Syntheses, crystal structures and thermal analyses of two new ionic complexes based on 3,4-diamino-1,2,4-triazole

Article abstract of DOI:10.1080/00958972.2016.1160378

Two new ionic complexes, (DATr)₂[Li₂(TNR)₂·2H₂O]·2H₂O (1) and (DATr)[Zn(DATr)Cl₃] (2), were synthesized by using 3,4-diamino-1,2,4-triazole (DATr) as outer cation. X-ray single-crystal diff

Full text of DOI:10.1080/00958972.2016.1160378

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Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20
Syntheses, crystal structures and thermal
analyses of two new ionic complexes based on 3,4-
diamino-1,2,4-triazole
Jin-Ting Wu, Jian-Guo Zhang, Xin Jin, Xin Yin & Tong-Lai Zhang
To cite this article: Jin-Ting Wu, Jian-Guo Zhang, Xin Jin, Xin Yin & Tong-Lai Zhang
(2016): Syntheses, crystal structures and thermal analyses of two new ionic complexes
based on 3,4-diamino-1,2,4-triazole, Journal of Coordination Chemistry, DOI:
10.1080/00958972.2016.1160378
To link to this article: http://dx.doi.org/10.1080/00958972.2016.1160378
Accepted author version posted online: 04
Mar 2016.
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Date: 11 March 2016, At: 00:55

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Publisher: Taylor & Francis
Journal: Journal of Coordination Chemistry
DOI: http://dx.doi.org/10.1080/00958972.2016.1160378
Syntheses, crystal structures and thermal analyses of two new ionic complexes
based on 3,4-diamino-1,2,4-triazole
JIN-TING WU, JIAN-GUO ZHANG, XIN JIN, XIN YIN and TONG-LAI ZHANG
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, China
Two new ionic complexes, (DATr)2[Li2(TNR)2·2H2O]·2H2O (1) and (DATr)[Zn(DATr)Cl3] (2),
were synthesized by using 3,4-diamino-1,2,4-triazole (DATr) as outer cation. X-ray
single-crystal diffraction analysis revealed that the two complexes crystallize in triclinic and
orthorhombic crystal systems, respectively. Differential scanning calorimetry (DSC) was applied
to assess the thermal decomposition behavior and kinetic parameters of decomposition were
studied by using Kissinger’s and Ozawa-Doyle’s methods. Furthermore, the critical temperature
of thermal explosion and parameters of thermodynamics were obtained.
Keywords: Complexes; 3,4-Diamino-1,2,4-triazole; Crystal structure; Thermal analysis
1. Introduction
Many efforts were made to explore new energetic materials aimed at meeting requirements of
future military and civilian applications [1-3]. Nitrogen-rich compounds have attracted interest of
materials chemists due to their potential applications, such as gas storage [4, 5], energetic
metal-organic frameworks (MOFs) [3, 6, 7] and explosives [8-10]. Nitrogen-rich azoles have
been widely studied and exhibit smokeless combustion, good thermal stability and positive heats
of formation [11-15]. Their high heats of formation depend on the existence of a large number of
Corresponding author. Email: zjgbit@bit.edu.cn
1

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N–N and C–N bonds [16-19]. Owing to nitrogen-rich azoles’ merits, they are mainly used in the
field of energetic materials [20-24].
As a high nitrogen azole [N% = 70.7], 3,4-diamino-1,2,4-triazole (DATr) is a promising
energetic material. The two amino groups reduce the sensitivity and increase the possibility of
hydrogen bonds that will enhance the thermal stability [25-27]. Thus, numerous ionic salts and
complexes based on DATr have been reported [28-30]. Mostly DATr as neutral ligand was
found in these reported coordination compounds. Research on complexes with central metal
cation and DATr+ cation is rarely investigated, and the properties of complexes constructed by
this unique combination are not well known.
Herein, complexes of nitrogen-rich cation 3,4-diamino-1,2,4-triazolium as the outer
cation were synthesized and characterized. Their crystal structures were obtained and their
thermal stabilities were also investigated.
2. Experimental
2.1. Materials and general methods
All reagents and solvents were of analytical grade and used without purification as commercially
obtained. 3,4-Diamino-1,2,4-triazole was prepared according to the literature [31].
Elemental analyses were performed with a Flash EA 1112 full-automatic trace elemental
analyzer. Infrared spectra were recorded by Fourier transform techniques on a Bruker Equinox
55 spectrometer (KBr pellets) from 4000 to 400 cm−1. Differential scanning calorimetry (DSC)
was carried out on a Pyris-1 differential scanning calorimeter.
2.2. Synthesis of 3,4-diamino-1,2,4-triazole (DATr)
Sodium hydrogen carbonate (0.84 g, 10 mmol) was slowly added to a solution of DATr·HCl
(1.36 g, 10 mmol) in 10 mL of distilled water. The mixture was stirred until there was no further
gas released and then the water was evaporated under vacuum, the mixture was dissolved in 30
mL absolute methanol and the inorganic salt was removed by filtration. After filtering, the
2

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solvent was removed under reduced pressure to produce a colorless solid at 82% yield. IR (KBr,
+
cm-1): 3483, 3055, 1631, 1568, 1341, 1137, 962, 641. MS(DEI+): m/z=100.00[C2H6N5 ].
C2H5N5 (99.11): calcd. C 24.24, H 5.09, N 70.67; found C 24.27, H 5.07, N 70.65.
2.3. Synthesis of (DATr)2[Li2(TNR)2·2H2O]·2H2O (1)
A mixture of DATr•HCl (0.41 g, 3 mmol) and LiOH (0.13 g, 3 mmol) in 15 mL of water was
stirred at 45 °C while a solution of 2,4,6-trinitro-resresorcinol (styphnate acid) (0.74 g, 3 mmol)
in methanol (20 mL) was added. After 30 min the precipitate was filtered and air-dried to yield 2
as a yellow solid. The yield was 34.3%. IR (KBr, cm-1): 3427, 3336, 1658, 1615, 1350, 1214,
1027, 890. C16H22Li2N16O20 (772.38): calcd. C 24.88, H 2.87, N 29.02; found C 24.81, H 2.90, N
29.05.
2.4. Synthesis of (DATr)[Zn(DATr)Cl3] (2)
A solution of ZnCl2 (50 wt%, 0.82 g) in 10 mL absolute methanol was added dropwise to
solution of DATr (0.6 g, 6 mmol) in 20 mL absolute methanol under stirring at 40 ~ 45 °C. After
1 h, the precipitate was collected by filtration, rinsed with distilled water, and dried in air to yield
1 as a colorless solid. The yield was 37.4%. IR (KBr, cm-1): 3412, 1691, 1472, 1330, 1232, 1016,
948. C4H11N10Cl3Zn (370.97): calcd. C 12.95, H 2.99, N 37.76; found C 12.99, H 2.92, N 37.77.
Scheme 1. Synthesis of 1 and 2.
3