Multivalent hy­dro­gen-bonded architectures directed by self-com­plementarity between [Cu(2,2′-bi­imid­az­ole)] and malonate building blocks

Atencio, R.; Linares, M.M.; González, T.; Briceño, A.

doi:10.1107/S2053229624007897

crystallography in latin america

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 80| Part 9| September 2024| Pages 487-496

https://doi.org/10.1107/S2053229624007897

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Multivalent hydrogen-bonded architectures directed by self-complementarity between [Cu(2,2′-biimidazole)] and malonate building blocks

Reinaldo Atencio,^a,^b ^* Marciel M. Linares,^a Teresa González ^a and Alexander Briceño ^a

^aLaboratorio de Síntesis y Caracterización de Nuevos Materiales, Centro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Apto. 21827, Caracas 1020-A, Venezuela, and ^bDepartamento de Ciencias Químicas y Ambientales, Facultad de Ciencias Naturales y Matemáticas (FCNM), and Center of Nanotechnology Research and Development, CIDNA, Escuela Superior Politécnica del Litoral (ESPOL), 30.5 vía Perimetral, Guayaquil, Ecuador
^*Correspondence e-mail: ratenciof@gmail.com

Edited by T. Ohhara, J-PARC Center, Japan Atomic Energy Agency, Japan (Received 14 June 2024; accepted 12 August 2024; online 19 August 2024)

This article is part of the collection Crystallography in Latin America: a vibrant community.

The synthesis and structural characterization of four novel supramolecular hydrogen-bonded arrangements based on self-assembly from molecular `[Cu(2,2′-biimidazole)]' modules and malonate anions are presented, namely, tetrakis(2,2′-biimidazole)di-μ-chlorido-dimalonatotricopper(II) pentahydrate, [Cu₃(C₃H₂O₄)₂Cl₂(C₆H₆N₄)₄]·5H₂O or [Cu(H₂biim)₂(μ-Cl)Cu_0.5(mal)]₂·5H₂O, aqua(2,2′-biimidazole)malonatocopper(II) dihydrate, [Cu(C₃H₂O₄)(C₆H₆N₄)(H₂O)]·2H₂O or [Cu(H₂biim)(mal)(H₂O)]·2H₂O, bis[aquabis(2,2′-biimidazole)copper(II)] dimalonatodiperchloratocopper(II) 2.2-hydrate, [Cu(C₆H₆N₄)₂(H₂O)]₂[Cu(C₃H₂O₄)(ClO₄)₂]·2.2H₂O or [Cu(H₂biim)₂(H₂O)]₂[Cu(mal)₂(ClO₄)₂]·2.2H₂O, and bis(2,2′-biimidazole)copper(II) bis[bis(2,2′-biimidazole)(2-carboxyacetato)malonatocopper(II)] tridecahydrate, [Cu(C₆H₆N₄)₂][Cu(C₃H₂O₄)(C₃H₃O₄)(C₆H₆N₄)₂]·13H₂O or [Cu(H₂biim)₂][Cu(H₂biim)₂(Hmal)(mal)]₂·13H₂O. These assemblies are characterized by self-complementary donor–acceptor molecular interactions, demonstrating a recurrent and distinctive pattern of hydrogen-bonding preferences among the carboxylate, carboxylic acid and N—H groups of the coordinated 2,2′-biimidazole and malonate ligands. Additionally, coordination of the carboxylate group with the metallic centre helps sustain remarkable supramolecular assemblies, such as layers, helices, double helix columns or 3D channeled architectures, including mixed-metal complexes, into a single structure.

Keywords: crystal structure; 2,2′-biimidazole; malonate; hydrogen bonding; supramolecular; copper(II).

CCDC references: 2358575; 2358576; 2358577; 2358578

1. Introduction

The construction of supramolecular assemblies sustained from hydrogen-bonded interactions has led to the development of many materials with attractive properties, finding applications in both academic and industrial settings (Lehn, 1990 ; Brammer et al., 2000 ; Mali et al., 2012 ; Ewen & Steinke, 2008 ; Burrows, 2003 ). A notable example is the family of inorganic–organic hybrid materials, which have garnered significant attention and hold immense potential (Gomez-Romero, 2001 ; Al Zoubi et al., 2020 ; Song et al., 2023 ). These materials can incorporate the functionality of both classes of components in a single solid, opening a world of possibilities for innovative applications (Sanchez et al., 2011 ; Mir et al., 2018 ; Gomez-Romero, 2001).

In this context, we have exploited the ability of multivalent metal–organic building blocks based on the harmonization of hydrogen bonds and metal coordination as a strategy to engineer novel functional metal assemblies bearing specific ligands with variable multivalent binding donor–acceptor sites (Briceño et al., 2006 , 2009 ; Hill & Briceño, 2007 ; Briceño & Escalona, 2015 ). Rational control of the supramolecular domain introduces inherent structural malleability and diversity (different geometric coordination, multivalency capacity, switching from neutral to distinctive ionic metal complexes) for the potential design of novel multicomponent hydrogen-bonded supramolecular arrays (Hill & Briceño, 2007; Atencio et al., 1999 ; Brammer et al., 2000; Mulder et al., 2004 ). These structural features can also be explored to intercalate secondary molecules or mixed metal–organic building units through self-recognition directed by complementary hydrogen-bonded synthons between correctly oriented pendant functional groups in metal coordination building blocks (e.g. carboxyl, carboxylate, N—H and O—H groups; Fig. 1).

Figure 1
Representation of the hydrogen-bonded heterosynthons formed between 2,2′-biimidazole molecules (free and coordinated) with the different complementary moieties (carboxylic acid, carboxylate and halogen). An isographic R₂²(9) graph set can be designated for Ia, Ib, Ic and Id, while an R₂¹(7) graph set is assigned for Ie and If (Etter et al., 1990

A particularly intriguing and versatile organic species for creating hybrid materials is the molecule 2,2′-biimidazole (H₂biim) (Tadokoro et al., 1996 , 2002 ; Barquín et al., 2003 ). As a neutral organic molecular entity, it can form hydrogen-bonded assemblies with carboxylic acid groups (Ia in Fig. 1). It can also coordinate with metal centres while acting as a donor in hydrogen-bonding interactions (Ib–If in Fig. 1). In our research group, these coordinated fragments are considered molecular modules that can be assembled through their N—H groups to a second module with electronically and geometrically complementary functional groups. Thus, `M(H₂biim)₂' combined with aromatic carboxylic acid groups (see Ib and Ic in Fig. 1) form planar supramolecular modules, which improves the possibility of generating one- (1D) or two-dimensional (2D) assemblies, as we have reported previously (Atencio et al., 2004 ). The carboxylate group (Id in Fig. 1), linked directly to arene or pyridine rings, has been used as a second module to design robust 1D or 2D supramolecular species capable of performing reversibly water sorption–desorption processes preserving the crystallinity of the solid (Atencio et al., 2004). In these cases, two molecules of H₂biim occupy the equatorial plane of a Co²⁺ or Ni²⁺ complex with octahedral coordination geometry, with two coordination water molecules located at the remaining axial positions. The energy of these R₂²(9) hydrogen bonds were theoretically estimated to be 24.5 and 27.8 kcal mol⁻¹ between carboxylic acid or carboxylate and coordinated biimidazole entities, respectively (Atencio et al., 2004). These values lie above the upper limit of the range invoked for a medium–strong hydrogen bond, with an energy range of 6–20 kcal mol⁻¹ (Giacovazzo et al., 2011 ). This approach has also been achieved for building extended hydrogen-bonded systems with discrete anions like chloride (Ramírez et al., 2002 ; Atencio et al., 2005 ) (If in Fig. 1). Accordingly, we focused on using dicarboxylates with more considerable conformational flexibility (e.g. malonate) to increase the structural diversity. It has been observed (vide infra) that direct coordination of the carboxylate to the metal centre increases the likelihood of driving three-dimensional (3D) architectures (Delgado et al., 2012 ). These possibilities, included within the field of crystal engineering, are demonstrated with the synthesis and structural characterization of the four novel complexes [Cu(H₂biim)₂(μ-Cl)Cu_0.5(mal)]₂·5H₂O, (1), [Cu(H₂biim)(mal)(H₂O)]·2H₂O, (2), [Cu(H₂biim)₂(H₂O)]₂[Cu(mal)₂(ClO₄)₂]·2.2H₂O, (3), and [Cu(H₂biim)₂][Cu(H₂biim)₂(Hmal)(mal)]₂·13H₂O, (4), where H₂biim is 2,2′-biimidazole, mal is malonate and Hmal is hydrogen malonate (or 2-carboxyacetate).

2. Experimental

All reagents were obtained from commercial sources and used without further purification, except for 2,2′-biimidazole, which was synthesized following the previously reported procedure of Ramírez et al. (2002). The elemental analyses (C, H and N) were performed on an EA1108 Fisons elemental analyzer. The FT–IR spectra were recorded from KBr discs using a Nicolet Magna-IR 560 spectrophotometer.

2.1. Synthesis and crystallization

The syntheses of 1–4 were carried out by dissolving 2,2′-biimidazole (0.3728 mmol) in 50 ml of an ethanol/water (1:1 v/v) mixture under reflux at boiling temperature. The corresponding salt [CuCl₂ for 1, Cu(AcO)₂·H₂O for 2 and 4, and Cu(ClO₄)₂·6H₂O for 3] was added with constant stirring. The solution turned light green, at which point malonic acid was added. The final molar ratio of Cu–biimidazole–H₂mal was 1:2:1, except in the case of 4, where a final ratio of 1:2:2 was used. The resulting solutions were evaporated slowly over a period of three weeks. The products were separated by decantation, washed with a cold ethanol/water mixture and dried at room temperature, yielding dark-green crystals that were stable in air (yield: 70% for 1, 63% for 2, 60% for 3 and 35% for 4).

For 1: elemental analysis (%) calculated for C₃₀H₂₈Cl₂Cu₃N₁₆O₈·5H₂O: C 32.83, H 3.55, N 20.42; found: C 33.12, H 3.43, N 19.98. FT–IR [KBr, ν(cm⁻¹)]: 3395, 3119–3011, 2901, 1569, 1375.

For 2: elemental analysis calculated (%) for C₉H₁₀CuN₄O₅·2.2H₂O: C 30.56, H 3.99, N 15.83; found: C 30.90, H 3.90, N 16.02. FT–IR [KBr, ν(cm⁻¹)]: 3421, 3201, 2923, 1533, 1370, 1185–1130.

For 3: elemental analysis calculated (%) for C₃₀H₃₂Cl₂Cu₃N₁₆O₁₈·2.22H₂O: C 29.87, H 3.05, N 18.58; found: C 29.98, H 2.99, N 19.00. FT–IR [KBr, ν(cm⁻¹)]: 3549, 3136–3007, 2938, 1576, 1429, 1108, 621.

For 4: elemental analysis calculated (%) for C₂₄H₂₃Cu_1.5N₁₂O₈·6.5H₂O: C 35.08, H 4.44, N 20.46; found: C 35.42, H 4.31, N 20.73. FT–IR [KBr, ν(cm⁻¹)]: 3427, 3127–3002, 2918, 1905, 1561, 1359, 1130.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms on C, N and O atoms were placed at fixed positions. They were refined using the riding model, with isotropic displacement parameters set at 1.2U_eq(C,N) or 1.5U_eq(O). Most of the positions of the crystallization water molecules in all structures were disordered. Thus, a solvent mask was implemented and the corresponding calculated number of electrons was consistent with 2.5H₂O (in 1), 2.2H₂O (in 2) and 6.5H₂O (in 4) per asymmetric unit. For 3, only one crystallization water molecule was found, and the position was refined freely. The remaining water molecules were estimated using a solvent-mask approach. The perchlorate group in 3 was found to be disordered over two positions and was modelled using a restricted Cl—O distance of ∼1.42 Å (Olmstead, 2020 ). The occupancies of both orientations was refined and converged to 0.83 and 0.17, respectively. Displacement ellipsoid plots for 2–4 are shown in Figs. S7–S9, respectively, of the supporting information.

Table 1
Experimental details

Experiments were carried out at 298 K with Mo Kα radiation on a Rigaku AFC-7S diffractometer equipped with a Mercury CCD bidimensional detector. Absorption was corrected for by multi-scan methods (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ). H-atom parameters were constrained.

	1	2	3	4
Crystal data
Chemical formula	[Cu₃(C₃H₂O₄)₂Cl₂(C₆H₆N₄)₄]·5H₂O	[Cu(C₃H₂O₄)(C₆H₆N₄)(H₂O)]·2H₂O	[Cu(C₆H₆N₄)₂(H₂O)]₂·[Cu(C₃H₂O₄)(ClO₄)₂]·2.2H₂O	[Cu(C₆H₆N₄)₂][Cu(C₃H₂O₄)(C₃H₃O₄)(C₆H₆N₄)₂]·13H₂O
M_r	1092.28	353.78	1205.87	1639.91
Crystal system, space group	Orthorhombic, Ccce	Monoclinic, P2₁/c	Monoclinic, C2/c	Monoclinic, P2₁/c
a, b, c (Å)	13.766 (3), 20.162 (4), 30.654 (6)	7.0587 (4), 20.3107 (12), 18.9523 (10)	17.9569 (11), 15.2466 (6), 16.6781 (10)	7.7912 (6), 12.5972 (10), 32.481 (3)
α, β, γ (°)	90, 90, 90	90, 91.770 (4), 90	90, 95.296 (5), 90	90, 96.802 (2), 90
V (Å³)	8508 (3)	2715.8 (3)	4546.7 (4)	3165.5 (4)
Z	8	8	4	2
μ (mm⁻¹)	1.69	1.65	1.60	1.11
Crystal size (mm)	0.3 × 0.2 × 0.2	0.36 × 0.11 × 0.09	0.38 × 0.36 × 0.33	0.14 × 0.11 × 0.09

Data collection
T_min, T_max	0.600, 0.710	0.903, 1.000	0.681, 1.000	0.557, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	44434, 4454, 3252	21646, 4229, 2925	17890, 3848, 2674	33363, 5454, 2735
R_int	0.056	0.047	0.048	0.153
(sin θ/λ)_max (Å⁻¹)	0.666	0.591	0.595	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.154, 1.04	0.040, 0.108, 1.04	0.069, 0.199, 1.07	0.070, 0.179, 1.01
No. of reflections	4454	4229	3848	5454
No. of parameters	267	343	338	413
No. of restraints	0	0	50	0
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.61	0.58, −0.40	1.14, −0.79	0.46, −0.40
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), DIAMOND (Brandenburg, 1996 ) and OLEX2 (Dolomanov et al., 2009).

2.3. Computational calculations

The geometry optimization was performed using the GAUSSIAN09 package of ab initio programs for quantum chemical density functional theory (DFT) computations (Frisch et al., 2016 ). The calculations were conducted in the gas phase at the B3YLP/DGTZVP level of theory. The starting geometric coordinates were taken from the Cu11 complex of the asymmetric unit of the crystal structure of 2, based on crystallographic information files (CIFs) previously generated from the single-crystal XRD study. Using the optimized coordinates in the DFT study, no imaginary frequencies were obtained, confirming that the molecular structure corresponds to an energy minimum. GaussView was used as an interface to set up the GAUSSIAN09 input and visualize the results (Dennington et al., 2016 ).

3. Results and discussion

The crystal structure of 1 is built up from a trinuclear entity consisting of two `Cu(H₂biim)₂' and one `Cu(mal)₂' module (Fig. 2). Two Cl ligands serve as bridging ligands from Cu²⁺ ions to form the final [Cu(H₂biim)₂(μ-Cl)Cu(mal)]₂ complex. Thus, each Cu1 atom in `Cu(H₂biim)₂' displays a distorted square-pyramidal coordination environment, with two molecules of 2,2′-biimidazole coordinated in a chelating fashion through the two N atoms, forming the base of the coordination geometry [average Cu1—N = 2.025 (3) Å]. In contrast, the apical position is occupied by one Cl ligand [Cu1—Cl1 = 2.5062 (12) Å]. The Cu2 atom in `Cu(mal)₂' sits on a twofold special position (Wykoff position 8h), showing a pseudo-octahedral geometry, with two malonate anions coordinated is trans and in a bidentate chelating manner through two O atoms in the equatorial plane [average Cu2—O = 1.962 (2) Å]. The remaining axial positions are occupied by the Cl ligands, with a Cu—Cl distance [Cu2—Cl1 = 2.7522 (11) Å] significantly longer than that found for Cu1—Cl1, which is characteristic of Jahn–Teller distortion (Halcrow, 2013 ). The packing appears to be dominated by R₂²(9)-Id hydrogen bonding between neighbouring complexes (Fig. 3). There are two of these intermolecular interactions, i.e. one involving N2—H2⋯O3 [N2⋯O3 = 2.871 (4) Å and N6—H6⋯O1 = 173°] and N4—H4⋯O4 [N4⋯O4 = 2.678 (5) Å and N4—H4⋯O4 = 167°], and the second comprising N6—H6⋯O2 [N6⋯O2 = 2.704 (5) Å and N6—H6⋯O2 = 175°] and N8—H8⋯O1 [N8⋯O1 = 2.822 (4) Å and N8—H8⋯O1 = 158°]. In addition, there also exist π–π intermolecular interactions between consecutive imidazole rings in the a direction [Cg1⋯Cg2 = 3.6742 (5) Å and Cg3⋯Cg3′ = 3.7019 (7) Å, where Cg1 is the centroid of the N2/C1/N1/C2/C3 ring, Cg2 is the centroid of N2/C4/N4/C6/C5, Cg3 is the centroid of N7/C10/N8/C12/C11 and Cg3′ is the centroid of N7′/C10′/N8′/C12′/C11′]. Thus, the hydrogen bonding and π–π interactions help to sustain an extended layer in the ac plane (see Fig. 3). The final 3D packing is achieved by stacking of the 2D arrays along the b axis, which leaves enough space between layers to accommodate the water molecules of crystallization (Fig. 4).

Figure 2
Representation of the trimetallic coordinated module found in the crystal structure of 1. H atoms have been omitted for clarity.

Figure 3
Representation of the 2D array in the crystal structure 1, displaying the observed R₂²(9)-Id hydrogen bonds. H atoms on C atoms have been omitted for clarity.

Figure 4
Representation of the 2D array stacking along the b axis in the crystal structure of 1.

The asymmetric unit of the crystal structure of 2 contains two chemically equivalent [Cu(H₂biim)(mal)(H₂O)] complexes [Fig. 5(a)], which are crystallographically independent. In contrast to 1, the Cu²⁺ ions display a distorted square-pyramidal coordination geometry, with one 2,2′-biimidazole chelated via two N atoms [Cu11—N11 = 2.006 (4) Å and Cu11—N31 = 2.007 (4) Å; Cu12—N12 = 1.999 (4) Å and Cu12—N32 = 2.003 (4) Å] and one bidentate malonate ligand, which is coordinated in a slightly asymmetric manner [Cu11—O21 = 1.928 (3) Å and Cu11—O41 = 1.943 (3) Å; Cu12—O22 = 1.944 (3) Å and Cu12—O42 = 1.933 (3) Å] and is trans to biimidazole. In both cases, the apical position is occupied by a coordinated water molecule [Cu11—O11 = 2.282 (3) Å and Cu11—O12 = 2.287 (3) Å]. The biimidazole bidentate coordination generates a five-membered ring [Cu1x—N3x—C4x—C1x—N1x, with x = 1 or 2 for the complexes containing Cu11 and Cu12, respectively; see Fig. 5(a)], which is almost planar, with the most significant deviations from the best plane being only 0.054 (4) and 0.069 (4) Å for the Cu11 and Cu12 complexes, respectively. However, the six-membered ring (Cu1x—O4x—C9x—C8x—C7x—O2x, with x = 1 or 2) formed by the coordination of the malonate ligand enables deviations from the mean plane of up to 0.607 (5) and 0.637 (5) Å for the C81 and C82 atoms, respectively.

Figure 5
(a) Representation of the two crystallographically independent complexes found in the asymmetric unit of 2. (b) The helical-like columns of a pair of complexes along the a axis. The vertical dashed line corresponds to the helical axis.

It should be noted that both complexes are completely asymmetric in the solid state due to their distorted coordination geometry and the positions of the H atoms on the coordinated water molecules. The observed distortion might be associated with electronic effects, typically occurring in coordination compounds with specific electronic configurations. These effects lower the symmetry to stabilize the system (Halcrow, 2013; Deshpande et al., 2021 ). To discern whether this distortion is an intrinsic property of the complexes or if it arises due to crystal packing effects, we performed theoretical calculations at the density functional theory (B3LYP/DGDZVP) level. The calculations revealed a molecular geometry with minimal energy in the gas phase, resembling the distorted geometry observed in the crystalline state (see Table S10 in the supporting information). This result strongly suggests that the observed distortion and symmetry breaking are mainly inherent to the complex rather than induced by the crystal environment.

These [Cu(H₂biim)(mal)(H₂O)] complexes fit together via bifurcated asymmetric intermolecular O—H⋯O hydrogen bonds involving one coordinated water molecule as a donor group and two O atoms from a carboxylate group as acceptors [O11⋯O22 = 2.833 (4) Å and O11—H11B⋯O22 = 173.8 (2)°; O11⋯O32 = 3.187 (5) Å and O11—H11B⋯O32 = 129.1 (2)°]. The same kind of bifurcated hydrogen bonding enables stacking of this pair of complexes in columns along the a axis. A striking feature is that such columns are hosted in a site that facilitates the formation of helical-like columns of the complexes. Columns are interdigitated, one beside the other, in the ac plane (Fig. 6), assisted by two R₂¹(7)-Ie hydrogen bonds [O32⋯N22 = 2.695 (5) Å and N22—H22⋯O32 = 147.4 (3)°; O32⋯N42 = 2.912 (5) Å and N42—H42⋯O32 = 139.6 (3)°; O51⋯N21 = 2.872 (5) Å and N21—H21⋯O51 = 141.0 (3)°; O51⋯N41 = 2.693 (5) Å and N41—H41⋯O51 = 147.8 (3)°]. The interdigitation also enables two π–π interactions between imidazole rings [Cg1⋯Cg2 = 3.688 (4) Å and Cg1⋯Cg2′ = 3.773 (5) Å, where Cg1 is the centroid of the N11/C21/C31/N21/C11 ring, Cg2 of the N32/C52/C62/N42/C42 ring and Cg2′ of the N32′/C52′/C62′/N42′/C42′ ring] that help to sustain this 2D array. The final 3D crystal structure is defined by stacking of the 2D array along the b axis in a ABAB⋯AB sequence. Such packing leaves two distinctive channels parallel to the a axis where crystallization water molecules are hosted (see Fig. S1 in the supporting information).

Figure 6
(a) Representation displaying (a) the interdigitation of columns in the ac plane assisted by π–π interactions and (b) the R₂²(9)-Id hydrogen-bond type observed in the crystal structure of 2.

The asymmetric unit of the crystal structure of 3 contains one [Cu(H₂biim)₂(H₂O)]²⁺ cation, one half of the [Cu(mal)₂(ClO₄)₂]⁴⁻ anion and water molecules of crystallization. The metal centre for the cation displays a pseudo-square-pyramidal coordination geometry, with two bidentate biimidazole [mean Cu1—N = 2.018 (6) Å] and one coordinated water molecule [Cu1—O1 = 2.194 (6) Å] [Fig. 7(a)]. On the other hand, the Cu²⁺ ion of the anion sits on a twofold special position (Wykoff position 4e), exhibiting a quite distorted octahedral environment involving two chelating malonate ligands coordinated in the equatorial plane [Cu2—O2 = 1.925 (4) Å and Cu2—O4 = 1.922 (5) Å] and with the axial positions occupied by two perchlorate groups [Cu2—O2A = 2.781 (15) Å] [Fig. 7(b)]. As anticipated, cation–anion interactions occur via R₂²(9)-Id hydrogen bonds, in which each carboxylate group is assembled into one cationic complex. Therefore, such a cation–anion interaction drives the formation of hydrogen-bonded columns along the b axis. According to the coordination geometry on each metal centre, there exist two crystallographically independent hydrogen bonds [Fig. 8(a)] [O2⋯N6 = 2.959 (8) Å and N6—H6⋯O2 = 159.4 (5)°; O3⋯N8 = 2.740 (8) Å and N8—H8⋯O3 = 175.7 (4)°; O4⋯N4 = 3.107 (9) Å and N4—H4⋯O4 = 156.8 (5)°; O5⋯N2 = 2.720 (8) Å and N2—H2⋯O5 = 171.6 (4)°]. Thus, the multivalence concert between the coordination environment and the R₂²(9)-Id hydrogen bonding facilitates the assembly of double helical columns, as displayed in Fig. 8(b). Columns are aligned parallel to each other, building up the final 3D architecture, which leaves intricate channels along the b axis where the crystallization water molecules are hosted (Fig. S2 in the supporting information).

Figure 7
Representation of (a) the cationic and (b) the anionic complexes found in the crystal structure of 3.

Figure 8
Representation of the multivalent modular assembly displaying the columnar double helix found in the crystal structure of 3. (a) Double helix hydrogen-bonding column. (b) Zoom-up displaying the R₂²(9)-Id hydrogen bonds. [Symmetry codes: (−x + 1, −y + 1, −z + 1) and (x, −y, z + $[{1\over 2}]$ )].

The asymmetric unit of 4 can be described as being composed of two different modules, namely, half of a square-planar cationic [Cu(H₂biim)₂]²⁺ unit (Cu2 hereafter) and one pseudo-octahedral anionic [Cu(H₂biim)₂(Hmal)(mal)]⁻ complex (Cu1 hereafter) (Fig. 9). Two bidentate biimidazole ligands coordinate to the metal centre in the Cu2 complex [Cu2—N13 = 1.993 (6) Å and Cu2—N33 = 1.989 (6) Å] that sits on an inversion centre (Wykoff position 2a). Consequently, the mean plane involving the non-H atoms defines an almost perfect plane [maximum deviation at C13 = 0.055 (6) Å]. The Cu1 complex shows two H₂biim ligands [Cu1—N11 = 1.991 (5) Å, Cu1—N31 = 2.025 (5) Å, Cu1—N12 = 2.032 (5) Å and Cu1—N32 = 2.007 (5) Å] occupying the equatorial positions, while the axial sites are engaged by two malonate ligands coordinated in a monodentate manner, of which one is monoprotonated (Hmal) and the other one is fully deprotonated (mal). The axial Cu1—O distances [Cu1—O7(mal) = 2.647 (5) Å and Cu1—O3(Hmal) = 2.867 (5) Å] and their orientation angles from equatorial ligands (average 92.2 and 87.8° for O7 and O3, respectively) suggest relatively weak interactions between these monodentate malonates and the metal centre. The Cu—O(carboxylate) bond lengths of ∼2.8 Å have been suggested previously to be involved in assembling a tetranuclear complex (Colacio et al., 2000 ). A closer compound, [Cu₂(mal)₂(dpp)(H₂O)] [dpp = 2,3-bis(pyridyl)pyrazine], with long axial Cu—O bond distances of 2.751 (4) and 2.810 (5) Å, was also reported previously (Delgado et al., 2008 ). Unlike the Cu2 complex, the Cu1 ion sits on a general position with an equatorial mean plane, defined by all the non-H atoms, displaying a deviation of up to 0.407 (6) Å. An alternative description for the crystal packing of 4 results from separating the understanding of the supramolecular assembly concerning each modular ionic complex. The Cu1 complex forms two crystallographically independent R₂²(9)-Id hydrogen bonding, in one of which the complex acts as a donor through the biimidazole N—H groups [N22⋯O4′ = 2.678 (7) Å and N22—H22⋯O4′ = 176.9 (4)°; N42⋯O3′ = 2.673 (7) Å and N42—H42⋯O3′ = 172.6 (4)°]. In the other, a coordinated carboxylate group turns into the acceptor [N21′′⋯O7 = 2.744 (7) Å and N21—H21⋯O7= 170.7 (4)°; N41′′⋯O8 = 2.689 (7) Å and N41—H41⋯O8= 164.8 (4)°]. This hydrogen bonding enables the self-assembly of the Cu1 complex in an extended 2D array in the bc plane [Fig. 10(a)]. Two consecutive 2D arrays are sustained through the Cu2 complexes via R₂²(9)–Ic hydrogen bonds. In this case, the uncoordinated carboxylic acid group of the anionic Cu1 complexes acts as an acceptor [N23⋯O1 = 2.634 (8) Å and N23—H23⋯O1 = 170.2 (4)°; N42⋯O3 = 2.673 (7) Å and N42—H42⋯O3 = 172.6 (4)°] [Fig. 10(b)]. The interplay between the Cu1 and Cu2 complexes is also manifested by the axial weak interactions Cu2⋯O6 [2.926 (5) Å], suggesting the remaining uncoordinated carboxylate on the Cu1 complex (O6/C4/O5) [Fig. 11(a)]. The construction of the 3D architecture is also assisted by O—H⋯O hydrogen bonding involving the carboxylic acid groups [O2⋯O5 = 2.606 (7) Å and O2—H2⋯O5 = 116.4 (4) Å]. The final 3D network leaves channels along the a axis where crystallization water molecules are hosted [Fig. 11(b)].

Figure 9
Representation of the molecular modules found in the crystal structure of 4. (a) The square-planar Cu2 complex, in which the metal centre sits on an inversion centre, is displayed. [Symmetry code: (′) −x, −y, −z]. (b) The Cu1 complex displaying the monoprotonated malonate entities coordinated in a monodentate mode.

Figure 10
Representation of the modular assembly involving hydrogen bonds found in the crystal structure of 4. (a) Self-assembly through R₂¹(7)-Ie hydrogen bonding of the Cu1 complex forming a 2D array. Only coordinated carboxylate groups and H atoms engaged in hydrogen bonds are displayed for clarity. (b) One uncoordinated carboxylic acid group in the Cu1 complex linking to the Cu2 complex via R₂²(9)–Ic hydrogen bonding. [Symmetry codes: (−x + 2, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ); (−x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ); (−x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ).]

Figure 11
(a) View of the Cu2 complex module sustained by Cu⋯O interactions observed in the crystal structure of 4. (b) The final 3D packing representation of 4, displaying channels along the a axis where crystallization water molecules are hosted.

4. Conclusions

In summary, we demonstrated the potential of the Cu²⁺/H₂biim/mal system as a versatile multivalent hydrogen-bonded metal–organic architecture to anticipate supramolecular assemblies. From a structural perspective, the supramolecular domains of these metal complexes can be fine-tuned by varying the hydrogen-bonded multivalency, compensating anion and dimensionality. This approach allowed various structural architectures, including a 1D helix, double helix columns, and 2D and 3D hydrogen-bonded networks. This structural versatility is associated with the metal coordination flexibility of the Cu²⁺ centres and the remarkable robustness of the hydrogen-bonded heterosynthons formed between carboxylate/carboxylic and N—H groups (types Ib–Ie).

These novel supramolecular architectures, with their potential applications in hybrid inorganic–organic materials, underscore the importance and impact of this approach and promise new tools for materials design and synthesis. In addition, the possibility of chemical coupling of mixtures of distinctive metal–organic building blocks in a single phase opens new perspectives in materials science toward the study of providing supramolecular assistance to materials engineering. To increase the level of sophistication, further studies are underway both on the preparation of novel mixed-metallic complexes and on molecular adsorption on solids exploiting such hydrogen-bonded synthons.

Supporting information

CCDC references: 2358575; 2358576; 2358577; 2358578

Crystal structure: contains datablocks 1, 2, 3, 4, global. DOI: https://doi.org/10.1107/S2053229624007897/oj3021sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2053229624007897/oj30211sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2053229624007897/oj30212sup3.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2053229624007897/oj30213sup4.hkl

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2053229624007897/oj30214sup5.hkl

Additional figures, spectra and geometry. DOI: https://doi.org/10.1107/S2053229624007897/oj3021sup6.pdf

Computing details top

Tetrakis(2,2'-biimidazole)-1κ⁴N,N';3κ⁴N,N'-di-µ-chlorido-1:2κ²Cl:Cl;2:3κ²Cl:Cl-dimalonato-2κ⁴O,O'-tricopper(II) pentahydrate (1) top

Crystal data top

[Cu₃(C₃H₂O₄)₂Cl₂(C₆H₆N₄)₄]·5H₂O	D_x = 1.705 Mg m⁻³
M_r = 1092.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Ccce	Cell parameters from 17143 reflections
a = 13.766 (3) Å	θ = 1.9–27.8°
b = 20.162 (4) Å	µ = 1.69 mm⁻¹
c = 30.654 (6) Å	T = 298 K
V = 8508 (3) Å³	Block, green
Z = 8	0.3 × 0.2 × 0.2 mm
F(000) = 4440

Data collection top

Rigaku AFC-7S/Mercury (2x2 bin mode) diffractometer	4454 independent reflections
Radiation source: sealed X-ray tube	3252 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω scans	θ_max = 28.3°, θ_min = 1.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	h = −16→16
T_min = 0.600, T_max = 0.710	k = −23→23
44434 measured reflections	l = −29→36

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.0728P)² + 14.9339P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4454 reflections	Δρ_max = 0.54 e Å⁻³
267 parameters	Δρ_min = −0.61 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Intensity data for 1–4 were recorded at room temperature on a Rigaku AFC-7S diffractometer equipped with a Mercury CCD bidimensional detector using monochromated Mo Kα radiation (λ = 0.71073 Å). An empirical absorption correction (multi-scan) was applied for all data using the package CrysAlis PRO (Agilent, 2014). All crystal structures were solved by direct methods using the SHELXT and refined using full-matrix least-squares methods with SHELXL (Sheldrick, 2015) included in the GUI OLEX2 (Dolomanov et al., 2009). All non-H atoms were refined anisotropically. Finally, DIAMOND (Brandenburg, 1996) was used for graphical representations. CCDC 2358575, 2358576, 2358577, and 2358578 contain supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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

	x	y	z	U_iso*/U_eq
Cu1	0.59208 (3)	−0.00504 (2)	0.12719 (2)	0.03589 (17)
Cu2	0.250000	0.000000	0.12246 (2)	0.03365 (19)
Cl1	0.42931 (7)	−0.06037 (6)	0.12314 (3)	0.0502 (3)
O1	0.19974 (18)	−0.05900 (11)	0.16807 (7)	0.0371 (6)
O2	0.1631 (2)	−0.15618 (13)	0.19633 (8)	0.0571 (8)
O3	0.20776 (18)	−0.06096 (11)	0.07631 (7)	0.0365 (6)
O4	0.1863 (3)	−0.16109 (14)	0.04916 (8)	0.0848 (13)
N1	0.5927 (2)	0.03016 (15)	0.06557 (9)	0.0378 (7)
N2	0.6265 (2)	0.00945 (15)	−0.00354 (9)	0.0400 (7)
H2	0.646510	−0.010543	−0.026639	0.048*
N3	0.6635 (2)	−0.08191 (15)	0.09847 (9)	0.0406 (7)
N4	0.6945 (3)	−0.13052 (16)	0.03579 (9)	0.0502 (8)
H4	0.699828	−0.136831	0.008151	0.060*
N5	0.5862 (2)	0.08437 (15)	0.15783 (9)	0.0412 (7)
N6	0.6134 (2)	0.13775 (15)	0.21918 (9)	0.0446 (8)
H6	0.626632	0.145143	0.246165	0.053*
N7	0.6150 (2)	−0.03624 (15)	0.18865 (9)	0.0412 (7)
N8	0.6304 (2)	−0.00952 (16)	0.25794 (9)	0.0436 (7)
H8	0.635322	0.014053	0.281217	0.052*
C1	0.6293 (2)	−0.01403 (18)	0.03760 (10)	0.0358 (8)
C2	0.5651 (3)	0.08357 (19)	0.04054 (11)	0.0431 (9)
H2A	0.536588	0.122205	0.051079	0.052*
C3	0.5857 (3)	0.07119 (19)	−0.00147 (12)	0.0454 (9)
H3	0.574301	0.099455	−0.024896	0.055*
C4	0.6633 (3)	−0.07564 (18)	0.05516 (10)	0.0374 (8)
C5	0.6964 (3)	−0.1451 (2)	0.10619 (12)	0.0511 (10)
H5	0.703769	−0.164181	0.133595	0.061*
C6	0.7165 (4)	−0.1752 (2)	0.06788 (13)	0.0603 (12)
H6A	0.740499	−0.217896	0.064069	0.072*
C7	0.6070 (3)	0.07867 (18)	0.20007 (11)	0.0375 (8)
C8	0.5772 (3)	0.15121 (18)	0.15031 (12)	0.0448 (9)
H8A	0.561293	0.170542	0.123707	0.054*
C9	0.5951 (3)	0.18458 (19)	0.18794 (12)	0.0475 (9)
H9	0.595040	0.230345	0.191729	0.057*
C10	0.6200 (3)	0.01301 (18)	0.21724 (10)	0.0360 (8)
C11	0.6218 (3)	−0.09369 (19)	0.21274 (12)	0.0487 (10)
H11	0.619856	−0.136595	0.201634	0.058*
C12	0.6317 (3)	−0.0771 (2)	0.25552 (12)	0.0508 (10)
H12	0.638129	−0.106340	0.278798	0.061*
C13	0.1897 (3)	−0.12118 (17)	0.16521 (10)	0.0356 (8)
C14	0.2160 (4)	−0.15692 (19)	0.12365 (9)	0.0469 (9)
H14A	0.283939	−0.169259	0.125766	0.056*
H14B	0.178928	−0.197823	0.123004	0.056*
C15	0.2021 (3)	−0.12340 (17)	0.08030 (10)	0.0406 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0465 (3)	0.0383 (3)	0.0229 (3)	0.00165 (19)	−0.00055 (16)	−0.00320 (15)
Cu2	0.0510 (4)	0.0299 (4)	0.0201 (3)	−0.0072 (3)	0.000	0.000
Cl1	0.0391 (5)	0.0562 (7)	0.0552 (6)	0.0002 (4)	−0.0007 (4)	−0.0003 (4)
O1	0.0558 (16)	0.0308 (14)	0.0245 (11)	−0.0038 (11)	0.0055 (10)	−0.0005 (9)
O2	0.103 (2)	0.0366 (15)	0.0312 (13)	−0.0163 (15)	0.0119 (13)	0.0034 (10)
O3	0.0538 (16)	0.0307 (14)	0.0249 (11)	−0.0016 (11)	−0.0046 (10)	−0.0004 (9)
O4	0.188 (4)	0.0342 (16)	0.0317 (14)	−0.013 (2)	−0.0201 (18)	−0.0048 (11)
N1	0.0450 (18)	0.0387 (18)	0.0295 (15)	0.0020 (13)	0.0013 (11)	−0.0022 (12)
N2	0.0488 (19)	0.0456 (18)	0.0256 (14)	−0.0044 (14)	0.0038 (12)	−0.0028 (12)
N3	0.0412 (17)	0.0477 (19)	0.0328 (16)	0.0027 (14)	0.0025 (12)	−0.0024 (12)
N4	0.072 (2)	0.0454 (19)	0.0334 (16)	0.0116 (16)	0.0082 (15)	−0.0007 (13)
N5	0.0512 (19)	0.0436 (18)	0.0288 (15)	0.0007 (14)	−0.0005 (12)	−0.0046 (12)
N6	0.057 (2)	0.0424 (18)	0.0344 (16)	0.0022 (15)	−0.0059 (13)	−0.0090 (13)
N7	0.055 (2)	0.0382 (18)	0.0301 (15)	−0.0005 (14)	−0.0022 (13)	−0.0042 (12)
N8	0.058 (2)	0.0461 (19)	0.0270 (15)	−0.0009 (15)	−0.0088 (13)	−0.0029 (12)
C1	0.0342 (19)	0.046 (2)	0.0272 (17)	−0.0060 (16)	0.0014 (13)	−0.0029 (14)
C2	0.051 (2)	0.040 (2)	0.038 (2)	0.0033 (17)	0.0003 (15)	0.0010 (15)
C3	0.059 (2)	0.044 (2)	0.0331 (19)	−0.0042 (18)	−0.0058 (16)	0.0055 (15)
C4	0.040 (2)	0.040 (2)	0.0324 (18)	0.0017 (16)	0.0039 (14)	−0.0002 (14)
C5	0.058 (3)	0.057 (3)	0.038 (2)	0.016 (2)	0.0035 (17)	0.0067 (17)
C6	0.084 (3)	0.051 (3)	0.046 (2)	0.020 (2)	0.011 (2)	0.0057 (18)
C7	0.0378 (19)	0.041 (2)	0.0338 (19)	−0.0011 (16)	0.0002 (14)	−0.0054 (14)
C8	0.055 (2)	0.038 (2)	0.042 (2)	0.0007 (17)	−0.0008 (16)	0.0031 (15)
C9	0.063 (3)	0.038 (2)	0.041 (2)	0.0057 (18)	0.0000 (16)	−0.0034 (15)
C10	0.040 (2)	0.040 (2)	0.0277 (17)	−0.0013 (16)	−0.0031 (14)	−0.0019 (14)
C11	0.070 (3)	0.037 (2)	0.039 (2)	−0.0020 (19)	−0.0091 (17)	−0.0009 (15)
C12	0.062 (3)	0.053 (3)	0.038 (2)	0.001 (2)	−0.0077 (17)	0.0094 (17)
C13	0.047 (2)	0.0291 (19)	0.0303 (17)	−0.0038 (15)	0.0013 (14)	0.0004 (13)
C14	0.081 (3)	0.032 (2)	0.0277 (19)	−0.001 (2)	0.0052 (16)	−0.0024 (13)
C15	0.063 (3)	0.032 (2)	0.0274 (17)	−0.0024 (17)	−0.0034 (15)	−0.0051 (13)

Geometric parameters (Å, º) top

Cu1—Cl1	2.5062 (12)	N6—H6	0.8600
Cu1—N1	2.018 (3)	N6—C7	1.330 (4)
Cu1—N3	2.036 (3)	N6—C9	1.368 (5)
Cu1—N5	2.034 (3)	N7—C10	1.326 (4)
Cu1—N7	2.011 (3)	N7—C11	1.377 (5)
Cu2—Cl1ⁱ	2.7522 (11)	N8—H8	0.8600
Cu2—Cl1	2.7522 (11)	N8—C10	1.335 (4)
Cu2—O1	1.962 (2)	N8—C12	1.364 (5)
Cu2—O1ⁱ	1.962 (2)	C1—C4	1.432 (5)
Cu2—O3ⁱ	1.962 (2)	C2—H2A	0.9300
Cu2—O3	1.962 (2)	C2—C3	1.342 (5)
O1—C13	1.264 (4)	C3—H3	0.9300
O2—C13	1.242 (4)	C5—H5	0.9300
O3—C15	1.267 (4)	C5—C6	1.351 (5)
O4—C15	1.239 (4)	C6—H6A	0.9300
N1—C1	1.335 (4)	C7—C10	1.436 (5)
N1—C2	1.376 (5)	C8—H8A	0.9300
N2—H2	0.8600	C8—C9	1.358 (5)
N2—C1	1.348 (4)	C9—H9	0.9300
N2—C3	1.367 (5)	C11—H11	0.9300
N3—C4	1.334 (4)	C11—C12	1.361 (5)
N3—C5	1.372 (5)	C12—H12	0.9300
N4—H4	0.8600	C13—C14	1.508 (4)
N4—C4	1.327 (5)	C14—H14A	0.9700
N4—C6	1.367 (5)	C14—H14B	0.9700
N5—C7	1.331 (4)	C14—C15	1.503 (4)
N5—C8	1.373 (5)

N1—Cu1—Cl1	96.53 (9)	C10—N8—C12	106.9 (3)
N1—Cu1—N3	82.01 (11)	C12—N8—H8	126.6
N1—Cu1—N5	96.93 (12)	N1—C1—N2	110.8 (3)
N3—Cu1—Cl1	94.10 (9)	N1—C1—C4	117.4 (3)
N5—Cu1—Cl1	112.46 (9)	N2—C1—C4	131.7 (3)
N5—Cu1—N3	153.31 (12)	N1—C2—H2A	125.3
N7—Cu1—Cl1	92.73 (9)	C3—C2—N1	109.3 (3)
N7—Cu1—N1	170.49 (13)	C3—C2—H2A	125.3
N7—Cu1—N3	95.22 (12)	N2—C3—H3	126.2
N7—Cu1—N5	81.43 (12)	C2—C3—N2	107.5 (3)
Cl1ⁱ—Cu2—Cl1	179.13 (4)	C2—C3—H3	126.2
O1ⁱ—Cu2—Cl1ⁱ	92.45 (8)	N3—C4—C1	117.2 (3)
O1—Cu2—Cl1	92.45 (8)	N4—C4—N3	111.4 (3)
O1—Cu2—Cl1ⁱ	86.93 (8)	N4—C4—C1	131.3 (3)
O1ⁱ—Cu2—Cl1	86.93 (8)	N3—C5—H5	125.2
O1ⁱ—Cu2—O1	89.08 (13)	C6—C5—N3	109.6 (3)
O1ⁱ—Cu2—O3	176.55 (10)	C6—C5—H5	125.2
O1ⁱ—Cu2—O3ⁱ	91.69 (10)	N4—C6—H6A	126.8
O1—Cu2—O3ⁱ	176.54 (10)	C5—C6—N4	106.5 (4)
O1—Cu2—O3	91.69 (10)	C5—C6—H6A	126.8
O3ⁱ—Cu2—Cl1ⁱ	89.67 (8)	N5—C7—C10	117.6 (3)
O3—Cu2—Cl1	89.67 (8)	N6—C7—N5	111.4 (3)
O3—Cu2—Cl1ⁱ	90.96 (8)	N6—C7—C10	131.0 (3)
O3ⁱ—Cu2—Cl1	90.96 (8)	N5—C8—H8A	125.4
O3ⁱ—Cu2—O3	87.74 (13)	C9—C8—N5	109.1 (3)
Cu1—Cl1—Cu2	127.26 (5)	C9—C8—H8A	125.4
C13—O1—Cu2	126.2 (2)	N6—C9—H9	126.7
C15—O3—Cu2	124.8 (2)	C8—C9—N6	106.6 (3)
C1—N1—Cu1	111.6 (2)	C8—C9—H9	126.7
C1—N1—C2	105.6 (3)	N7—C10—N8	111.6 (3)
C2—N1—Cu1	142.8 (2)	N7—C10—C7	116.2 (3)
C1—N2—H2	126.6	N8—C10—C7	132.0 (3)
C1—N2—C3	106.7 (3)	N7—C11—H11	125.8
C3—N2—H2	126.6	C12—C11—N7	108.5 (3)
C4—N3—Cu1	110.9 (2)	C12—C11—H11	125.8
C4—N3—C5	105.1 (3)	N8—C12—H12	126.4
C5—N3—Cu1	142.3 (2)	C11—C12—N8	107.3 (3)
C4—N4—H4	126.3	C11—C12—H12	126.4
C4—N4—C6	107.4 (3)	O1—C13—C14	120.4 (3)
C6—N4—H4	126.3	O2—C13—O1	122.8 (3)
C7—N5—Cu1	111.4 (2)	O2—C13—C14	116.6 (3)
C7—N5—C8	105.5 (3)	C13—C14—H14A	107.3
C8—N5—Cu1	142.8 (2)	C13—C14—H14B	107.3
C7—N6—H6	126.3	H14A—C14—H14B	106.9
C7—N6—C9	107.3 (3)	C15—C14—C13	120.1 (3)
C9—N6—H6	126.3	C15—C14—H14A	107.3
C10—N7—Cu1	113.1 (2)	C15—C14—H14B	107.3
C10—N7—C11	105.8 (3)	O3—C15—C14	121.6 (3)
C11—N7—Cu1	140.9 (2)	O4—C15—O3	123.1 (3)
C10—N8—H8	126.6	O4—C15—C14	115.3 (3)

Cu1—N1—C1—N2	178.2 (2)	N6—C7—C10—N8	9.5 (7)
Cu1—N1—C1—C4	−1.7 (4)	N7—C11—C12—N8	0.4 (5)
Cu1—N1—C2—C3	−176.9 (3)	C1—N1—C2—C3	−0.4 (4)
Cu1—N3—C4—N4	−169.2 (3)	C1—N2—C3—C2	0.1 (4)
Cu1—N3—C4—C1	9.7 (4)	C2—N1—C1—N2	0.5 (4)
Cu1—N3—C5—C6	163.5 (3)	C2—N1—C1—C4	−179.4 (3)
Cu1—N5—C7—N6	173.3 (2)	C3—N2—C1—N1	−0.4 (4)
Cu1—N5—C7—C10	−5.8 (4)	C3—N2—C1—C4	179.5 (4)
Cu1—N5—C8—C9	−170.1 (3)	C4—N3—C5—C6	0.8 (5)
Cu1—N7—C10—N8	176.9 (2)	C4—N4—C6—C5	0.6 (5)
Cu1—N7—C10—C7	0.9 (4)	C5—N3—C4—N4	−0.4 (4)
Cu1—N7—C11—C12	−175.2 (3)	C5—N3—C4—C1	178.5 (3)
Cu2—O1—C13—O2	175.4 (3)	C6—N4—C4—N3	−0.1 (5)
Cu2—O1—C13—C14	−0.9 (5)	C6—N4—C4—C1	−178.8 (4)
Cu2—O3—C15—O4	−171.1 (3)	C7—N5—C8—C9	1.5 (4)
Cu2—O3—C15—C14	7.8 (5)	C7—N6—C9—C8	0.5 (4)
O1—C13—C14—C15	−33.1 (6)	C8—N5—C7—N6	−1.2 (4)
O2—C13—C14—C15	150.3 (4)	C8—N5—C7—C10	179.6 (3)
N1—C1—C4—N3	−5.6 (5)	C9—N6—C7—N5	0.5 (4)
N1—C1—C4—N4	173.0 (4)	C9—N6—C7—C10	179.5 (4)
N1—C2—C3—N2	0.2 (4)	C10—N7—C11—C12	−0.6 (4)
N2—C1—C4—N3	174.5 (4)	C10—N8—C12—C11	−0.1 (5)
N2—C1—C4—N4	−6.8 (7)	C11—N7—C10—N8	0.6 (4)
N3—C5—C6—N4	−0.8 (5)	C11—N7—C10—C7	−175.4 (3)
N5—C7—C10—N7	3.5 (5)	C12—N8—C10—N7	−0.3 (4)
N5—C7—C10—N8	−171.5 (4)	C12—N8—C10—C7	174.8 (4)
N5—C8—C9—N6	−1.3 (4)	C13—C14—C15—O3	29.5 (6)
N6—C7—C10—N7	−175.5 (4)	C13—C14—C15—O4	−151.5 (4)

Symmetry code: (i) −x+1/2, −y, z.

Aqua(2,2'-biimidazole-κ²N,N')(malonato-κ²O,O')copper(II) dihydrate (2) top

Crystal data top

[Cu(C₃H₂O₄)(C₆H₆N₄)(H₂O)]·2H₂O	F(000) = 1448
M_r = 353.78	D_x = 1.730 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.0587 (4) Å	Cell parameters from 6782 reflections
b = 20.3107 (12) Å	θ = 3.2–27.0°
c = 18.9523 (10) Å	µ = 1.65 mm⁻¹
β = 91.770 (4)°	T = 298 K
V = 2715.8 (3) Å³	Plate, green
Z = 8	0.36 × 0.11 × 0.09 mm

Data collection top

Rigaku AFC diffractometer	4229 independent reflections
Radiation source: sealed X-ray tube, Enhance (Mo) X-ray Source	2925 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω scans	θ_max = 24.8°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	h = −6→6
T_min = 0.903, T_max = 1.000	k = −23→23
21646 measured reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0411P)² + 6.8869P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4229 reflections	Δρ_max = 0.58 e Å⁻³
343 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Cu11	0.42536 (8)	0.82052 (3)	0.18851 (3)	0.02555 (17)
Cu12	0.92614 (8)	0.68105 (3)	0.31015 (3)	0.02619 (17)
O11	0.1067 (4)	0.83742 (16)	0.17496 (17)	0.0351 (8)
H11A	0.023623	0.867206	0.190546	0.053*
H11B	0.043803	0.800356	0.185467	0.053*
O12	0.6085 (4)	0.66516 (16)	0.32368 (17)	0.0347 (8)
H12A	0.555383	0.704161	0.312489	0.052*
H12B	0.539873	0.630551	0.308019	0.052*
O21	0.5061 (5)	0.90321 (16)	0.22934 (16)	0.0365 (8)
O22	0.9078 (4)	0.72406 (16)	0.21856 (15)	0.0319 (8)
O31	0.5118 (6)	0.97758 (19)	0.31415 (19)	0.0542 (11)
O32	0.8681 (5)	0.72086 (17)	0.10302 (16)	0.0379 (8)
O41	0.4120 (4)	0.77879 (15)	0.28048 (15)	0.0307 (8)
O42	0.9960 (5)	0.59806 (16)	0.26836 (16)	0.0354 (8)
O51	0.3819 (5)	0.78240 (17)	0.39580 (16)	0.0388 (9)
O52	0.9763 (6)	0.52341 (18)	0.18392 (18)	0.0483 (10)
N11	0.4949 (5)	0.85173 (19)	0.09227 (19)	0.0295 (9)
N12	0.8997 (5)	0.76600 (19)	0.36224 (19)	0.0274 (9)
N21	0.5017 (6)	0.8291 (2)	−0.02103 (19)	0.0336 (10)
H21	0.491782	0.806685	−0.061870	0.040*
N22	0.8726 (6)	0.8133 (2)	0.4657 (2)	0.0348 (10)
H22	0.873093	0.818880	0.512802	0.042*
N31	0.3884 (5)	0.73506 (18)	0.13670 (18)	0.0255 (9)
N32	0.9974 (5)	0.64836 (19)	0.4071 (2)	0.0308 (9)
N41	0.3615 (6)	0.6865 (2)	0.0335 (2)	0.0352 (10)
H41	0.363092	0.680094	−0.013424	0.042*
N42	1.0034 (6)	0.6685 (2)	0.52080 (19)	0.0348 (10)
H42	0.994689	0.690364	0.561843	0.042*
C11	0.4664 (6)	0.8059 (2)	0.0432 (2)	0.0274 (11)
C12	0.9147 (6)	0.7577 (2)	0.4316 (2)	0.0284 (11)
C21	0.5500 (7)	0.9069 (3)	0.0567 (3)	0.0350 (12)
H21A	0.578086	0.946011	0.076628	0.042*
C22	0.8458 (7)	0.8305 (2)	0.3522 (3)	0.0328 (11)
H22A	0.825031	0.849872	0.309989	0.039*
C31	0.5555 (7)	0.8933 (3)	−0.0131 (3)	0.0405 (13)
H31	0.588315	0.921123	−0.047484	0.049*
C32	0.8287 (7)	0.8603 (3)	0.4159 (3)	0.0378 (12)
H32	0.795376	0.902330	0.423785	0.045*
C41	0.4080 (6)	0.7420 (2)	0.0676 (2)	0.0271 (11)
C42	0.9688 (6)	0.6929 (2)	0.4563 (2)	0.0279 (11)
C51	0.3279 (7)	0.6716 (2)	0.1463 (3)	0.0325 (11)
H51	0.303094	0.653035	0.188085	0.039*
C52	1.0499 (7)	0.5913 (3)	0.4426 (3)	0.0360 (12)
H52	1.076370	0.552414	0.422532	0.043*
C61	0.3114 (7)	0.6413 (2)	0.0825 (3)	0.0382 (12)
H61	0.274612	0.599514	0.074336	0.046*
C62	1.0544 (7)	0.6044 (3)	0.5127 (3)	0.0413 (13)
H62	1.085312	0.575909	0.547534	0.050*
C71	0.4595 (7)	0.9246 (2)	0.2899 (3)	0.0323 (11)
C72	0.8653 (6)	0.6937 (2)	0.1613 (2)	0.0277 (11)
C81	0.3289 (7)	0.8815 (2)	0.3334 (2)	0.0345 (12)
H81A	0.328492	0.897521	0.377589	0.041*
H81B	0.210354	0.885224	0.315109	0.041*
C82	0.8027 (7)	0.6227 (2)	0.1651 (2)	0.0342 (12)
H82A	0.790993	0.606745	0.120926	0.041*
H82B	0.687436	0.621334	0.183962	0.041*
C91	0.3782 (6)	0.8096 (2)	0.3374 (2)	0.0278 (11)
C92	0.9343 (7)	0.5781 (2)	0.2076 (2)	0.0315 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu11	0.0366 (4)	0.0268 (3)	0.0133 (3)	−0.0022 (2)	0.0012 (2)	−0.0010 (2)
Cu12	0.0373 (4)	0.0280 (3)	0.0133 (3)	0.0027 (2)	−0.0001 (2)	0.0002 (2)
O11	0.036 (2)	0.0307 (19)	0.038 (2)	0.0037 (14)	0.0036 (15)	0.0009 (15)
O12	0.039 (2)	0.0272 (19)	0.038 (2)	−0.0038 (14)	0.0010 (15)	0.0026 (15)
O21	0.052 (2)	0.036 (2)	0.0213 (18)	−0.0115 (16)	0.0045 (15)	−0.0037 (15)
O22	0.046 (2)	0.032 (2)	0.0171 (17)	−0.0025 (15)	0.0007 (14)	0.0000 (14)
O31	0.085 (3)	0.039 (2)	0.040 (2)	−0.020 (2)	0.0131 (19)	−0.0156 (18)
O32	0.058 (2)	0.042 (2)	0.0135 (18)	−0.0001 (17)	−0.0006 (15)	0.0021 (15)
O41	0.049 (2)	0.0278 (19)	0.0149 (17)	0.0024 (14)	−0.0008 (13)	0.0008 (14)
O42	0.051 (2)	0.036 (2)	0.0190 (18)	0.0114 (15)	−0.0057 (14)	−0.0023 (15)
O51	0.063 (2)	0.039 (2)	0.0148 (18)	0.0030 (17)	0.0038 (15)	0.0059 (15)
O52	0.072 (3)	0.035 (2)	0.037 (2)	0.0136 (18)	−0.0130 (18)	−0.0087 (17)
N11	0.038 (3)	0.032 (2)	0.019 (2)	−0.0023 (17)	0.0051 (16)	0.0005 (18)
N12	0.035 (2)	0.031 (2)	0.017 (2)	−0.0024 (17)	0.0002 (15)	0.0024 (17)
N21	0.043 (3)	0.044 (3)	0.014 (2)	0.0042 (19)	0.0061 (16)	0.0030 (18)
N22	0.050 (3)	0.037 (3)	0.017 (2)	−0.0001 (19)	−0.0030 (17)	−0.0068 (19)
N31	0.034 (2)	0.026 (2)	0.017 (2)	0.0038 (16)	0.0005 (15)	0.0039 (16)
N32	0.036 (3)	0.032 (2)	0.024 (2)	0.0037 (17)	−0.0033 (16)	−0.0003 (18)
N41	0.052 (3)	0.037 (3)	0.017 (2)	−0.002 (2)	0.0019 (17)	−0.0063 (19)
N42	0.046 (3)	0.045 (3)	0.013 (2)	−0.004 (2)	−0.0042 (17)	0.0013 (18)
C11	0.030 (3)	0.036 (3)	0.017 (2)	0.004 (2)	0.0047 (18)	0.001 (2)
C12	0.029 (3)	0.038 (3)	0.018 (3)	−0.005 (2)	0.0001 (19)	−0.006 (2)
C21	0.034 (3)	0.036 (3)	0.034 (3)	−0.007 (2)	0.002 (2)	0.003 (2)
C22	0.040 (3)	0.030 (3)	0.028 (3)	−0.003 (2)	−0.001 (2)	0.003 (2)
C31	0.044 (3)	0.048 (4)	0.030 (3)	−0.001 (2)	0.010 (2)	0.015 (3)
C32	0.048 (3)	0.031 (3)	0.033 (3)	0.000 (2)	0.003 (2)	−0.004 (2)
C41	0.034 (3)	0.034 (3)	0.014 (2)	0.007 (2)	0.0008 (18)	−0.003 (2)
C42	0.029 (3)	0.039 (3)	0.016 (2)	−0.003 (2)	−0.0045 (18)	0.001 (2)
C51	0.037 (3)	0.032 (3)	0.029 (3)	0.004 (2)	0.005 (2)	0.002 (2)
C52	0.039 (3)	0.035 (3)	0.033 (3)	0.006 (2)	−0.002 (2)	0.007 (2)
C61	0.052 (4)	0.027 (3)	0.036 (3)	−0.002 (2)	0.001 (2)	−0.005 (2)
C62	0.045 (4)	0.049 (4)	0.029 (3)	−0.001 (2)	−0.008 (2)	0.017 (3)
C71	0.039 (3)	0.030 (3)	0.028 (3)	0.002 (2)	−0.003 (2)	0.000 (2)
C72	0.031 (3)	0.032 (3)	0.020 (3)	0.007 (2)	−0.0005 (19)	0.002 (2)
C81	0.049 (3)	0.032 (3)	0.023 (3)	0.000 (2)	0.009 (2)	−0.004 (2)
C82	0.045 (3)	0.035 (3)	0.022 (3)	0.001 (2)	−0.009 (2)	−0.001 (2)
C91	0.031 (3)	0.032 (3)	0.020 (3)	−0.002 (2)	0.0004 (19)	0.000 (2)
C92	0.034 (3)	0.034 (3)	0.027 (3)	0.001 (2)	0.002 (2)	0.004 (2)

Geometric parameters (Å, º) top

Cu11—O11	2.282 (3)	N31—C41	1.329 (5)
Cu11—O21	1.928 (3)	N31—C51	1.372 (6)
Cu11—O41	1.943 (3)	N32—C42	1.319 (6)
Cu11—N11	2.006 (4)	N32—C52	1.384 (6)
Cu11—N31	2.007 (4)	N41—H41	0.8990
Cu12—O12	2.287 (3)	N41—C41	1.336 (6)
Cu12—O22	1.944 (3)	N41—C61	1.361 (6)
Cu12—O42	1.933 (3)	N42—H42	0.8990
Cu12—N12	1.999 (4)	N42—C42	1.335 (6)
Cu12—N32	2.003 (4)	N42—C62	1.362 (6)
O11—H11A	0.8990	C11—C41	1.442 (6)
O11—H11B	0.8995	C12—C42	1.443 (6)
O12—H12A	0.8991	C21—H21A	0.8990
O12—H12B	0.8991	C21—C31	1.352 (7)
O21—C71	1.281 (5)	C22—H22A	0.8990
O22—C72	1.276 (5)	C22—C32	1.361 (7)
O31—C71	1.222 (6)	C31—H31	0.8990
O32—C72	1.235 (5)	C32—H32	0.8990
O41—C91	1.275 (5)	C51—H51	0.8990
O42—C92	1.283 (6)	C51—C61	1.358 (7)
O51—C91	1.237 (5)	C52—H52	0.8990
O52—C92	1.239 (6)	C52—C62	1.356 (7)
N11—C11	1.327 (6)	C61—H61	0.8990
N11—C21	1.370 (6)	C62—H62	0.8990
N12—C12	1.327 (5)	C71—C81	1.531 (7)
N12—C22	1.375 (6)	C72—C82	1.511 (6)
N21—H21	0.8990	C81—H81A	0.8990
N21—C11	1.336 (6)	C81—H81B	0.8990
N21—C31	1.365 (6)	C81—C91	1.502 (6)
N22—H22	0.8990	C82—H82A	0.8990
N22—C12	1.340 (6)	C82—H82B	0.8990
N22—C32	1.371 (6)	C82—C92	1.512 (6)

O21—Cu11—O11	101.09 (13)	N12—C12—N22	111.0 (4)
O21—Cu11—O41	92.40 (13)	N12—C12—C42	116.7 (4)
O21—Cu11—N11	90.69 (15)	N22—C12—C42	132.3 (4)
O21—Cu11—N31	169.11 (15)	N11—C21—H21A	125.3
O41—Cu11—O11	95.25 (12)	C31—C21—N11	109.3 (4)
O41—Cu11—N11	166.75 (15)	C31—C21—H21A	125.3
O41—Cu11—N31	93.00 (14)	N12—C22—H22A	125.3
N11—Cu11—O11	96.79 (14)	C32—C22—N12	109.4 (4)
N11—Cu11—N31	81.97 (15)	C32—C22—H22A	125.3
N31—Cu11—O11	87.83 (13)	N21—C31—H31	126.7
O22—Cu12—O12	97.18 (12)	C21—C31—N21	106.7 (4)
O22—Cu12—N12	92.78 (14)	C21—C31—H31	126.7
O22—Cu12—N32	167.40 (15)	N22—C32—H32	127.0
O42—Cu12—O12	100.73 (13)	C22—C32—N22	106.1 (4)
O42—Cu12—O22	92.11 (13)	C22—C32—H32	127.0
O42—Cu12—N12	169.67 (15)	N31—C41—N41	110.8 (4)
O42—Cu12—N32	91.53 (14)	N31—C41—C11	116.8 (4)
N12—Cu12—O12	87.68 (13)	N41—C41—C11	132.3 (4)
N12—Cu12—N32	81.83 (15)	N32—C42—N42	111.4 (4)
N32—Cu12—O12	93.99 (14)	N32—C42—C12	116.2 (4)
Cu11—O11—H11A	135.7	N42—C42—C12	132.3 (4)
Cu11—O11—H11B	109.9	N31—C51—H51	125.5
H11A—O11—H11B	99.1	C61—C51—N31	109.1 (4)
Cu12—O12—H12A	104.6	C61—C51—H51	125.5
Cu12—O12—H12B	126.4	N32—C52—H52	125.9
H12A—O12—H12B	113.2	C62—C52—N32	108.1 (5)
C71—O21—Cu11	125.1 (3)	C62—C52—H52	125.9
C72—O22—Cu12	123.4 (3)	N41—C61—H61	126.7
C91—O41—Cu11	124.0 (3)	C51—C61—N41	106.6 (4)
C92—O42—Cu12	124.0 (3)	C51—C61—H61	126.7
C11—N11—Cu11	112.3 (3)	N42—C62—H62	126.3
C11—N11—C21	105.6 (4)	C52—C62—N42	107.4 (4)
C21—N11—Cu11	141.9 (3)	C52—C62—H62	126.3
C12—N12—Cu12	111.9 (3)	O21—C71—C81	117.6 (4)
C12—N12—C22	105.8 (4)	O31—C71—O21	123.6 (5)
C22—N12—Cu12	141.5 (3)	O31—C71—C81	118.8 (4)
C11—N21—H21	126.4	O22—C72—C82	118.8 (4)
C11—N21—C31	107.2 (4)	O32—C72—O22	122.4 (4)
C31—N21—H21	126.4	O32—C72—C82	118.8 (4)
C12—N22—H22	126.2	C71—C81—H81A	108.2
C12—N22—C32	107.7 (4)	C71—C81—H81B	108.2
C32—N22—H22	126.2	H81A—C81—H81B	107.4
C41—N31—Cu11	112.0 (3)	C91—C81—C71	116.2 (4)
C41—N31—C51	105.8 (4)	C91—C81—H81A	108.2
C51—N31—Cu11	141.6 (3)	C91—C81—H81B	108.2
C42—N32—Cu12	112.4 (3)	C72—C82—H82A	108.5
C42—N32—C52	106.0 (4)	C72—C82—H82B	108.5
C52—N32—Cu12	141.2 (3)	C72—C82—C92	114.9 (4)
C41—N41—H41	126.1	H82A—C82—H82B	107.5
C41—N41—C61	107.7 (4)	C92—C82—H82A	108.5
C61—N41—H41	126.1	C92—C82—H82B	108.5
C42—N42—H42	126.5	O41—C91—C81	118.9 (4)
C42—N42—C62	107.1 (4)	O51—C91—O41	122.6 (4)
C62—N42—H42	126.5	O51—C91—C81	118.5 (4)
N11—C11—N21	111.2 (4)	O42—C92—C82	118.4 (4)
N11—C11—C41	116.4 (4)	O52—C92—O42	122.0 (4)
N21—C11—C41	132.3 (4)	O52—C92—C82	119.6 (4)

Cu11—O21—C71—O31	−179.4 (4)	N22—C12—C42—N32	178.9 (5)
Cu11—O21—C71—C81	−0.2 (6)	N22—C12—C42—N42	−3.8 (9)
Cu11—O41—C91—O51	−175.5 (3)	N31—C51—C61—N41	−0.2 (5)
Cu11—O41—C91—C81	5.5 (6)	N32—C52—C62—N42	0.6 (6)
Cu11—N11—C11—N21	175.9 (3)	C11—N11—C21—C31	−0.6 (5)
Cu11—N11—C11—C41	−5.0 (5)	C11—N21—C31—C21	−0.3 (5)
Cu11—N11—C21—C31	−173.8 (4)	C12—N12—C22—C32	−0.1 (5)
Cu11—N31—C41—N41	−172.9 (3)	C12—N22—C32—C22	0.2 (5)
Cu11—N31—C41—C11	5.0 (5)	C21—N11—C11—N21	0.4 (5)
Cu11—N31—C51—C61	169.9 (4)	C21—N11—C11—C41	179.5 (4)
Cu12—O22—C72—O32	−174.5 (3)	C22—N12—C12—N22	0.2 (5)
Cu12—O22—C72—C82	7.7 (6)	C22—N12—C12—C42	179.5 (4)
Cu12—O42—C92—O52	−177.0 (4)	C31—N21—C11—N11	−0.1 (5)
Cu12—O42—C92—C82	1.5 (6)	C31—N21—C11—C41	−179.0 (5)
Cu12—N12—C12—N22	−172.1 (3)	C32—N22—C12—N12	−0.2 (5)
Cu12—N12—C12—C42	7.2 (5)	C32—N22—C12—C42	−179.4 (5)
Cu12—N12—C22—C32	168.4 (4)	C41—N31—C51—C61	−0.2 (5)
Cu12—N32—C42—N42	175.2 (3)	C41—N41—C61—C51	0.5 (5)
Cu12—N32—C42—C12	−6.9 (5)	C42—N32—C52—C62	−1.1 (5)
Cu12—N32—C52—C62	−172.2 (4)	C42—N42—C62—C52	0.2 (5)
O21—C71—C81—C91	45.7 (6)	C51—N31—C41—N41	0.5 (5)
O22—C72—C82—C92	−51.8 (6)	C51—N31—C41—C11	178.4 (4)
O31—C71—C81—C91	−135.1 (5)	C52—N32—C42—N42	1.3 (5)
O32—C72—C82—C92	130.4 (5)	C52—N32—C42—C12	179.1 (4)
N11—C11—C41—N31	0.0 (6)	C61—N41—C41—N31	−0.6 (5)
N11—C11—C41—N41	177.3 (5)	C61—N41—C41—C11	−178.1 (5)
N11—C21—C31—N21	0.5 (5)	C62—N42—C42—N32	−0.9 (5)
N12—C12—C42—N32	−0.2 (6)	C62—N42—C42—C12	−178.3 (5)
N12—C12—C42—N42	177.1 (5)	C71—C81—C91—O41	−48.7 (6)
N12—C22—C32—N22	−0.1 (5)	C71—C81—C91—O51	132.3 (5)
N21—C11—C41—N31	178.8 (5)	C72—C82—C92—O42	46.4 (6)
N21—C11—C41—N41	−3.8 (9)	C72—C82—C92—O52	−135.0 (5)

Bis[aquabis(2,2'-biimidazole-κ²N,N')copper(II)] bis(malonato-κ²O,O')bis(perchlorato-κO)copper(II) 2.2-hydrate (3) top

Crystal data top

[Cu(C₆H₆N₄)₂(H₂O)]₂·[Cu(C₃H₂O₄)₂(ClO₄)₂]·2.2H₂O	F(000) = 2428
M_r = 1201.84	D_x = 1.756 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.9569 (11) Å	Cell parameters from 7335 reflections
b = 15.2466 (6) Å	θ = 1.8–27.0°
c = 16.6781 (10) Å	µ = 1.60 mm⁻¹
β = 95.296 (5)°	T = 298 K
V = 4546.7 (4) Å³	Block, green
Z = 4	0.38 × 0.36 × 0.33 mm

Data collection top

Rigaku AFC diffractometer	3848 independent reflections
Radiation source: sealed X-ray tube, Enhance (Mo) X-ray Source	2674 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	h = −20→20
T_min = 0.681, T_max = 1.000	k = −18→18
17890 measured reflections	l = −17→18

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.070	H-atom parameters constrained
wR(F²) = 0.204	w = 1/[σ²(F_o²) + (0.085P)² + 59.2856P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3848 reflections	Δρ_max = 1.14 e Å⁻³
338 parameters	Δρ_min = −0.79 e Å⁻³
50 restraints

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu2	0.000000	0.33157 (7)	0.750000	0.0342 (4)
Cu1	0.41749 (5)	0.33255 (5)	0.65057 (6)	0.0401 (3)
O2	0.0362 (3)	0.2404 (3)	0.6837 (3)	0.0376 (12)
O4	0.0612 (3)	0.4233 (3)	0.7121 (3)	0.0426 (13)
O1	0.3289 (3)	0.3280 (4)	0.5509 (3)	0.0519 (14)
H1A	0.346008	0.319169	0.496830	0.078*
H1B	0.300468	0.382999	0.539461	0.078*
O5	0.1578 (3)	0.4752 (3)	0.6560 (4)	0.0561 (16)
N5	0.3956 (4)	0.4566 (4)	0.6827 (4)	0.0414 (15)
O3	0.0969 (4)	0.1922 (3)	0.5848 (4)	0.0613 (18)
N1	0.3655 (4)	0.2711 (4)	0.7372 (4)	0.0414 (15)
N3	0.4490 (4)	0.2095 (4)	0.6282 (4)	0.0448 (16)
N7	0.5043 (4)	0.3925 (4)	0.6028 (4)	0.0435 (16)
N8	0.5602 (4)	0.5178 (4)	0.5849 (4)	0.0464 (17)
H8	0.570562	0.572891	0.587101	0.056*
N2	0.3469 (4)	0.1458 (4)	0.7971 (4)	0.0502 (18)
H2	0.348680	0.090807	0.808472	0.060*
N6	0.4273 (4)	0.5945 (4)	0.6784 (4)	0.0494 (18)
H6	0.452139	0.641120	0.669288	0.059*
C7	0.4448 (4)	0.5130 (4)	0.6594 (5)	0.0375 (17)
N4	0.4446 (4)	0.0711 (4)	0.6604 (5)	0.0545 (19)
H4	0.433899	0.023767	0.684918	0.065*
C13	0.0859 (4)	0.2482 (4)	0.6352 (5)	0.0384 (18)
C15	0.1165 (4)	0.4134 (4)	0.6712 (5)	0.0382 (18)
C10	0.5043 (4)	0.4789 (4)	0.6163 (5)	0.0398 (18)
C1	0.3805 (5)	0.1855 (4)	0.7389 (5)	0.0421 (19)
C4	0.4245 (5)	0.1521 (4)	0.6790 (5)	0.046 (2)
C8	0.3427 (5)	0.5048 (5)	0.7174 (5)	0.050 (2)
H8A	0.300475	0.482557	0.738765	0.060*
C5	0.4875 (5)	0.1624 (5)	0.5751 (6)	0.052 (2)
H5	0.511050	0.185352	0.532367	0.062*
C9	0.3626 (5)	0.5906 (5)	0.7152 (5)	0.051 (2)
H9	0.337006	0.637804	0.734959	0.061*
C12	0.5989 (5)	0.4543 (5)	0.5481 (5)	0.052 (2)
H12	0.641042	0.462491	0.520449	0.062*
C11	0.5644 (5)	0.3781 (5)	0.5598 (6)	0.052 (2)
H11	0.579055	0.323686	0.541505	0.062*
C14	0.1383 (6)	0.3256 (5)	0.6396 (7)	0.068 (3)
C6	0.4849 (5)	0.0769 (5)	0.5958 (6)	0.057 (2)
H6A	0.506764	0.030473	0.570471	0.068*
C2	0.3207 (5)	0.2855 (5)	0.7980 (5)	0.0462 (19)
H2A	0.301217	0.339513	0.811552	0.055*
C3	0.3093 (5)	0.2084 (5)	0.8351 (5)	0.049 (2)
H3	0.281123	0.199831	0.878462	0.058*
O1W	0.2382 (5)	0.4718 (6)	0.5226 (5)	0.097 (3)
H1WA	0.219063	0.479480	0.566669	0.146*
H1WB	0.222928	0.515145	0.493478	0.146*
Cl1B	0.1417 (8)	0.3378 (14)	0.9124 (16)	0.0579 (10)	0.229 (11)
O2B	0.138 (3)	0.312 (3)	0.8300 (18)	0.088 (4)	0.229 (11)
O1A	0.0732 (4)	0.3842 (6)	0.9155 (6)	0.115 (3)
O4B	0.2149 (12)	0.370 (2)	0.933 (2)	0.088 (3)	0.229 (11)
O3B	0.134 (2)	0.258 (2)	0.955 (3)	0.148 (5)	0.229 (11)
O4A	0.1899 (6)	0.4188 (6)	0.8769 (7)	0.088 (3)	0.771 (11)
Cl1A	0.1447 (2)	0.3502 (4)	0.9040 (4)	0.0579 (10)	0.771 (11)
O3A	0.1746 (9)	0.3107 (11)	0.9750 (7)	0.148 (5)	0.771 (11)
O2A	0.1314 (8)	0.2861 (6)	0.8419 (7)	0.088 (4)	0.771 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu2	0.0437 (7)	0.0085 (5)	0.0535 (8)	0.000	0.0204 (6)	0.000
Cu1	0.0521 (6)	0.0097 (4)	0.0601 (7)	−0.0008 (4)	0.0132 (4)	0.0037 (4)
O2	0.048 (3)	0.011 (2)	0.057 (3)	−0.001 (2)	0.021 (2)	−0.003 (2)
O4	0.055 (3)	0.011 (2)	0.065 (3)	−0.001 (2)	0.026 (3)	−0.003 (2)
O1	0.061 (4)	0.048 (3)	0.047 (3)	0.007 (3)	0.005 (3)	−0.002 (3)
O5	0.069 (4)	0.017 (3)	0.088 (4)	−0.018 (3)	0.042 (3)	−0.010 (3)
N5	0.048 (4)	0.014 (3)	0.062 (4)	−0.004 (3)	0.004 (3)	0.001 (3)
O3	0.087 (5)	0.026 (3)	0.078 (4)	−0.017 (3)	0.045 (4)	−0.021 (3)
N1	0.052 (4)	0.015 (3)	0.059 (4)	−0.005 (3)	0.010 (3)	0.003 (3)
N3	0.058 (4)	0.017 (3)	0.062 (4)	0.000 (3)	0.019 (3)	0.003 (3)
N7	0.047 (4)	0.019 (3)	0.064 (4)	0.000 (3)	0.005 (3)	0.010 (3)
N8	0.053 (4)	0.023 (3)	0.062 (4)	−0.012 (3)	0.001 (3)	0.005 (3)
N2	0.060 (4)	0.021 (3)	0.071 (5)	0.001 (3)	0.019 (4)	0.015 (3)
N6	0.070 (5)	0.013 (3)	0.064 (4)	−0.007 (3)	0.001 (4)	0.001 (3)
C7	0.043 (4)	0.015 (3)	0.053 (5)	−0.002 (3)	−0.004 (3)	0.004 (3)
N4	0.075 (5)	0.011 (3)	0.081 (5)	0.007 (3)	0.021 (4)	0.006 (3)
C13	0.054 (5)	0.015 (3)	0.048 (5)	0.001 (3)	0.015 (4)	−0.003 (3)
C15	0.044 (4)	0.017 (3)	0.054 (5)	−0.003 (3)	0.013 (4)	−0.003 (3)
C10	0.047 (5)	0.018 (3)	0.053 (5)	−0.006 (3)	0.000 (4)	0.003 (3)
C1	0.055 (5)	0.019 (3)	0.055 (5)	−0.003 (3)	0.014 (4)	0.007 (3)
C4	0.058 (5)	0.013 (3)	0.067 (5)	0.003 (3)	0.008 (4)	0.009 (3)
C8	0.049 (5)	0.027 (4)	0.075 (6)	0.000 (4)	0.010 (4)	−0.004 (4)
C5	0.060 (5)	0.030 (4)	0.069 (6)	0.008 (4)	0.020 (4)	0.007 (4)
C9	0.063 (6)	0.019 (4)	0.071 (6)	0.007 (4)	0.004 (5)	−0.005 (4)
C12	0.053 (5)	0.037 (5)	0.065 (6)	−0.009 (4)	0.005 (4)	0.007 (4)
C11	0.048 (5)	0.032 (4)	0.077 (6)	0.008 (4)	0.012 (4)	0.008 (4)
C14	0.075 (6)	0.020 (4)	0.119 (8)	−0.019 (4)	0.052 (6)	−0.028 (5)
C6	0.079 (7)	0.019 (4)	0.075 (6)	0.007 (4)	0.018 (5)	−0.006 (4)
C2	0.060 (5)	0.029 (4)	0.052 (5)	0.007 (4)	0.015 (4)	0.002 (3)
C3	0.049 (5)	0.041 (5)	0.058 (5)	−0.002 (4)	0.018 (4)	0.006 (4)
O1W	0.105 (6)	0.090 (6)	0.106 (6)	0.054 (5)	0.054 (5)	0.045 (5)
Cl1B	0.0674 (16)	0.045 (2)	0.062 (2)	0.0058 (14)	0.0106 (12)	−0.0048 (16)
O2B	0.108 (7)	0.045 (8)	0.111 (7)	−0.019 (6)	0.018 (5)	−0.027 (6)
O1A	0.119 (6)	0.087 (5)	0.147 (6)	0.017 (5)	0.050 (5)	−0.002 (5)
O4B	0.083 (6)	0.078 (6)	0.106 (7)	−0.023 (5)	0.027 (5)	−0.021 (5)
O3B	0.158 (10)	0.157 (10)	0.120 (8)	0.000 (8)	−0.040 (7)	0.017 (8)
O4A	0.083 (6)	0.078 (6)	0.106 (7)	−0.023 (5)	0.027 (5)	−0.021 (5)
Cl1A	0.0674 (16)	0.045 (2)	0.062 (2)	0.0058 (14)	0.0106 (12)	−0.0048 (16)
O3A	0.158 (10)	0.157 (10)	0.120 (8)	0.000 (8)	−0.040 (7)	0.017 (8)
O2A	0.108 (7)	0.045 (8)	0.111 (7)	−0.019 (6)	0.018 (5)	−0.027 (6)

Geometric parameters (Å, º) top

Cu2—O2	1.925 (4)	N6—C7	1.327 (9)
Cu2—O2ⁱ	1.925 (4)	N6—C9	1.364 (11)
Cu2—O4ⁱ	1.922 (5)	C7—C10	1.439 (11)
Cu2—O4	1.922 (5)	N4—H4	0.8600
Cu2—O2B	2.72 (5)	N4—C4	1.332 (9)
Cu2—O2A	2.781 (15)	N4—C6	1.355 (11)
Cu1—O1	2.194 (6)	C13—C14	1.507 (10)
Cu1—N5	2.015 (6)	C15—C14	1.503 (10)
Cu1—N1	2.021 (6)	C1—C4	1.423 (11)
Cu1—N3	2.005 (6)	C8—H8A	0.9300
Cu1—N7	2.032 (6)	C8—C9	1.359 (11)
O2—C13	1.265 (8)	C5—H5	0.9300
O4—C15	1.265 (9)	C5—C6	1.351 (11)
O1—H1A	0.9889	C9—H9	0.9300
O1—H1B	0.9906	C12—H12	0.9300
O5—C15	1.238 (8)	C12—C11	1.340 (11)
N5—C7	1.316 (9)	C11—H11	0.9300
N5—C8	1.371 (10)	C6—H6A	0.9300
O3—C13	1.226 (8)	C2—H2A	0.9300
N1—C1	1.333 (9)	C2—C3	1.353 (11)
N1—C2	1.369 (10)	C3—H3	0.9300
N3—C4	1.321 (10)	O1W—H1WA	0.8483
N3—C5	1.376 (10)	O1W—H1WB	0.8499
N7—C10	1.336 (9)	Cl1B—O2B	1.426 (8)
N7—C11	1.368 (10)	Cl1B—O1A	1.423 (8)
N8—H8	0.8600	Cl1B—O4B	1.417 (8)
N8—C10	1.316 (10)	Cl1B—O3B	1.421 (8)
N8—C12	1.370 (11)	O1A—Cl1A	1.414 (7)
N2—H2	0.8600	O4A—Cl1A	1.422 (7)
N2—C1	1.334 (10)	Cl1A—O3A	1.391 (7)
N2—C3	1.358 (10)	Cl1A—O2A	1.427 (7)
N6—H6	0.8600

O2—Cu2—O2ⁱ	87.6 (3)	O2—C13—C14	121.0 (6)
O2—Cu2—O2B	82.0 (6)	O3—C13—O2	122.7 (7)
O2ⁱ—Cu2—O2B	88.7 (10)	O3—C13—C14	116.1 (7)
O2ⁱ—Cu2—O2A	79.5 (3)	O4—C15—C14	122.4 (6)
O2—Cu2—O2A	79.8 (2)	O5—C15—O4	122.3 (6)
O4ⁱ—Cu2—O2	161.4 (2)	O5—C15—C14	115.3 (7)
O4ⁱ—Cu2—O2ⁱ	95.9 (2)	N7—C10—C7	116.9 (7)
O4—Cu2—O2	95.89 (19)	N8—C10—N7	111.4 (7)
O4—Cu2—O2ⁱ	161.4 (2)	N8—C10—C7	131.7 (6)
O4ⁱ—Cu2—O4	86.6 (3)	N1—C1—N2	110.8 (7)
O4—Cu2—O2B	73.7 (10)	N1—C1—C4	117.3 (6)
O4ⁱ—Cu2—O2B	116.3 (7)	N2—C1—C4	131.8 (7)
O4ⁱ—Cu2—O2A	118.8 (2)	N3—C4—N4	110.5 (7)
O4—Cu2—O2A	83.2 (3)	N3—C4—C1	116.9 (6)
N5—Cu1—O1	94.9 (2)	N4—C4—C1	132.5 (7)
N5—Cu1—N1	97.5 (2)	N5—C8—H8A	126.0
N5—Cu1—N7	81.8 (3)	C9—C8—N5	108.0 (7)
N1—Cu1—O1	100.2 (2)	C9—C8—H8A	126.0
N1—Cu1—N7	155.6 (3)	N3—C5—H5	126.1
N3—Cu1—O1	91.6 (3)	C6—C5—N3	107.9 (7)
N3—Cu1—N5	173.5 (3)	C6—C5—H5	126.1
N3—Cu1—N1	81.7 (2)	N6—C9—H9	126.5
N3—Cu1—N7	96.2 (3)	C8—C9—N6	107.0 (7)
N7—Cu1—O1	104.2 (2)	C8—C9—H9	126.5
C13—O2—Cu2	126.5 (4)	N8—C12—H12	126.7
C15—O4—Cu2	126.4 (4)	C11—C12—N8	106.7 (8)
Cu1—O1—H1A	115.5	C11—C12—H12	126.7
Cu1—O1—H1B	116.4	N7—C11—H11	125.2
H1A—O1—H1B	97.9	C12—C11—N7	109.6 (8)
C7—N5—Cu1	112.5 (5)	C12—C11—H11	125.2
C7—N5—C8	106.6 (6)	C15—C14—C13	122.3 (7)
C8—N5—Cu1	140.8 (5)	N4—C6—H6A	126.3
C1—N1—Cu1	111.3 (5)	C5—C6—N4	107.5 (7)
C1—N1—C2	105.8 (6)	C5—C6—H6A	126.3
C2—N1—Cu1	142.8 (5)	N1—C2—H2A	125.6
C4—N3—Cu1	112.6 (5)	C3—C2—N1	108.8 (7)
C4—N3—C5	106.6 (6)	C3—C2—H2A	125.6
C5—N3—Cu1	140.8 (5)	N2—C3—H3	126.4
C10—N7—Cu1	111.4 (5)	C2—C3—N2	107.2 (7)
C10—N7—C11	105.0 (6)	C2—C3—H3	126.4
C11—N7—Cu1	143.5 (5)	H1WA—O1W—H1WB	104.6
C10—N8—H8	126.4	O1A—Cl1B—O2B	102 (2)
C10—N8—C12	107.3 (6)	O4B—Cl1B—O2B	107 (2)
C12—N8—H8	126.4	O4B—Cl1B—O1A	127 (2)
C1—N2—H2	126.3	O4B—Cl1B—O3B	108 (2)
C1—N2—C3	107.3 (6)	O3B—Cl1B—O2B	104 (2)
C3—N2—H2	126.3	O3B—Cl1B—O1A	106.4 (19)
C7—N6—H6	126.4	Cl1B—O2B—Cu2	114 (2)
C7—N6—C9	107.3 (6)	O1A—Cl1A—O4A	108.9 (7)
C9—N6—H6	126.4	O1A—Cl1A—O2A	104.8 (8)
N5—C7—N6	111.2 (7)	O4A—Cl1A—O2A	109.6 (7)
N5—C7—C10	117.4 (6)	O3A—Cl1A—O1A	109.1 (9)
N6—C7—C10	131.4 (7)	O3A—Cl1A—O4A	113.7 (10)
C4—N4—H4	126.2	O3A—Cl1A—O2A	110.3 (10)
C4—N4—C6	107.5 (7)	Cl1A—O2A—Cu2	107.8 (7)
C6—N4—H4	126.2

Cu2—O2—C13—O3	−166.7 (6)	N6—C7—C10—N8	2.2 (15)
Cu2—O2—C13—C14	16.8 (11)	C7—N5—C8—C9	−1.0 (9)
Cu2—O4—C15—O5	−172.5 (6)	C7—N6—C9—C8	0.1 (9)
Cu2—O4—C15—C14	5.7 (12)	C10—N7—C11—C12	−0.2 (10)
Cu1—N5—C7—N6	177.4 (5)	C10—N8—C12—C11	−0.6 (9)
Cu1—N5—C7—C10	0.0 (8)	C1—N1—C2—C3	−0.1 (10)
Cu1—N5—C8—C9	−175.6 (7)	C1—N2—C3—C2	0.5 (10)
Cu1—N1—C1—N2	179.0 (5)	C4—N3—C5—C6	0.0 (10)
Cu1—N1—C1—C4	−3.8 (9)	C4—N4—C6—C5	−1.1 (11)
Cu1—N1—C2—C3	−177.9 (7)	C8—N5—C7—N6	1.1 (9)
Cu1—N3—C4—N4	178.0 (6)	C8—N5—C7—C10	−176.3 (7)
Cu1—N3—C4—C1	0.6 (10)	C5—N3—C4—N4	−0.7 (10)
Cu1—N3—C5—C6	−178.1 (7)	C5—N3—C4—C1	−178.1 (8)
Cu1—N7—C10—N8	−179.6 (5)	C9—N6—C7—N5	−0.8 (9)
Cu1—N7—C10—C7	−0.9 (9)	C9—N6—C7—C10	176.2 (8)
Cu1—N7—C11—C12	178.9 (7)	C12—N8—C10—N7	0.5 (9)
O2—C13—C14—C15	−28.3 (14)	C12—N8—C10—C7	−177.9 (8)
O4—C15—C14—C13	16.3 (15)	C11—N7—C10—N8	−0.2 (9)
O5—C15—C14—C13	−165.4 (9)	C11—N7—C10—C7	178.5 (7)
N5—C7—C10—N7	0.6 (10)	C6—N4—C4—N3	1.2 (10)
N5—C7—C10—N8	179.0 (8)	C6—N4—C4—C1	178.0 (9)
N5—C8—C9—N6	0.5 (10)	C2—N1—C1—N2	0.4 (9)
O3—C13—C14—C15	155.0 (9)	C2—N1—C1—C4	177.7 (7)
N1—C1—C4—N3	2.2 (12)	C3—N2—C1—N1	−0.6 (10)
N1—C1—C4—N4	−174.5 (9)	C3—N2—C1—C4	−177.3 (9)
N1—C2—C3—N2	−0.3 (10)	O1A—Cl1B—O2B—Cu2	−13 (2)
N3—C5—C6—N4	0.7 (11)	O1A—Cl1A—O2A—Cu2	25.6 (7)
N8—C12—C11—N7	0.5 (10)	O4B—Cl1B—O2B—Cu2	−148 (2)
N2—C1—C4—N3	178.7 (9)	O3B—Cl1B—O2B—Cu2	98 (3)
N2—C1—C4—N4	2.1 (17)	O4A—Cl1A—O2A—Cu2	−91.2 (7)
N6—C7—C10—N7	−176.2 (8)	O3A—Cl1A—O2A—Cu2	142.9 (9)

Symmetry code: (i) −x, y, −z+3/2.

Bis(2,2'-biimidazole-κ²N,N')copper(II) bis[bis(2,2'-biimidazole-κ²N,N')(2-carboxyacetato-κO²)(malonato-κO)copper(II)] 13-hydrate (4) top

Crystal data top

[Cu(C₆H₆N₄)₂][Cu(C₃H₂O₄)(C₃H₃O₄)(C₆H₆N₄)₂]·13H₂O	F(000) = 1694
M_r = 1639.91	D_x = 1.721 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 7.7912 (6) Å	Cell parameters from 12816 reflections
b = 12.5972 (10) Å	θ = 1.7–27.9°
c = 32.481 (3) Å	µ = 1.11 mm⁻¹
β = 96.802 (2)°	T = 298 K
V = 3165.5 (4) Å³	Block, green
Z = 2	0.14 × 0.11 × 0.09 mm

Data collection top

4-circle diffractometer	2735 reflections with I > 2σ(I)
ω scans	R_int = 0.153
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	θ_max = 25.0°, θ_min = 2.1°
T_min = 0.557, T_max = 1.000	h = −9→7
33363 measured reflections	k = −14→14
5454 independent reflections	l = −37→37

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.070	H-atom parameters constrained
wR(F²) = 0.179	w = 1/[σ²(F_o²) + (0.0623P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
5454 reflections	Δρ_max = 0.46 e Å⁻³
413 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.77333 (10)	0.13334 (6)	0.24077 (3)	0.0439 (3)
Cu2	1.000000	0.000000	0.000000	0.0532 (4)
O1	0.4231 (7)	0.2137 (4)	0.3880 (2)	0.085 (2)
O2	0.6020 (6)	0.3487 (4)	0.39351 (17)	0.0591 (14)
H2	0.707406	0.354219	0.395055	0.089*
O3	0.5425 (6)	0.0973 (4)	0.30181 (16)	0.0491 (12)
O4	0.6185 (7)	0.0128 (4)	0.36139 (16)	0.0635 (15)
O5	1.1145 (6)	−0.0666 (4)	0.12665 (16)	0.0620 (15)
O6	1.1400 (6)	0.0668 (4)	0.08355 (17)	0.0589 (14)
O7	1.0180 (6)	0.1638 (4)	0.19198 (16)	0.0516 (13)
O8	0.9569 (7)	0.2617 (4)	0.13543 (16)	0.0709 (16)
N11	0.7413 (6)	−0.0229 (4)	0.23463 (17)	0.0393 (14)
N21	0.7972 (6)	−0.1807 (4)	0.26323 (18)	0.0404 (14)
H21	0.840359	−0.228932	0.280138	0.048*
N31	0.9470 (6)	0.0896 (4)	0.28917 (17)	0.0396 (14)
N41	1.0400 (7)	−0.0443 (4)	0.32994 (17)	0.0433 (14)
H41	1.051288	−0.107575	0.339829	0.052*
N12	0.5954 (6)	0.1774 (4)	0.19301 (17)	0.0424 (15)
C22	0.4080 (9)	0.2237 (6)	0.1383 (2)	0.0491 (19)
H22	0.329656	0.220730	0.114395	0.059*
N32	0.7769 (6)	0.2903 (4)	0.25148 (17)	0.0382 (14)
N42	0.6642 (6)	0.4454 (4)	0.23369 (17)	0.0392 (14)
H42	0.602586	0.493598	0.220267	0.047*
N13	0.9649 (7)	−0.1431 (5)	0.02380 (19)	0.0558 (17)
N23	0.8059 (7)	−0.2409 (5)	0.06113 (18)	0.0550 (17)
H23	0.724183	−0.258943	0.075337	0.066*
N33	0.7782 (7)	0.0303 (5)	0.02232 (18)	0.0490 (16)
N43	0.5775 (7)	−0.0284 (5)	0.05859 (17)	0.0466 (15)
H43	0.521203	−0.070728	0.072873	0.056*
C11	0.6513 (8)	−0.0999 (5)	0.2108 (2)	0.0406 (17)
H11	0.578360	−0.087589	0.186441	0.049*
C21	0.6858 (8)	−0.1958 (6)	0.2283 (2)	0.0458 (19)
H21A	0.641424	−0.260554	0.218206	0.055*
C31	0.8266 (8)	−0.0755 (6)	0.2662 (2)	0.0385 (17)
C41	0.9376 (8)	−0.0131 (6)	0.2960 (2)	0.0368 (16)
C61	1.1226 (8)	0.0453 (6)	0.3456 (2)	0.0442 (18)
H61	1.203023	0.049473	0.369117	0.053*
C51	1.0653 (8)	0.1267 (6)	0.3206 (2)	0.0404 (17)
H51	1.100629	0.196929	0.324062	0.048*
C12	0.4895 (8)	0.1407 (5)	0.1590 (2)	0.0442 (18)
H12	0.475909	0.069749	0.151272	0.053*
N22	0.4644 (7)	0.3122 (4)	0.15983 (17)	0.0445 (15)
H22A	0.434078	0.376377	0.153489	0.053*
C32	0.5755 (8)	0.2826 (5)	0.1927 (2)	0.0383 (17)
C42	0.6698 (8)	0.3430 (6)	0.2243 (2)	0.0387 (17)
C62	0.7769 (8)	0.4587 (6)	0.2692 (2)	0.0412 (17)
H62	0.801630	0.522337	0.283175	0.049*
C52	0.8451 (8)	0.3633 (5)	0.2801 (2)	0.0396 (17)
H52	0.924760	0.349321	0.303071	0.048*
C13	1.0359 (11)	−0.2444 (7)	0.0294 (3)	0.078 (3)
H13	1.135714	−0.267092	0.018982	0.094*
C23	0.9401 (11)	−0.3045 (7)	0.0521 (3)	0.076 (3)
H23A	0.960210	−0.374784	0.060036	0.091*
C33	0.8254 (9)	−0.1453 (6)	0.0438 (2)	0.0484 (19)
C43	0.7236 (9)	−0.0503 (6)	0.0430 (2)	0.0456 (19)
C63	0.5335 (9)	0.0720 (6)	0.0479 (2)	0.051 (2)
H63	0.437314	0.108917	0.054678	0.061*
C53	0.6563 (10)	0.1089 (7)	0.0256 (2)	0.059 (2)
H53	0.658527	0.176452	0.014133	0.071*
C1	0.5572 (10)	0.2552 (6)	0.3816 (2)	0.0484 (19)
C2	0.6811 (8)	0.1960 (5)	0.3577 (2)	0.0480 (19)
H2A	0.713005	0.241331	0.335642	0.058*
H2B	0.785426	0.180283	0.376036	0.058*
C3	0.6074 (8)	0.0941 (6)	0.3390 (3)	0.0460 (19)
C6	0.9692 (8)	0.1753 (6)	0.1540 (3)	0.0444 (18)
C5	0.9172 (8)	0.0752 (5)	0.1285 (2)	0.0492 (19)
H5A	0.867439	0.024029	0.145962	0.059*
H5B	0.829438	0.093666	0.105896	0.059*
C4	1.0685 (8)	0.0253 (6)	0.1110 (2)	0.0415 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0486 (5)	0.0299 (5)	0.0510 (6)	0.0020 (4)	−0.0029 (4)	−0.0024 (4)
Cu2	0.0491 (8)	0.0576 (10)	0.0553 (9)	−0.0045 (6)	0.0168 (6)	0.0101 (7)
O1	0.064 (4)	0.071 (4)	0.130 (5)	−0.031 (3)	0.056 (4)	−0.055 (4)
O2	0.056 (3)	0.046 (4)	0.080 (4)	−0.005 (3)	0.028 (3)	−0.017 (3)
O3	0.055 (3)	0.040 (3)	0.051 (4)	0.005 (2)	0.002 (2)	−0.003 (3)
O4	0.096 (4)	0.037 (3)	0.055 (4)	−0.005 (3)	−0.002 (3)	0.001 (3)
O5	0.076 (4)	0.055 (4)	0.059 (4)	0.022 (3)	0.023 (3)	0.021 (3)
O6	0.058 (3)	0.046 (3)	0.077 (4)	−0.001 (2)	0.021 (3)	0.010 (3)
O7	0.062 (3)	0.042 (3)	0.046 (3)	0.001 (2)	−0.013 (2)	−0.006 (3)
O8	0.129 (5)	0.037 (4)	0.042 (4)	0.009 (3)	−0.008 (3)	−0.004 (3)
N11	0.045 (3)	0.031 (4)	0.042 (4)	−0.005 (3)	0.006 (3)	−0.004 (3)
N21	0.046 (3)	0.023 (4)	0.054 (4)	0.003 (2)	0.010 (3)	0.002 (3)
N31	0.039 (3)	0.032 (4)	0.049 (4)	0.001 (2)	0.006 (3)	−0.004 (3)
N41	0.048 (3)	0.038 (4)	0.044 (4)	0.002 (3)	0.004 (3)	0.002 (3)
N12	0.039 (3)	0.035 (4)	0.050 (4)	−0.002 (2)	−0.007 (3)	−0.003 (3)
C22	0.061 (5)	0.033 (5)	0.048 (5)	0.000 (4)	−0.013 (4)	−0.009 (4)
N32	0.042 (3)	0.025 (3)	0.049 (4)	−0.003 (3)	0.012 (3)	−0.008 (3)
N42	0.040 (3)	0.030 (4)	0.047 (4)	0.004 (2)	0.003 (3)	−0.001 (3)
N13	0.056 (4)	0.056 (5)	0.059 (4)	−0.003 (3)	0.023 (3)	0.009 (4)
N23	0.064 (4)	0.048 (4)	0.057 (4)	−0.004 (3)	0.028 (3)	0.015 (3)
N33	0.043 (4)	0.053 (4)	0.050 (4)	−0.009 (3)	0.006 (3)	−0.004 (3)
N43	0.047 (4)	0.048 (4)	0.045 (4)	−0.008 (3)	0.005 (3)	0.006 (3)
C11	0.049 (4)	0.024 (4)	0.047 (5)	0.003 (3)	0.000 (3)	−0.002 (4)
C21	0.038 (4)	0.032 (5)	0.067 (6)	−0.006 (3)	0.005 (4)	−0.010 (4)
C31	0.036 (4)	0.033 (5)	0.048 (5)	0.001 (3)	0.013 (3)	0.004 (4)
C41	0.031 (4)	0.039 (5)	0.040 (5)	−0.001 (3)	0.003 (3)	−0.007 (4)
C61	0.047 (4)	0.041 (5)	0.043 (5)	−0.003 (3)	0.002 (3)	−0.002 (4)
C51	0.041 (4)	0.036 (5)	0.043 (5)	−0.006 (3)	0.000 (3)	−0.006 (4)
C12	0.059 (4)	0.026 (4)	0.046 (5)	0.003 (3)	−0.003 (3)	−0.015 (4)
N22	0.049 (4)	0.033 (4)	0.051 (4)	0.000 (3)	0.005 (3)	−0.002 (3)
C32	0.035 (4)	0.027 (5)	0.054 (5)	0.002 (3)	0.009 (3)	−0.001 (4)
C42	0.043 (4)	0.034 (5)	0.040 (5)	−0.005 (3)	0.008 (3)	−0.006 (4)
C62	0.050 (4)	0.040 (5)	0.035 (4)	−0.014 (3)	0.007 (3)	−0.007 (4)
C52	0.039 (4)	0.032 (4)	0.050 (5)	0.000 (3)	0.013 (3)	0.002 (4)
C13	0.094 (7)	0.055 (6)	0.096 (8)	0.005 (5)	0.051 (6)	0.014 (5)
C23	0.086 (6)	0.052 (6)	0.098 (7)	0.013 (5)	0.043 (5)	0.035 (5)
C33	0.049 (5)	0.051 (6)	0.046 (5)	−0.009 (4)	0.007 (4)	0.008 (4)
C43	0.045 (5)	0.053 (5)	0.040 (5)	−0.009 (4)	0.010 (3)	0.003 (4)
C63	0.049 (5)	0.048 (5)	0.058 (5)	−0.006 (4)	0.008 (4)	−0.002 (4)
C53	0.059 (5)	0.066 (6)	0.053 (5)	−0.013 (4)	0.013 (4)	0.012 (4)
C1	0.055 (5)	0.041 (5)	0.051 (5)	−0.007 (4)	0.013 (4)	−0.012 (4)
C2	0.044 (4)	0.029 (4)	0.075 (6)	−0.012 (3)	0.022 (4)	−0.011 (4)
C3	0.039 (4)	0.042 (5)	0.060 (6)	0.008 (3)	0.019 (4)	−0.003 (5)
C6	0.039 (4)	0.043 (5)	0.050 (5)	0.009 (3)	0.001 (3)	0.000 (4)
C5	0.051 (5)	0.045 (5)	0.052 (5)	0.001 (3)	0.005 (3)	−0.021 (4)
C4	0.044 (4)	0.042 (5)	0.039 (5)	−0.007 (3)	0.004 (3)	−0.004 (4)

Geometric parameters (Å, º) top

Cu1—O3	2.867 (5)	N13—C13	1.394 (10)
Cu1—O7	2.647 (5)	N13—C33	1.330 (8)
Cu1—N11	1.991 (5)	N23—H23	0.8600
Cu1—N31	2.025 (5)	N23—C23	1.377 (9)
Cu1—N12	2.032 (5)	N23—C33	1.345 (8)
Cu1—N32	2.007 (5)	N33—C43	1.317 (8)
Cu2—O6	2.926 (5)	N33—C53	1.384 (9)
Cu2—N13ⁱ	1.993 (6)	N43—H43	0.8600
Cu2—N13	1.993 (6)	N43—C43	1.328 (8)
Cu2—N33	1.989 (6)	N43—C63	1.345 (8)
Cu2—N33ⁱ	1.989 (6)	C11—H11	0.9300
O1—C1	1.208 (8)	C11—C21	1.349 (9)
O2—H2	0.8200	C21—H21A	0.9300
O2—C1	1.275 (8)	C31—C41	1.449 (9)
O3—C3	1.255 (8)	C61—H61	0.9300
O4—C3	1.252 (8)	C61—C51	1.351 (9)
O5—C4	1.298 (8)	C51—H51	0.9300
O6—C4	1.223 (8)	C12—H12	0.9300
O7—C6	1.256 (8)	N22—H22A	0.8600
O8—C6	1.242 (8)	N22—C32	1.344 (8)
N11—C11	1.380 (8)	C32—C42	1.413 (9)
N11—C31	1.332 (8)	C62—H62	0.9300
N21—H21	0.8600	C62—C52	1.344 (8)
N21—C21	1.358 (8)	C52—H52	0.9300
N21—C31	1.347 (8)	C13—H13	0.9300
N31—C41	1.317 (8)	C13—C23	1.343 (10)
N31—C51	1.373 (8)	C23—H23A	0.9300
N41—H41	0.8600	C33—C43	1.434 (10)
N41—C41	1.342 (8)	C63—H63	0.9300
N41—C61	1.368 (8)	C63—C53	1.350 (9)
N12—C12	1.379 (8)	C53—H53	0.9300
N12—C32	1.334 (8)	C1—C2	1.507 (9)
C22—H22	0.9300	C2—H2A	0.9700
C22—C12	1.359 (9)	C2—H2B	0.9700
C22—N22	1.361 (8)	C2—C3	1.504 (9)
N32—C42	1.319 (8)	C6—C5	1.536 (9)
N32—C52	1.369 (8)	C5—H5A	0.9700
N42—H42	0.8600	C5—H5B	0.9700
N42—C42	1.328 (8)	C5—C4	1.505 (9)
N42—C62	1.375 (8)

O7—Cu1—O3	172.90 (14)	N11—C31—C41	116.6 (6)
N11—Cu1—O3	80.28 (17)	N21—C31—C41	131.7 (7)
N11—Cu1—O7	100.02 (18)	N31—C41—N41	112.7 (6)
N11—Cu1—N31	82.7 (2)	N31—C41—C31	117.5 (6)
N11—Cu1—N12	97.3 (2)	N41—C41—C31	129.7 (7)
N11—Cu1—N32	172.0 (2)	N41—C61—H61	126.4
N31—Cu1—O3	80.58 (18)	C51—C61—N41	107.1 (6)
N31—Cu1—O7	92.40 (18)	C51—C61—H61	126.4
N31—Cu1—N12	178.8 (2)	N31—C51—H51	125.2
N12—Cu1—O3	98.29 (18)	C61—C51—N31	109.5 (6)
N12—Cu1—O7	88.72 (18)	C61—C51—H51	125.2
N32—Cu1—O3	91.91 (17)	N12—C12—H12	125.1
N32—Cu1—O7	87.97 (17)	C22—C12—N12	109.7 (6)
N32—Cu1—N31	98.0 (2)	C22—C12—H12	125.1
N32—Cu1—N12	81.8 (2)	C22—N22—H22A	125.7
N13ⁱ—Cu2—O6	92.7 (2)	C32—N22—C22	108.6 (6)
N13—Cu2—O6	87.3 (2)	C32—N22—H22A	125.7
N13ⁱ—Cu2—N13	180.0	N12—C32—N22	110.2 (6)
N33ⁱ—Cu2—O6	98.56 (18)	N12—C32—C42	118.6 (6)
N33—Cu2—O6	81.44 (18)	N22—C32—C42	131.2 (6)
N33—Cu2—N13ⁱ	97.6 (2)	N32—C42—N42	111.8 (6)
N33—Cu2—N13	82.4 (2)	N32—C42—C32	116.7 (6)
N33ⁱ—Cu2—N13	97.6 (2)	N42—C42—C32	131.4 (7)
N33ⁱ—Cu2—N13ⁱ	82.4 (2)	N42—C62—H62	126.1
N33ⁱ—Cu2—N33	180.0	C52—C62—N42	107.7 (6)
C1—O2—H2	109.5	C52—C62—H62	126.1
C3—O3—Cu1	117.2 (4)	N32—C52—H52	125.9
C4—O6—Cu2	113.7 (4)	C62—C52—N32	108.3 (6)
C6—O7—Cu1	116.7 (4)	C62—C52—H52	125.9
C11—N11—Cu1	143.2 (5)	N13—C13—H13	124.7
C31—N11—Cu1	111.7 (4)	C23—C13—N13	110.5 (7)
C31—N11—C11	104.9 (6)	C23—C13—H13	124.7
C21—N21—H21	126.7	N23—C23—H23A	127.1
C31—N21—H21	126.7	C13—C23—N23	105.9 (7)
C31—N21—C21	106.5 (6)	C13—C23—H23A	127.1
C41—N31—Cu1	110.6 (4)	N13—C33—N23	111.3 (7)
C41—N31—C51	104.8 (5)	N13—C33—C43	117.2 (7)
C51—N31—Cu1	144.3 (5)	N23—C33—C43	131.6 (7)
C41—N41—H41	127.1	N33—C43—N43	112.2 (7)
C41—N41—C61	105.8 (6)	N33—C43—C33	116.1 (7)
C61—N41—H41	127.1	N43—C43—C33	131.7 (7)
C12—N12—Cu1	144.1 (5)	N43—C63—H63	126.7
C32—N12—Cu1	110.2 (4)	N43—C63—C53	106.7 (7)
C32—N12—C12	105.6 (5)	C53—C63—H63	126.7
C12—C22—H22	127.1	N33—C53—H53	125.3
C12—C22—N22	105.9 (6)	C63—C53—N33	109.4 (7)
N22—C22—H22	127.1	C63—C53—H53	125.3
C42—N32—Cu1	112.6 (4)	O1—C1—O2	124.0 (7)
C42—N32—C52	106.2 (6)	O1—C1—C2	119.6 (7)
C52—N32—Cu1	140.9 (5)	O2—C1—C2	116.4 (6)
C42—N42—H42	127.0	C1—C2—H2A	109.0
C42—N42—C62	106.0 (6)	C1—C2—H2B	109.0
C62—N42—H42	127.0	H2A—C2—H2B	107.8
C13—N13—Cu2	143.9 (5)	C3—C2—C1	113.1 (5)
C33—N13—Cu2	111.5 (5)	C3—C2—H2A	109.0
C33—N13—C13	104.5 (6)	C3—C2—H2B	109.0
C23—N23—H23	126.1	O3—C3—C2	116.8 (7)
C33—N23—H23	126.1	O4—C3—O3	125.2 (7)
C33—N23—C23	107.8 (6)	O4—C3—C2	117.9 (8)
C43—N33—Cu2	112.7 (5)	O7—C6—C5	117.7 (7)
C43—N33—C53	104.3 (6)	O8—C6—O7	125.1 (7)
C53—N33—Cu2	143.0 (5)	O8—C6—C5	117.2 (7)
C43—N43—H43	126.2	C6—C5—H5A	109.2
C43—N43—C63	107.5 (6)	C6—C5—H5B	109.2
C63—N43—H43	126.2	H5A—C5—H5B	107.9
N11—C11—H11	125.4	C4—C5—C6	112.2 (5)
C21—C11—N11	109.3 (6)	C4—C5—H5A	109.2
C21—C11—H11	125.4	C4—C5—H5B	109.2
N21—C21—H21A	126.2	O5—C4—C5	114.7 (6)
C11—C21—N21	107.6 (6)	O6—C4—O5	122.6 (6)
C11—C21—H21A	126.2	O6—C4—C5	122.7 (7)
N11—C31—N21	111.6 (6)

Cu1—O3—C3—O4	−111.0 (7)	N23—C33—C43—N43	−1.5 (13)
Cu1—O3—C3—C2	67.4 (6)	N43—C63—C53—N33	−0.1 (8)
Cu1—O7—C6—O8	101.0 (7)	C11—N11—C31—N21	0.9 (7)
Cu1—O7—C6—C5	−77.7 (6)	C11—N11—C31—C41	178.2 (5)
Cu1—N11—C11—C21	−173.9 (5)	C21—N21—C31—N11	−0.8 (7)
Cu1—N11—C31—N21	176.6 (4)	C21—N21—C31—C41	−177.6 (7)
Cu1—N11—C31—C41	−6.1 (7)	C31—N11—C11—C21	−0.6 (7)
Cu1—N31—C41—N41	−174.7 (4)	C31—N21—C21—C11	0.4 (7)
Cu1—N31—C41—C31	7.1 (7)	C41—N31—C51—C61	−0.6 (7)
Cu1—N31—C51—C61	172.3 (5)	C41—N41—C61—C51	0.5 (7)
Cu1—N12—C12—C22	−175.8 (6)	C61—N41—C41—N31	−0.9 (7)
Cu1—N12—C32—N22	176.8 (4)	C61—N41—C41—C31	177.1 (6)
Cu1—N12—C32—C42	−2.2 (7)	C51—N31—C41—N41	0.9 (7)
Cu1—N32—C42—N42	175.3 (4)	C51—N31—C41—C31	−177.3 (5)
Cu1—N32—C42—C32	−1.1 (7)	C12—N12—C32—N22	−0.8 (7)
Cu1—N32—C52—C62	−173.5 (5)	C12—N12—C32—C42	−179.8 (6)
Cu2—O6—C4—O5	86.0 (7)	C12—C22—N22—C32	−0.6 (7)
Cu2—O6—C4—C5	−92.3 (7)	N22—C22—C12—N12	0.1 (8)
Cu2—N13—C13—C23	176.2 (7)	N22—C32—C42—N32	−176.5 (6)
Cu2—N13—C33—N23	−177.6 (5)	N22—C32—C42—N42	8.0 (12)
Cu2—N13—C33—C43	2.9 (8)	C32—N12—C12—C22	0.4 (8)
Cu2—N33—C43—N43	178.6 (4)	C42—N32—C52—C62	−0.2 (7)
Cu2—N33—C43—C33	−3.5 (8)	C42—N42—C62—C52	−0.6 (7)
Cu2—N33—C53—C63	−177.4 (6)	C62—N42—C42—N32	0.5 (7)
O1—C1—C2—C3	8.1 (11)	C62—N42—C42—C32	176.2 (7)
O2—C1—C2—C3	−171.0 (7)	C52—N32—C42—N42	−0.2 (7)
O7—C6—C5—C4	−89.2 (8)	C52—N32—C42—C32	−176.6 (5)
O8—C6—C5—C4	92.1 (8)	C13—N13—C33—N23	−0.1 (8)
N11—C11—C21—N21	0.1 (7)	C13—N13—C33—C43	−179.6 (7)
N11—C31—C41—N31	−0.8 (9)	C23—N23—C33—N13	0.1 (9)
N11—C31—C41—N41	−178.7 (6)	C23—N23—C33—C43	179.4 (8)
N21—C31—C41—N31	175.9 (6)	C33—N13—C13—C23	0.1 (10)
N21—C31—C41—N41	−2.0 (12)	C33—N23—C23—C13	0.0 (10)
N41—C61—C51—N31	0.1 (7)	C43—N33—C53—C63	−0.2 (8)
N12—C32—C42—N32	2.3 (9)	C43—N43—C63—C53	0.3 (8)
N12—C32—C42—N42	−173.2 (6)	C63—N43—C43—N33	−0.5 (8)
C22—N22—C32—N12	0.9 (7)	C63—N43—C43—C33	−178.0 (7)
C22—N22—C32—C42	179.7 (7)	C53—N33—C43—N43	0.4 (8)
N42—C62—C52—N32	0.5 (7)	C53—N33—C43—C33	178.4 (6)
N13—C13—C23—N23	−0.1 (11)	C1—C2—C3—O3	96.6 (8)
N13—C33—C43—N33	0.4 (10)	C1—C2—C3—O4	−84.8 (8)
N13—C33—C43—N43	177.8 (7)	C6—C5—C4—O5	112.4 (7)
N23—C33—C43—N33	−178.9 (7)	C6—C5—C4—O6	−69.2 (9)

Symmetry code: (i) −x+2, −y, −z.

Acknowledgements

This project has been partially funded by FONACIT. The Frank Allen International Research & Education Programme (FAIRE) of the Cambridge Crystallographic Data Centre (CCDC) made access to the Cambridge Structural Database (CSD) possible. The authors declare that there are no conflicts of interest.

Funding information

The following funding is acknowledged: Fondo Nacional de Ciencia Tecnología e Innovación (project No. Lab-97000821).

References

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crystallography in latin america\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Multivalent hy­dro­gen-bonded architectures directed by self-com­plementarity between [Cu(2,2′-bi­imid­az­ole)] and malonate building blocks

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

2.2. Refinement

2.3. Computational calculations

3. Results and discussion

4. Conclusions

Supporting information

Acknowledgements

Funding information

References

crystallography in latin america

Multivalent hydrogen-bonded architectures directed by self-complementarity between [Cu(2,2′-biimidazole)] and malonate building blocks