Syntheses, Characterization, and X-Ray Crystal Structure of a Co-Crystal Containing One Neutral Mononuclear Copper (II) Unit and One Cationic Dinuclear Copper (II) Unit Assembled with Schiff Base and Perchlorate Copper(II) Salt
Abstract
The use of 2-{[2-(2-hydroxybenzylideneamino)phenylimino]methyl}phenol (H2L) in metal transition chemistry has yielded a co-crystal which is composed by one neutral mononuclear, one cationic dinuclear and one perchlorate anion. During the formation of the complex, one of the salicylaldimine groups of one of the molecules of the H2L ligand hydrolyzed to form an asymmetrical ligand with an amino group leading to the molecule (2-((2-aminophenylimino)methyl)phenol (HL'). The complex was formulated as {[Cu(L)].[Cu2(L)(L')]}.(ClO4). The structure of the complex was solved by single crystal X-ray crystallography. In the mononuclear unit, the Cu2+ atom is coordinated by one dideprotonated molecule of the ligand acting in tetradentate fashion. In the dinuclear unit, one the Cu2+ atom is coordinated by one dideprotonated molecule of the ligand acting in tetradentate fashion and the other Cu2+ is coordinated by the monodeprotonated (2-((2-aminophenylimino)methyl)phenol (HL') acting in tridentate fashion. The two Cu2+ are bridged by the two phenoxo oxygen atoms of the dideprotonated molecule of the ligand. The complex crystallizes in the triclinic space group Pī with the following parameters: a = 13.8864 (3) Å, b = 14.2078 (4) Å, c = 14.5007 (4)) Å, α = 64.593 (3), β = 71.353 (2), γ = 71.707 (2)°, V = 2395.80 (13) Å3, Z = 2, R1 = 0.037, wR2 = 0.041. The supramolecular structures are consolidated by multiple hydrogen bonds.
References
Shimizu, T., Matsumoto, T., Goto, A., Yoshimura, K., & Kosuge, K. (2003). Cu-O-Cu bond-angle dependence of magnetic interactions in antiferromagnetic cuprates, Physica B: Condensed Matter, 329-333, 765-766. https://doi.org/10.1016/S0921-4526(02)02506-1
Kambe, S., & Ishii, O. (2000). Correlation between Tc, in-plane Cu-O-Cu bond length, and buckling of the CuO2 plane in cuprate superconductors, Physica C: Superconductivity, 341-348, 555-556. https://doi.org/10.1016/S0921-4534(00)00589-X
Cicco, A.D., & Sperandini, F. (1996). Cu-O-Cu in-plane angle distribution in layered superconductors probed by EXAFS, Physica C: Superconductivity, 258, 349-359. https://doi.org/10.1016/0921-4534(96)00014-7
Butcher, R.J., Diven, G., Erickson, G., Mockler, G.M., & Sinn, E. (1986). Copper complexes of binucleating N,N′-hydroxy-alkyldiaminebis(salicylidine) ligands containing a Cu-O-Cu bridge and an exogenous bridge, Inorganica Chimica Acta, 111, L55-L56. https://doi.org/10.1016/S0020-1693(00)84634-4
Venegas-Yazigi, D., Aravena, D., Spodine, E., Ruiz, E., & Alvarez, S. (2010). Structural and electronic effects on the exchange interactions in dinuclear bis(phenoxo)-bridged copper(II) complexes, Coordination Chemistry Reviews, 254, 2086-2095. https://doi.org/10.1016/j.ccr.2010.04.003
Kowsalya, P., Neelakantan, M.A., & Bhuvanesh, N.S.P. (2022). Tetranuclear Cu(II) complex with [2+4] Cu4O4 cubane based core framework derived from 2-[2-(1-hydroxy-ethyl)-phenylimino-methyl]-6-methoxy-phenol: Quantifying conventional and unconventional interactions and QTAIM analysis, Journal of Molecular Structure, 1254, 132396. https://doi.org/10.1016/j.molstruc.2022.132396
Kébé, M., Thiam, I.E., Sow, M.M., Diouf, O., Barry, A.H., Sall, A.S., Retailleau, P., & Gaye, M. (2021). Hexanuclear Copper(II) complex of 2-hydroxy-N,N'-bis-[1-(2-hydroxyphenyl)ethylidene]propane-1,3-di-amine incorporating an open-cubane core, Acta Crystallographica Section E, 77, 708-713. https://doi.org/10.1107/S2056989021005570
Mukherjee, D., Nag, P., Shteinman, A.A., Vennapusa, S.R., Mandal, U., & Mitra, M. (2021). Catechol oxidation promoted by bridging phenoxo moieties in a bis(μ-phenoxo)-bridged dicopper(ii) complex, RSC Advances, 11, 22951-22959. https://doi.org/10.1039/D1RA02787E
Nandi, N.B., Purkayastha, A., Roy, S., Kłak, J., Ganguly, R., Alkorta, I., & Misra, T.K. (2021). Tetranuclear copper(II) cubane complexes derived from self-assembled 1,3-dimethyl-5-(o-phenolate-azo)-6-aminouracil: structures, non-covalent interactions and magnetic property, New Journal of Chemistry, 45, 2742-2753. https://doi.org/10.1039/D0NJ05232A
Newns, D.M., & Tsuei, C.C. (2007). Fluctuating Cu-O-Cu bond model of high-temperature superconductivity, Nature Physics, 3, 184-191. https://doi.org/10.1038/nphys542
Agarwal, P., Kumar, A., Richa, Verma, I., Erande, R.D., Kłak, J., Mota, A.J., Arora, H., & Rajput, A. (2021). The reversible inter-conversion of copper(II) dimers bearing phenolate-based ligands in their monomers: theoretical and experimental viewpoints, New Journal of Chemistry, 45, 1203-1215. https://doi.org/10.1039/D0NJ00484G
Mallajosyula, S.S., & Pati, S.K. (2009). Conformational Tuning of Magnetic Interactions in Metal-DNA Complexes, Angewandte Chemie International Edition, 48, 4977-4981. https://doi.org/10.1002/anie.200806056
Elmali, A., Zeyrek, C.T., & Elerman, Y. (2004). Crystal structure, magnetic properties and molecular orbital calculations of a binuclear copper(II) complex bridged by an alkoxo-oxygen atom and an acetate ion, Journal of Molecular Structure, 693, 225-234. https://doi.org/10.1016/j.molstruc.2004.02.037
Sen, N., Butcher, R.J., Jasinski, J.P., & Gupta, S.K. (2021). A novel single-pot synthesis of dinuclear and mononuclear copper(II) complexes with sterically demanding Schiff bases: Structural, spectral, magnetic, electrochemical, DNA binding and theoretical investigation, Journal of Molecular Structure, 1231, 129955. https://doi.org/10.1016/j.molstruc.2021.129955
Bhaumik, P.K., & Chattopadhyay, S. (2021). Synthetic methodology, structures and properties of mixed valence copper(I/II) complexes with various Schiff bases and their reduced analogues, Polyhedron, 199, 115086. https://doi.org/10.1016/j.poly.2021.115086
Jana, N. Ch., Ghorai, P., Brandão, P., Jagličić, Z., & Panja, A. (2021). Proton controlled synthesis of two dicopper(ii) complexes and their magnetic and biomimetic catalytic studies together with probing the binding mode of the substrate to the metal center, Dalton Transactions, 50, 15233-15247. https://doi.org/10.1039/D1DT02369A
Tas, E., Kilic, A., Konak, N., & Yilmaz, I. (2008). The sterically hindered salicylaldimine ligands with their copper(II) metal complexes: Synthesis, spectroscopy, electrochemical and thin-layer spectroelectrochemical features, Polyhedron, 27, 1024-1032. https://doi.org/10.1016/j.poly.2007.11.038
Zhang, D., & Jin, G.-X. (2006). Bimetallic nickel complexes of trimethyl phenyl linked salicylaldimine ligands: Synthesis, structure and their ethylene polymerization behaviors, Inorganic Chemistry Communications, 9, 1322-1325. https://doi.org/10.1016/j.inoche.2006.08.017
Kaczmarek, M.T., Pospieszna-Markiewicz, I., Kubicki, M., & Radecka-Paryzek, W. (2004). Novel lanthanide salicylaldimine complexes with unusual coordination mode, Inorganic Chemistry Communications, 7, 1247-1249. https://doi.org/10.1016/j.inoche.2004.09.022
Radecka-Paryzek, W., Pospieszna-Markiewicz, I., & Kubicki, M. (2007). Self-assembled two-dimensional salicylaldimine lanthanum(III) nitrate coordination polymer, Inorganica Chimica Acta, 360, 488-496. https://doi.org/10.1016/j.ica.2006.07.071
Radecka-Paryzek, W., Pospieszna-Markiewicz, I., & Kubicki, M. (2010). Self-assembly as a route to one-dimensional lanthanum(III) salicylaldimine coordination polymer, Journal of Rare Earths, 28, 51-55. https://doi.org/10.1016/S1002-0721(10)60387-0
Majumder, I., Chakraborty, P., Álvarez, R., Gonzalez-Diaz, M., Peláez, R., Ellahioui, Y., Bauza, A., Frontera, A., Zangrando, E., Gómez-Ruiz, S., & Das, D. (2018). Bioactive heterometallic CuII-ZnII complexes with potential biomedical applications, ACS Omega, 3, 13343-13353. https://doi.org/10.1021/acsomega.8b01260
Chakraborty, T., Sarkar, A., Adhikary, A., Chakiroy, N., & Das, D. (2019). Synthesis of structurally diverse ferrimagnetically and antiferromagnetically coupled MII-MnII (M = Cu, Ni) heterometallic Schiff base compounds with a dicyanamide spacer and study of biomimetic catalytic activity, Crystal Growth & Design, 19, 7336-7348. https://doi.org/10.1021/acs.cgd.9b01205
Dong, R., Liu, Y., Wu, X., Zhou, H., & Shen, X. (2018). Synthesis, structure and magnetic properties of two new 3d-3d′-4f clusters of NiIIHoIIIMIII (M = Fe, Co), Inorganica Chimica Acta, 482, 687-690. https://doi.org/10.1016/j.ica.2018.07.013
Sarr, M., Diop, M., Thiam, E.I., Gaye, M., Barry, A.H., Orton, J.B., & Coles, S.J. (2018). A New co-Crystal dinuclear/trinuclear ZnII-ZnII/ZnII-SmIII-ZnII complex with a salen-type Schiff base ligand, Acta Crystallographica Section E, 74, 1862-1866. https://doi.org/10.1107/S2056989018016109
Sarr, M., Thiam, E.I., Gaye, M., Barry, A.H., Alvarez, N. & Ellena, J. (2018). European Journal of Chemistry, 9, 67-73. https://doi.org/10.5155/eurjchem.9.2.67-73.1688
Costes, J.-P., Dahan, F., Vendier, L., Shova, S., Lorusso, G., & Evangelisti, M. (2018). NiII-LnIII complexes with o-vanillin as the main ligand: syntheses, structures, magnetic and magnetocaloric properties, Dalton Transactions, 47, 1106-1116. https://doi.org/10.1039/C7DT04293K
Costes, J.-P., Novitchi, G., Shova, S., Dahan, F., Donnadieu, B., & Tuchagues, J.-P. (2004). Synthesis, structure, and magnetic properties of heterometallic dicyanamide-bridged Cu−Na and Cu−Gd one-dimensional polymers, Inorganic Chemistry, 43, 7792-7799. https://doi.org/10.1021/ic048942i
Haba, P., Sow, M.M., Sarr, M., Thiam, I.E., Diaw, M., & Gaye, M.L. (2020). Syntheses, characterization and X-ray crystal structure of polymeric heteronuclear oxo-bridged Fe/Na assembled with Salen-type Schiff base and dicyanamide, Science Journal of Chemistry, 8, 20-27. https://doi.org/doi:10.11648/j.sjc.20200802.11
Haba, P., Sow, M.M., Sarr, M., Thiam, I.E., Diaw, M., Retailleau, P., & Gaye, M.L. (2020). Syntheses, characterization, and X-ray crystal structure of heteronuclear Zn/Na assembled with Salen-type schiff base, Science Journal of Chemistry, 8, 113-118. https://doi.org/doi:10.11648/j.sjc.20200805.13
Routaray, A., Nath, N., Maharana, T., Sahoo, P.K., Das, J.P., & Sutar, A.K. (2016). Salicylaldimine Copper(II) complex catalyst: Pioneer for ring opening Polymerization of Lactide, Journal of Chemical Sciences, 128, 883-891. https://doi.org/10.1007/s12039-016-1091-3
Malgas-Enus, R., & Mapolie, S.F. (2012). A novel nickel (II) complex based on a cyclam-cored generation-one dendrimeric salicylaldimine ligand and its application as a catalyst precursor in norbornene polymerization: Comparative study with some other first generation DAB-polypropyleneimine metallodendrimers, Polyhedron, 47, 87-93. https://doi.org/10.1016/j.poly.2012.08.015
Sheldrick, G.M. (2015). SHELXT - Integrated space-group and crystal-structure determination, Acta Crystallographica Section A, 71, 3-8. https://doi.org/10.1107/S2053273314026370
Sheldrick, G.M. (2015). Crystal structure refinement with SHELXL, Acta Crystallographica Section C, 71, 3-8. https://doi.org/10.1107/S2053229614024218
Farrugia, L.J. (2012). WinGX and ORTEP for Windows: an update, Journal of Applied Crystallography, 45, 849-854. https://doi.org/10.1107/S0021889812029111
Smrečki, N., Stilinović, V., Jović, O., Kukovec, B.-M., & Popović, Z. (2017). Copper(II) perchlorate complexes with N-arylalkyliminodiacetamide ligands: X-ray structural, vibrational spectroscopic, DFT and thermogravimetric studies, Inorganica Chimica Acta, 462, 57-63. https://doi.org/10.1016/j.ica.2017.03.011
Burgos-Lopez, Y., Plá, J.D., Balsa, L.M., León, I.E., Echeverría, G.A., Piro, O.E., García-Tojal, J., Pis-Diez, R., González-Baró, A.C., & Parajón-Costa, B.S. (2019). Synthesis, crystal structure and cytotoxicity assays of a copper(II) nitrate complex with a tridentate ONO acylhydrazone ligand. Spectroscopic and theoretical studies of the complex and its ligand, Inorganica Chimica Acta, 487, 31-40. https://doi.org/10.1016/j.ica.2018.11.039
Kurup, M.R.P., Varghese, B., Sithambaresan, M., Krishnan, S., Sheeja, S.R., & Suresh, E. (2011). Synthesis, spectral characterization and crystal structure of copper(II) complexes of 2-benzoylpyridine-N(4)-phenylsemicarbazone, Polyhedron, 30, 70-78. https://doi.org/10.1016/j.poly.2010.09.030
Geary, W.J. (1971). The use of conductivity measurements in organic solvents for the characterisation of coordination compounds, Coordination Chemistry Reviews, 7, 81-122. https://doi.org/10.1016/S0010-8545(00)80009-0
Addison, A.W., Rao, T.N., Reedijk, J., van Rijn, J., & Verschoor, G.C. (1984). Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen-sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate, J. Chem. Soc., Dalton Trans., 1984, 1349-1356. https://doi.org/10.1039/DT9840001349
Dutta, G., Debnath, R.K., Kalita, A., Kumar, P., Sarma, M., Shankar, R.B., & Mondal, B. (2011). An asymmetric dinuclear copper(II) complex with phenoxo and acetate bridges: Synthesis, structure and magnetic studies, Polyhedron, 30, 293-298. https://doi.org/10.1016/j.poly.2010.10.029
Choudhury, C.R., Dey, S.K., Karmakar, R., Wu, C.-D., Lu, C.-Z., El Fallah, M.S., & Mitra, S. (2003). First report of singly phenoxo-bridged copper(II) dimeric complexes: synthesis, crystal structure and low-temperature magnetic behaviour study, New Journal of Chemistry, 27, 1360-1366. https://doi.org/10.1039/B300217A
Ray, M.S., Mukhopadhyay, G., Drew, M.G.B., Lu, T.-H., Chaudhuri, S., & Ghosh, A. (2003). A diphenoxo bridged antiferromagnetically coupled dimer of copper(II) having bridging methanol, Inorganic Chemistry Communications, 6, 961-965. https://doi.org/10.1016/S1387-7003(03)00143-6
Thakurta, S., Rizzoli, C., Butcher, R.J., Gómez-García, C.J., Garribba, E., & Mitra, S. (2010). Sterically-controlled nuclearity in new copper(II) complexes with di-compartmental ligands: Formation of antiferromagnetically coupled angular trimer and mononuclear inclusion complex, Inorganica Chimica Acta, 363, 1395-1403. https://doi.org/10.1016/j.ica.2009.12.053
Singh, Y.P., Patel, R.N., Singh, Y., Choquesillo-Lazarte, D., & Butcher, R.J. (2017). Classical hydrogen bonding and stacking of chelate rings in new copper(ii) complexes, Dalton Transactions, 46, 2803-2820. https://doi.org/10.1039/C6DT04661D
Marinovich, A.F., O’Mahony, R.S., Waters, J.M., & Waters, T.N.M. (1999). Schiff base complexes of copper(II). Croatica Chemica Acta, 72, 685-703. https://hrcak.srce.hr/132265
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