (13)
C23—C24—C25—N23	177.5 (9)	N33—C46—C54—C50	−177.0 (7)
C25—N23—C26—C27	−0.7 (15)	C49—C50—C54—N34	176.2 (11)
C25—N23—C26—C34	−177.6 (8)	C51—C50—C54—N34	−3.0 (11)
N23—C26—C27—C28	−176.8 (8)	C49—C50—C54—C46	−3.4 (11)
C34—C26—C27—C28	−0.2 (14)	C51—C50—C54—C46	177.4 (11)
C26—C27—C28—C29	0.8 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N1	0.87	2.21	2.661 (10)	112
N3—H3N···N4	0.87	2.23	2.667 (10)	111
C7—H7···O1	0.94	2.36	2.967 (13)	122
N23—H23N···N21	0.87	2.22	2.662 (10)	112
N23—H23N···N24	0.87	2.24	2.675 (11)	110
C21—H21···O2ⁱ	0.94	2.64	3.264 (12)	125
C22—H22···O2ⁱ	0.94	2.64	3.278 (13)	125
C27—H27···O2	0.94	2.34	2.912 (13)	119
N33—H33N···N31	0.87	2.21	2.667 (10)	113
N33—H33N···N34	0.87	2.26	2.674 (11)	109
C44—H44···O1ⁱⁱ	0.94	2.61	3.244 (11)	125
C47—H47···O3	0.94	2.27	2.893 (12)	123

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

Hexa-µ-acetato-1:2κ²O:O';2:3κ⁸O:O'; 3:4κ²O:O'-dimethanol-1κO,2κO-bis[N-(quinolin-8-yl)pyrazine-2-carboxamide]-1κ³N,N',N''; 4κ³N,N',N''-tetracopper(II) methanol disolvate (I) top

Crystal data top

[Cu₄(C₄₂H₄₄N₈O₁₆)]·2CH₄O	Z = 1
M_r = 1235.09	F(000) = 632
Triclinic, P1	D_x = 1.645 Mg m⁻³
a = 8.1485 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2132 (9) Å	Cell parameters from 8000 reflections
c = 14.2662 (12) Å	θ = 2.2–25.9°
α = 98.352 (9)°	µ = 1.76 mm⁻¹
β = 93.668 (10)°	T = 153 K
γ = 103.578 (9)°	Block, green
V = 1247.11 (19) Å³	0.50 × 0.30 × 0.25 mm

Data collection top

STOE IPDS 1 diffractometer	4499 independent reflections
Radiation source: fine-focus sealed tube	3906 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.050
φ rotation scans	θ_max = 25.9°, θ_min = 2.2°
Absorption correction: multi-scan (MULABS; Spek, 2009)	h = −10→10
T_min = 0.564, T_max = 1.000	k = −13→13
9825 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: mixed
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0579P)²] where P = (F_o² + 2F_c²)/3
4499 reflections	(Δ/σ)_max = 0.001
344 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.66 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
Cu1	0.39598 (3)	0.31687 (2)	0.17585 (2)	0.01373 (9)
O2	0.1648 (2)	0.37443 (17)	0.10360 (12)	0.0196 (4)
H2O	0.208 (3)	0.440 (3)	0.081 (2)	0.020 (7)*
C15	0.0276 (3)	0.3951 (3)	0.15486 (19)	0.0295 (6)
H15C	−0.070186	0.391617	0.109933	0.044*
H15B	0.061424	0.477100	0.195227	0.044*
H15A	−0.003095	0.330750	0.194798	0.044*
N1	0.5500 (2)	0.49209 (19)	0.19753 (13)	0.0158 (4)
N2	0.7940 (2)	0.7145 (2)	0.20796 (15)	0.0220 (4)
N3	0.5020 (2)	0.30915 (19)	0.05748 (13)	0.0143 (4)
N4	0.2904 (2)	0.13793 (19)	0.12373 (13)	0.0151 (4)
O1	0.6953 (2)	0.42282 (17)	−0.02929 (12)	0.0214 (4)
C1	0.6469 (3)	0.5128 (2)	0.12584 (15)	0.0145 (4)
C2	0.7678 (3)	0.6243 (2)	0.13166 (17)	0.0193 (5)
H2	0.834295	0.637233	0.080020	0.023*
C3	0.6944 (3)	0.6927 (2)	0.27740 (17)	0.0221 (5)
H3	0.707511	0.755074	0.331961	0.027*
C4	0.5719 (3)	0.5817 (2)	0.27251 (16)	0.0193 (5)
H4	0.503163	0.569718	0.323337	0.023*
C5	0.6164 (3)	0.4088 (2)	0.04218 (15)	0.0145 (5)
C6	0.4453 (3)	0.1982 (2)	−0.00583 (15)	0.0142 (4)
C7	0.4895 (3)	0.1676 (2)	−0.09636 (15)	0.0174 (5)
H7	0.568342	0.227202	−0.122700	0.021*
C8	0.4187 (3)	0.0487 (2)	−0.14995 (16)	0.0209 (5)
H8	0.450487	0.029735	−0.212245	0.025*
C9	0.3049 (3)	−0.0406 (2)	−0.11458 (16)	0.0209 (5)
H9	0.258555	−0.120132	−0.152212	0.025*
C10	0.2569 (3)	−0.0133 (2)	−0.02131 (16)	0.0172 (5)
C11	0.1416 (3)	−0.0996 (2)	0.02149 (18)	0.0212 (5)
H11	0.088973	−0.180113	−0.012911	0.025*
C12	0.1067 (3)	−0.0660 (2)	0.11283 (17)	0.0221 (5)
H12	0.030098	−0.123070	0.142415	0.027*
C13	0.1849 (3)	0.0530 (2)	0.16210 (16)	0.0183 (5)
H13	0.161656	0.074312	0.225945	0.022*
C14	0.3277 (3)	0.1054 (2)	0.03234 (15)	0.0141 (4)
Cu2	0.44706 (3)	0.08030 (3)	0.45535 (2)	0.01311 (9)
O3	0.3072 (2)	0.34649 (16)	0.29775 (11)	0.0178 (3)
O4	0.3848 (2)	0.19608 (16)	0.36021 (11)	0.0195 (4)
O5	0.5820 (2)	0.21036 (16)	0.55744 (12)	0.0220 (4)
O6	0.6575 (2)	0.08152 (17)	0.39303 (11)	0.0208 (4)
O7	0.3245 (2)	−0.07186 (17)	0.36824 (12)	0.0250 (4)
O8	0.25541 (19)	0.05939 (17)	0.53366 (12)	0.0214 (4)
C16	0.3260 (3)	0.2889 (2)	0.36657 (15)	0.0144 (4)
C17	0.2738 (4)	0.3410 (3)	0.46051 (17)	0.0300 (6)
H17A	0.225199	0.411380	0.452304	0.045*
H17B	0.373388	0.369265	0.507758	0.045*
H17C	0.188966	0.276304	0.482413	0.045*
C18	0.6718 (3)	0.1805 (2)	0.62131 (16)	0.0179 (5)
C19	0.7880 (3)	0.2856 (3)	0.69104 (19)	0.0294 (6)
H19A	0.736862	0.295786	0.751097	0.044*
H19B	0.804464	0.362812	0.664396	0.044*
H19C	0.897884	0.266140	0.702785	0.044*
C20	0.7617 (3)	0.0184 (2)	0.40933 (15)	0.0159 (5)
C21	0.9158 (3)	0.0332 (3)	0.35565 (17)	0.0227 (5)
H21C	1.015191	0.034582	0.398686	0.034*
H21B	0.934162	0.111348	0.330169	0.034*
H21A	0.898758	−0.036643	0.303063	0.034*
O9	0.7083 (3)	0.2935 (2)	0.28288 (15)	0.0402 (5)
H9O	0.646942	0.230274	0.299405	0.060*
C22	0.7910 (4)	0.3767 (3)	0.3638 (2)	0.0457 (8)
H22A	0.853986	0.453730	0.344812	0.069*
H22B	0.869998	0.339429	0.397142	0.069*
H22C	0.707048	0.395299	0.406157	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01849 (15)	0.01031 (18)	0.01175 (14)	0.00192 (11)	0.00404 (10)	0.00134 (11)
O2	0.0199 (8)	0.0199 (11)	0.0213 (8)	0.0052 (7)	0.0047 (6)	0.0088 (8)
C15	0.0202 (12)	0.0357 (18)	0.0291 (13)	0.0058 (11)	0.0026 (10)	−0.0044 (12)
N1	0.0172 (9)	0.0165 (12)	0.0143 (9)	0.0048 (7)	0.0002 (7)	0.0042 (8)
N2	0.0228 (10)	0.0146 (12)	0.0249 (10)	−0.0001 (8)	−0.0024 (8)	0.0016 (9)
N3	0.0158 (8)	0.0126 (11)	0.0137 (9)	0.0013 (7)	0.0013 (7)	0.0028 (8)
N4	0.0155 (8)	0.0142 (11)	0.0158 (9)	0.0044 (7)	0.0020 (7)	0.0021 (8)
O1	0.0257 (8)	0.0193 (10)	0.0188 (8)	0.0015 (7)	0.0093 (7)	0.0052 (7)
C1	0.0143 (10)	0.0146 (13)	0.0165 (10)	0.0061 (8)	−0.0003 (8)	0.0055 (9)
C2	0.0171 (10)	0.0168 (14)	0.0228 (11)	0.0019 (9)	0.0007 (9)	0.0040 (10)
C3	0.0273 (12)	0.0150 (14)	0.0212 (12)	0.0032 (9)	−0.0031 (9)	−0.0008 (10)
C4	0.0238 (11)	0.0187 (14)	0.0151 (10)	0.0059 (9)	0.0003 (9)	0.0016 (9)
C5	0.0141 (10)	0.0141 (14)	0.0163 (10)	0.0049 (8)	−0.0006 (8)	0.0044 (9)
C6	0.0149 (9)	0.0134 (13)	0.0151 (10)	0.0055 (8)	−0.0014 (8)	0.0029 (9)
C7	0.0208 (10)	0.0206 (14)	0.0123 (10)	0.0068 (9)	0.0020 (8)	0.0045 (9)
C8	0.0265 (12)	0.0248 (15)	0.0126 (10)	0.0108 (10)	0.0014 (9)	0.0002 (10)
C9	0.0277 (12)	0.0164 (14)	0.0162 (11)	0.0061 (9)	−0.0031 (9)	−0.0036 (9)
C10	0.0174 (10)	0.0158 (14)	0.0172 (11)	0.0047 (9)	−0.0030 (8)	0.0002 (9)
C11	0.0209 (11)	0.0125 (14)	0.0264 (12)	0.0009 (9)	−0.0027 (9)	−0.0015 (10)
C12	0.0198 (11)	0.0177 (15)	0.0258 (12)	−0.0026 (9)	0.0035 (9)	0.0049 (10)
C13	0.0201 (11)	0.0165 (14)	0.0176 (11)	0.0021 (9)	0.0050 (8)	0.0034 (9)
C14	0.0149 (9)	0.0147 (13)	0.0135 (10)	0.0057 (8)	−0.0001 (8)	0.0019 (9)
Cu2	0.01474 (14)	0.01284 (18)	0.01143 (14)	0.00311 (10)	0.00007 (10)	0.00198 (11)
O3	0.0262 (8)	0.0157 (10)	0.0141 (7)	0.0083 (6)	0.0048 (6)	0.0043 (7)
O4	0.0279 (8)	0.0187 (10)	0.0140 (7)	0.0094 (7)	0.0004 (6)	0.0046 (7)
O5	0.0240 (8)	0.0170 (10)	0.0218 (8)	0.0028 (7)	−0.0047 (7)	−0.0003 (7)
O6	0.0231 (8)	0.0236 (11)	0.0198 (8)	0.0098 (7)	0.0079 (6)	0.0081 (7)
O7	0.0314 (9)	0.0198 (11)	0.0204 (8)	0.0039 (7)	−0.0073 (7)	0.0006 (7)
O8	0.0191 (8)	0.0252 (11)	0.0234 (8)	0.0077 (7)	0.0059 (6)	0.0103 (8)
C16	0.0140 (10)	0.0149 (14)	0.0133 (10)	0.0022 (8)	−0.0002 (8)	0.0026 (9)
C17	0.0464 (15)	0.0338 (18)	0.0164 (12)	0.0196 (13)	0.0102 (11)	0.0066 (11)
C18	0.0141 (10)	0.0203 (15)	0.0165 (11)	0.0023 (9)	0.0021 (8)	−0.0028 (9)
C19	0.0265 (12)	0.0227 (17)	0.0313 (14)	0.0005 (10)	−0.0082 (11)	−0.0064 (11)
C20	0.0174 (10)	0.0140 (14)	0.0131 (10)	0.0011 (8)	−0.0002 (8)	−0.0030 (9)
C21	0.0198 (11)	0.0244 (16)	0.0234 (12)	0.0041 (9)	0.0048 (9)	0.0037 (10)
O9	0.0560 (13)	0.0284 (14)	0.0405 (11)	0.0107 (10)	0.0252 (10)	0.0108 (10)
C22	0.0507 (18)	0.033 (2)	0.053 (2)	0.0066 (14)	0.0113 (15)	0.0083 (16)

Geometric parameters (Å, º) top

Cu1—N1	2.037 (2)	C11—C12	1.370 (4)
Cu1—N3	1.9457 (18)	C11—H11	0.9500
Cu1—N4	1.998 (2)	C12—C13	1.397 (4)
Cu1—O2	2.3541 (16)	C12—H12	0.9500
Cu1—O3	1.9401 (15)	C13—H13	0.9500
O2—C15	1.420 (3)	Cu2—Cu2ⁱ	2.6202 (6)
O2—H2O	0.85 (3)	Cu2—O4	2.1255 (16)
C15—H15C	0.9800	Cu2—O5	1.9703 (17)
C15—H15B	0.9800	Cu2—O6	1.9793 (15)
C15—H15A	0.9800	Cu2—O7	1.9692 (18)
N1—C4	1.328 (3)	Cu2—O8	1.9671 (16)
N1—C1	1.345 (3)	O3—C16	1.271 (3)
N2—C3	1.334 (3)	O4—C16	1.238 (3)
N2—C2	1.343 (3)	O5—C18	1.264 (3)
N3—C5	1.331 (3)	O6—C20	1.258 (3)
N3—C6	1.388 (3)	O7—C18ⁱ	1.256 (3)
N4—C13	1.332 (3)	O8—C20ⁱ	1.267 (3)
N4—C14	1.375 (3)	C16—C17	1.510 (3)
O1—C5	1.249 (3)	C17—H17A	0.9800
C1—C2	1.386 (3)	C17—H17B	0.9800
C1—C5	1.506 (3)	C17—H17C	0.9800
C2—H2	0.9500	C18—C19	1.513 (3)
C3—C4	1.391 (3)	C19—H19A	0.9800
C3—H3	0.9500	C19—H19B	0.9800
C4—H4	0.9500	C19—H19C	0.9800
C6—C7	1.380 (3)	C20—C21	1.501 (3)
C6—C14	1.436 (3)	C21—H21C	0.9800
C7—C8	1.407 (4)	C21—H21B	0.9800
C7—H7	0.9500	C21—H21A	0.9800
C8—C9	1.375 (4)	O9—C22	1.396 (4)
C8—H8	0.9500	O9—H9O	0.8400
C9—C10	1.422 (3)	C22—H22A	0.9800
C9—H9	0.9500	C22—H22B	0.9800
C10—C14	1.406 (3)	C22—H22C	0.9800
C10—C11	1.418 (3)

O3—Cu1—N3	172.66 (8)	C11—C12—H12	120.3
O3—Cu1—N4	105.05 (7)	C13—C12—H12	120.3
N3—Cu1—N4	82.29 (8)	N4—C13—C12	123.0 (2)
O3—Cu1—N1	91.72 (7)	N4—C13—H13	118.5
N3—Cu1—N1	80.94 (8)	C12—C13—H13	118.5
N4—Cu1—N1	162.67 (8)	N4—C14—C10	122.1 (2)
O3—Cu1—O2	88.87 (6)	N4—C14—C6	116.8 (2)
N3—Cu1—O2	91.42 (7)	C10—C14—C6	121.1 (2)
N4—Cu1—O2	90.51 (7)	O8—Cu2—O7	88.94 (8)
N1—Cu1—O2	94.20 (7)	O8—Cu2—O5	89.35 (7)
C15—O2—Cu1	121.65 (14)	O7—Cu2—O5	169.04 (7)
C15—O2—H2O	109.0 (19)	O8—Cu2—O6	168.74 (7)
Cu1—O2—H2O	105.5 (18)	O7—Cu2—O6	91.16 (7)
O2—C15—H15C	109.5	O5—Cu2—O6	88.42 (7)
O2—C15—H15B	109.5	O8—Cu2—O4	102.95 (6)
H15C—C15—H15B	109.5	O7—Cu2—O4	92.05 (7)
O2—C15—H15A	109.5	O5—Cu2—O4	98.88 (7)
H15C—C15—H15A	109.5	O6—Cu2—O4	88.31 (6)
H15B—C15—H15A	109.5	O8—Cu2—Cu2ⁱ	86.81 (5)
C4—N1—C1	118.3 (2)	O7—Cu2—Cu2ⁱ	82.29 (5)
C4—N1—Cu1	129.20 (16)	O5—Cu2—Cu2ⁱ	86.81 (5)
C1—N1—Cu1	112.44 (15)	O6—Cu2—Cu2ⁱ	82.04 (5)
C3—N2—C2	116.5 (2)	O4—Cu2—Cu2ⁱ	168.68 (5)
C5—N3—C6	125.59 (19)	C16—O3—Cu1	124.70 (15)
C5—N3—Cu1	118.94 (16)	C16—O4—Cu2	135.91 (14)
C6—N3—Cu1	115.44 (14)	C18—O5—Cu2	119.47 (16)
C13—N4—C14	118.3 (2)	C20—O6—Cu2	125.71 (15)
C13—N4—Cu1	129.49 (17)	C18ⁱ—O7—Cu2	125.03 (15)
C14—N4—Cu1	112.08 (15)	C20ⁱ—O8—Cu2	120.48 (15)
N1—C1—C2	120.3 (2)	O4—C16—O3	123.9 (2)
N1—C1—C5	116.22 (19)	O4—C16—C17	120.1 (2)
C2—C1—C5	123.5 (2)	O3—C16—C17	116.0 (2)
N2—C2—C1	122.1 (2)	C16—C17—H17A	109.5
N2—C2—H2	118.9	C16—C17—H17B	109.5
C1—C2—H2	118.9	H17A—C17—H17B	109.5
N2—C3—C4	122.2 (2)	C16—C17—H17C	109.5
N2—C3—H3	118.9	H17A—C17—H17C	109.5
C4—C3—H3	118.9	H17B—C17—H17C	109.5
N1—C4—C3	120.7 (2)	O7ⁱ—C18—O5	126.2 (2)
N1—C4—H4	119.6	O7ⁱ—C18—C19	116.8 (2)
C3—C4—H4	119.6	O5—C18—C19	117.0 (2)
O1—C5—N3	128.5 (2)	C18—C19—H19A	109.5
O1—C5—C1	120.2 (2)	C18—C19—H19B	109.5
N3—C5—C1	111.34 (18)	H19A—C19—H19B	109.5
C7—C6—N3	128.8 (2)	C18—C19—H19C	109.5
C7—C6—C14	118.3 (2)	H19A—C19—H19C	109.5
N3—C6—C14	112.89 (19)	H19B—C19—H19C	109.5
C6—C7—C8	120.5 (2)	O6—C20—O8ⁱ	124.8 (2)
C6—C7—H7	119.8	O6—C20—C21	118.0 (2)
C8—C7—H7	119.8	O8ⁱ—C20—C21	117.2 (2)
C9—C8—C7	121.8 (2)	C20—C21—H21C	109.5
C9—C8—H8	119.1	C20—C21—H21B	109.5
C7—C8—H8	119.1	H21C—C21—H21B	109.5
C8—C9—C10	119.6 (2)	C20—C21—H21A	109.5
C8—C9—H9	120.2	H21C—C21—H21A	109.5
C10—C9—H9	120.2	H21B—C21—H21A	109.5
C14—C10—C11	117.6 (2)	C22—O9—H9O	109.5
C14—C10—C9	118.7 (2)	O9—C22—H22A	109.5
C11—C10—C9	123.6 (2)	O9—C22—H22B	109.5
C12—C11—C10	119.5 (2)	H22A—C22—H22B	109.5
C12—C11—H11	120.3	O9—C22—H22C	109.5
C10—C11—H11	120.3	H22A—C22—H22C	109.5
C11—C12—C13	119.4 (2)	H22B—C22—H22C	109.5

C4—N1—C1—C2	1.0 (3)	C8—C9—C10—C11	−179.5 (2)
Cu1—N1—C1—C2	−175.58 (16)	C14—C10—C11—C12	−1.5 (3)
C4—N1—C1—C5	−179.55 (19)	C9—C10—C11—C12	178.1 (2)
Cu1—N1—C1—C5	3.9 (2)	C10—C11—C12—C13	0.3 (4)
C3—N2—C2—C1	−1.6 (3)	C14—N4—C13—C12	−2.0 (3)
N1—C1—C2—N2	0.5 (3)	Cu1—N4—C13—C12	173.02 (17)
C5—C1—C2—N2	−178.9 (2)	C11—C12—C13—N4	1.5 (4)
C2—N2—C3—C4	1.3 (3)	C13—N4—C14—C10	0.7 (3)
C1—N1—C4—C3	−1.4 (3)	Cu1—N4—C14—C10	−175.18 (16)
Cu1—N1—C4—C3	174.59 (16)	C13—N4—C14—C6	−178.42 (19)
N2—C3—C4—N1	0.2 (4)	Cu1—N4—C14—C6	5.8 (2)
C6—N3—C5—O1	−0.8 (4)	C11—C10—C14—N4	1.0 (3)
Cu1—N3—C5—O1	−178.55 (18)	C9—C10—C14—N4	−178.6 (2)
C6—N3—C5—C1	179.67 (18)	C11—C10—C14—C6	−179.94 (19)
Cu1—N3—C5—C1	1.9 (2)	C9—C10—C14—C6	0.4 (3)
N1—C1—C5—O1	176.57 (19)	C7—C6—C14—N4	178.15 (19)
C2—C1—C5—O1	−4.0 (3)	N3—C6—C14—N4	−0.7 (3)
N1—C1—C5—N3	−3.8 (3)	C7—C6—C14—C10	−0.9 (3)
C2—C1—C5—N3	175.59 (19)	N3—C6—C14—C10	−179.77 (18)
C5—N3—C6—C7	−1.5 (4)	Cu2—O4—C16—O3	176.52 (15)
Cu1—N3—C6—C7	176.32 (18)	Cu2—O4—C16—C17	−2.7 (3)
C5—N3—C6—C14	177.16 (19)	Cu1—O3—C16—O4	−9.5 (3)
Cu1—N3—C6—C14	−5.0 (2)	Cu1—O3—C16—C17	169.72 (17)
N3—C6—C7—C8	179.5 (2)	Cu2—O5—C18—O7ⁱ	−6.0 (3)
C14—C6—C7—C8	0.8 (3)	Cu2—O5—C18—C19	173.09 (16)
C6—C7—C8—C9	−0.3 (4)	Cu2—O6—C20—O8ⁱ	2.5 (3)
C7—C8—C9—C10	−0.2 (4)	Cu2—O6—C20—C21	−179.18 (15)
C8—C9—C10—C14	0.1 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1ⁱⁱ	0.86 (3)	1.84 (3)	2.689 (3)	178 (3)
O9—H9O···O4	0.84	2.33	2.955 (3)	132
O9—H9O···O6	0.84	2.30	3.000 (3)	141
C3—H3···O8ⁱⁱⁱ	0.95	2.56	3.508 (3)	174
C7—H7···O1	0.95	2.36	2.943 (3)	119
C9—H9···O9^iv	0.95	2.57	3.415 (3)	149
C13—H13···O4	0.95	2.54	3.175 (3)	124
C21—H21C···O8^v	0.98	2.59	3.563 (3)	170

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

π–π interactions (Å, °) in the crystal of ligand HL1 top

Ring_pz	ring_quin	centroid–centroid	α	β	γ	interplanar_1	interplanar_2	offset
Cg1	Cg8ⁱ	3.589 (5)	2.9 (4)	9.2	8.2	3.552 (4)	3.543 (4)	0.572
Cg1	Cg12ⁱ	3.493 (5)	4.1 (4)	12.2	8.6	3.453 (4)	3.414 (3)	0.737
Cg5	Cg4ⁱⁱ	3.367 (5)	3.8 (4)	4.7	2.3	3.364 (4)	3.355 (4)	0.275
Cg5	Cg12ⁱⁱⁱ	3.492 (5)	4.1 (4)	2.7	6.7	3.468 (4)	3.488 (3)	0.163
Cg9	Cg4^iv	3.455 (6)	4.2 (4)	11.0	8.0	3.420 (4)	3.390 (4)	0.662
Cg9	Cg8^v	3.532 (6)	2.9 (4)	3.4	5.7	3.515 (4)	3.526 (4)	0.211

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

Relative percentage contributions of close contacts to the Hirshfeld surface of ligand HL1, and for the individual molecules top

Contact	HL1	Molecule A	Molecule B	Molecule C
H···H	43.0	44.5	41.7	43.0
N···H/H···N	14.5	13.5	14.6	14.3
C···H/H···C	11.8	10.5	11.7	11.1
O···H/H···O	8.1	9.2	10.2	9.4
C···C	10.8	10.6	10.6	10.5
C···N	10.7	10.5	10.1	10.7

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Volume 75| Part 6| June 2019| Pages 755-761

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

The crystal structures of the ligand N-(quinolin-8-yl)pyrazine-2-carboxamide and of a tetra­nuclear copper(II) complex

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis of ligand HL1

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

References

research communications

The crystal structures of the ligand N-(quinolin-8-yl)pyrazine-2-carboxamide and of a tetranuclear copper(II) complex

3. Supramolecular features