Month 2017
Synthesis, Crystal Structure, and Properties of Energetic Complex Magnesium
0 0
,5 -Dinitramino-3,3 -bi[1,2,4-triazolate] Hexahydrate
5
triclinic space group P-1(2) with 1 molecular in the unit
cell. The thermal stabilities were analyzed by differential
thermal gravity/thermal gravity analysis, the complex of
magnesium is more stable than neutral DNABT, and the
complex 1 has high decomposition temperature of 227°C.
The sensitivities were determined against impact and
friction. The complex turned out to insensitive toward
impact (P = 0%) and friction (P = 12%). The complex 1
has good color performance and combustion behavior.
1085(m), 1054(s), 989(m), 947(s), 849(m), 778(s),
1
766(s), 751(s). H NMR (300 MHz, DMSO-d , 25°C,
6
13
ppm): = 5.51 ppm (s, 2H, Triazole. C NMR (75 MHz,
DMSO-d , 25°C, ppm): = 153.2, 143.6 ppm. Elemental
6
analysis (C H N O ): calcd. C 16.44, H 2.74, N 47.95;
4
8 10 6
found: C 16.61, H, 2.68, N 47.58.
0
0
Synthesis of magnesium 5,5 -dinitramino-3,3 -bi[1,2,4-
0
triazolate] hexahydrate [Mg(DNABT)(H
2
O)
6
] (1).
5,5 -
0
Dinitrimino-3,3 -bis(1H-1,2,4-triazole) dihydrate (2.92 g,
1
0 mmol) was dissolved in distilled water (60 mL). A
solution of magnesium acetate (3.21 g, 15 mmol) in
water (30 mL) was added, and the suspension was stirred
for 60 min at 60°C, then cooled down and filtered. The
obtained solid was washed with water then dried in air to
a yellow solid (2.6 g, 66%).
IR: ν(cm ) = 3191(m), 3152(m), 1566(vs), 1510(s),
1445(s), 1381(m), 1229(vs), 1138(m), 1088(m), 1055(s),
989(m), 949(s), 849(m), 768(s), 755(s). Elemental
EXPERIMENTAL
Caution. DNABT and its coordination compound are
energetic materials with increased sensitivities toward
shock and friction. Therefore, proper safer precautions
ꢀ
1
(
safety glass, face shield, earthed equipment, shoes,
gloves, and ear plugs) have to be applied when
synthesizing and handling the described compounds.
analysis (C H N O Mg): calcd. C 12.17, H 5.58, N
4
22 10 10
0
0
35.48; found: C 12.32, H, 5.49, N 35.15.
Synthesis of 5,5 -diamino-3,3 -bis(1H-1,2,4-triazole) (3).
Hydrochloric acid (60 mL) was added to a stirred mixture
of oxalic acid (20.0 g, 159 mmol) and aminoguanidinium
bicarbonate (45.4 g, 332 mmol). The reaction was stirred
at 70°C for 1 h, and the precipitate was collected by
filtration. The colorless solid was dissolved in water
REFERENCES AND NOTES
[
1] Chavez, D. E.; Hiskey, M. A.; Gilardi, R. D. Angew Chem Int
Ed 2000, 39, 1791.
[2] Zhang, G. F.; Wang, Y.; Cai, M. Y.; Dai, D. M. J Coord Chem
010, 63, 1480.
3] Singh, G.; Felix, S. P. J Hazard Mater 2002, 90, 1.
4] Feng, J. L.; Zhang, J. G.; Li, Z. M.; Zhang, T. L. Acta Chim
Sin. 2010, 68, 2493.
[5] Cui, Y.; Zhang, J. G.; Zhang, T. L. J Hazard Mater 2008, 160,
(
240 mL) and alkalized with sodium hydroxide to
pH = 14. The resulting precipitate was collected by
2
[
[
filtration, washed with water (~200 mL), and dried in air
0
0
to yield 3,3 -diamino-5,5 -bis(1H-1,2,4-triazole) (18.6 g,
1
12 mmol, 70%) as a colorless solid.
IR: ν(cm ) = 3325(m), 3116(m), 2863(m), 2784(m),
706(m), 1668(s), 1654(s), 1618(m), 1606(m), 1484(m),
457(m), 1267(m), 1104(vs), 1061(s), 987(w), 956(w),
ꢀ
1
45.
[6] Jiao, B. J.; Chen, S. P.; Zhao, F. Q. J Hazard Mater 2007, 142,
1
1
7
=
2
(
550.
[7] Klapötke, T. M.; Stierstorfer, J.; Weber, B. Inorg Chim Acta
2009, 362, 2311.
[8] Damavarapu, R.; Klapotke, T. M.; Stierstorfer, J.; Tarantik, K.
1
21(s). H NMR (300 MHz, DMSO-d , 25°C, ppm):
6
1
3
6.48 ppm (s, 2H, NH2). C NMR (75 MHz, DMSO-d6,
5°C, ppm): =157.7, 149.1 ppm. Elemental analysis
C H N ): calcd. C 28.92, H 3.62, N 67.46; found: C
R. Propellants, Explos, Pyrotech 2010, 35, 395.
[9] Xia, Z. Q.; Chen, S. P.; Wei, Q.; Qiao, C. F. J Solid State Chem
2011, 184, 1777.
4
6 8
[10] Cudzilo, S.; Trzcinsiki, W.; Nita, M.; Michalik, S.; Krompiec,
2
8.73, H, 3.59, N 67.88.
S.; Kruszynski, R.; Kusz, J. Propellants, Explos, Pyrotech 2011, 36, 151.
[11] Dippold, A. A.; Klapötke, T. M. J Eur Chem 2012, 18, 16742.
[12] Dippold, A. A.; Klapötke, T. M.; Martin, F. A.; Anorg, J. Z.
Allg Chem 2011, 637, 181.
0
0
Synthesis
dihydrate (4).
of
5,5 -dinitramino-3,3 -bi[1,2,4-triazolate]
Nitric acid (98%, 3.0 mL) was added
0
0
slowly to a solution of 5,5 -diamino-3,3 -bis(1H-1,2,4-
[13] Fischer, N.; Izsák, D.; Klapötke, T. M.; Rappenglück, S.;
triazole) (1.0 g, 6.0 mmol) in concentrated sulfuric acid
Stierstorfer, J. J Eur Chem 2012, 18, 4051.
(
9.0 mL) at 0°C. The mixture was allowed to warm to
[14] Wang, X. J.; Chen, S. S.; Jin, S. H.; Zhang, C. Y.; Li, L. J.;
Shu, Q. H. J Chin Chem 2015, 33, 1229.
room temperature and stirred for 1 h. The solution
was poured on ice, and the precipitate was collected
by filtration and recrystallized from boiling water to
yield 5,5 -dinitrimino-3,3 -bis(1H-1,2,4-triazole) dihydrate
(
[
15] Wang, R. H.; Xu, H. Y.; Guo, Y.; Sa, R. J.; Shreeve, J. J Am
Chem Soc 2010, 132, 11904.
16] Shvedenkov, Y.; Bushuev, M.; Romanenko, G. J Hazard Mater
011, 197, 199.
[
0
0
2
[17] Abdellatif, B.; Cherouana, A.; Dahaoui, S. Acta Crystallogr C
1.35 g, 4.6 mmol, 77%) as yellow crystalline solid.
2015, 71, 222.
ꢀ
1
IR: ν(cm ) = 3165(m), 3154(m), 1706(m), 1565(vs),
[18] Nie, X. D.; Liang, Y. Z.; Xie, H. L.; Fu, L.; Huang, H. S. J
1508(s), 1446(s), 1380(m), 1298(vs), 1229(vs), 1140(m),
Wuhan University Technol-Mater 2012, 27, 679.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet