Synthesis and crystal structure of the copper (II) carboxylate with 2,2-bipyridine, [Cu(4-mba)2(bipy)(H2O)] European Journal of Chemistry 14 (1) (2023) 109-113 European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2023 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. https://dx.doi.org/10.5155/eurjchem.14.1.109-113.2390 European Journal of Chemistry View Journal Online View Article Online Synthesis and crystal structure of the copper (II) carboxylate with 2,2-bipyridine, [Cu(4-mba)2(bipy)(H2O)] Sibel Demir Kanmazalp 1,*, Adnan Qadir 2 and Necmi Dege 3 1 Naci Topçuoğlu Vocational School, Biomedical Device Technology Program, Gaziantep University, Gaziantep, 27600, Turkey 2 Department of Chemistry, College of Science, Salahaddin University, Erbil, 44001, Iraq 3 Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139, Samsun, Turkey * Corresponding author at: Naci Topçuoğlu Vocational School, Biomedical Device Technology Program, Gaziantep University, Gaziantep, 27600, Turkey. e-mail: sibeld@gantep.edu.tr (S.D. Kanmazalp). 10.5155/eurjchem.14.1.109-113.2390 Received: 22 December 2022 Received in revised form: 11 January 2023 Accepted: 25 January 2023 Published online: 31 March 2023 Printed: 31 March 2023 The new Cu(II) carboxylate complex, aqua(2,2'-bipyridine-κ2N,N')bis(4-methylbenzoato- κO)copper(II) [Cu(4-mba)2(bipy)(H2O)] (4-mba: 4-methylbenzoate, bipy: 2,2'-bipyridine) was synthesized, and the molecular structure of the complex was characterized by the single crystal X-ray diffraction technique. The X-ray diffraction analysis indicated that the asymmetric unit comprises an independent molecule. Crystal data for [Cu(4-meb)2(2,2- bipy)(H2O)]: Triclinic, space group P-1 (no. 2), a = 7.0452(13) Å, b = 11.260(2) Å, c = 16.635(3) Å, α = 103.543(7)°, β = 91.002(7)°, γ = 104.106(6)°, V = 1240.4(4) Å3, Z = 2, T = 296 K, μ(MoKα) = 0.918 mm-1, Dcalc = 1.360 g/cm3, 51364 reflections measured (5.054° ≤ 2Θ ≤ 57.38°), 6258 unique (Rint = 0.0398, Rsigma = 0.0284) which were used in all calculations. The final R1 was 0.0392 (I > 2σ(I)) and wR2 was 0.1021 (all data). The Cu(II) ion was found to be coordinated with two nitrogen atoms of the 2,2'-bipyridine ligand, two oxygen atoms of the 4-methyl benzoate molecule, and one oxygen atom of the aqua ligand. In the three- dimensional supramolecular architecture, molecules are connected through pairs of O-H···O and C-H···O intermolecular interactions, consisting of chains. The molecule also demonstrates Cg···Cg intermolecular interactions between six-membered rings of 2,2'- bipyridine. Synthesis Carboxylate Cu(II) complex Crystal structure Single-crystal XRD Hydrogen bonding Cite this: Eur. J. Chem. 2023, 14(1), 109-113 Journal website: www.eurjchem.com 1. Introduction To coordinate compound formation, 2,2'-bipyridine (bipy) and phenanthroline are used due to their effectiveness in catalysis, electrochemistry, analytical chemistry and bio- chemistry [1]. These ligands have extended π-systems and their complexes show various π-π interactions that participate in the supramolecular architecture [2]. Generally, the substituents have steric effects on the 2,2'-bipyridine rings, which affect the bond distance between the metal and nitrogen atoms. For example, in the two complexes of type [Cu(L)Cl(NO3)]2 (L = 2,2'- Bipyridine (1A), L = 4,4-Dimethyl-2,2-bipyridine (2A)), the Cu- N bond distances (2.004-2.008 Å) in complex 2A are longer than those (1.993-1.994 Å) in complex 1A due to the steric effect of the methyl groups on 4,4-dimethyl-2,2-bipyridine rings [3]. Cu(II) complexes with the d9 configuration exhibit four, five, and six coordinates that adopt tetrahedral, square planar, square pyramidal, and distorted octahedral coordinates due to the Jahn-Teller effect [4]. In our previous work, we synthesized a Cu(II) complex {bisaqua-bis(3-methylbenzoato-κO)(N,N,N', N'-tetramethylethylenediamine-κ2N,N')copper(II), [Cu(3-mba)2 (tmeda)(H2O)2]} involving 3-methyl benzoate (3-mba) and N,N,N',N'-tetramethylethylenediamine (tmeda) [5]. The [Cu(3- mba)2(tmeda)(H2O)2] was characterized by X-ray diffraction analysis and showed a distorted octahedral geometry with carboxylate ligands acting as monodentate. The Cu(II) ion exists in many enzymes including; such as cytochrome C oxidase [6], dopamine hydroxylase [7], tyrosinate [8], superoxide dismutase [9] and ceruloplasmin [10]. Further- more, the Cu (II) carboxylate complexes showed different biolo- gical activities, such as antibacterial [11], antifungal [12], antiviral [13], and antitumor activities [14]. Given the biological importance of Cu(II) carboxylate complexes, a new Cu(II) complex with 4-methyl benzoate and 2,2'-bipyridine has been synthesized and characterized by single crystal X-ray diffract- tion analysis. 2. Experimental 2.1. Synthesis of [Cu(4-mba)2(bipy)(H2O)] 4-Methylbenzoic acid (4 mmol, 0.54 g) and sodium hydroxide (4 mmol, 0.16 g) were dissolved in water (20 mL). Then, a solution of Cu(NO3)2·3H2O (2 mmol, 0.48 g) in water (20 mL) was added with stirring to the prepared solution. Subsequently, a solution of 2,2'-bipyridine (2 mmol, 0.3 g) in MeOH (25 mL) was added and blue sediment was formed. ABSTRACT RESEARCH ARTICLE KEYWORDS https://dx.doi.org/10.5155/eurjchem.14.1.109-113.2390 https://www.eurjchem.com/ https://dx.doi.org/10.5155/eurjchem.14.1.109-113.2390 mailto:sibeld@gantep.edu.tr http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.14.1.109-113.2390&domain=pdf&date_stamp=2023-03-31 110 Kanmazalp et al. / European Journal of Chemistry 14 (1) (2023) 109-113 2023 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.14.1.109-113.2390 Table 1. Crystal data and structure refinement for [Cu(4-mba)2(bipy)(H2O)]. Empirical formula C26H24CuN2O5 Formula weight (g/mol) 508.01 Temperature (K) 296 Crystal system Triclinic Space group P-1 a, (Å) 7.0452(13) b, (Å) 11.260(2) c, (Å) 16.635(3) α (°) 103.543(7) β (°) 91.002(7) γ (°) 104.106(6) Volume (Å3) 1240.4(4) Z 2 ρcalc (g/cm3) 1.360 μ (mm-1) 0.918 F(000) 526.0 Crystal size (mm3) 0.11 × 0.07 × 0.05 Radiation MoKα (λ = 0.71073) 2Θ range for data collection (°) 5.054 to 57.38 Index ranges -9 ≤ h ≤ 9, -15 ≤ k ≤ 15, -22 ≤ l ≤ 22 Reflections collected 51364 Independent reflections 6258 [Rint = 0.0398, Rsigma = 0.0284] Data/restraints/parameters 6258/2/317 Goodness-of-fit on F2 1.082 Final R indexes [I≥2σ (I)] R1 = 0.0392, wR2 = 0.0933 Final R indexes [all data] R1 = 0.0545, wR2 = 0.1021 Largest diff. peak/hole (e.Å-3) 0.32/-0.28 Scheme 1. The synthesis scheme of [Cu(4-mba)2(bipy)(H2O)]. Figure 1. Crystal structure of [Cu(4-mba)2(bipy)(H2O)], indicating the atom numbering scheme. The sediment was filtered, washed with water, and dried at room temperature. The obtained product was recrystallised from ethanol (Scheme 1). 2.2. Crystal structure analysis XRD measurements for [Cu(4-mba)2(bipy)(H2O)] were taken on a Bruker D8 QUEST diffractometer (MoKα radiation, λ = 0.71073 Å; graphite monochromator) at 296 K. WinGX software [15] was used to solve the molecular structure. The structure was refined by the full-matrix least squares method using SHELXL-97 [16]. All non-H atoms were first refined isotropically and then with anisotropic displacement para- meters. The residual electron density was a troublesome model and therefore the SQUEEZE routine [17] in PLATON [18] was used to subtract the contribution of the electron density in the solvent zone from the intensity data and the solvent-free model was used for the final refinement. The details of the structure refinement for [Cu(4-mba)2(bipy)(H2O)] are given in Table 1. Kanmazalp et al. / European Journal of Chemistry 14 (1) (2023) 109-113 111 2023 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.14.1.109-113.2390 Table 2. Bond lengths and bond angles for [Cu(4-mba)2(bipy)(H2O)]. Atom Atom Length (Å) Atom Atom Length (Å) Cu1 O3 1.9824(14) C5 C6 1.480(3) Cu1 O1 1.9484(15) C5 C4 1.388(3) Cu1 O5 2.3532(18) C12 C11 1.505(3) Cu1 N1 2.0183(17) C12 C17 1.388(3) Cu1 N2 2.0066(16) C6 C7 1.385(3) O3 C19 1.273(2) C14 C15 1.383(3) O4 C19 1.251(2) C10 C9 1.374(3) O1 C11 1.272(2) C21 C22 1.378(3) O2 C11 1.228(3) C23 C24 1.374(4) N1 C5 1.341(3) C23 C22 1.379(4) N1 C1 1.339(3) C23 C26 1.516(3) N2 C6 1.352(2) C17 C16 1.381(3) N2 C10 1.336(3) C9 C8 1.375(4) C20 C19 1.498(3) C15 C16 1.379(4) C20 C25 1.386(3) C15 C18 1.516(3) C20 C21 1.385(3) C4 C3 1.375(4) C13 C12 1.384(3) C1 C2 1.382(4) C13 C14 1.378(3) C2 C3 1.359(4) C25 C24 1.391(3) C8 C7 1.378(3) Atom Atom Atom Angle (°) Atom Atom Atom Angle (°) O3 Cu1 O5 107.36(6) C13 C12 C11 121.90(18) O3 Cu1 N1 163.22(6) C13 C12 C17 118.35(19) O3 Cu1 N2 92.31(6) C17 C12 C11 119.74(19) O1 Cu1 O3 90.88(7) N2 C6 C5 114.49(17) O1 Cu1 O5 91.48(7) N2 C6 C7 121.21(19) O1 Cu1 N1 94.56(7) C7 C6 C5 124.30(18) O1 Cu1 N2 172.36(6) O1 C11 C12 115.67(18) N1 Cu1 O5 88.38(7) O2 C11 O1 125.1(2) N2 Cu1 O5 94.19(6) O2 C11 C12 119.21(19) N2 Cu1 N1 80.50(7) C13 C14 C15 121.1(2) C19 O3 Cu1 104.67(12) N2 C10 C9 122.5(2) C11 O1 Cu1 124.17(13) C22 C21 C20 121.2(2) C5 N1 Cu1 115.07(13) C24 C23 C22 117.7(2) C1 N1 Cu1 125.91(16) C24 C23 C26 122.2(3) C1 N1 C5 119.02(19) C22 C23 C26 120.1(3) C6 N2 Cu1 115.11(13) C16 C17 C12 120.2(2) C10 N2 Cu1 125.95(14) C10 C9 C8 118.9(2) C10 N2 C6 118.88(18) C14 C15 C18 120.6(3) C25 C20 C19 121.62(18) C16 C15 C14 117.9(2) C21 C20 C19 120.11(18) C16 C15 C18 121.5(3) C21 C20 C25 118.27(19) C3 C4 C5 118.6(2) O3 C19 C20 118.35(17) C23 C24 C25 122.1(2) O4 C19 O3 122.35(18) N1 C1 C2 121.8(2) O4 C19 C20 119.29(17) C3 C2 C1 119.1(2) C14 C13 C12 120.9(2) C21 C22 C23 121.1(2) C20 C25 C24 119.6(2) C15 C16 C17 121.6(2) N1 C5 C6 114.68(16) C9 C8 C7 119.4(2) N1 C5 C4 121.5(2) C8 C7 C6 119.1(2) C4 C5 C6 123.77(19) C2 C3 C4 119.9(2) The PLATON program [18] was used for structure analysis. Molecular structure illustrations have been drawn with MERCURY [19] and the OLEX program [20] for publication. 3. Results and discussion The crystallographic data for [Cu(4-mba)2(bipy)(H2O)] are indicated in Table 1 and the essential geometrical parameters are shown in Table 2. The single-crystal structure of [Cu(4- meb)2(bipy)(H2O)] crystallises in the triclinic crystal system with the space group P-1, as indicated in Figure 1. The Cu(II) ion is coordinated with the two nitrogen donors of the 2,2'-bipyridine ligand, two oxygen atoms of 4-methyl benzoate molecules, and one oxygen atom of the aqua ligand. As shown in Figure 1, the Cu1 atom is five-coordinated in a slightly distorted square pyramidal configuration (τ5 = 0.15; τ5 = (β- α)/60, where β = O1-Cu1-N2 172.36(6)° and α = O3-Cu1-N1 163.22(6)°, Table 2). The τ5 parameter is 0 and 1 for perfect square pyramidal and trigonal bipyramidal geometries, res- pectively [21-23], by two nitrogen atoms from a 2,2’-bipyridine (N1 and N2 are in the equatorial position) and two oxygen atoms from 4-methyl benzoate molecules (O1 and O3 are in the equatorial position) and an oxygen atom from the aqua ligand (O5 in the axial position) [24]. The bond lengths of Cu1-O1 (1.9484(15) Å) and Cu1-O3 (1.9824(14) Å) in the equatorial position are found to be shorter than Cu1-O5 (2.3532(18) Å) in the axial position, for the square pyramidal complex. Furthermore, at the axial position, the Cu1-O5 bond length in the aqua ligand is shorter in five- coordinated aqua complexes (on average 2.25 Å [24] than in the six-coordinated ones (on average 2.56 Å [24]). The bond lengths of Cu-Nbipy, 2.0066(16) and 2.0183(17) Å, are slightly shorter than those obtained in [Cu(bpdc)(dap) (H2O)]·2H2O, 2.075(6) and 2.036(5) Å [24] and agree well with the complex [tetra-azido-tris(2-pyridyl)amine]dicopper(II) [25]. As a result, the bond length variation can be clarified by the effect of the neighbouring functional group. The bond angle of N1-Cu1-N2 (80.50(7)°) is closer to that found in [Cu(bp5dc) (en)(H2O)2]2·5H2O (80.87(2)°) [26]. In the 2,2'-bipyridine ring, the C-C and C-N bond lengths are in good agreement in the literature for 2-substituted pyridine derivatives [27-30]. The lengths of the C-O bonds in 4-methyl benzoate molecules range from 1.251(2) to 1.273(2) Å, due to all C-O bonds showing a single-bond character (Table 2). Furthermore, the bond angles of O2-C11-O1 (125.1(2)°) and O4-C19-O3 (122.35(18)°) in the 4-methyl benzoate molecules conform which is close to those notified in the similar structure 123.28(10)° [31]. 112 Kanmazalp et al. / European Journal of Chemistry 14 (1) (2023) 109-113 2023 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.14.1.109-113.2390 Table 3. Hydrogen bonds for [Cu(4-mba)2(bipy)(H2O)] *. D H A d(D-H) (Å) d(H-A) (Å) d(D-A) (Å) ∠ D-H-A (°) C10 H10 O3 0.93 2.54 3.035(3) 113.5 C4 H4 O41 0.93 2.48 3.367(3) 159.0 C2 H2 O22 0.93 2.64 3.448(3) 146.3 C7 H7 O41 0.93 2.46 3.348(3) 160.6 O5 H5A O2 0.792(17) 1.904(19) 2.658(3) 159(3) O5 H5B O43 0.809(17) 1.975(18) 2.774(2) 170(3) * Symmtery codes: 1 1-x, 1-y, 1-z, 2 2-x, 2-y, 1-z, 3 1+x, +y, +z Figure 2. A packing view of the molecules along with the b-axis. Figure 3. The Cg···Cg intermolecular interactions are shown as green dashed lines. In this molecular conformation, two O5-H5A···O2 and C10- H10···O3 are stabilised by intramolecular contacts. As shown in Figure 1, O5-H5A···O2 intramolecular hydrogen bond interac- tion forms a pseudo-five-membered ring with the S(5) graph set motif [32]. The crystal packing diagram for [Cu(4-mba)2 (bipy)(H2O)] consists of intramolecular and intermolecular O5- H5A···O2, O5-H5B···O4 hydrogen bonds, respectively, in the crystal packing as detailed in Table 3 and shown in Figure 2. These intramolecular and intermolecular interactions are influential in stabilising the molecular crystal structure and the creation of the 3-D chain supramolecular combination. There are also Cg···Cg interactions in the molecular system between 2,2’-bipyridine rings belonging to different symmetry codes, Cg3···Cg4. The distances are 3.6973(15) and 4.1869(15) Å, symmetry codes are −x+1, −y+1, −z+1, and x, y, z; and Cg3 and Cg4 are the center mass of the rings (Cg3: N1/C1/C2/C3/ C4/C5) and (Cg4: N2/C6/C7/C8/C9/C10), as indicated in Figure 3. 4. Conclusions In this work, the [Cu(4-meb)2(bipy)(H2O)]) complex was synthesized and characterized by the single crystal X-ray diffraction method. The molecular structure and coordination properties comprising the geometrical parameters of the prepared complex were designated. The obtained molecular geometry showed a square pyramidal configuration with the carboxylate ligand acting as a monodentate ligand. X-ray crystallographic studies of [Cu(4-mba)2(bipy)(H2O)] show that the molecular structure has two intramolecular interactions and four intermolecular interactions. Acknowledgments The authors acknowledge the Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST diffractometer. Supporting information CCDC-2141370 contains the supplementary crystallographic data for this article. These data can be obtained free of charge via https://www.ccdc.cam .ac.uk/structures/, or 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(0)1223-336033. Disclosure statement Conflict of interest: The authors declare that they have no conflict of interest. Ethical approval: All ethical guidelines have adhered. Sample availability: Sample of the compound is available from the author. CRediT authorship contribution statement Conceptualization: Sibel Demir Kanmazalp; Methodology: Sibel Demir Kanmazalp, Adnan Qadir; Software: Sibel Demir Kanmazalp, Necmi Dege; Validation: Adnan Qadir, Necmi Dege; Formal Analysis: Adnan Qadir, Necmi Dege; Investigation: Sibel Demir Kanmazalp; Resources: Sibel Demir Kanmazalp, Adnan Qadir; Data Curation: Necmi Dege; Writing - Original Draft: Sibel Demir Kanmazalp, Adnan Qadir; Writing - Review and Editing: mailto:data_request@ccdc.cam.ac.uk Kanmazalp et al. / European Journal of Chemistry 14 (1) (2023) 109-113 113 2023 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.14.1.109-113.2390 Sibel Demir Kanmazalp; Visualization: Sibel Demir Kanmazalp; Project Administration: Sibel Demir Kanmazalp. ORCID and Email Sibel Demir Kanmazalp sibeld@gantep.edu.tr ssibdemir@gmail.com https://orcid.org/0000-0002-5896-0966 Adnan Qadir adnan.qadir@su.edu.krd https://orcid.org/0000-0002-9286-0344 Necmi Dege necmid@omu.edu.tr https://orcid.org/0000-0003-0660-4721 References [1]. Jennifer, S. J.; Muthiah, P. T. Synthesis, crystal structures and supramolecular architectures of square pyramidal Cu(II) complexes containing aromatic chelating N,N’-donor ligands. Chemistry Central Journal 2014, 8, 42. [2]. Liu, F.-Y.; Zhang, M.-H.; Kou, J.-F. (2,2’-Bi-pyridine-κ(2) N,N’)bis- (nitrato-κ(2) O,O’)copper(II). Acta Crystallogr. Sect. E Struct. Rep. Online 2013, 69, m609. [3]. Atria, A. M.; Cortés, P.; Acevedo, L.; Trujillo, R.; Manzur, J.; Peña, O.; Baggio, R. PREPARATION, STRUCTURE AND PROPERTIES OF BIS (M2- CHLORO)-(NITRATO-O)-(2,2’-BIPYRIDINE- N.n’)-COPPER(II):[cu(2,2’-BP)cl NO3]2. J. Chil. Chem. Soc. 2004, 49, 341–344. [4]. Cody, C. C.; Kelly, H. R.; Mercado, B. Q.; Batista, V. S.; Crabtree, R. 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The full terms of this license are available at http://www.eurjchem.com/index.php/eurjchem/pages/view/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution, or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). mailto:sibeld@gantep.edu.tr mailto:ssibdemir@gmail.com https://orcid.org/0000-0002-5896-0966 mailto:adnan.qadir@su.edu.krd https://orcid.org/0000-0002-9286-0344 mailto:necmid@omu.edu.tr https://orcid.org/0000-0003-0660-4721 https://doi.org/10.1007/s10870-022-00960-2 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms http://creativecommons.org/licenses/by-nc/4.0 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms 1. Introduction 2. Experimental 2.1. Synthesis of [Cu(4-mba)2(bipy)(H2O)] 2.2. Crystal structure analysis 3. Results and discussion 4. Conclusions Acknowledgments Supporting information Disclosure statement CRediT authorship contribution statement ORCID and Email References PrintField10: PrintField11: PrintField12: PrintField13: PrintField14: PrintField20: PrintField21: PrintField22: PrintField23: PrintField24: