Coordination structure and inter­molecular inter­actions in copper(II) acetate com­plexes with 1,10-phenanthroline and 2,2′-bi­py­ri­dine

Guimaraes, S.P.; Dos Santos, L.H.R.; Rodrigues, B.L.

doi:10.1107/S2053229624007617

crystallography in latin america

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 80| Part 9| September 2024| Pages 505-513

https://doi.org/10.1107/S2053229624007617

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Coordination structure and intermolecular interactions in copper(II) acetate complexes with 1,10-phenanthroline and 2,2′-bipyridine

Samuel P. Guimaraes,^a Leonardo H. R. Dos Santos ^a and Bernardo L. Rodrigues ^a ^*

^aDepartment of Chemistry, Federal University of Minas Gerais, Avenida Antonio Carlos, 6627 Pampulha, Belo Horizonte – MG, CEP 31270-901, Brazil
^*Correspondence e-mail: bernardo@qui.ufmg.br

Edited by M. Rosales-Hoz, Cinvestav, Mexico (Received 29 May 2024; accepted 1 August 2024; online 23 August 2024)

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

The crystal structures of two coordination compounds, (acetato-κO)(2,2′-bipyridine-κ²N,N′)(1,10-phenanthroline-κ²N,N′)copper(II) acetate hexahydrate, [Cu(C₂H₃O₂)(C₁₀H₈N₂)(C₁₂H₈N₂)](C₂H₃O₂)·6H₂O or [Cu(bipy)(phen)Ac]Ac·6H₂O, and (acetato-κO)bis(2,2′-bipyridine-κ²N,N′)copper(II) acetate–acetic acid–water (1/1/3), [Cu(C₂H₃O₂)(C₁₀H₈N₂)₂](C₂H₃O₂)·C₂H₄O₂·3H₂O or [Cu(bipy)₂Ac]Ac·HAc·3H₂O, are reported and compared with the previously published structure of [Cu(phen)₂Ac]Ac·7H₂O (phen is 1,10-phenanthroline, bipy for 2,2′-bipyridine, ac is acetate and Hac is acetic acid). The geometry around the metal centre is pentacoordinated, but highly distorted in all three cases. The coordination number and the geometric distortion are both discussed in detail, and all complexes belong to the space group P $[\overline{1}]$ . The analysis of the geometric parameters and the Hirshfeld surface properties d_norm and curvedness provide information about the metal–ligand interactions in these complexes and allow comparison with similar systems.

Keywords: crystal structure; distorted geometry; Hirshfeld surface analysis; curvedness; d_norm; copper complexes; bipyridine; phenanthroline.

CCDC references: 2375111; 2375112; 2379507; 2379508; 2379509; 2379510

1. Introduction

The biological activities of metal complexes is a well studied topic in chemistry. The antimicrobial activities of copper complexes with chelated ligands such as 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) have been reported in the literature (Agwara et al., 2010 ; Vignesh et al., 2012 ). Potentially correlated with such biochemical behaviour is the fact that the coordination geometry around the copper centre is distorted. The distortion can be significant also when an acetate anion is additionally coordinated to the metal centre (Lobana et al., 2014 ). These systems are interesting from a structural point of view because the deviation from the expected and usual coordination polyhedra may shed some light on the chemical origin of the overall distortion and on the nature of the coordination.

Acetate can coordinate in several different ways in a metal complex: monodentate or bidentate, to one or more metal centres, forming usual coordination geometry (e.g. octahedral) around the metal or highly distorting the metal coordination, for example, when coordinating as a chelating ligand. The metal–acetate interaction may be one of the reasons which forces a distorted geometry in the structures discussed in this study. The distortion presented here is similar to cases already reported in other complexes with bipyridine and nitrate (Hisayoshi, 1980 ), as well as in systems having other functional groups containing two O atoms covalently bonded to the same atom within the ligand (Zhong, 2011 , 2012 ). It is also possible to rationalize the acetate effect by comparing the structures of this study with other complexes having three coordinated phen or bipy ligands, which also cause distortions but in a different way; while [Cu(phen)₃](ClO₄)₂ (Hu et al., 2009 ) is hexacoordinated and has two elongated Cu—O bonds trans to each other (with Cu—O around 2.30 Å), [Cu(bipy)₃](ClO₄)₂ (Liu et al., 1991 ) shows one shorter (2.23 Å) and another more elongated Cu—O distance of 2.469 Å, suggesting the Cu atom in this complex should be pentacoordinated. The other Cu—N distances for both complexes are around 2.0 Å.

It is relevant to understand the mechanism by which these structures become distorted (Pinto et al., 2020a ). Therefore, in addition to the more traditional geometric properties, it is important to consider features of the Hirshfeld surface (HS) (Hirshfeld, 1977 ) around the metal. This study promotes a discussion (a) on the general shape of the Hirshfeld surfaces and (b) on the local properties d_norm and curvedness of the surfaces (Spackman & Jayatilaka, 2009 ) in the direction of the M—O interactions. The d_norm property is defined by Spackman & Jayatilaka (2009):

$[d_{\rm norm} = {{d_{\rm i} - r_{\rm i}^{\rm vdW}}\over{r_{\rm i}^{\rm vdW}}} +{{d_{\rm e} - r_{\rm e}^{\rm vdW}}\over{r_{\rm e}^{\rm vdW}}} \eqno(1)]$

The d_norm property is a measure of the distance between the closest atoms inside (d_i) and outside (d_e) each point of the Hirshfeld surface in comparison to the van der Waals radii (r_i^vdW and r_e^vdW) of these atoms. The d_norm value is negative for contacts shorter than the sum of the van der Waals radii and positive for contacts longer than that sum.

The curvedness (C) is defined by:

$[C = {{2}\over{\pi}}\ln \sqrt{{{k_1^2 + k_2^2}\over{2}}} \eqno(2)]$

C is a measure of the curvature of the HS in terms of the principal curvatures k₁ and k₂. Complementary surfaces (such as the Hirshfeld surfaces of bonded atoms) should have the same values of C.

This article reports the structures of copper complexes with (a) one bipy, one phen and one acetate ligand, namely, (acetato-κO)(2,2′-bipyridine-κ²N,N′)(1,10-phenanthroline-κ²N,N′)copper(II) acetate hexahydrate, (I) (see Scheme 1), and (b) two bipy and one acetate ligand, namely, (acetato-κO)bis(2,2′-bipyridine-κ²N,N′)copper(II) acetate–acetic acid–water (1/1/3), (III) (see Scheme 2). Together with a previously published complex with two phen and one acetate ligand, (II) (Jing et al., 2011 ), these complexes are discussed herein. The structure in each case is unique because of the different proportions of the bipy and phen ligands, and the way the acetate ligand coordinates in each complex.

2. Experimental

2.1. Synthesis and crystallization

2.1.1. [Cu(bipy)(phen)(Ac)]Ac·6H₂O, (I)

A mixture was prepared containing ethanol (20.0 ml), acetic acid (0.5 ml), copper acetate monohydrate (0.99 mmol, 0.198 g), 2,2′-bipyridine (1.29 mmol, 0.201 g) and 1,10-phenanthroline (0.70 mmol, 0.127 g). The mixture was stirred for 1 h at room temperature. Afterward, the resulting solution was filtered and left to crystallize. Blue single crystals of (I) (Fig. 1) had formed in the solution after one month.

Figure 1
The asymmetric unit of [Cu(bipy)(phen)Ac]Ac·6H₂O, (I)

, drawn with 50% probability displacement ellipsoids.

2.1.2. [Cu(phen)₂Ac]Ac·7H₂O, (II)

The previously reported structure (Jing et al., 2011) is herein revisited and discussed because it completes the series (Fig. 2). The data presented here for this system were taken from the original publication.

Figure 2
The asymmetric unit of [Cu(phen)₂Ac]Ac·7H₂O, (II), drawn with 50% probability displacement ellipsoids from previously published data (Jing et al., 2011

; CCDC deposition No. 820064).

2.1.3. [Cu(bipy)₂Ac]Ac·HAc·3H₂O, (III)

Single crystals of (III) (Fig. 3) were obtained from a solution of ethanol (18.0 ml) and water (2.0 ml) containing acetic acid (0.5 ml), copper acetate monohydrate (1.58 mmol, 0.316 g) and 2,2′-bipyridine (1.29 mmol, 0.201 g). The solution was mixed for 1 h at room temperature, filtered and left to rest to crystallize. A month later, blue crystals had formed at the bottom and on the walls of the beaker.

Figure 3
The asymmetric unit of [Cu(bipy)₂(Ac)]Ac·HAc·3H₂O, (III)

, drawn with 50% probability displacement ellipsoids.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms in both systems were fixed or assigned from residual density. The positional and vibrational parameters were fixed for all H atoms.

Table 1
Experimental details

For both structures: triclinic, P $[\overline{1}]$ , Z = 2. Experiments were carried out at 293 K for (I) and 150 K for (III) using a Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix 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.

	(I)	(III)
Crystal data
Chemical formula	[Cu(C₂H₃O₂)(C₁₀H₈N₂)(C₁₂H₈N₂)](C₂H₃O₂)·6H₂O	[Cu(C₂H₃O₂)(C₁₀H₈N₂)₂](C₂H₃O₂)·C₂H₄O₂·3H₂O
M_r	626.12	608.09
a, b, c (Å)	8.1778 (1), 12.3323 (1), 15.9879 (2)	11.0826 (18), 11.1840 (19), 12.1880 (18)
α, β, γ (°)	69.166 (1), 77.689 (1), 88.572 (1)	86.537 (1), 69.820 (1), 83.261 (1)
V (Å³)	1470.03 (3)	1407.8 (4)
Radiation type	Cu Kα	Mo Kα
μ (mm⁻¹)	1.57	0.83
Crystal size (mm)	0.29 × 0.13 × 0.07	0.13 × 0.07 × 0.06

Data collection
T_min, T_max	0.758, 1.000	0.995, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	57004, 6248, 5734	36611, 7452, 6436
R_int	0.040	0.029
(sin θ/λ)_max (Å⁻¹)	0.638	0.718

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.135, 0.86	0.030, 0.082, 1.05
No. of reflections	6248	7452
No. of parameters	378	364
No. of restraints	20	4
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.52	0.42, −0.37
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SIR92 (Altomare et al., 1994 ), SHELXL2018 (Sheldrick, 2015 ), and ORTEP-3 for Windows (Farrugia, 2012 ).

3. Results and discussion

3.1. Coordination and geometry

Compounds (I)–(III) show distorted coordination geometries for the metal atom. The Cu atom is bonded to two nitrogenated ligands (1,10-phenanthroline and/or 2,2′-bipyridine) in a chelating manner and to one O atom (O2) from an acetate ligand. The second acetate O atom (O1) interacts with the Cu atom with distances over 2.6 Å for all three cases. This interaction plays a fundamental role in distorting the geometry around the metal atom.

In all the systems, the copper coordination consists of four Cu—N bonds involving the ligands bipy and phen, as well as one Cu—O bond to the acetate ligand. The second O atom of the acetate is further from the Cu atom (Figs. 1, 2 and 3), with the Cu⋯O1 distances varying from 2.6404 (1) Å for (II) to 2.859 (1) Å for (III).

The Cu—N bond lengths for the three complexes are within the interval from 2.0 to 2.2 Å (Tables 2, 3 and 4). Interestingly, the longest Cu—N bond length in each complex is observed for the N atom that is located in an approximate trans position with respect to O1. In the case of bipy/phen compound (I), the longest bond length occurs between the Cu atom and a phen N atom. The angles between the planes of the rings of the bipy ligands are 5.57 (2)°. This value is intermediate compared to the angles in bipy/bipy complex (III) of 1.18 (2)° for the N1/N2 ligand and 7.76 (9)° for the N3/N4 ligand.

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

Cu1—O2	1.9594 (10)	Cu1—N2	2.0958 (12)
Cu1—N1	1.9796 (12)	Cu1—N3	2.1522 (12)
Cu1—N4	1.9810 (12)

O2—Cu1—N1	91.16 (5)	N4—Cu1—N2	96.61 (5)
O2—Cu1—N4	95.59 (5)	O2—Cu1—N3	127.23 (4)
N1—Cu1—N4	172.71 (5)	N1—Cu1—N3	94.57 (5)
O2—Cu1—N2	139.29 (4)	N4—Cu1—N3	79.16 (4)
N1—Cu1—N2	79.92 (5)	N2—Cu1—N3	93.23 (4)

Table 3
Bond lengths of the coordination of copper (Å) and the angles between these bonds (°) in [Cu(phen)₂Ac]Ac·7H₂O, (II) (Jing et al., 2011)

Cu—O2	2.001 (3)	Cu—N3	1.988 (3)
Cu—N1	1.989 (3)	Cu—N4	2.051 (3)
Cu—N2	2.191 (4)

N1—Cu—N2	79.82 (14)	N3—Cu—N4	81.55 (13)
N1—Cu—N3	177.12 (15)	O2—Cu—N1	89.98 (13)
N1—Cu—N4	96.80 (13)	O2—Cu—N2	101.51 (13)
N2—Cu—N3	98.35 (13)	O2—Cu—N3	92.58 (13)
N2—Cu—N4	106.69 (14)	O2—Cu—N4	151.73 (14)

Table 4
Selected geometric parameters (Å, °) for (III)

Cu—O2	1.9908 (16)	Cu—N1	2.0231 (19)
Cu—N2	1.9982 (18)	Cu—N4	2.2356 (18)
Cu—N3	2.0206 (19)

O2—Cu—N2	93.79 (7)	N3—Cu—N1	94.62 (7)
O2—Cu—N3	89.88 (7)	O2—Cu—N4	88.34 (6)
N2—Cu—N3	173.22 (7)	N2—Cu—N4	107.16 (7)
O2—Cu—N1	164.36 (7)	N3—Cu—N4	78.61 (7)
N2—Cu—N1	80.37 (7)	N1—Cu—N4	107.23 (7)

The acetate coordination to the metal is another feature to be discussed across the systems. One aspect that needs to be addressed is the relationship between the distances from the Cu atom to the O atoms of the acetate groups involving the clearly coordinated O2 atom and the further removed O1 atom, considering that the Cu—O1 distance is always bigger than the Cu—O2 distance. In mixed complex (I), the Cu—O2 distance is 1.9908 (16) Å, while the Cu—O1 distance is 2.742 (2) Å. For phen/phen complex (II), the distances are 2.001 (3) and 2.640 (1) Å, respectively, and for bipy/bipy complex (III), they are 1.9594 (10) and 2.859 (2) Å, respectively. It is clear that the shorter the coordinated Cu—O2 distance, the longer the Cu—O1 distance becomes. In this manner, bipy/bipy complex (III) has the smallest coordination bond and the longest Cu—O1 distance. On the other hand, phen/phen complex (II) has the longest Cu—O2 coordination bond and the shortest Cu—O1 distance.

It is possible to note that the geometry of the acetate ligand also differs from one system to another. This can be seen by analysing the distance from the acetate C atom to atoms O1 and O2, and the O1—Cu—O2 bite angle. In mixed complex (I), the C23—O1 distance is 1.231 (3) Å and the C23—O2 distance is 1.271 (3) Å. The equivalent distances are 1.242 (5)and 1.257 (5) Å for phen/phen complex (II), and 1.2396 (18) (C21—O1) and 1.2820 (17) Å (C21—O2) for bipy/bipy complex (III). These data correlate with data in the previous paragraph in such a way to indicate that the longer the C—O2 distance, the shorter the coordination Cu—O2 distance.

For the O1—Cu—O2 bite angles, the values are 54.12 (3), 52.30 (6) and 50.89 (4)°, respectively, for (II), (I) and (III). In this way, the smaller the O1—Cu—O2 bite angle, the shorter the coordination distance (Cu—O2) and the longer the C—O2 distance (Table 5).

Table 5
Selected geometric parameters over the three reported systems

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Angle between N ligands (°)	111.53 (4)	109.3 (3)	80.51 (3)
Longest bond (Å)	2.2360 (15)	2.191 (4)	2.1521 (12)
τ₅	0.148	0.423	0.557
Cu—O2 (Å)	1.991(2′	2.001 (3)	1.959 (1)
Cu—O1 (Å)	2.742 (2)	2.6404 (1)	2.859 (1)
O1—Cu—O2 (°)	52.30 (6)	54.12 (3)	50.89 (4)

Another aspect to observe in the coordination are the angles (Tables 2, 3 and 4) formed by the coordination bonds. The first consideration is that all the systems have nonconventional angles when comparing either standard square-pyramidal or standard bipyramidal–trigonal geometries. The angles can be used to calculate the `angular structural parameter' τ₅ (Addison et al., 1984 ), a parameter used to measure distortion for pentacoordinated complexes. The obtained values are 0.148 for (I), 0.423 for (II) and 0.557 for (III). These results show that the first complex is close to standard square-pyramidal geometry, while the coordination geometry in the other two complexes deviate more towards standard bipyramidal–trigonal geometry, but both are very intermediate geometries. In sequence, the HSs were generated (Fig. 4) around the Cu atom in the systems and their general shape was analysed. The shapes of the surfaces and the τ₅ values are in agreement with previously reported HSs around the Cu atom and their respective τ₅ values (Pinto et al., 2020b). In this way, the use of the HSs confirms the metal as pentacoordinated, and its shape (Fig. 4) and the τ₅ value can be taken with security as a result of the geometry and distortion index. Therefore associating these two parameters, it is possible to truly characterize the systems as distorted pentacoordinated complexes, since the τ₅ values are proved valid after confirming that the metal is pentacoordinated using the HSs.

Figure 4
d_norm Hirshfeld surfaces generated around copper in CrystalExplorer (Turner et al., 2017

; Spackman et al., 2021

) for (a) [Cu(bipy)(phen)Ac]Ac·6H₂O, (I)

, (b) [Cu(phen)₂Ac]Ac·7H₂O, (II), and (c) [Cu(bipy)₂Ac)]Ac·HAc·3H₂O, (III)

The data relating to the global properties of the surfaces, such as volume (V), area (A), globularity (G, a measure of the deviation of the surface area from the area of a sphere with the same volume) and asphericity (Ω, a measure of the surface anisotropy) can be found in Table 6. The values of G and Ω for the three compounds are somehow similar despite the differences observed for V and A. Besides the global data, it is interesting in these systems to look at the local properties d_norm and curvedness in the points where the Cu—O2 bond goes through the surfaces, and in the points where the Cu—O1 hypothetical bond would cross the surfaces (Tables 7, 8 and 9). It is possible to note that the local data on the surface around the Cu atom reinforces the tendency observed before regarding the acetate coordination across the systems for d_norm.

Table 6
Information regarding Hirshfeld surfaces generated around the Cu atoms in the title systems

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Volume (Å³)	11.25	10.53	10.85
Area (Å²)	28.78	27.97	27.71
Globularity, G	0.844	0.830	0.855
Asphericity, Ω	0.058	0.040	0.065

Table 7
Data regarding the d_norm surface generated around the Cu atoms in the title systems

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Minimum	−0.6413	−0.6476	−0.6542
Mean	−0.0391	−0.0735	−0.0611
Maximum	0.9876	0.8396	0.8727
Cu—O2 point	−0.6297	−0.6196	−0.6520
Cu—O1 point	−0.1165	−0.1858	−0.0885

Table 8
Data regarding the curvedness of the surface generated around the Cu atoms in the title systems

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Minimum	−3.6299	−3.3323	−3.4610
Mean	−0.9290	−0.9396	−0.8808
Maximum	0.9472	1.0547	0.7287
Cu—O2 point	−2.4528	−2.6100	−2.4644
Cu—O1 point	−0.7427	−0.9443	−0.6101

Table 9
Values of Hirshfeld surface properties around the coordinated acetate in the title systems

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
d_norm
O2—Cu point	−0.6293	−0.6221	−0.6508
O1—Cu point	−0.1135	−0.1865	0.0651
Curvedness
O2—Cu point	−2.3655	−2.4345	−2.3591
O1—Cu point	−0.7621	−0.8754	−0.7456

In order to understand and compare the interactions between the Cu atom and both O atoms of the coordinated acetate in each system, graphs relating interatomic distances and local HS properties were plotted [Figs. 5(a) and 5(b)], using the series data and some published data (Pinto et al., 2019 ). The values of the HS properties (d_norm and curvedness) were obtained in surface points that correspond to the directions Cu—O2 and Cu—O1 in the copper and acetate surfaces. The values of these points reproduce well previous studies correlating the values of the properties with the distances between the atoms (Pinto et al., 2019).

Figure 5
(a) d_norm and (b) curvedness values in the Cu—O directions for the Hirshfeld surfaces generated around the Cu atoms (Cu surfaces) and acetate groups (O surfaces). The points for the series are highlighted in red (O surfaces) and blue (Cu surfaces).

Remarkably, this comparison using the copper surfaces and the acetate surfaces is interesting for understanding especially the effectiveness of the interactions between atoms Cu and O1 in the systems, which can be easily visualized in the graphs as very different across the three structures. For (III), with Cu—O1 = 2.859 (1) Å, the curvedness on the Cu surface is bigger than the curvedness on the acetate surface and the values present a significant difference, while for (II), with Cu—O1 = 2.640 (1) Å, the C values show the opposite behaviour in terms of which surface presents the greater value, but the values are closer to each other. The C values observed on both surfaces for (I) are also very close to each other, suggesting the complementarity of the surfaces in the Cu—O1 direction. This suggests a Cu—O1 interaction that is more effective in these systems in comparison with (III). The complementary aspect of the surfaces indicates the effectiveness of the interaction, and the inversion over the distance indicates that at some point around these distances, there is an inflection point for the curvedness values between both surfaces [Fig. 5(b)].

The comparison of local values for the surfaces around the Cu atom was extended to new data from complexes of the type [CuAB(OXO)], where A and B are 2,2′-bipyridine and/or 1,10-phenanthroline, and OXO is a third group with two O atoms around the Cu atom, such as, but not restricted to, acetate. The new data were obtained from a search for the structures made with Conquest (Groom & Allen, 2014 ; Groom et al., 2016 ). The search considered structures refined with Cu—O distances from 2.4 to 3.1 Å and R < 0.10.

The d_norm versus d[Cu—O1] plot shows a change in behaviour around a distance of 2.8 Å [Fig. 6(a)], similar to the previous data. Therefore, another graph was made considering only the points with Cu—O1 distances below 2.767 Å. Using this selection it was possible to fit well a linear regression for the data from the literature together with the data from our series [Fig. 6(b)], showing a great correlation. In this way, it was possible to attribute the nonlinearity of the graph d_norm versus d[Cu—O1] for long distances [Fig. 6(a)] to the fact that the external atom closest to the interest surface point is not O1 anymore but rather another neighbour within the supramolecular structure. Another way to verify this idea was by studying the curvedness property for the same systems.

Figure 6
(a) d_norm versus Cu—O distance plot relating the series of complexes of this study (red) and many other already published complexes; the Pinto et al. (2019

) data are in black. (b) Comparison for the Cu—O distances below 2.767 Å and the linear regression.

The curvedness property was analysed using the same methodology applied to the d_norm property: the plot of the values of the curvedness obtained for the Cu Hirshfeld surface in the direction of Cu—O against the Cu—O distances. The nonlinearity in the C versus d[Cu—O1] plot occurs in the same region observed for the d_norm [evidenced when comparing Fig. 7 to Fig. 6(a)]. However, the presence of a neighbouring atom besides O1 affects more d_norm than the curvedness due to the nature of the two properties: while the definition of d_norm depends only on the internal and external atoms closest to the copper HS, the definition of curvedness depends on the entire neighbourhood (Spackman & Jayatilaka, 2009). Moreover, the changes observed for the curvedness can also be traced back to the interference of atoms that are closer than the acetate O atom to the analysed point on the Hirshfeld surface of the metal centre.

Figure 7
Curvedness versus Cu—O distance graph, showing the series of complexes of this study, many other already published complexes and the Pinto et al. (2019

) data.

3.2. Intermolecular interactions

It is well known that intermolecular interactions, such as hydrogen bonds, have a huge impact on the relative positioning of some groups inside the crystal lattice. Therefore, it is important to identify the presence of these interactions in the systems.

In the asymmetric unit of (I) (Fig. 1), there are six crystallographically independent water molecules besides the acetate counter-ion. Complex (II) (Fig. 2) shows the same components, with seven water molecules instead of six. The asymmetric unit of (II) (Fig. 3) contains three water molecules, one acetate counter-ion and one acetic acid molecule. Each complex has the asymmetric unit completed by the cationic part containing the metal and the coordinated ligands.

In the mixed complex, the coordinated acetate and the acetate counter-ion are connected through hydrogen bonds linked by two water molecules. It is therefore possible to see a network of hydrogen bonds formed by the water molecules and the acetate counter-ions. For (I) and (II), two water molecules link the coordinated and the counter-ion acetates [Figs. 8a(a) and 8(b)]. Additionally, the three compounds show hydrogen-bonding networks in the ac plane involving the acetic acid molecule [for (III)], the water molecules and the acetate counter-ion (Fig. 9). The O—H⋯O-type hydrogen bonds are of medium-to-weak strength, with O⋯O distances greater than 2.69 A (see Tables S3 and S4 in the supporting information).

Figure 8
Hydrogen bonds in the asymmetric units of (a) [Cu(bipy)(phen)Ac]Ac·6H₂O, (I), (b) [Cu(phen)₂Ac]Ac·7H₂O, (II), and (c) [Cu(bipy)₂Ac)]Ac·HAc·3H₂O, (III).

Figure 9
Two-dimensional hydrogen-bond network in the ac plane, viewed down the b axis, in (a) [Cu(bipy)(phen)Ac]Ac·6H₂O, (I)

, (b) [Cu(phen)₂Ac]Ac·7H₂O, (II), and (c) [Cu(bipy)₂Ac)]Ac·HAc·3H₂O, (III)

. The cationic units have been omitted for clarity.

π–π interactions between the rings of the ligands are observed as well (Table 10). In mixed complex (I), these interactions occur between the phen rings that stack on top of each other across the crystal structure in the direction of the a axis; this feature is not observed for the bipy rings of the same system. In the case of (II), only one of the phen rings is stacked inside the unit cell with π–π interactions; this stacking also extends in the direction of the a axis. For (III), there is no continuous structure of stacked rings inside one unit cell, but on the edge of two unit cells, two bipy rings interact in this way.

Table 10
Geometric parameters (Å) for π–π interactions

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Centroid–centroid distance	3.888	3.783	3.596
Centroid–plane distance	3.463	3.493	3.380
Plane–plane distance	3.493	3.505	3.377

The presence of stacking of rings across the crystal structures (Fig. 10) is confirmed by measuring the centroid-to-centroid distances. In this case, the centroids of the ligands and the planes were made across the ligands using Mercury (Macrae et al., 2020 ). These objects were used to measure the distances corresponding to the π–π interactions. Values around 3.3 and 3.9 Å were obtained. These distances are compatible with expected values for π–π interactions.

Figure 10
Stacking of rings showing the π–π interactions in (a) [Cu(bipy)(phen)Ac]Ac·6H₂O, (I)

, (b) [Cu(phen)₂Ac]Ac·7H₂O, (II), and (c) [Cu(bipy)₂Ac)]Ac·HAc·3H₂O, (III)

HSs around the cationic part (the metal and the bonded ligands) for each complex were created to analyse the interactions. Interestingly, while (I) and (II) have around 9% of C⋯C interactions (9.2 and 9.3%, respectively), (III) has 6.1%. This is expected because of the smaller significance of π–π stacking interactions for this compound.

4. Conclusion

In this work, we have described in detail systems containing the nitrogenous ligands bipy and phen, as well as a third group with two O atoms around a Cu atom, namely, acetate. The complexes show that the longer the coordination bond to one O atom of the acetate ligand, the closer the other acetate O atom gets to the Cu atom. In other words, the weaker the Cu—O2 bond, the stronger the Cu—O1 interaction becomes. Analysing the data related to the noncoordinated O atom (O1), it was possible to note that there is a significant interaction between this atom and the Cu atom, which is reflected in the values of the Hirshfeld surface properties at the point where the Cu—O1 interaction would take place. This is one important source for the geometric distortion around the metal centre.

The discussion of the coordination of the Cu atom in these systems is not simple because the data points to the existence of an interaction between Cu and O1 mainly when the Cu—O1 distance is shorter. Therefore, it is possible to understand that the Cu—O1 interaction gets stronger as the Cu—O2 distance gets longer and that complexes with a shorter coordination bond between Cu and O2 are those that are more clearly five-coordinated. On the other hand, the shape of the HS around the Cu atom agrees well with the shapes already reported for similar five-coordinated distorted complexes (Pinto et al., 2020b ) and suggests that the Cu atom is five-coordinated for the three systems, with the coordination being approximately square-pyramidal in [Cu(bipy)(phen)Ac]Ac·5.5H₂O, (I), distorted square-pyramidal in [Cu(phen)₂Ac]Ac·7H₂O, (II), and is closest to trigonal bipyramidal in [Cu(bipy)₂Ac)]Ac·HAc·3H₂O, (III), as confirmed by the τ₅ parameter.

The present study was also important for understanding the difference in behaviour, presented in graphs relating d_norm and curvedness with distance for this type of system. The difference is caused by the proximity of another atom closer to the surface than atom O1 itself for long Cu—O1 distances.

Finally, it is important to say that this work shows the use of Hirshfeld surfaces to analyse distorted geometries, and the use of the properties of surfaces to better understand interactions between the metal atom and the ligands.

Supporting information

CCDC references: 2375111; 2375112; 2379507; 2379508; 2379509; 2379510

Crystal structure: contains datablocks I, III, global. DOI: https://doi.org/10.1107/S2053229624007617/zo3050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2053229624007617/zo3050Isup2.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2053229624007617/zo3050IIIsup3.hkl

Additional tables and hydrogen-bond data. DOI: https://doi.org/10.1107/S2053229624007617/zo3050sup4.pdf

Computing details top

(Acetato-κO)(2,2'-bipyridine-κ²N,N')(1,10-phenanthroline-κ²N,N')copper(II) acetate hexahydrate (I) top

Crystal data top

[Cu(C₂H₃O₂)(C₁₀H₈N₂)(C₁₂H₈N₂)](C₂H₃O₂)·6H₂O	Z = 2
M_r = 626.12	F(000) = 654
Triclinic, P1	D_x = 1.415 Mg m⁻³
a = 8.1778 (1) Å	Cu Kα radiation, λ = 1.54184 Å
b = 12.3323 (1) Å	Cell parameters from 33446 reflections
c = 15.9879 (2) Å	θ = 3.0–78.6°
α = 69.166 (1)°	µ = 1.57 mm⁻¹
β = 77.689 (1)°	T = 293 K
γ = 88.572 (1)°	Prism, blue
V = 1470.03 (3) Å³	0.29 × 0.13 × 0.07 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	6248 independent reflections
Radiation source: micro-focus sealed X-ray tube	5734 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.040
ω scans	θ_max = 79.5°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	h = −7→10
T_min = 0.758, T_max = 1.000	k = −15→15
57004 measured reflections	l = −20→20

Refinement top

Refinement on F²	20 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.1175P)² + 0.3778P] where P = (F_o² + 2F_c²)/3
S = 0.86	(Δ/σ)_max = 0.001
6248 reflections	Δρ_max = 0.53 e Å⁻³
378 parameters	Δρ_min = −0.52 e Å⁻³

Special details top

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

Refinement. Single crystals were selected for the diffraction experiments that were performed using the XtaLAB Synergy diffractometer equipped with a HyPix detector. Data collections were done using the software CrysAlisPro 1.171.42.62a (Rigaku OD, 2022). In sequence, the structures were solved using SIR-92 (Altomare et al., 1994) and refined with the software SHELXL (Sheldrick, 2015). The experimental details are given in Table 1.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu	0.34620 (3)	0.95913 (2)	0.23435 (2)	0.04449 (11)
N2	0.45718 (19)	0.86470 (12)	0.16164 (10)	0.0470 (3)
N3	0.23922 (19)	1.07071 (13)	0.29390 (10)	0.0485 (3)
O2	0.13253 (16)	0.86198 (11)	0.28036 (9)	0.0529 (3)
N1	0.54462 (19)	1.06922 (13)	0.15441 (10)	0.0470 (3)
C18	0.5903 (2)	0.91769 (14)	0.09431 (11)	0.0448 (3)
N4	0.39798 (18)	0.87998 (13)	0.37479 (10)	0.0483 (3)
C17	0.6407 (2)	1.03392 (14)	0.09074 (11)	0.0456 (3)
O5	0.0514 (2)	0.67497 (14)	0.45096 (11)	0.0728 (4)
C23	0.0337 (2)	0.90311 (17)	0.22638 (12)	0.0530 (4)
O1	0.0759 (2)	0.98642 (16)	0.15379 (11)	0.0771 (5)
C9	0.3257 (2)	0.94119 (16)	0.42682 (12)	0.0479 (4)
C4	0.2450 (2)	1.04500 (16)	0.38291 (12)	0.0474 (4)
C10	0.4649 (3)	0.78111 (18)	0.41548 (16)	0.0595 (5)
H10	0.514291	0.737917	0.380476	0.071*
C13	0.5854 (3)	1.17125 (17)	0.15940 (16)	0.0603 (5)
H13	0.518725	1.195910	0.203391	0.072*
C1	0.1588 (3)	1.16331 (17)	0.25307 (15)	0.0599 (5)
H1	0.153681	1.180350	0.192186	0.072*
C19	0.6739 (3)	0.86440 (18)	0.03631 (13)	0.0585 (4)
H19	0.765168	0.902394	−0.010399	0.070*
C8	0.3231 (3)	0.9070 (2)	0.52105 (13)	0.0597 (5)
C16	0.7796 (3)	1.09997 (18)	0.02952 (15)	0.0600 (5)
H16	0.843804	1.074380	−0.014606	0.072*
C12	0.3955 (3)	0.8025 (2)	0.56101 (16)	0.0741 (6)
H12	0.396757	0.776244	0.623070	0.089*
C5	0.1704 (3)	1.11354 (19)	0.43262 (15)	0.0584 (4)
C14	0.7237 (3)	1.2407 (2)	0.1011 (2)	0.0741 (6)
H14	0.750491	1.310618	0.106160	0.089*
C20	0.6190 (3)	0.7526 (2)	0.04910 (16)	0.0694 (6)
H20	0.673357	0.714943	0.010786	0.083*
C11	0.4638 (3)	0.7397 (2)	0.50936 (18)	0.0744 (7)
H11	0.509676	0.669359	0.536069	0.089*
C22	0.4057 (3)	0.75699 (17)	0.17375 (15)	0.0608 (5)
H22	0.314238	0.720331	0.220787	0.073*
C15	0.8211 (3)	1.2046 (2)	0.03528 (19)	0.0737 (6)
H15	0.914119	1.250322	−0.004956	0.088*
C3	0.0898 (3)	1.2111 (2)	0.38736 (18)	0.0685 (6)
H3	0.041406	1.259560	0.417896	0.082*
C24	−0.1396 (3)	0.8467 (2)	0.25600 (18)	0.0727 (6)
H24A	−0.220099	0.903276	0.261271	0.109*
H24B	−0.150728	0.784829	0.314326	0.109*
H24C	−0.159090	0.815998	0.211389	0.109*
C21	0.4851 (3)	0.69868 (18)	0.11814 (17)	0.0715 (6)
H21	0.447652	0.623739	0.127722	0.086*
C2	0.0825 (3)	1.23518 (19)	0.29798 (18)	0.0700 (6)
H2	0.027068	1.298981	0.267617	0.084*
C6	0.1750 (3)	1.0768 (2)	0.52851 (17)	0.0738 (6)
H6	0.126827	1.121592	0.562425	0.089*
C7	0.2482 (3)	0.9786 (3)	0.56974 (16)	0.0765 (7)
H7	0.249623	0.957304	0.631515	0.092*
O8	−0.5156 (2)	0.37513 (15)	0.23832 (12)	0.0725 (4)
O7	−0.6243 (2)	0.5185 (2)	0.33944 (13)	0.0863 (5)
O6	−0.2227 (2)	0.52867 (19)	0.47839 (13)	0.0849 (5)
O10	0.375730	0.433990	0.074441	0.0946 (6)
O4	−0.2848 (2)	0.5416 (2)	0.31665 (15)	0.0924 (6)
O3	−0.1967 (2)	0.4602 (2)	0.21364 (16)	0.0969 (6)
C26	−0.1723 (3)	0.5166 (2)	0.2604 (2)	0.0776 (6)
C25	0.0075 (4)	0.5560 (3)	0.2511 (3)	0.1105 (12)
H25A	0.075076	0.553983	0.194683	0.166*
H25B	0.050335	0.505142	0.301722	0.166*
H25C	0.010557	0.633911	0.250838	0.166*
O9A	0.0569 (14)	0.4625 (11)	0.0668 (8)	0.229 (7)	0.5
O9B	0.0407 (7)	0.4170 (6)	0.0815 (3)	0.0796 (13)	0.5
H5A	0.073210	0.724010	0.397330	0.076*
H5B	0.119580	0.623816	0.461950	0.076*
H7A	−0.524240	0.538898	0.337830	0.076*
H7B	−0.657690	0.500628	0.397297	0.076*
H6B	−0.250772	0.534204	0.428521	0.076*
H10A	0.404387	0.421950	0.123878	0.076*
H10B	0.276061	0.433187	0.066881	0.076*
H8B	−0.416950	0.403172	0.228354	0.076*
H8A	−0.567557	0.408504	0.273704	0.076*
H6A	−0.147779	0.582788	0.463609	0.076*
H9A	−0.027178	0.407022	0.051894	0.076*
H9B	0.009130	0.421885	0.132586	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.04657 (17)	0.04038 (16)	0.04396 (16)	0.00148 (10)	−0.00701 (11)	−0.01366 (11)
N2	0.0522 (8)	0.0402 (7)	0.0481 (7)	0.0023 (6)	−0.0108 (6)	−0.0153 (6)
N3	0.0507 (8)	0.0436 (7)	0.0477 (7)	0.0051 (6)	−0.0084 (6)	−0.0137 (6)
O2	0.0472 (7)	0.0530 (7)	0.0523 (7)	−0.0006 (5)	−0.0109 (5)	−0.0114 (5)
N1	0.0484 (8)	0.0425 (7)	0.0498 (7)	0.0005 (6)	−0.0098 (6)	−0.0165 (6)
C18	0.0505 (9)	0.0420 (8)	0.0415 (7)	0.0051 (6)	−0.0142 (6)	−0.0122 (6)
N4	0.0424 (7)	0.0473 (7)	0.0510 (7)	0.0002 (6)	−0.0119 (6)	−0.0113 (6)
C17	0.0474 (9)	0.0427 (8)	0.0443 (8)	0.0039 (6)	−0.0127 (7)	−0.0114 (6)
O5	0.0769 (10)	0.0638 (9)	0.0680 (9)	0.0008 (7)	−0.0094 (8)	−0.0155 (7)
C23	0.0540 (10)	0.0562 (10)	0.0473 (9)	0.0054 (8)	−0.0097 (7)	−0.0176 (8)
O1	0.0844 (11)	0.0785 (11)	0.0515 (8)	0.0013 (8)	−0.0117 (7)	−0.0046 (7)
C9	0.0415 (8)	0.0527 (9)	0.0461 (8)	−0.0057 (7)	−0.0099 (7)	−0.0131 (7)
C4	0.0434 (8)	0.0496 (9)	0.0482 (8)	−0.0044 (7)	−0.0046 (7)	−0.0189 (7)
C10	0.0492 (10)	0.0506 (9)	0.0715 (12)	0.0045 (8)	−0.0173 (9)	−0.0108 (9)
C13	0.0605 (11)	0.0504 (10)	0.0727 (12)	−0.0041 (8)	−0.0080 (9)	−0.0286 (9)
C1	0.0667 (12)	0.0482 (9)	0.0599 (10)	0.0111 (8)	−0.0128 (9)	−0.0148 (8)
C19	0.0690 (12)	0.0553 (10)	0.0484 (9)	0.0070 (9)	−0.0076 (8)	−0.0186 (8)
C8	0.0539 (10)	0.0724 (12)	0.0478 (9)	−0.0110 (9)	−0.0123 (8)	−0.0139 (8)
C16	0.0543 (11)	0.0583 (11)	0.0594 (10)	−0.0005 (8)	−0.0035 (8)	−0.0164 (8)
C12	0.0695 (14)	0.0832 (15)	0.0571 (11)	−0.0050 (12)	−0.0236 (10)	−0.0043 (11)
C5	0.0526 (10)	0.0623 (11)	0.0639 (11)	−0.0045 (8)	−0.0029 (8)	−0.0319 (9)
C14	0.0693 (14)	0.0556 (11)	0.0969 (17)	−0.0121 (10)	−0.0087 (12)	−0.0313 (12)
C20	0.0933 (16)	0.0579 (11)	0.0631 (12)	0.0120 (11)	−0.0128 (11)	−0.0321 (10)
C11	0.0626 (13)	0.0665 (13)	0.0767 (14)	0.0032 (10)	−0.0283 (11)	0.0028 (11)
C22	0.0689 (12)	0.0431 (9)	0.0669 (11)	−0.0032 (8)	−0.0064 (9)	−0.0201 (8)
C15	0.0593 (12)	0.0621 (12)	0.0855 (15)	−0.0149 (10)	0.0005 (11)	−0.0177 (11)
C3	0.0656 (13)	0.0605 (12)	0.0844 (15)	0.0058 (9)	−0.0036 (11)	−0.0396 (11)
C24	0.0557 (12)	0.0824 (15)	0.0778 (14)	0.0035 (10)	−0.0250 (10)	−0.0200 (12)
C21	0.0925 (16)	0.0455 (10)	0.0797 (14)	0.0017 (10)	−0.0139 (12)	−0.0291 (10)
C2	0.0706 (13)	0.0489 (10)	0.0854 (15)	0.0140 (9)	−0.0109 (11)	−0.0222 (10)
C6	0.0751 (15)	0.0860 (16)	0.0681 (13)	−0.0059 (12)	−0.0056 (11)	−0.0421 (12)
C7	0.0767 (15)	0.1015 (19)	0.0537 (11)	−0.0116 (13)	−0.0120 (10)	−0.0310 (12)
O8	0.0728 (10)	0.0762 (10)	0.0762 (10)	−0.0021 (8)	−0.0222 (8)	−0.0329 (8)
O7	0.0727 (11)	0.1068 (15)	0.0738 (10)	0.0131 (10)	−0.0167 (9)	−0.0257 (10)
O6	0.0743 (11)	0.1004 (13)	0.0709 (10)	−0.0130 (10)	−0.0077 (8)	−0.0234 (9)
O10	0.0834 (12)	0.1274 (17)	0.0819 (12)	0.0139 (11)	−0.0329 (10)	−0.0404 (12)
O4	0.0665 (11)	0.1221 (17)	0.0971 (14)	−0.0054 (10)	−0.0155 (10)	−0.0502 (13)
O3	0.0664 (11)	0.1311 (18)	0.1074 (14)	−0.0125 (11)	−0.0102 (10)	−0.0638 (14)
C26	0.0618 (13)	0.0755 (15)	0.0933 (18)	−0.0037 (11)	−0.0178 (12)	−0.0266 (13)
C25	0.0637 (16)	0.112 (2)	0.176 (4)	−0.0042 (15)	−0.0189 (19)	−0.080 (3)
O9A	0.123 (6)	0.295 (15)	0.171 (8)	−0.052 (8)	−0.064 (6)	0.055 (8)
O9B	0.062 (2)	0.120 (4)	0.0541 (18)	−0.018 (2)	−0.0104 (16)	−0.028 (2)

Geometric parameters (Å, º) top

Cu—O2	1.9897 (13)	C5—C3	1.397 (3)
Cu—N2	1.9979 (15)	C5—C6	1.445 (3)
Cu—N3	2.0204 (15)	C14—C15	1.377 (4)
Cu—N1	2.0251 (15)	C14—H14	0.9300
Cu—N4	2.2358 (15)	C20—C21	1.364 (4)
N2—C22	1.338 (2)	C20—H20	0.9300
N2—C18	1.344 (2)	C11—H11	0.9300
N3—C1	1.333 (2)	C22—C21	1.384 (3)
N3—C4	1.355 (2)	C22—H22	0.9300
O2—C23	1.273 (2)	C15—H15	0.9300
N1—C17	1.342 (2)	C3—C2	1.367 (4)
N1—C13	1.343 (2)	C3—H3	0.9300
C18—C19	1.378 (3)	C24—H24A	0.9600
C18—C17	1.479 (2)	C24—H24B	0.9600
N4—C10	1.328 (2)	C24—H24C	0.9600
N4—C9	1.351 (2)	C21—H21	0.9300
C17—C16	1.385 (3)	C2—H2	0.9300
O5—H5A	0.8391	C6—C7	1.351 (4)
O5—H5B	0.8276	C6—H6	0.9300
C23—O1	1.233 (2)	C7—H7	0.9300
C23—C24	1.498 (3)	O8—H8B	0.8460
C9—C8	1.408 (3)	O8—H8A	0.8510
C9—C4	1.443 (3)	O7—H7A	0.855
C4—C5	1.401 (3)	O7—H7B	0.8538
C10—C11	1.401 (3)	O6—H6B	0.8552
C10—H10	0.9300	O6—H6A	0.8506
C13—C14	1.383 (3)	O10—H10A	0.8340
C13—H13	0.9300	O10—H10B	0.8499
C1—C2	1.387 (3)	O4—C26	1.257 (3)
C1—H1	0.9300	O3—C26	1.235 (3)
C19—C20	1.391 (3)	C26—C25	1.520 (4)
C19—H19	0.9300	C25—H25A	0.9600
C8—C12	1.399 (3)	C25—H25B	0.9600
C8—C7	1.421 (4)	C25—H25C	0.9600
C16—C15	1.381 (3)	O9A—H9A	1.099
C16—H16	0.9300	O9A—H9B	0.984
C12—C11	1.353 (4)	O9B—H9A	0.838
C12—H12	0.9300	O9B—H9B	0.826

O2—Cu—N2	93.69 (6)	C11—C12—C8	120.0 (2)
O2—Cu—N3	89.87 (6)	C11—C12—H12	120.0
N2—Cu—N3	173.29 (6)	C8—C12—H12	120.0
O2—Cu—N1	164.31 (6)	C3—C5—C4	117.95 (19)
N2—Cu—N1	80.33 (6)	C3—C5—C6	123.7 (2)
N3—Cu—N1	94.77 (6)	C4—C5—C6	118.3 (2)
O2—Cu—N4	88.34 (5)	C15—C14—C13	118.9 (2)
N2—Cu—N4	107.19 (6)	C15—C14—H14	120.6
N3—Cu—N4	78.57 (6)	C13—C14—H14	120.6
N1—Cu—N4	107.26 (6)	C21—C20—C19	119.6 (2)
C22—N2—C18	119.39 (16)	C21—C20—H20	120.2
C22—N2—Cu	125.01 (14)	C19—C20—H20	120.2
C18—N2—Cu	115.58 (11)	C12—C11—C10	119.7 (2)
C1—N3—C4	118.81 (17)	C12—C11—H11	120.1
C1—N3—Cu	124.68 (14)	C10—C11—H11	120.1
C4—N3—Cu	116.44 (12)	N2—C22—C21	121.7 (2)
C23—O2—Cu	110.02 (12)	N2—C22—H22	119.1
C17—N1—C13	118.96 (16)	C21—C22—H22	119.1
C17—N1—Cu	114.67 (12)	C14—C15—C16	119.5 (2)
C13—N1—Cu	126.37 (13)	C14—C15—H15	120.2
N2—C18—C19	121.59 (17)	C16—C15—H15	120.2
N2—C18—C17	114.43 (15)	C2—C3—C5	119.70 (19)
C19—C18—C17	123.95 (17)	C2—C3—H3	120.2
C10—N4—C9	118.10 (17)	C5—C3—H3	120.2
C10—N4—Cu	131.76 (15)	C23—C24—H24A	109.5
C9—N4—Cu	109.52 (11)	C23—C24—H24B	109.5
N1—C17—C16	121.99 (17)	H24A—C24—H24B	109.5
N1—C17—C18	114.65 (15)	C23—C24—H24C	109.5
C16—C17—C18	123.32 (17)	H24A—C24—H24C	109.5
H5A—O5—H5B	114.9	H24B—C24—H24C	109.5
O1—C23—O2	122.29 (19)	C20—C21—C22	119.1 (2)
O1—C23—C24	120.95 (19)	C20—C21—H21	120.5
O2—C23—C24	116.74 (17)	C22—C21—H21	120.5
N4—C9—C8	123.12 (18)	C3—C2—C1	119.2 (2)
N4—C9—C4	117.57 (15)	C3—C2—H2	120.4
C8—C9—C4	119.30 (18)	C1—C2—H2	120.4
N3—C4—C5	121.81 (18)	C7—C6—C5	121.1 (2)
N3—C4—C9	117.73 (16)	C7—C6—H6	119.4
C5—C4—C9	120.42 (17)	C5—C6—H6	119.4
N4—C10—C11	122.2 (2)	C6—C7—C8	121.6 (2)
N4—C10—H10	118.9	C6—C7—H7	119.2
C11—C10—H10	118.9	C8—C7—H7	119.2
N1—C13—C14	121.9 (2)	H8B—O8—H8A	100.24
N1—C13—H13	119.0	H7A—O7—H7B	94.81
C14—C13—H13	119.0	H6B—O6—H6A	105.7
N3—C1—C2	122.5 (2)	H10A—O10—H10B	126.533
N3—C1—H1	118.8	O3—C26—O4	124.7 (2)
C2—C1—H1	118.8	O3—C26—C25	117.6 (3)
C18—C19—C20	118.6 (2)	O4—C26—C25	117.7 (3)
C18—C19—H19	120.7	C26—C25—H25A	109.5
C20—C19—H19	120.7	C26—C25—H25B	109.5
C12—C8—C9	116.8 (2)	H25A—C25—H25B	109.5
C12—C8—C7	124.0 (2)	C26—C25—H25C	109.5
C9—C8—C7	119.2 (2)	H25A—C25—H25C	109.5
C15—C16—C17	118.7 (2)	H25B—C25—H25C	109.5
C15—C16—H16	120.6	H9A—O9A—H9B	88.5
C17—C16—H16	120.6	H9A—O9B—H9B	122.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···N3	0.93	2.62	3.140 (3)	116
C13—H13···O8ⁱ	0.93	2.46	3.210 (3)	138
C19—H19···O1ⁱⁱ	0.93	2.33	3.220 (3)	161
C16—H16···O1ⁱⁱ	0.93	2.55	3.435 (3)	160
C22—H22···O2	0.93	2.57	3.062 (3)	113
C22—H22···O7ⁱⁱⁱ	0.93	2.65	3.153 (3)	115
O5—H5A···O2	0.8391	2.0046	2.833 (2)	169.32
O5—H5B···O6^iv	0.8276	2.036	2.833 (3)	161.52
O7—H7A···O4	0.86	1.91	2.731 (3)	160
O7—H7B···O6^v	0.85	1.93	2.768 (3)	168
O6—H6B···O4	0.86	1.84	2.689 (3)	173
O10—H10A···O8ⁱⁱⁱ	0.83	1.96	2.7910 (17)	173
O10—H10B···O9A^a	0.85	1.82	2.645 (12)	163
O8—H8B···O3	0.85	1.89	2.731 (2)	177
O8—H8A···O7	0.85	1.98	2.806 (3)	162
C13—H13···N3	0.93	2.62	3.140 (3)	116
C13—H13···O8ⁱ	0.93	2.46	3.210 (3)	138
C19—H19···O1ⁱⁱ	0.93	2.33	3.220 (3)	161
C16—H16···O1ⁱⁱ	0.93	2.55	3.435 (3)	160
C22—H22···O2	0.93	2.57	3.062 (3)	113
C22—H22···O7ⁱⁱⁱ	0.93	2.65	3.153 (3)	115
O5—H5A···O2	0.8391	2.0046	2.833 (2)	169.32
O5—H5B···O6^iv	0.8276	2.036	2.833 (3)	161.52
O7—H7A···O4	0.86	1.91	2.731 (3)	160
O7—H7B···O6^v	0.85	1.93	2.768 (3)	168
O6—H6B···O4	0.86	1.84	2.689 (3)	173
O10—H10A···O8ⁱⁱⁱ	0.83	1.96	2.7910 (17)	173
O10—H10B···O9A^a	0.85	1.82	2.645 (12)	163
O8—H8B···O3	0.85	1.89	2.731 (2)	177
O8—H8A···O7	0.85	1.98	2.806 (3)	162
O6—H6A···O5	0.85	1.94	2.774 (3)	165
C13—H13···N3	0.93	2.62	3.140 (3)	116
C13—H13···O8ⁱ	0.93	2.46	3.210 (3)	138
C19—H19···O1ⁱⁱ	0.93	2.33	3.220 (3)	161
C16—H16···O1ⁱⁱ	0.93	2.55	3.435 (3)	160
C22—H22···O2	0.93	2.57	3.062 (3)	113
C22—H22···O7ⁱⁱⁱ	0.93	2.65	3.153 (3)	115
O5—H5A···O2	0.8391	2.0046	2.833 (2)	169.32
O5—H5B···O6^iv	0.8276	2.036	2.833 (3)	161.52
O7—H7A···O4	0.86	1.91	2.731 (3)	160
O7—H7B···O6^v	0.85	1.93	2.768 (3)	168
O6—H6B···O4	0.86	1.84	2.689 (3)	173
O10—H10A···O8ⁱⁱⁱ	0.83	1.96	2.7910 (17)	173
O10—H10B···O9A^a	0.85	1.82	2.645 (12)	163
O8—H8B···O3	0.85	1.89	2.731 (2)	177
O8—H8A···O7	0.85	1.98	2.806 (3)	162
O6—H6A···O5	0.85	1.94	2.774 (3)	165

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

(Acetato-κO)bis(2,2'-bipyridine-κ²N,N')copper(II) acetate–acetic acid–water (1/1/3) (III) top

Crystal data top

[Cu(C₂H₃O₂)(C₁₀H₈N₂)₂](C₂H₃O₂)·C₂H₄O₂·3H₂O	Z = 2
M_r = 608.09	F(000) = 634
Triclinic, P1	D_x = 1.435 Mg m⁻³
a = 11.0826 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1840 (19) Å	Cell parameters from 25526 reflections
c = 12.1880 (18) Å	θ = 2.5–31.0°
α = 86.537 (1)°	µ = 0.83 mm⁻¹
β = 69.820 (1)°	T = 150 K
γ = 83.261 (1)°	Prism, blue
V = 1407.8 (4) Å³	0.13 × 0.07 × 0.06 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	7452 independent reflections
Radiation source: micro-focus sealed X-ray tube	6436 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.029
ω scans	θ_max = 30.7°, θ_min = 2.5°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	h = −14→15
T_min = 0.995, T_max = 1.000	k = −16→15
36611 measured reflections	l = −17→17

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0432P)² + 0.4639P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.078
7452 reflections	Δρ_max = 0.42 e Å⁻³
364 parameters	Δρ_min = −0.37 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	0.27208 (2)	0.50390 (2)	0.20980 (2)	0.01722 (6)
C2	0.20686 (16)	0.19209 (14)	0.42857 (15)	0.0319 (3)
H2	0.219242	0.109182	0.418838	0.038*
C20	0.27380 (14)	0.67774 (13)	0.01845 (12)	0.0220 (3)
H20	0.192645	0.654420	0.028961	0.026*
O2	0.20865 (9)	0.40753 (9)	0.11614 (9)	0.0216 (2)
O4	0.20081 (11)	0.99389 (11)	0.76859 (11)	0.0363 (3)
N3	0.46735 (11)	0.49874 (10)	0.20837 (10)	0.0191 (2)
O1	0.02070 (10)	0.51918 (10)	0.19082 (9)	0.0282 (2)
C17	0.51367 (14)	0.74396 (12)	−0.01368 (13)	0.0221 (3)
H17	0.595780	0.764818	−0.024124	0.026*
C8	0.11046 (16)	0.76062 (16)	0.54841 (16)	0.0344 (4)
H8	0.081830	0.806154	0.615656	0.041*
N1	0.21842 (11)	0.38984 (10)	0.34423 (10)	0.0187 (2)
N2	0.19928 (11)	0.62534 (10)	0.34739 (10)	0.0200 (2)
C19	0.32137 (15)	0.76594 (13)	−0.06415 (13)	0.0252 (3)
H19	0.272712	0.802220	−0.108145	0.030*
O3	0.01773 (12)	0.95657 (14)	0.74876 (13)	0.0493 (4)
N4	0.34123 (11)	0.62436 (10)	0.08437 (10)	0.0178 (2)
C1	0.23192 (14)	0.26982 (13)	0.33276 (14)	0.0242 (3)
H1	0.258859	0.238229	0.258286	0.029*
C6	0.16399 (13)	0.57070 (13)	0.45367 (12)	0.0202 (3)
C15	0.52739 (12)	0.59088 (12)	0.14451 (11)	0.0173 (2)
C18	0.44278 (15)	0.79961 (13)	−0.08053 (13)	0.0255 (3)
H18	0.476656	0.858955	−0.135786	0.031*
C13	0.70201 (14)	0.55011 (14)	0.21823 (14)	0.0267 (3)
H13	0.780400	0.567623	0.222134	0.032*
C4	0.14524 (15)	0.36336 (15)	0.55193 (13)	0.0289 (3)
H4	0.113584	0.396516	0.625898	0.035*
C12	0.64192 (15)	0.45412 (15)	0.28189 (14)	0.0286 (3)
H12	0.679836	0.405328	0.328158	0.034*
C5	0.17558 (13)	0.43706 (13)	0.45203 (12)	0.0198 (3)
C11	0.52418 (14)	0.43187 (14)	0.27555 (13)	0.0249 (3)
H11	0.482997	0.368161	0.319549	0.030*
C21	0.08728 (13)	0.43137 (13)	0.13494 (12)	0.0208 (3)
C14	0.64414 (14)	0.62022 (13)	0.14831 (13)	0.0224 (3)
H14	0.682800	0.685421	0.104979	0.027*
C23	0.07964 (15)	1.01243 (14)	0.79120 (13)	0.0260 (3)
C7	0.11925 (14)	0.63576 (15)	0.55621 (13)	0.0278 (3)
H7	0.095642	0.596292	0.628728	0.033*
C16	0.45967 (12)	0.65679 (11)	0.06886 (11)	0.0170 (2)
C24	0.00919 (19)	1.11281 (17)	0.87447 (18)	0.0421 (4)
H24A	0.019512	1.188813	0.833044	0.063*
H24B	0.044333	1.111701	0.936373	0.063*
H24C	−0.081002	1.101669	0.906858	0.063*
C10	0.18965 (15)	0.74613 (13)	0.34065 (14)	0.0274 (3)
H10	0.213843	0.784045	0.267379	0.033*
C9	0.14479 (16)	0.81604 (15)	0.43951 (17)	0.0360 (4)
H9	0.137909	0.899605	0.432432	0.043*
C22	0.02787 (17)	0.34497 (16)	0.08280 (16)	0.0338 (4)
H22A	−0.063504	0.349434	0.124309	0.051*
H22B	0.066226	0.264444	0.088993	0.051*
H22C	0.043135	0.366143	0.001959	0.051*
C3	0.16311 (17)	0.23957 (16)	0.53906 (15)	0.0356 (4)
H3	0.145692	0.188654	0.604642	0.043*
O5	0.35995 (12)	0.84096 (11)	0.63105 (10)	0.0344 (3)
O6	0.36637 (12)	0.95964 (10)	0.47589 (10)	0.0327 (3)
O7	0.31574 (12)	0.09111 (11)	0.90556 (12)	0.0373 (3)
O8	0.57412 (14)	0.06406 (14)	0.77043 (11)	0.0469 (3)
H8B	0.636127	0.034513	0.792909	0.070*
H8A	0.578784	0.040323	0.705070	0.070*
O9	0.75565 (13)	0.94767 (14)	0.85495 (13)	0.0477 (3)
H9B	0.826163	0.978724	0.825294	0.072*
H9A	0.737103	0.958906	0.928370	0.072*
C25	0.40392 (15)	0.86879 (14)	0.51924 (13)	0.0278 (3)
C26	0.5051 (2)	0.7765 (2)	0.44747 (17)	0.0507 (5)
H26A	0.467064	0.728772	0.407821	0.076*
H26B	0.540202	0.725416	0.497661	0.076*
H26C	0.572964	0.816326	0.390973	0.076*
H7A	0.273421	0.103127	0.867949	0.050*
H7B	0.393502	0.085423	0.858788	0.050*
H5	0.302883	0.895436	0.668488	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01914 (9)	0.01857 (9)	0.01475 (9)	−0.00464 (6)	−0.00622 (6)	0.00140 (6)
C2	0.0304 (8)	0.0228 (7)	0.0390 (9)	−0.0009 (6)	−0.0093 (7)	0.0084 (6)
C20	0.0192 (6)	0.0265 (7)	0.0213 (7)	−0.0007 (5)	−0.0088 (5)	0.0008 (5)
O2	0.0198 (5)	0.0254 (5)	0.0205 (5)	−0.0033 (4)	−0.0072 (4)	−0.0047 (4)
O4	0.0284 (6)	0.0469 (7)	0.0334 (6)	0.0029 (5)	−0.0098 (5)	−0.0173 (5)
N3	0.0173 (5)	0.0219 (5)	0.0183 (6)	−0.0014 (4)	−0.0066 (4)	0.0011 (4)
O1	0.0219 (5)	0.0361 (6)	0.0259 (5)	0.0004 (4)	−0.0071 (4)	−0.0072 (4)
C17	0.0206 (7)	0.0204 (6)	0.0226 (7)	−0.0031 (5)	−0.0037 (5)	−0.0002 (5)
C8	0.0251 (8)	0.0422 (9)	0.0352 (9)	−0.0038 (7)	−0.0057 (7)	−0.0220 (7)
N1	0.0172 (5)	0.0203 (5)	0.0178 (5)	−0.0028 (4)	−0.0047 (4)	0.0007 (4)
N2	0.0174 (5)	0.0211 (5)	0.0209 (6)	−0.0041 (4)	−0.0048 (4)	−0.0032 (4)
C19	0.0271 (7)	0.0252 (7)	0.0222 (7)	0.0039 (6)	−0.0096 (6)	0.0036 (5)
O3	0.0317 (7)	0.0640 (9)	0.0511 (8)	−0.0033 (6)	−0.0071 (6)	−0.0373 (7)
N4	0.0172 (5)	0.0197 (5)	0.0165 (5)	−0.0016 (4)	−0.0057 (4)	0.0002 (4)
C1	0.0221 (7)	0.0205 (6)	0.0274 (7)	−0.0024 (5)	−0.0050 (6)	0.0001 (5)
C6	0.0144 (6)	0.0277 (7)	0.0196 (7)	−0.0032 (5)	−0.0062 (5)	−0.0037 (5)
C15	0.0160 (6)	0.0198 (6)	0.0147 (6)	0.0004 (5)	−0.0036 (5)	−0.0035 (5)
C18	0.0281 (7)	0.0215 (7)	0.0223 (7)	−0.0012 (6)	−0.0038 (6)	0.0050 (5)
C13	0.0193 (7)	0.0361 (8)	0.0280 (8)	−0.0023 (6)	−0.0115 (6)	−0.0050 (6)
C4	0.0271 (7)	0.0406 (9)	0.0186 (7)	−0.0038 (6)	−0.0083 (6)	0.0051 (6)
C12	0.0251 (7)	0.0352 (8)	0.0298 (8)	0.0015 (6)	−0.0166 (6)	0.0013 (6)
C5	0.0146 (6)	0.0276 (7)	0.0178 (6)	−0.0028 (5)	−0.0063 (5)	0.0012 (5)
C11	0.0228 (7)	0.0274 (7)	0.0252 (7)	−0.0022 (6)	−0.0101 (6)	0.0045 (6)
C21	0.0215 (7)	0.0269 (7)	0.0158 (6)	−0.0069 (5)	−0.0078 (5)	0.0024 (5)
C14	0.0202 (7)	0.0254 (7)	0.0218 (7)	−0.0041 (5)	−0.0062 (5)	−0.0030 (5)
C23	0.0297 (8)	0.0265 (7)	0.0201 (7)	0.0004 (6)	−0.0068 (6)	−0.0041 (5)
C7	0.0211 (7)	0.0415 (9)	0.0219 (7)	−0.0040 (6)	−0.0071 (6)	−0.0088 (6)
C16	0.0167 (6)	0.0177 (6)	0.0156 (6)	−0.0007 (5)	−0.0044 (5)	−0.0028 (5)
C24	0.0392 (10)	0.0395 (9)	0.0461 (11)	0.0062 (8)	−0.0125 (8)	−0.0231 (8)
C10	0.0246 (7)	0.0223 (7)	0.0319 (8)	−0.0062 (6)	−0.0037 (6)	−0.0035 (6)
C9	0.0313 (8)	0.0259 (7)	0.0476 (10)	−0.0071 (6)	−0.0059 (7)	−0.0146 (7)
C22	0.0310 (8)	0.0401 (9)	0.0372 (9)	−0.0112 (7)	−0.0169 (7)	−0.0065 (7)
C3	0.0361 (9)	0.0385 (9)	0.0305 (9)	−0.0052 (7)	−0.0117 (7)	0.0170 (7)
O5	0.0416 (7)	0.0336 (6)	0.0227 (6)	0.0095 (5)	−0.0084 (5)	−0.0003 (4)
O6	0.0350 (6)	0.0327 (6)	0.0290 (6)	0.0043 (5)	−0.0121 (5)	0.0034 (5)
O7	0.0401 (7)	0.0338 (6)	0.0448 (7)	−0.0021 (5)	−0.0228 (6)	−0.0053 (5)
O8	0.0434 (7)	0.0672 (9)	0.0290 (7)	−0.0044 (7)	−0.0130 (6)	0.0093 (6)
O9	0.0324 (7)	0.0670 (9)	0.0451 (8)	−0.0046 (6)	−0.0135 (6)	−0.0126 (7)
C25	0.0269 (7)	0.0322 (8)	0.0240 (7)	0.0037 (6)	−0.0104 (6)	−0.0018 (6)
C26	0.0540 (12)	0.0563 (12)	0.0302 (9)	0.0280 (10)	−0.0099 (9)	−0.0051 (8)

Geometric parameters (Å, º) top

Cu1—O2	1.9594 (10)	C13—C12	1.382 (2)
Cu1—N1	1.9796 (12)	C13—C14	1.390 (2)
Cu1—N4	1.9810 (12)	C13—H13	0.9300
Cu1—N2	2.0958 (12)	C4—C3	1.386 (3)
Cu1—N3	2.1522 (12)	C4—C5	1.392 (2)
C2—C3	1.381 (3)	C4—H4	0.9300
C2—C1	1.381 (2)	C12—C11	1.385 (2)
C2—H2	0.9300	C12—H12	0.9300
C20—N4	1.3461 (17)	C11—H11	0.9300
C20—C19	1.379 (2)	C21—C22	1.511 (2)
C20—H20	0.9300	C14—H14	0.9300
O2—C21	1.2820 (17)	C23—C24	1.512 (2)
O4—C23	1.268 (2)	C7—H7	0.9300
N3—C11	1.3407 (18)	C24—H24A	0.9600
N3—C15	1.3480 (18)	C24—H24B	0.9600
O1—C21	1.2396 (18)	C24—H24C	0.9600
C17—C16	1.3870 (19)	C10—C9	1.386 (2)
C17—C18	1.391 (2)	C10—H10	0.9300
C17—H17	0.9300	C9—H9	0.9300
C8—C9	1.378 (3)	C22—H22A	0.9600
C8—C7	1.388 (2)	C22—H22B	0.9600
C8—H8	0.9300	C22—H22C	0.9600
N1—C1	1.3435 (18)	C3—H3	0.9300
N1—C5	1.3510 (18)	O5—C25	1.3106 (19)
N2—C10	1.3424 (19)	O5—H5	0.8506
N2—C6	1.3473 (18)	O6—C25	1.2133 (19)
C19—C18	1.384 (2)	O7—H7A	0.7577
C19—H19	0.9300	O7—H7B	0.8511
O3—C23	1.230 (2)	O8—H8B	0.8498
N4—C16	1.3500 (17)	O8—H8A	0.8376
C1—H1	0.9300	O9—H9B	0.8459
C6—C7	1.391 (2)	O9—H9A	0.8599
C6—C5	1.486 (2)	C25—C26	1.500 (2)
C15—C14	1.3880 (19)	C26—H26A	0.9600
C15—C16	1.4908 (18)	C26—H26B	0.9600
C18—H18	0.9300	C26—H26C	0.9600

O2—Cu1—N1	91.16 (5)	C13—C12—H12	120.6
O2—Cu1—N4	95.59 (5)	C11—C12—H12	120.6
N1—Cu1—N4	172.71 (5)	N1—C5—C4	121.09 (13)
O2—Cu1—N2	139.29 (4)	N1—C5—C6	114.84 (12)
N1—Cu1—N2	79.92 (5)	C4—C5—C6	124.07 (13)
N4—Cu1—N2	96.61 (5)	N3—C11—C12	122.47 (14)
O2—Cu1—N3	127.23 (4)	N3—C11—H11	118.8
N1—Cu1—N3	94.57 (5)	C12—C11—H11	118.8
N4—Cu1—N3	79.16 (4)	O1—C21—O2	123.73 (13)
N2—Cu1—N3	93.23 (4)	O1—C21—C22	120.78 (13)
C3—C2—C1	118.86 (15)	O2—C21—C22	115.48 (13)
C3—C2—H2	120.6	C15—C14—C13	118.59 (13)
C1—C2—H2	120.6	C15—C14—H14	120.7
N4—C20—C19	122.00 (13)	C13—C14—H14	120.7
N4—C20—H20	119.0	O3—C23—O4	124.72 (14)
C19—C20—H20	119.0	O3—C23—C24	118.88 (15)
C21—O2—Cu1	113.10 (9)	O4—C23—C24	116.38 (15)
C11—N3—C15	118.64 (12)	C8—C7—C6	118.84 (15)
C11—N3—Cu1	128.67 (10)	C8—C7—H7	120.6
C15—N3—Cu1	111.60 (9)	C6—C7—H7	120.6
C16—C17—C18	118.78 (13)	N4—C16—C17	121.46 (12)
C16—C17—H17	120.6	N4—C16—C15	115.27 (11)
C18—C17—H17	120.6	C17—C16—C15	123.26 (12)
C9—C8—C7	118.98 (14)	C23—C24—H24A	109.5
C9—C8—H8	120.5	C23—C24—H24B	109.5
C7—C8—H8	120.5	H24A—C24—H24B	109.5
C1—N1—C5	119.72 (12)	C23—C24—H24C	109.5
C1—N1—Cu1	123.21 (10)	H24A—C24—H24C	109.5
C5—N1—Cu1	116.87 (9)	H24B—C24—H24C	109.5
C10—N2—C6	118.84 (12)	N2—C10—C9	122.01 (15)
C10—N2—Cu1	127.93 (10)	N2—C10—H10	119.0
C6—N2—Cu1	113.17 (9)	C9—C10—H10	119.0
C20—C19—C18	118.91 (13)	C8—C9—C10	119.39 (15)
C20—C19—H19	120.5	C8—C9—H9	120.3
C18—C19—H19	120.5	C10—C9—H9	120.3
C20—N4—C16	119.39 (12)	C21—C22—H22A	109.5
C20—N4—Cu1	123.11 (10)	C21—C22—H22B	109.5
C16—N4—Cu1	117.44 (9)	H22A—C22—H22B	109.5
N1—C1—C2	121.78 (14)	C21—C22—H22C	109.5
N1—C1—H1	119.1	H22A—C22—H22C	109.5
C2—C1—H1	119.1	H22B—C22—H22C	109.5
N2—C6—C7	121.92 (14)	C2—C3—C4	119.80 (14)
N2—C6—C5	114.82 (12)	C2—C3—H3	120.1
C7—C6—C5	123.25 (13)	C4—C3—H3	120.1
N3—C15—C14	122.15 (12)	C25—O5—H5	110.82
N3—C15—C16	114.79 (12)	H7A—O7—H7B	106.32
C14—C15—C16	123.05 (12)	H8B—O8—H8A	114.12
C19—C18—C17	119.45 (13)	H9B—O9—H9A	102.25
C19—C18—H18	120.3	O6—C25—O5	124.02 (14)
C17—C18—H18	120.3	O6—C25—C26	122.16 (15)
C12—C13—C14	119.32 (13)	O5—C25—C26	113.81 (14)
C12—C13—H13	120.3	C25—C26—H26A	109.5
C14—C13—H13	120.3	C25—C26—H26B	109.5
C3—C4—C5	118.70 (15)	H26A—C26—H26B	109.5
C3—C4—H4	120.6	C25—C26—H26C	109.5
C5—C4—H4	120.6	H26A—C26—H26C	109.5
C13—C12—C11	118.80 (14)	H26B—C26—H26C	109.5

N4—C20—C19—C18	0.7 (2)	C15—N3—C11—C12	0.1 (2)
C19—C20—N4—C16	−0.7 (2)	Cu1—N3—C11—C12	−166.81 (12)
C19—C20—N4—Cu1	176.51 (11)	C13—C12—C11—N3	1.2 (2)
C5—N1—C1—C2	−2.0 (2)	Cu1—O2—C21—O1	11.48 (17)
Cu1—N1—C1—C2	172.74 (11)	Cu1—O2—C21—C22	−169.15 (10)
C3—C2—C1—N1	2.0 (2)	N3—C15—C14—C13	1.6 (2)
C10—N2—C6—C7	−0.7 (2)	C16—C15—C14—C13	−177.43 (13)
Cu1—N2—C6—C7	176.81 (11)	C12—C13—C14—C15	−0.2 (2)
C10—N2—C6—C5	178.80 (12)	C9—C8—C7—C6	0.8 (2)
Cu1—N2—C6—C5	−3.74 (14)	N2—C6—C7—C8	0.2 (2)
C11—N3—C15—C14	−1.5 (2)	C5—C6—C7—C8	−179.19 (13)
Cu1—N3—C15—C14	167.52 (10)	C20—N4—C16—C17	−0.06 (19)
C11—N3—C15—C16	177.56 (12)	Cu1—N4—C16—C17	−177.41 (10)
Cu1—N3—C15—C16	−13.37 (14)	C20—N4—C16—C15	−178.93 (12)
C20—C19—C18—C17	0.0 (2)	Cu1—N4—C16—C15	3.72 (15)
C16—C17—C18—C19	−0.7 (2)	C18—C17—C16—N4	0.7 (2)
C14—C13—C12—C11	−1.1 (2)	C18—C17—C16—C15	179.53 (13)
C1—N1—C5—C4	0.1 (2)	N3—C15—C16—N4	7.18 (17)
Cu1—N1—C5—C4	−174.95 (11)	C14—C15—C16—N4	−173.72 (12)
C1—N1—C5—C6	−179.71 (12)	N3—C15—C16—C17	−171.67 (12)
Cu1—N1—C5—C6	5.21 (15)	C14—C15—C16—C17	7.4 (2)
C3—C4—C5—N1	1.7 (2)	C6—N2—C10—C9	0.1 (2)
C3—C4—C5—C6	−178.43 (14)	Cu1—N2—C10—C9	−176.95 (12)
N2—C6—C5—N1	−0.71 (17)	C7—C8—C9—C10	−1.3 (2)
C7—C6—C5—N1	178.73 (13)	N2—C10—C9—C8	0.9 (3)
N2—C6—C5—C4	179.45 (13)	C1—C2—C3—C4	0.0 (3)
C7—C6—C5—C4	−1.1 (2)	C5—C4—C3—C2	−1.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O6ⁱ	0.93	2.44	3.1081 (19)	129
C1—H1···O9ⁱⁱ	0.93	2.61	3.398 (2)	142
C14—H14···O7ⁱⁱ	0.93	2.50	3.306 (2)	146
O8—H8B···O9ⁱ	0.85	1.89	2.7306 (19)	170
O9—H9B···O3ⁱⁱⁱ	0.85	1.99	2.753 (2)	149
O9—H9A···O7^iv	0.86	1.97	2.769 (2)	154
O8—H8A···O6ⁱⁱ	0.84	2.08	2.8648 (18)	157
O7—H7B···O8	0.8511	1.9119	2.758 (2)	172.63

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

Bond lengths of coordination of copper (Å) and angles between these bonds (°) in [Cu(phen)₂Ac]Ac.7H₂O (Jing et al., 2011) top

Cu—O2	2.001 (3)	Cu—N3	1.988 (3)
Cu—N1	1.989 (3)	Cu—N4	2.051 (3)
Cu—N2	2.191 (4)

N1—Cu—N2	79.82 (14)	N3—Cu—N4	81.55 (13)
N1—Cu—N3	177.12 (15)	O2—Cu—N1	89.98 (13)
N1—Cu—N4	96.80 (13)	O2—Cu—N2	101.51 (13)
N2—Cu—N3	98.35 (13)	O2—Cu—N3	92.58 (13)
N2—Cu—N4	106.69 (14)	O2—Cu—N4	151.73 (14)

Selected geometric parameters over the three title systems top

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Angle between N ligands (°)	111.53 (4)	109.3 (3)	80.51 (3)
Longest bond (Å)	2.2360 (15)	2.191 (4)	2.1521 (12)
τ₅	0.148	0.423	0.557
Cu—O2 (Å)	1.991(2'	2.001 (3)	1.959 (1)
Cu—O1 (Å)	2.742 (2)	2.6404 (1)	2.859 (1)
O1—Cu—O2 (°)	52.30 (6)	54.12 (3)	50.89 (4)

Information regarding Hirshfeld surfaces generated around the Cu atoms in the title systems top

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Volume (Å³)	11.25	10.53	10.85
Area (Å²)	28.78	27.97	27.71
Globularity, G	0.844	0.830	0.855
Asphericity, A	0.058	0.040	0.065

Data regarding the d_norm surface generated around the Cu atoms in the title systems top

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Minimum	-0.6413	-0.6476	-0.6542
Mean	-0.0391	-0.0735	-0.0611
Maximum	0.9876	0.8396	0.8727
Cu—O2 point	-0.6297	-0.6196	-0.6520
Cu—O1 point	-0.1165	-0.1858	-0.0885

Data regarding the curvedness of the surface generated around the Cu atoms in the title systems top

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Minimum	-3.6299	-3.3323	-3.4610
Mean	-0.9290	-0.9396	-0.8808
Maximum	0.9472	1.0547	0.7287
Cu—O2 point	-2.4528	-2.6100	-2.4644
Cu—O1 point	-0.7427	-0.9443	-0.6101

Values of Hirshfeld surface properties around the coordinated acetate in the title systems top

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
	_norm
O2—Cu point	-0.6293	-0.6221	-0.6508
O1—Cu point	-0.1135	-0.1865	0.0651
	Curvedness
O2—Cu point	-2.3655	-2.4345	-2.3591
O1—Cu point	-0.7621	-0.8754	-0.7456

Geometric parameters (Å) for π–π interactions top

System	[Cu(bipy)(phen)Ac]Ac, (I)	[Cu(phen)₂Ac]Ac, (II)	[Cu(bipy)₂Ac]Ac, (III)
Centroid–centroid distance	3.888	3.783	3.596
Centroid–plane distance	3.463	3.493	3.380
Plane–pPlane distance	3.493	3.505	3.377

Acknowledgements

The authors thank Brazilian agencies CNPq, FAPEMIG and FINEP for financial support.

Funding information

Funding for this research was provided by: Conselho Nacional de Desenvolvimento Cientfico e Tecnolgico; Fundao de Amparo Pesquisa do Estado de Minas Gerais; Financiadora de Estudos e Projetos.

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

Coordination structure and inter­molecular inter­actions in copper(II) acetate com­plexes with 1,10-phenanthroline and 2,2′-bi­py­ri­dine

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

2.1.1. [Cu(bipy)(phen)(Ac)]Ac·6H2O, (I)

2.1.2. [Cu(phen)2Ac]Ac·7H2O, (II)

2.1.3. [Cu(bipy)2Ac]Ac·HAc·3H2O, (III)

2.2. Refinement

3. Results and discussion

3.1. Coordination and geometry

3.2. Inter­molecular inter­actions

4. Conclusion

Supporting information

Acknowledgements

Funding information

References

crystallography in latin america

Coordination structure and intermolecular interactions in copper(II) acetate complexes with 1,10-phenanthroline and 2,2′-bipyridine

2.1.1. [Cu(bipy)(phen)(Ac)]Ac·6H₂O, (I)

2.1.2. [Cu(phen)₂Ac]Ac·7H₂O, (II)

2.1.3. [Cu(bipy)₂Ac]Ac·HAc·3H₂O, (III)

3.2. Intermolecular interactions