Citation: Chong-Yu LI, Peng YU. Solvothermal Synthesis, Crystal Structure and Characterization of a New Binuclear Copper(Ⅱ) Complex with K³:N¹:N²:N⁴-3-(Pyridin-2-yl)-1,2,4-triazole (HPT)[J]. Chinese Journal of Structural Chemistry, ;2021, 40(4): 453-458. doi: 10.14102/j.cnki.0254-5861.2011-3049 shu

Solvothermal Synthesis, Crystal Structure and Characterization of a New Binuclear Copper(Ⅱ) Complex with K³:N¹:N²:N⁴-3-(Pyridin-2-yl)-1,2,4-triazole (HPT)

Chong-Yu LI ,
Peng YU ^,

School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128, China

Corresponding author: Peng YU, pengy7505@hunau.edu.cn
Received Date: 29 November 2020
Accepted Date: 14 January 2021

Fund Project: the Key Research and Development Plan of Hunan Province 2019NK2031

Figures(5)

A new binuclear copper(Ⅱ) complex [Cu₂(MBBA)₂(HPT)₂(H₂O)₂]·2H₂O (1) was synthesized with copper acetate, 2-(4-methylbenzoyl) benzoic acid (MBBA) and 3-(pyridin-2-yl)-1H-1,2,4-triazole (HPT). It crystallizes in the monoclinic space group P2₁/c with a = 14.722(2), b = 8.8907(12), c = 18.5565(18) Å, β = 116.820(7)º, V = 2167.6(5) Å³, M_r = 483.96, D_c = 1.483 g/cm³, Z = 4, μ(MoKa) = 1.049 mm^-1, F(000) = 981, the final GOOF = 0.952, R = 0.0586 and wR = 0.0823. The whole molecule consists of two copper ions bridged by two HPT molecules. The central Cu(Ⅱ) ion is coordinated by six atoms to give a distorted octahedral coordination geometry. The structure of 1 has been determined by X-ray diffraction, IR spectrum and thermal stability analysis. The solid-state fluorescence displays an obvious emission band at 412 nm upon excitation at 330 nm. Magnetic properties indicate that 1 exhibits antiferromagnetic properties.
- binuclear copper(Ⅱ) complex,
- thermal stability,
- fluorescence,
- magnetic property
1. [1]
  Cui, L.; Luan, X. J.; Zhang, C. R.; Kang, Y. F.; Zhang, W. T.; Wang, Y. Y.; Shi, Q. Z. Four 3D "brick-wall"-like metal-organic frameworks with a flexible ligand of (S,S,R,R)-l,2,3,4-cyclopentanetetra carboxylic acid: crystal structures, luminescent and magnetic properties. Dalton Trans. 2013, 42, 1637–1644. doi: 10.1039/C2DT32022C
2. [2]
  Ling, Y.; Zhang, L.; Li, J.; Du, M. A robust porous Pt S-type Cu(Ⅱ) metal-organic framework: single-crystal-to-single-crystal transformation with reversible guest intercalation accompanied by colour change. CrystEngComm. 2011, 13, 768–770. doi: 10.1039/C0CE00775G
3. [3]
  Zhang, Q.; Shu, J.; Zhang, Y. J.; Xu, Z. G.; Yue, J.; Liu, X. Q.; Xu, B.; Chen, Z. Z.; Jiang, W. D. Structures and esterolytic reactivity of novel binuclear copper(Ⅱ) complexes with reduced-serine schiff bases as mimic carboxylesterases. Dalton Trans. 2020, 49, 10261–10269. doi: 10.1039/D0DT01823F
4. [4]
  Wen, L. L.; Zhao, J. B.; Lv, K.; Wu, Y. H.; Deng, K. J.; Leng, X. K.; Li, D. F. Visible-light-driven photocatalysts of metal-organic frameworks derived from multi-carboxylic acid and imidazole-based spacer. Cryst. Growth Des. 2017, 12, 1603–1612.
5. [5]
  (a) Mohapatra, B.; Venkatesh, V.; Verma, S. Crystal engineering with 2-aminopurine containing a carboxylic acid pendant. Cryst. Growth Des. 2014, 14, 5042–5052. (b) Li, W.; Li, C. H.; Yang, Y. Q.; Li, Y. L. Hydrothermal synthesis, crystal structure and thermal stability of binuclear cadmium complex with the o-methylbenzoyl-benzoic acid. Chin. J. Inorg. Chem. 2010, 26, 166–170.
6. [6]
  Adonin, S. A.; Novikov, A. S.; Fedin, V. P. Heteroleptic binuclear iodoacetate copper(Ⅱ) complexes with 3-bromopyridine and 4-ethylpyridine: crystal structures and peculiarities of contacts halogen center dot center dot center dot halogen. Koord. Khim. 2020, 46, 119–124. doi: 10.1134/S1070328420020013
7. [7]
  Caglar, S.; Demir, S. K. A crystallographic, spectroscopic, thermal, and DFT investigation of mixed ligand Cu(Ⅱ) complexes of 2–benzoylbenzoate. Synthesis and Reactivity in Inorganic, Metal-Org. and Nano-Metal Chem. 2012, 42, 1449–1458. . doi: 10.1080/15533174.2012.684263
8. [8]
  Crowston, B. J.; Shipp, J. D.; Chekulaev, D.; Heteronuclear d-d and d-f Ru(Ⅱ)/M complexes M = Gd(Ⅲ), Yb(Ⅲ), Nd(Ⅲ), Zn(Ⅱ) or Mn(Ⅱ) of ligands combining phenanthroline and aminocarboxylate binding sites: combined relaxivity, cell imaging and photophysical studies. Dalton Trans. 2019, 48, 6132–6152. doi: 10.1039/C9DT00954J
9. [9]
  Alexandru, M. G.; Visinescu, D.; Braun-Cula, B.; Lloret, F.; Julve, M. Synthesis, crystal structure and magnetic properties of three {(CrMn(Ⅱ)-Mn(Ⅲ} heterodimetallic complexes based on heteroleptic cyanido-bearing Cr(Ⅲ) building blocks. Eur. J. Inorg. Chem. 2018, 3–4, 349–359.
10. [10]
  Gusev, A.; Nemec, I.; Herchel, R.; Shul'gin, V.; Ryush, I.; Kiskin, M.; Efimov, N.; Ugolkova, E.; Minin, V.; Lyssenko, K.; Eremenko, I.; Linert, W. Copper(Ⅱ) self-assembled clusters of bis((pyridin-2-yl)-1,2,4-triazol-3-yl)alkanes. Unusual rearrangement of ligands under reaction conditions. Dalton Trans. 2019, 48, 3052–3060. doi: 10.1039/C8DT04816A
11. [11]
  Muzaffar, S.; Shahid, W.; Saleem, M.; Ashraf, M.; Aziz-ur, R.; Bashir, B.; Ali, M.; Al-Rashida, M.; Baral, B.; Bhattarai, K.; Riaz, N. Evaluation of ethylated phenylcarbamoylazinane-1,2,4-triazole amides derivatives as 5-lipoxygenase inhibitors together with cytotoxic, ADME and molecular modeling studies. Chemistryselect. 2020, 44, 14210–14216.
12. [12]
  Fang, Z. Y.; Zhang, L.; Ma, J. P.; Zhao, L.; Wang, S. L.; Xie, N. H.; Liu, Y. Q.; Guo, X. Y.; Qin, J. Dinuclear cobalt and nickel complexes of a mercaptoacetic acid substituted 1,2,4-triazole ligand: syntheses, structures and urease inhibitory studies. Acta Crystallogr, Sect. C 2019, 75, 1658–1664. doi: 10.1107/S2053229619015602
13. [13]
  Zhang, Y. J.; Yin, L.; Li, J.; Hu, Z. B.; Ouyang, Z. W.; Song, Y.; Wang, Z. X.; Synthesis, crystal structures, HF-EPR, and magnetic properties of six-coordinate transition metal (Co, Ni, and Cu) compounds with a 4-amino-1,2,4-triazole Schiff-base ligand. RSC Adv. 2020, 10, 12833–12840. doi: 10.1039/C9RA10851C
14. [14]
  Liu, F. Y.; Zhou, D. M.; Zhao, X. L.; Kou, J. F. Complexes of nickel(Ⅱ) and copper(Ⅱ) with 1,2,4-triazole-3-carboxylic acid and of cobalt(Ⅲ) with 3-amino-1,2,4-triazole-5-carboxylic acid. Acta Crystallogr., Sect. C 2017, 73, 1010–1029. doi: 10.1107/S2053229617012943
15. [15]
  Liu, F. Y.; Zhou, D. M.; Zhao, X. L.; Kou, J. F. Complexes of nickel(Ⅱ) and copper(Ⅱ) with 1,2,4-triazole-3-carboxylic acid and of cobalt(Ⅲ) with 3-amino-1,2,4-triazole-5-carboxylic acid. Acta Cryst. Sect. C 2017, 73, 1010–1029. doi: 10.1107/S2053229617012943
16. [16]
  Sheldrick, G. M. SHELXL-2014, Program for Crystal Structure Refinement. University of Gottingen, Gottingen, Germany 2014.
17. [17]
  Li, W.; Liu, Y.; Li, C. H.; Yang, Y. Q. Crystal structure, electrochemical and fluorescent properties of a new copper(Ⅱ) coordination polymer with 2,3-pyridinedi-carboxylic acid. Chin. J. Struct. Chem. 2019, 38, 1940–1946.
18. [18]
  Nakamota, K. Translated by Huang, D. R.; Wang, R. Q. Infrared and Raman Spectra of Inorganic and Coordination Compounds, 3rd edn. Beijing: Chemical Industry Press 1986.
19. [19]
  (a) Li, W.; Li, C. H.; Yang, Y. Q.; Li, H. F. Crystal structure, magnetic, fluorescent, electrochemical properties and thermal stability of a new copper(Ⅱ) coordination polymer [Cu₂(C₅H₄NCOO)₂(C₇H₅N₄)₂]_n. Z. Naturfors-chung, Section B 2015, 70, 215–219. (b) Li, W.; Li, Y. L.; Li, C. H.; Tan, X. W. Synthesis, crystal structure and properties of a new binuclear copper(Ⅱ) complex with 5-oxo-4-oxa-tricyclo[4.2. 1.0]nonane-9-carboxylic acid (TNCA). Chin. J. Struct. Chem. 2018, 37, 819–824.
20. [20]
  Chen, X. M.; Cai, J. W. Principle and Practice of Single Crystal Structural Analysis. Beijing, Science Press 2004.
21. [21]
  Chen, M. S.; Luo, L.; Chen, S. S.; Shu, Z.; Sun, W. Y. Hydrothermal syntheses, crystal structures and magnetic property of two copper(Ⅱ) complexes constructed from 5-(isonicotinamido)isophthalic acid and n-donor ligands. Chin. J. Inorg. Chim. 2010, 26, 2227–2236.
22. [22]
  (a) Ferrer, S.; Koningsbruggen, P. J.; Haasnoot, J. G.; Reedijk, J.; Kooijman, H.; Spek, A. L.; Lezama, L.; Arif, A. M.; Miller, J. S. Dimetallic complexes derived from a novel dinucleating chelating symmetric triazole ligand; crystal structure, magnetic properties and ESR study of bis[mu-3,5-diacetylamino-1,2,4-triazolato-O΄, N-1, N-2, O΄΄]bis[(nitrato)(aqua)copper(Ⅱ)]. J. Chem. Soc., Dalton Trans. 1999, 23, 4269–4276. (b) Gusev, A. N.; Shul'gin, V. F.; Ugolkova, E. A.; Efimov, N. N.; Aleksandrov, G. G.; Minin, V. V.; Eremenko, I. L. Binuclear copper(Ⅱ) complexes of functionalized 1,2,4-triazoles: synthesis, structure, and magnetic properties. Russian J. Inorg. Chem. 2014, 59, 699–705.
23. [23]
  (a) Nagao, K.; Heiman Lam, W.; Andrew, N.; Pave, J.; Clifford, C. L.; Hirofusa, S. Synthesis, spectroscopy, electrochemistry, spectroelectrochemistry, langmuir-blodgett film formation, and molecular orbital calculations of planar binuclear phthalocyanines. J. Am. Chem. Soc. 1994, 116, 879–890. (b) Li, D. P.; Wang, Q.; Xie, Y. B.; Zhang, J.; Lian, Q. Y.; Li, Y. X. Mononuclear Dy(Ⅲ) and Ho(Ⅲ) complexes with slow magnetic relaxation behavior. Chin. J. Inorg. Chim. 2018, 34, 1547–1554.
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Solvothermal Synthesis, Crystal Structure and Characterization of a New Binuclear Copper(Ⅱ) Complex with K3:N1:N2:N4-3-(Pyridin-2-yl)-1,2,4-triazole (HPT)

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通讯作者: 陈斌, bchen63@163.com

Solvothermal Synthesis, Crystal Structure and Characterization of a New Binuclear Copper(Ⅱ) Complex with K³:N¹:N²:N⁴-3-(Pyridin-2-yl)-1,2,4-triazole (HPT)