Online First

Synthesis and Structure of the Novel Mononuclear Copper(II) Complex of the Unsymmetrical Pyrimidine-Modulated Long-Chain Hexapyridylpentaamine Ligand

Authors

  • Sabina Z. Ismayilova Institute of Catalysis and Inorganic Chemistry named after acad. M. Nagiyev, Ministry of Science and Education of the Republic of Azerbaijan, Baku, Azerbaijan https://orcid.org/0000-0002-3957-7996
  • Lala Sh. Guliyeva Institute of Catalysis and Inorganic Chemistry named after acad. M. Nagiyev, Ministry of Science and Education of the Republic of Azerbaijan, Baku, Azerbaijan https://orcid.org/0009-0000-8477-916X
  • Rayyat H. Ismayilov Institute of Catalysis and Inorganic Chemistry named after acad. M. Nagiyev, Ministry of Science and Education of the Republic of Azerbaijan, Baku, Azerbaijan https://orcid.org/0009-0004-7753-6468
  • Dilgam B. Tagiyev Institute of Catalysis and Inorganic Chemistry named after acad. M. Nagiyev, Ministry of Science and Education of the Republic of Azerbaijan, Baku, Azerbaijan
  • Fuad F. Valiyev “OilGasScientificResearchProject” Institute, SOCAR, Baku, Azerbaijan https://orcid.org/0009-0004-1120-8728
  • Bahattin Yalcin Department of Chemistry, Marmara University, Kadikoy, Istanbul, Turkiye
  • Ajdar A. Medjidov Institute of Catalysis and Inorganic Chemistry named after acad. M. Nagiyev, Ministry of Science and Education of the Republic of Azerbaijan, Baku, Azerbaijan https://orcid.org/0000-0002-1766-5450
  • Mansura T. Huseynova Institute of Chemistry and Additives, Ministry of Science and Education of the Republic of Azerbaijan, Baku, Azerbaijan https://orcid.org/0000-0002-1534-6819
  • Su-Ying Chien X-Ray Laboratory, Institute of Chemistry, Academia Sinica, Taiwan, China
  • Gene-Hsiang Lee Department of Chemistry, National Taiwan University, Taipei, Taiwan, China
  • Shie-Ming Peng Department of Chemistry, National Taiwan University, Taipei, Taiwan, China

DOI:

https://doi.org/10.31489/2959-0663/4-25-6

Keywords:

modulated oligo-α-aminopyridine ligand, long-chain ligand, copper complex, crystal structure, addison parameter, hydrogen bonds, spectroscopy, magnetic measurement

Abstract

Through the pyrimidine-modulated hexapyridylpentaamine ligand N2-(pyridin-2-yl)-N6-(6-((6-((6-(pyrim­idin-2-ylamino)pyridin-2-yl)amino)pyridin-2-yl)amino)pyridin-2-yl)pyridine-2,6-diamine (H5N11-tpm), a new mononuclear copper(II) complex [Cu(H5N11-tpm)](ClO4)2 (1) were synthesized and structurally characterized. The single crystal X-ray analysis showed distorted trigonal bypyramidal geometry (Addison parameter value τ = 0.69) of the complex (1), which is well consistent with the “inverted type” of ESR spectra (g∥ < g⊥), measured magnetic susceptibility, and electronic spectroscopy studies. The equatorial copper-nitrogen distances (Cu–N(1) = 2.094(9) Å; Cu–N(5) = 2.045(9) Å; Cu–N(9) = 2.214(9) Å), along with the axial Cu–N distances (Cu–N(3) = 1.999(9) Å and Cu–N(7) = 2.001(9) Å), fall well within the range typically reported for Cu(II) complexes that incorporate this type of ligand. All Cu–N distances are short, ranging from 1.999(9) to 2.094(9) Å, which suggests a strong binding affinity of the chelating ligand. The monohelical H5N11-tpm ligand coordinates with the metal atom, exhibiting an all-anti conformation. The extensive hydrogen bonds were observed between the amino groups and uncoordinated perchlorate anions, resulting in the formation of a three-dimensional network (3D) of the complex. The synthesized complex has high potential for the creation of novel cholinesterase inhibitors since it contains a number of pyridine and pyrimidine rings.

References

Berry, J. F., Cotton, F. A., Daniels, L. M., & Murillo, C. A. (2002). Trinickel Dipyridylamido Complex with Metal-Metal Bonding Interaction: Prelude to Polynickel Molecular Wires and Devices. J. Am. Chem. Soc., 124, 3212–3213. https://doi.org/10.1021/ja025543i

Ting, T.C., Hsu, L.Y., Huang, M.J., Horng, E.C., Lu, H.C., Hsu, C.H., Jiang, C.H., Jin, B.Y., Peng, S.M., & Chen, C.H. (2015). Energy-Level Alignment for Single-Molecule Conductance of Extended Metal-Atom Chains. Angew. Chem. Int. Ed., 54, 15734–15738. https://doi.org/10.1002/anie.201508199

Ismayilov, R.H., Ismayilova, S.Z., Tagiyev, D.B., Medjidov, A.A., Jafarov, Y.I., Wang, W.Z., Yeh, C.Y., Chien, S.Y., Lee, G.H., & Peng, S.M. (2025). Linear nonanuclear chromium(II) complex with pyrazine-modulated pentapyridyltetraamine ligand: Synthesis, structure and properties. J. Mol. Struct. 1331, 141592. https://doi.org/10.1016/j.molstruc.2025.141592

Ismayilov, R.H., Valiyev, F.F., Tagiyev, D.B., Song, Y., Medjidov, A.A., Fatullayeva, P.A., Tüzün, B., Taslimi, P., Peng, C.H., Chien, S.Y., Lee, G.H., & Peng, S.M. (2024). Trinuclear nickel (II) string complexes and copper (II) coordination polymer with pyrazine modulated unsymmetrical dipyridylamino ligand: Synthesis, structure and bioactivity properties with molecular docking. J. Mol. Struct., 1307, 137966. https://doi.org/10.1016/j.molstruc.2024.137966

Chae, D.H., Berry, J.F., Jung, S., Cotton, F.A., Murillo, C.A., & Yao, Z. (2006). Vibrational Excitations in Single Trimetal-Molecule Transistors. Nano Lett., 6, 165–168. https://doi.org/10.1021/nl0519027

Ismayilov, R.H., Valiyev, F.F., Tagiyev, D.B., Song, Y., Israfilov, N.V., Wang, W.-Z., Lee, G.-H., Peng, S.-M., & Suleimanov, B.A. (2018). Linear pentanuclear nickel(II) and tetranuclear copper(II) complexes with pyrazine-modulated tripyridyldiamine ligand: Synthesis, structure and properties. Inorganica Chimica Acta 483, 386–391. https://doi.org/10.1016/j.ica.2018.08.045

Abbasova, G.G., Ismayilov, R.H., Tagiyev, D.B., Şenol, H., Song, Y., Medjidov, A.A., Huseynova, M.T., Fatullaeva, P.A., Taslimi, P., Sadeghian, N., Lee, G.H., & Peng, S.M. (2024). Synthesis, characterization, crystal structure, molecular dynamics simulations, MM-GBSA analysis, and bioactivity studies of pyrazine- and pyrimidine-modulated unsymmetrical dipyridylamide complexes. J. Mol. Struct., 1315, 138896. https://doi.org/10.1016/j.molstruc.2024.138896

Brogden, D.W. & Berry, J.F. (2015). Coordination Chemistry of 2,2’-Dipyridylamine: The Gift That Keeps on Giving. Comments Inorg. Chem., 17–37. https://doi.org/10.1080/02603594.2015.1079522

Ismayilov, R.H., Wang, W.Z., Wang, R.R., Yeh, C.Y., Lee, G.H., & Peng, S.M. (2007). Four quadruple metal–metal bonds lined up: linear nonachromium(II) metal string complexes. Chem. Commun. 1121–1123. https://doi.org/10.1039/B614597C

Yeh, C.Y., Wang, C.C., Chen, Y.H., & Peng, S.M. (2006). Redox Systems Under Nano-Space Control. Redox Systems Under Nano-Space Control. Springer Berlin Heidelberg. https://doi.org/10.1007/3-540-29580-1

Wang, W.Z., Ismayilov, R.H., Lee, G.H., Liu, I.P.C., Yeh, C.Y., & Peng, S.M. (2007). The nano-scale molecule with the longest delocalized metal–metal bonds: linear heptacobalt(II) metal string complexes [Co7(μ7-L)4X2]. Dalton Trans., 830–839. https://doi.org/10.1039/B614661A

Ismayilov, R.H., Wang, W.Z., Lee, G.H., & Peng, S.M. (2006). One-, two- and three-dimensional Cu(II) complexes built via new oligopyrazinediamine ligands: from antiferromagnetic to ferromagnetic coupling. Dalton Trans., 478–491. https://doi.org/10.1039/B507485A

Guliyeva, L. Sh., Ismayilova, S. Z., Ismayilov, R. H., Tagiyev, D. B., Yalcin, B., Medjidov, A. A., Peng, C. H., Chien, S. Y., & Lee, G. H. (2025, June 3–5). Copper(II) monohelix complex with pyrimidine-modulated long-chain oligo-α-aminopyridine ligand: Synthesis and crystal structure. In International UFAZ Conference: Chemistry, Process, Materials (pp. 42–43).

Hasanov, H., Tan, U.K., Wang, R.R., Lee, G.H., & Peng, S.M. (2004). Synthesis of long-chained oligo-a-aminopyridines by tandem Pd-catalyzed cross-coupling aminations and their helical dinuclear complexes. Tetrahedron Letters, 7765-7769. https://doi.org/10.1016/j.tetlet.2004.08.066

Sheldrick, G.M. (2008). A short history of SHELX. Acta Cryst., A64, 112. http://dx.doi.org/10.1107/S0108767307043930

Sheldrick, G.M. (2015). Crystal structure refinement with SHELXL. Acta Crys. C71, 3–8. http://dx.doi.org/10.1107/S2053229614024218

Ismayilova, S.Z., Ismayilov, R.H., Tagiyev, D.B., Yalcin, B., Şahin, O., Medjidov, A.A., Huseynova, M.T., Guliyeva, L.Sh., Gasimov, R.J., & Peng, S.M. (2025). Copper(II) complex of the pyrazine-modulated oligo-α-aminopyridine as a coordination polymers' promising building block. Chem. Probl., 4(23), 476–482. https://doi.org/10.32737/2221-8688-2025-4-476-482

Ismayilova, S.Z., Huseynova, M.T., Ismayilov, R.H., & Medjidov, A.A. (2024). Synthesis and properties of CuII complex of benzidine-N,N,N′,N′-tetraacetic acid. Azerbaijan Chem. J., 3, 69–75. https://doi.org/10.32737/0005-2531-2024-3-69-75

Vicente, M., Bastida, R., Macías, A., Valencia, L., Geraldes, C.F.G.C., & Brondino, C.D. (2005). Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex. Inorg. Chim. Acta, 358, 1141–1150. https://doi.org/10.1016/j.ica.2004.11.006

Aljahdali, M., & EL-Sherif, A.A. (2013). Synthesis, characterization, molecular modeling and biological activity of mixed ligand complexes of Cu(II), Ni(II) and Co(II) based on 1,10-phenanthroline and novel thiosemicarbazone. Inorg. Chim. Acta, 407, 58-68. https://doi.org/10.1016/j.ica.2013.06.040

Chandra, S., & Gupta, L.K. (2005). EPR, mass, IR, electronic, and magnetic studies on copper(II) complexes of semicarbazones and thiosemicarbazones. Spectrochimica Acta Part A, 61, 269–275. https://doi.org/10.1016/j.saa.2004.03.040

Jozefíkova, F., Perontsis, S., Konarikova, K., Svorc, L., Mazúr, M., Psomas, G., & Moncol, J. (2022). In vitro biological activity of copper(II) complexes with NSAIDs and nicotinamide: Characterization, DNA- and BSA-interaction study and anticancer activity. J. Inorg. Biochem., 228, 111696. https://doi.org/10.1016/j.jinorgbio.2021.111696

Valko, M., Pelikán, P., Biskupič, S., & Mazúr, M. (1990). ESR spectra of copper(II) complexes in the solids. Chem. Papers, 44, 805–813.

Korkmaz, Ş.A., Karadağ, A., Yerli Y., & Soylu, M.S. (2014). Synthesis and characterization of new heterometallic cyanido complexes based on [Co(CN)6]3– building blocks: crystal structure of [Cu2(N-bishydeten)2Co(CN)6]·3H2O having a strong antiferromagnetic exchange. New. Chem. 38, 5402–5410. https://doi.org/10.1039/C4NJ00737A

The molecular structure of [Cu(H5N11-tpm)](ClO4)2 1

Downloads

Additional Files

Published

2025-12-12

How to Cite

Ismayilova, S. Z., Guliyeva, L. S., Ismayilov, R. H., Tagiyev, D. B., Valiyev, F. F., Yalcin, B., … Peng, S.-M. (2025). Synthesis and Structure of the Novel Mononuclear Copper(II) Complex of the Unsymmetrical Pyrimidine-Modulated Long-Chain Hexapyridylpentaamine Ligand. EURASIAN JOURNAL OF CHEMISTRY. https://doi.org/10.31489/2959-0663/4-25-6

Issue

Online First

Section

ONLINE FIRST

License

Copyright (c) 2024 Sabina Z. Ismayilova, Lala Sh. Guliyeva, Rayyat H. Ismayilov, Dilgam B. Tagiyev, Fuad F. Valiyev, Bahattin Yalcin, Ajdar A. Medjidov, Mansura T. Huseynova, Su-Ying Chien, Gene-Hsiang Lee, Shie-Ming Peng

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License (CC BY-NC-ND 4.0) that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.