Citation: Ran ZHUANG, Xinru WANG, Ruwei SHEN, Dunru ZHU. Syntheses, crystal structures and Hirshfeld surface analyses of three 3-pyridazinyl-substituted triaryltriazoles and their Cu(Ⅱ) complexes[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(8): 1712-1722. doi: 10.11862/CJIC.20260136 shu

Syntheses, crystal structures and Hirshfeld surface analyses of three 3-pyridazinyl-substituted triaryltriazoles and their Cu(Ⅱ) complexes

Ran ZHUANG ¹ ,
Xinru WANG ¹ ,
Ruwei SHEN ¹ ,
Dunru ZHU ^{1, 2,,}

1.
College of Chemical Engineering, State Key Laboratory of Material-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, China
2.
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, China

Corresponding author: Dunru ZHU, zhudr@njtech.edu.cn
Received Date: 18 April 2026
Revised Date: 13 May 2026

Figures(6)

Three new 3-pyridazinyl-substituted triaryltriazoles, 4-(4-R-phenyl)-3-(2-pyridyl)-5-(3-pyridazinyl)-1,2,4-triazole (L¹: R=OCH₃; L²: R=H; L³: R=F) and their Cu(Ⅱ) complexes, trans-[Cu(L¹)₂(NO₃)₂]·H₂O (1), trans-[Cu(L²)₂(NO₃)₂] (2) and trans-[Cu(L³)₂(H₂O)₂](NO₃)₂ (3), have been synthesized and characterized by FTIR, ¹H NMR, elemental analysis and single crystal X-ray crystallography. Crystal structure analyses reveal that the supramolecular trimer (L¹)₃ and complex 3 crystallize in the triclinic P1 space group, the ligand L² and complexes 1 and 2 belong to the monoclinic P2₁/c space group, while the ligand L³ crystallizes in the monoclinic P2₁/n space group. There is a hydrogen-bonded trimer (L¹)₃ in the asymmetric unit of the ligand L¹. In the complexes 1-3, there is a distorted [CuN₄O₂] octahedron with two NO₃^- ions located in the axial positions in 1 and 2, whereas the two water molecules occupy the axial sites in 3. In the equatorial plane of 1-3, each L ligand adopts a chelating bidentate mode to bind the Cu(Ⅱ) ion through the pyridyl N atom and one triazole N atom, leaving the pyridazinyl group uncoordinated. The intermolecular interactions in the free ligands and the complexes have been explored by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main intermolecular interactions are H…H and C…H/H…C contacts in (L¹)₃, H…H and N…H/H…N contacts in L², H…H, N…H/H…N and C…H/H…C in L³, H…H and O…H/H…O contacts in both 1 and 2, H…H, N…H/H…N and O…H/H…O contacts in 3.
- synthesis,
- crystal structure,
- pyridazine,
- triaryltriazole,
- Cu(Ⅱ) complex,
- Hirshfeld surface analysis
1. [1]
  KITCHEN J A, BROOKER S. Spin crossover in iron(Ⅱ) complexes of 3, 5-di(2-pyridyl)-1,2,4-triazoles and 3, 5-di(2-pyridyl)-1,2,4-triazolates[J]. Coord. Chem. Rev., 2008, 252(18/19/20): 2072-2092
2. [2]
  QI L, CHENG H M, SHEN X, LU W, ZHU D R. Fe(Ⅱ) spin crossover molecule-based materials[J]. Prog. Chem., 2009, 21(6): 1187-1198
3. [3]
  ZHU D R, XU Y, YU Z, GUO Z J, SANG H, LIU T, YOU X Z. A novel bis(trans-thiocyanate)iron(Ⅱ) spin-transition molecular material with bidentate triaryltriazole ligands and its bis(cis-thiocyanate)iron(Ⅱ) high-spin isomer[J]. Chem. Mater., 2002, 14(2): 838-843 doi: 10.1021/cm010688u
4. [4]
  SHEU C F, SHIH C H, SUGIMOTO K, CHENG B M, TAKATA M, WANG Y. A long-lived photo-induced metastable state of linkage isomerization accompanied with a spin transition[J]. Chem. Commun., 2012, 48(46): 5715-5717 doi: 10.1039/c2cc31326j
5. [5]
  SHEN G P, QI L, WANG L, XU Y, JIANG J J, ZHU D R, LIU X Q, YOU X Z. Spin-crossover in a trans-[FeL₂(NCS)₂] family (L=triaryltriazole): Remote substituent effects on spin transition modes and temperature[J]. Dalton Trans., 2013, 42(48): 10144-10152
6. [6]
  PALIWODA D, VENDIER L, GETZNER L, ALABARSE F, COMBONI D, MARTIN B, ALAVI S E, BELLO M P, SALMON L, NICOLAZZI W, MOLNÁR G, BOUSSEKSOU A. Elastic properties of the iron(Ⅱ)-triazole spin crossover complexes [Fe(Htrz)₂trz]BF₄ and [Fe(NH₂trz)₃]SO₄[J]. Cryst. Growth Des., 2023, 23(3): 1903-1914 doi: 10.1021/acs.cgd.2c01396
7. [7]
  FENG Z, LING J J, SONG H J, ZHU D R. A water-tuned reversible spin transition with the largest hysteresis loop in 3D Hofmann frameworks pillared by flexible ligands[J]. Inorg. Chem. Front., 2023, 10(1): 305-315 doi: 10.1039/D2QI01873J
8. [8]
  ZHOU J, YANG J, QI L, SHEN X, ZHU D R. Synthesis, crystal structure and magnetic property of the novel dinuclear nickel(Ⅱ) complex with 4-(p-methoxyphenyl)-3, 5-bis(pyridine-2-yl)-1,2,4-triazole[J]. Transit. Metal Chem., 2007, 32(6): 711-715 doi: 10.1007/s11243-007-0234-2
9. [9]
  CHENG H M, ZHU D R, LU W, XU R H, SHEN X. Synthesis and crystal structure characterization of 3, 5-bis(2-quinolyl)-1,2,4-triazole[J]. J. Heterocycl. Chem., 2010, 47(1): 210-213 doi: 10.1002/jhet.262
10. [10]
  SHEN G P, ZHAO J, JIANG J J, LIU Q, SHEN X, XU Y, ZHU D R, LIU X Q. Abnormal conformation change of an asymmetrical triaryltriazole before and after its coordination[J]. J. Mol. Struct., 2011, 1002(1/2/3): 159-166
11. [11]
  CHEN L, ZHAO J, SHEN G P, SHEN X, XU Y, ZHU D R, WANG J. Syntheses, crystal structures, and spectral characterization of two new Cu(Ⅱ) and Co(Ⅱ) complexes with an asymmetrical substituted triaryltriazole[J]. J. Coord. Chem., 2011, 64(22): 3980-3991 doi: 10.1080/00958972.2011.634909
12. [12]
  ZHAO J, SHEN G P, ZHANG Y, SHEN X, ZHU D R. Syntheses, crystal structures, and spectral characterization of three new asymmetrical substituted triaryltriazoles[J]. J. Heterocycl. Chem., 2012, 49(5): 1114-1119 doi: 10.1002/jhet.949
13. [13]
  CHEN L, CHENG H M, JIANG J J, SHEN X, ZHU D R. Synthesis, crystal structure and thermal stability of [CuL₂(ClO₄)₂] (L=3-(p-bromophenyl)-4-(p-methylphenyl)-5-(2-pyridyl)-1,2,4-triazole)[J]. Chinese J. Inorg. Chem., 2012, 28(2): 381-385
14. [14]
  JIANG J J, CHEN L, ZHAO J, SHEN X, XU Y, ZHU D R. Abnormal change of triazole-pyridyl dihedral angle in a Co(Ⅱ) complex with asymmetrical substituted triaryltriazoles[J]. Chinese J. Inorg. Chem., 2012, 28(9): 1940-1944
15. [15]
  SHEN G P, JIANG J J, SUN F, SHEN X, ZHU D R, LIU X Q. Syntheses, crystal structures, and spectral characterization of two novel quinolyl substituted triazoles [J]. J. Heterocycl. Chem., 2013, 50(5): 1152-1156 doi: 10.1002/jhet.1611
16. [16]
  GONG J, HE X, CHEN L, SHEN X, ZHU D R. Syntheses, crystal structures, and spectral characterization of an asymmetrically substituted 1,2,4-triazole and its iron(Ⅱ) complex[J]. J. Coord. Chem., 2013, 66(16): 2875-2884 doi: 10.1080/00958972.2013.818139
17. [17]
  WANG L, JIANG J J, CHEN L, SHEN X, ZHU D R. Coexistence of two distinct axial ligands and their thermo-induced substitution in trans-[FeL₂(NCS)₂][FeL₂(CH₃OH)₂](NCS)₂ (L=4-amino-3-(p-chlorophenyl)-5-(2-pyridyl)-1,2,4-triazole)[J]. Inorg. Chem. Commun., 2013, 28: 104-108 doi: 10.1016/j.inoche.2012.11.022
18. [18]
  HE X, CAO D Y, JIANG J J, SHEN X, ZHU D R. Synthesis, crystal structures, and magnetic properties of three iron(Ⅱ) complexes with 3-(p-bromophenyl)-4-phenyl-5-(2-pyridyl)-1,2,4-triazole[J]. J. Coord. Chem., 2014, 67(2): 227-235 doi: 10.1080/00958972.2013.877585
19. [19]
  LI B, ZHOU Y F, ZHANG S P, QIN T, SHEN X, XU Y, ZHU D R. Synthesis, crystal structures, and magnetic properties of three new iron(Ⅱ) complexes with pyrrolyl-substituted triaryltriazoles[J]. J. Coord. Chem., 2016, 69(18): 2647-2655 doi: 10.1080/00958972.2016.1214724
20. [20]
  ZHOU Y F, ZHANG S P, FENG Z, SHEN X, ZHU D R. Syntheses, crystal structures, and spectral characterization of six novel benzimidazolyl substituted triaryltriazoles[J]. J. Heterocycl. Chem., 2017, 54(5): 2773-2780 doi: 10.1002/jhet.2880
21. [21]
  ZHANG S P, FENG Z, WU B, JIANG J J, ZHU D R, HE B F. Syntheses, crystal structures and antibacterial activities of two new Mn(Ⅱ) complexes based on triaryltriazoles[J]. J. Coord. Chem., 2018, 71(1): 46-56 doi: 10.1080/00958972.2018.1425838
22. [22]
  FENG Z, GAO J F, LI G, ZHU D R. Syntheses and crystal structures of two copper complexes based on quinolyl and pyridyl substituted triaryltriazoles[J]. Chinese J. Inorg. Chem., 2020, 36(6): 1169-1175
23. [23]
  LI G, FENG Z, NIE R R, ZHU D R. Syntheses and crystal structures of two copper complexes based on thienyl and pyridyl substituted triaryltriazoles[J]. Chinese J. Inorg. Chem., 2021, 37(3): 561-568
24. [24]
  GAO J F, NIE R R, FENG Z, ZHU D R. Coexistence of two unique Cu(Ⅱ) ions in mononuclear Cu(Ⅱ) complexes with furanyl substituted triaryltriazoles[J]. Chinese J. Inorg. Chem., 2021, 37(9): 1707-1712
25. [25]
  SONG H J, PENG R, ZUO Y, WANG T, ZHU D R. Syntheses, crystal structures and intermolecular interactions of six novel pyrimidin-2-yl-substituted triaryltriazoles[J]. Acta Crystallogr. Sect. C, 2024, C80(2): 104-114
26. [26]
  WANG T, SONG H J, ZHUANG R, ZHU D R. Syntheses, crystal structures, Hirshfeld surface analyses and magnetic property of a new dinuclear nickel(Ⅱ) and two mononuclear copper(Ⅱ) complexes with triaryltriazoles[J]. J. Coord. Chem., 2024, 77(22/23/24): 2844-2855
27. [27]
  JIMÉNEZ S R, FELTHAM H L C, BROOKER S. Non-porous iron(Ⅱ)-based sensor: Crystallographic insights into a cycle of colorful guest-induced topotactic transformations[J]. Angew. Chem. ‒ Int. Edit., 2016, 55(48): 15067-15071 doi: 10.1002/anie.201608813
28. [28]
  JIMÉNEZ S R, YANG M R, STEWARY I, GARDEN A L, BROOKER S. A simple method of predicting spin state in solution[J]. J. Am. Chem. Soc., 2017, 139(50): 18392-18396 doi: 10.1021/jacs.7b11069
29. [29]
  DOLOMANOV O V, BOURHIS L J, GILDEA R J, HOWARD J A K, PUSCHMANN H. OLEX2: A complete structure solution, refinement and analysis program[J]. J. Appl. Cryst., 2009, 42(2): 339-341 doi: 10.1107/S0021889808042726
30. [30]
  SPACKMAN P R, TUINER M J, MCKINNON J J, WOLFF S K, GRIMWOOD D J, JAYATILAKA D, SPACKMAN M A. CrystalExplorer: A program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals[J]. J. Appl. Cryst., 2021, 54(3): 1006-1011 doi: 10.1107/S1600576721002910
31. [31]
  SUN E X, FANG H Y, JIANG J J, ZHU D R. Syntheses, crystal structures, Hirshfeld surface analyses and fluorescence of binuclear complexes with unsymmetrical phenol-based compartmental ligands[J]. J. Coord. Chem., 2023, 76(7/8): 946-959
1. [1]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
2. [2]
  Lifang HE , Yaoze LUO , Qiying SHI , Jianxin TANG , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and properties of hydrated tricyclohexyltin theophylline-7-acetic acid complex. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 632-640. doi: 10.11862/CJIC.20250244
3. [3]
  Jiarong ZHU , Xiaohua ZHANG , Xinting XIONG , Xuliang NIE , Xiuying SONG , Miaomiao ZHANG , Dayong PENG , Xiuguang YI . Crystal structure, Hirshfeld surface analysis, and antifungal activity of five complexes based on 2,5-bis(carboxymethoxy)terephthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2358-2370. doi: 10.11862/CJIC.20250150
4. [4]
  Liping GUO . Synthesis and crystal structure characterization of yttrium imido complex: The reactivity of 2-substituted-1-amino-o-carborane with yttrium dialkyl complex. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1409-1415. doi: 10.11862/CJIC.20250065
5. [5]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
6. [6]
  Lulu DONG , Jie LIU , Hua YANG , Yupei FU , Hongli LIU , Xiaoli CHEN , Huali CUI , Lin LIU , Jijiang WANG . Synthesis, crystal structure, and fluorescence properties of Cd-based complex with pcu topology. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 809-820. doi: 10.11862/CJIC.20240171
7. [7]
  Yinxia SUN , Liping LIU , Xue BAI , Yu SUN , Wanhong SUN , Zhepeng DENG , Jianghai CHEN , Jianjun WANG , Li XU , Shuzhen ZHANG . Synthesis and crystal structures of Co(Ⅱ)/Cu(Ⅱ) coordination polymers based on solvent and ligand concentration regulation strategy. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 340-354. doi: 10.11862/CJIC.20250226
8. [8]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
9. [9]
  Zihe SONG , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Crystal structure, thermal analysis, and luminescence properties of six heterocyclic lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 181-192. doi: 10.11862/CJIC.20250126
10. [10]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
11. [11]
  Yao HUANG , Yingshu WU , Zhichun BAO , Yue HUANG , Shangfeng TANG , Ruixue LIU , Yancheng LIU , Hong LIANG . Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359
12. [12]
  Wenya DING , Fangfei XU , Jiayu GU , Xinran CHEN , Kai CHEN . Synthesis and crystal structure of three cucurbit[6]uril-cadmium supramolecular assemblies. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 808-816. doi: 10.11862/CJIC.20260012
13. [13]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
14. [14]
  Zhihui ZONG , Zijie ZHAO , Lei HUANG , Zhicheng PAN , Shan WANG , Lili LIANG , Huaqing LIU , Enli ZHANG . Synthesis, crystal structures, and antitumor activity of two metal complexes of imidazolyl acylhydrazones. Chinese Journal of Inorganic Chemistry, 2026, 42(5): 1048-1062. doi: 10.11862/CJIC.20250330
15. [15]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
16. [16]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
17. [17]
  Ri PENG , Yingxiang BAI , Yuxin XIE , Dunru ZHU . cis/trans-Octahedral configuration induced topologically different MOFs: Syntheses, structures, and Hirshfeld surface analyses. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1650-1660. doi: 10.11862/CJIC.20250143
18. [18]
  Shuangshuang GAI , Jixiang CAI , Moya YANG , Haijuan WU , Shuzhen FENG , Ming JIANG . Endoplasmic reticulum stress and mitochondrial apoptosis in thiosemicarbazone copper(Ⅱ) complex-triggered triple-negative breast cancer cell death. Chinese Journal of Inorganic Chemistry, 2026, 42(5): 1073-1084. doi: 10.11862/CJIC.20250328
19. [19]
  Fan LIU , Xiaoli CHEN , Jing REN , Yantao LEI , Huali CUI , Hua YANG , Jijiang WANG . Highly sensitive and multi-response Zn-MOF fluorescence sensor: Design, synthesis, and detection of 4-nitrophenol, Cu²⁺, and pyrimethanil. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 872-882. doi: 10.11862/CJIC.20250287
20. [20]
  Hexing SONG , Zan SUN . Synthesis, crystal structure, Hirshfeld surface analysis, and fluorescent sensing for Fe³⁺ of an Mn(Ⅱ) complex based on 1-naphthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 885-892. doi: 10.11862/CJIC.20240402

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(479)
HTML views(70)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142