Energetic oxygen-containing tetrazole salts based on 3,4-diaminotriazole

Article abstract of DOI:10.1002/asia.201500075

Energetic mono- and dicationic 3,4-diaminotriazolium salts have been prepared by combining stoichiometric amounts (1:1 or 2:1 molar ratio) of 3,4-diaminotriazole with various oxygen-containing tetrazoles, and the structures have been confirmed by single-crystal XRD for the first time. All structures are dominated by a strong hydrogen-bond network owing to both amino groups and oxygen in the molecule. All salts, except 7, exhibit excellent thermal stabilities with decomposition temperatures over 200C. Based on experimental densities and theoretical calculations carried out by using the Gaussian 03 suite of programs, all salts have calculated detonation pressures (20.3-33.9 GPa) and velocities (7095-8642 ms^-1).

Full text of DOI:10.1002/asia.201500075

CHEMISTRY
AN ASIAN JOURNAL
Accepted Article
Title: Energetic Oxygen-containing Tetrazole Salts Based on 3,4-Diamino-triazole
Authors: Jinting Wu; Jianguo Zhang; Xin Yin; Kun Wu
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To be cited as: Chem. Asian J. 10.1002/asia.201500075
Link to VoR: http://dx.doi.org/10.1002/asia.201500075
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Societies

Chemistry - An Asian Journal
10.1002/asia.201500075
Energetic Oxygen-containing Tetrazole Salts Based on
3
,4-Diamino-triazole
[
a]
[a]
[a]
[b]
Jin-Ting Wu , Jian-Guo Zhang* , Xin Yin , Kun Wu
Abstract: Energetic mono- and di-cationic 3,4-diamino-triazolium salts, have been
prepared by combining stoichiometric amounts (1:1 or 2:1 mol ratio) of
3
,4-diamino-triazole with various oxygen-containing tetrazoles and confirmed by
single-crystal X-ray diffraction for the first time. All structures are dominated by a
strong hydrogen bond network due to both amino groups and oxygen in the molecule.
All the salts except 7 exhibit excellent thermal stabilities with decomposition
o
temperatures over 200 C. Based on experimental densities and theoretical calculations
carried out by using the Gaussian 03 suite of programs, all the salts have calculated
-1
detonation pressures (20.3–33.9 GPa) and velocities (7095–8642 m·s ).
Keywords：energetic salts; detonation performance ; oxygen-containing tetrazoles
[a ]
Dr J.-T. Wu, Dr Y. Xin, Prof. J.-G Zhang
State Key Laboratory of Explosion Science and Technology
Beijing Institution of Technology
Beijing, 100081( P.R. China )
Fax: (+)86-10-68918091
E-mail: zjgbit@bit.edu.cn
[b]
Prof. K. Wu
Institute of Mechanical Equipment of China
Beijing, 100089 (P.R. China)
Supporting information for this article is available on the xxxx
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Chemistry - An Asian Journal
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Introduction
In the field of high-energy materials, the synthesis of energetic heterocyclic
compounds has attracted considerable interest in recent years, due to their rather high
[
1-4]
densities, high heats of formation and good oxygen balance . Along with the
development of ionic compounds and their applications in energetic fields,
nitrogen-rich heterocyclic halide-free energetic salts have gradually become a hot
topic, as these salts possess special properties, such as lower vapor pressures and
[
5-9]
higher densities than their atomically similar non-ionic analogs . This provides a
powerful methodology for design and synthesis energetic materials for specific
[
10-12]
purposes
.
One of the most promising energetic backbones for the tailoring of energetic
molecules is the tetrazole ring; due to the fact that their properties can be controlled
by selection of various substituents on position 5 of the ring, and the high nitrogen
[
13-16]
content of the heterocyclic leads to high energetic performances
. It can be stated
that the tetrazole heterocyclic tend to show a good compromise between high energy
content, high chemical/thermal stability, and low sensitivity, where the contradictory
nature of high performance and instability usually poses interesting but challenging
[
17, 18]
problems for the synthetic chemist in the development of energetic materials
.
This trend is exemplified in the range of five-membered azoles from pyrazole to
pentazole, where pyrazoles possess the lowest nitrogen content, and the few pentazole
[
19, 20]
derivatives known are highly unstable
.
The general methods for the preparation of energetic salts are by neutralization
and metathesis reactions with N-protonated anions, such as nitrate, azolate,
[
21-24]
dinitramide and so forth
. In order to pursue higher performance and lower
sensitivity, many energetic salts with nitrogen-containing heterocyclic cations or
nitrogen-containing heterocyclic anions have been synthesized through combination
[
25-29]
of various selected ions
.
As we all known, the introduction of oxygen-containing groups in energetic
[
30]
compounds can improve the oxygen balance and the density . The oxidizer part in
2

Chemistry - An Asian Journal
10.1002/asia.201500075
the compounds increases the oxygen balance, and provides the oxygen to convert all
carbon into carbon dioxide, and all hydrogen into water in order to enhance
[
31-34]
combustion, therefore lead to a better performance
-nitro-tetrazole, 5-dinitromethyl-tetrazole and 1-hydroxyl-5-amino-tetrazole are
structurally analogous energetic oxygen-containing tetrazoles and possess the several
. 5-Nitromino-tetrazole,
5
[
35-37]
merits mentioned above
. For example, nitromino- tetrazoles are some of the most
promising for practical use as their high thermal stabilities arise from the aromatic
nature of the tetrazole ring, whereas the high performances arise from the high heats
of formation of nitromino-tetrazoles, the ring strain of the five-membered ring, and
[
38, 39]
good oxygen balance
.
Theoretically, the amino groups are helpful at improving the thermal stability and
both amino groups and oxygen in the molecule can increase hydrogen bonds that help
[
40]
to stabilize the material substantially and general increase the density . Our main
interest in this work was to pairing 3,4-diamino-triazolium cations with the
oxygen-containing tetrazolate anions. As we expected, several of these ionic salts
exhibited potentially useful thermal stabilities, good detonation properties, and low
sensitivities as potential energetic materials.
Results and discussion
Synthesis. 3,4-Diamino-1,2,4-triazolium chloride (1) was synthesized according
[
41]
to literature . The synthesis is based on the reaction of diamino-guanidinium
chloride and formic acid in concentrated hydrochloric acid. Neutral molecule 2 was
accomplished by adding potassium hydroxide in the aqueous solution of 1, then
extracted with methanol subsequently.
Starting from 1, salts 3, 4 were synthesized after treating 1 with stoichiometric
amounts of the respective silver salts. The formation of the nitrogen-rich salts (5-8) is
straightforward (addition of acids on compound DATr). An overview is depicted in
Scheme 1.
3

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Scheme 1. Synthesis of energetic salts based on 3,4-diamino-1,2,4-triazole
Single Crystal X-ray Structure Analysis. Single crystal X-ray diffraction
studies were accomplished of compounds 1, 2 and salts 3-8. In the following, only
three examples (2, 3 and 6) of the determined crystal structures, which from the
crystallographic point of view appear to have interesting properties, are discussed. All
compounds except 1 and 7·H O were recrystallized from methanol and show
2
moderate crystal densities. Selected crystallographic data of all compounds 1-8 are
compiled in Table S1 in the Supporting Information.
The X-ray crystallographic analysis data for 3,4-diamino-triazole (2) showed that
-3
it crystallizes in the monoclinic space group P2(1)/n with a density of 1.552g·cm ,
which is low to be considered as being a possible useful energetic material, and a cell
3
volume of 424.04(7) Å (Figure 1a). In the neutral compound 2, the C-N bond lengths
were range from 1.294(5) to 1.363(6) Å, which were much shorter (1.341(3) than the
average value for a C-N single bond (1.47 Å), but significantly longer than a C=N
[
42]
double bond (1.22 Å), suggesting that some multiple bond character is present . A
similar trend is observed for the N1-N2 bond in 1.407(5)Å , which is significantly
shorter than a N-N single bond (1.48 Å) but considerably longer than a N=N double
[43]
bond (1.20 Å) .These findings support the presence of a delocalized π-system in the
five-membered ring of compound 2. The torsion angles of N4-N3-C1-N2 and
o
o
C2-N3-C1-N5 are -176.9(4) and -174.8(4) , illustrating the two amino group and
4

Chemistry - An Asian Journal
10.1002/asia.201500075
triazole ring are almost in the same plane. The packing structure of 2 is influenced by
strong hydrogen bonds (Figure 1b).
1
a
1b
Figure 1. Molecular structure of 2 (1a) and its packing diagram (1b).
Mixing the regents of DATr·HCl and disilver 5-nitramino-tetrazolate with the
ratio of 2:1, we can obtain the dication 5-nitramino-tetrazolate salt 3 . Compound
3
crystallizes in the monoclinic space group P2(1)/n with four molecules in the unit
-3
cell and a density of 1.674g·cm (Figure 2a). The crystal structures of the triazolium
ring and tetrazolate ring adopt a nearly planar conformation. When
3
3
,4-diamino-1,2,4-triazolium cation are compared with those in the parent
,4-diamino-1,2,4-triazole(2), slight changes can be seen. The bond length of N1-C2
stays essentially the same at 1.295~1.296Å. The process of protonation of triazole
causes some structural differences, and this is reflected in the N1-N2 and N2-C1 bond
lengths being 1.407(5), 1.321(5)Å in the neutral compound 2, whereas in
3
,4-diaminotrizolium cation they are 1.3871(19) , 1.336(2) Å, respectively. A similar
effect is seen for the angles N1-N2-C1 and C2-N3-C1 of 106.4(3), 105.8(3) in 2,
whereas in 3,4-diamino-trizolium cation they are 111.14(13), 107.20(13), respectively.
The hydrogen atoms of the amino group and triazolium ring, together with the oxygen
atom of tetrazolate add many intra- and intermolecular hydrogen-bond interactions in
all the salts, these may increase the density of the ionic salts and decrease the
sensitivity of the compounds. In the crystal structure, the strong intermolecular
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Chemistry - An Asian Journal
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hydrogen bond interactions between nitro groups, amino groups and adjacent
hydrogen are drive forces for the formation of the crystal (Figure 2b).
2
a
2
b
Figure 2.Molecular structure of 3(2a) and its packing diagram (2b).
Mixing the regents of DATr·HCl and silver 5-nitramino-tetrazolate with the
ratio of 1:1, we can obtain the monocation 5-nitromino-tetrazolate salt 6. Compound 6
is described by monoclinic space group P2(1) with two molecules per unit cell (Figure
-3
3
a), and has a density of 1.661g·cm which is a little lower than that of 3. Unlike the
compound 3, the triazolium ring and the triazolate ring of 6 are clearly twisted, with a
o
dihedral angle between them of 69.8 . While, the angles of the ring system and the
bond lengths behave in the same way as described for compound 3. The packing of 6
is also characterized by a three-dimensional network (Figure 3b).
The crystal structures of compounds 1, 4, 5, 7·H O and 8 were also determined
2
and are presented in the Supporting Information.
6

Chemistry - An Asian Journal
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(3a)
3b
Figure 3. Molecular structure of 6 (3a) and its packing diagram (3b).
Thermal Behavior. The phase-transition temperatures and thermal stabilities of
compounds 2-8 were determined by differential scanning calorimetric (DSC)
−
1
measurements scanning at 10 °C min ( Figure 4). All of the synthesized compounds
except 7 melt prior to decomposition. Their peak temperature of decomposition range
o
between 157.2 to 256.3 C. In these salts, the anions play the predominant role in
determining decomposition temperatures because most of them are less stable than the
DATr cation. The neutral compound 2 has quite high thermal stability, which is
expected on the basis of the other amino derivatives. While DATr decomposes at
o
2
00.0 C, most of its salts are less thermally stable, with onset decomposition
temperatures ranging from 132.9(7) to 224.9 °C (4). Among these compounds, except
the compound 7, the decomposition temperatures of 2-6 and 8 are above 200 °C,
which supports their thermal stability.
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Chemistry - An Asian Journal
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2
3
4
5
6
7
8
0
100
200
300
400
500
o
Temperature/ C
o
-1
Figure 4 DSC curves of compounds 2-8 at the heating rate of 10 C·min
Physical properties of the energetic compounds. The enthalpy of formation is
an important parameter in evaluating the performance of energetic salts and is directly
related to the number of the nitrogen-nitrogen bonds in an ionic species. This property
[
44-46]
of the salts can be calculated with good accuracy
. Calculation of the enthalpy of
formation of compounds 2-8 were performed by using the Gaussian 03 suite of
[
47]
programs . The geometric optimization of the structures and frequency analyses
carried out using B3LYP functional with the 6-31+G** basis set, and single-point
[
48]
energies were calculated at the MP2/6-311++G** level . All of the optimized
structures were characterized to be true local energy minima on the potential energy
surface without imaginary frequencies. According to the Born-Haber energy cycles
[
49]
(
Figure 5) , enthalpy of formation of salts could be simplified by the formula (1).
o
o
o
△
H (ionic salt, 298K) = △H (cation, 298K) + △Hf (anion, 298K) -△HL
f f
(1)
Where △H is the lattice energy of the salt, which could be predicted by the
L
formula (2)
H =U + [p(n /2 -2) +q(n /2 -2)] RT (2)
△
L
POT
M
X
+
-
Where n and n depend on the nature of the ions M and X , respectively, and
M
X
p
q
are equal to 3 for monatomic ions, 5 for linear polyatomic ions, and 6 for nonlinear
8

Chemistry - An Asian Journal
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polyatomic ions. The equation for lattice potential energy UPOT can be calculated by
formula (3)
UPOT =γ(ρ /M ) + δ (3)
1
/3
m
m
-
3
where density is ρ (g·cm ), M (g) is the chemical formula mass of the ionic
m
m
-1
-1
salt, and the coefficients γ/kJ·mol cm and δ/kJ·mol are values taken from the
[
50]
literature . The heats of formation of cations and anions are computed using the
[51]
o
method of isodesmic reactions . The enthalpy of reaction (△H
) is obtained by
r 298
combining energy difference for the reaction, the scaled zero-point energies, and other
thermal factors. The calculated results are listed in Table 1.
Figure 5. Born–Haber cycle for the formation of salts of 2
With the values for the enthalpy of formation and densities of energetic
compounds, the detonation pressures (P) and detonation velocities (D) are calculated
[52]
based on the Kamlet-Jacobs equations . The neutral compound 2 has a detonation
-1
pressure and velocity of 20.3Gpa and 7095 m·s , respectively. Detonation pressures
and velocities for all of the salts are found between 22.8 to 33.9 GPa, and 7717 to
-1
8
642 m·s , respectively. Salt 7 possesses a moderate heat of formation, the highest
density, and best oxygen balance among the salts, which guarantees its best detonation
performance among this family of salts, with a detonation pressure of 33.9GPa and a
-1
detonation velocity of 8642 m·s , which can comparable with those of RDX.
For initial safety testing, the sensitivities of the salts towards impact were
measured by using standard procedures, and are listed in Table 1. Of all these new
compounds, it is not surprising that neutral compound 2 is the least sensitive
explosive (IS >40J). Salts 3−8 are quite more impact sensitive (8−38 J) than 2, which
9

Chemistry - An Asian Journal
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suggests that the salts 4 and 8 can serve as promising candidates for safe energetic
materials. Obviously, the mono-DATr tetrazolate salts were much more sensitive than
its analogs di-DATr tetrazolate salts with the same anions, that can attribute to the
stability of DATr cation.
Conclusion
3
,5-Diamino-triazole (2) and its salts with oxygen-containing tetrazolate anions
were synthesized and fully characterized. The structures of all the compounds 1-8
were confirmed by single-crystal X-ray diffraction for the first time. All structures
are dominated by a strong hydrogen bond network due to both amino groups and
oxygen in the molecule. Promising detonation properties based on moderate density
and heats of formation. Overall, 7 is the most promising as a potentially applicable
energetic material.
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Chemistry - An Asian Journal
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Table 1 Properties of 2-8 compared with TNT, TATB and RDX
a
m
b
d
f
g
h
L
i
j
k
l
m
n
salts
T
T
d
OB
N
△H
△H
f
cation △H
f
anion △H
f
P
D
IS
c
d
c
c
c
e
2
3
4
5
6
7
8
215.0
157.2
200.1
140.5
196.5
-
254.1
227.4
256.3
247.8
204.9
157.5
225.3
230.0
1.552
1.670
1.629
1.739
1.661
1.870
1.692
1.82
-105.1
-68.3
-60.2
-52.3
-52.4
-44.0
-72.0
-21.6
70.7
68.3
60.2
65.4
67.2
56.4
70.0
-
-
-
329.9
868.5
622.9
484.0
564.6
619.4
571.9
20.3
25.2
22.8
27.1
25.6
33.9
26.4
35.2
7095
7706
7389
7892
7789
8642
7856
8783
>40
25
37
11
1269.0
1198.5
504.5
487.2
485.0
426.6
-
875.7
875.7
875.7
875.7
875.7
875.7
-
386.1
70.0
112.8
176.1
228.7
122.8
-
6.5
8
c
195.7
204.1
38
7.4
[53]
RDX
37.8
83.8
a
o
b
o
c
-3
d
Melting point ( C). Decomposition temperature ( C). X-ray density (g cm ) at room temperature. Corrected density at room
[
3] e
temperature from low temperature X-ray single crystal diffraction data . Measured density of anhydrate compound 7, obtained by using an
f
g
h
-1
i
ULTRAPYC 1200e Automatic Density Analyzer. Oxygen balance (OB). Nitrogen content (%). Lattice energy (kJ·mol ). Molar enthalpy
-1
j
-1
k
-1
l
of the formation of cation (kJ·mol ). Molar enthalpy of the formation of anion (kJ·mol ). Molar enthalpy of the formation of salt (kJ·mol ).
-
1
m
n
Detonation velocity (m·s ). Detonation pressure (GPa). Impact sensitivity (J).
11

Chemistry - An Asian Journal
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Experimental Section
All chemical reagents and solvents were obtained from Sinopharm Chemical
Reagent Co., Ltd. IR spectra were recorded as KBr pellets on a Bruker Equinox 55.
Differential scanning calorimeter (DSC) and was carried out on a model Pyris-1
differential scanning calorimeter. Computations were performed by using the
[
47]
Gaussian 03 suites of programs . The geometric optimization and frequency
analyses were carried out using B3LYP functional analyses with the 6-311+G** basis
set. Single energy points were calculated at the MP2/6-311++G** level. All of the
optimized structures were characterized to be true local energy minima on the
potential energy surface without imaginary frequencies.
The single crystal of 2-8 were cultured by slowly solvent evaporation method.
Collection of X-ray diffractions data was performed on a Rigaku Saturn724+ CCD
diffractometer equipped with a graphite mono-chromatized Mo K radiation. The
α
structure was solved using the direct methods and successive Fourier difference
[
54]
2
syntheses (SHELXS-97)
refined using full-matrix least-squares on F with
[
55]
anisotropic thermal parameters for all non-hydrogen atoms (SHELXL-97)
.
Hydrogen atoms were added theoretically and refined with riding model position
parameters and fixed isotropic thermal parameters.
3
,4-Diamino-1,2,4-triazolium chloride (1) and the oxygen-containing tetrazoles
[
41, 56-59]
were synthesized according to literature
.
3
,4-Diamino-1,2,4-triazole (2). 3,4-Diamino-1,2,4-triazolium chloride (2.7g, 20
mmol) was dissolved in a solution of water (30 ml) and the pH was meanwhile
adjusted to 6-7 by add potassium hydroxide (1.29 g, 20 mmol). The solution was
subsequently evaporation in vacuum. The mixture solid was extracted with methanol
(
5×30ml), and the solvent was evaporated to yield 2(82%).
General Procedure for Syntheses of the Di-DATr tetrazolate Salts 3-4.
To an aqueous solution (5mL) of DATr.HCl (0.27g, 2mmol) added silver
tetrazolate (1mmol). After the mixture had been stirred overnight, the solids were
12

Chemistry - An Asian Journal
10.1002/asia.201500075
removed by filtration. The filtrate was slowly evaporated to leave the solid product
in a good yield.
General Procedure for Syntheses of the DATr tetrazolate Salts 5-8.
DATr (0.1g, 1mmol) was soluble in water (5mL) of and an aqueous solution of
o
tetrazole (1 mmol) was added. After the mixture had been stirred at 45 C for 40 min,
the solvent was removed in vacuum to leave the desired product.
Di(3,4-diamino-1,2,4-triazolium) 5-nitromino-tetrazolate (3). Colorless solid
o
(
81%). Mp： 157.2 C. IR (KBr): ν= 3407, 3331, 3052, 1706, 1678, 1471, 1147, 1087,
-
1
+
1
1
1
023, 882 cm . MS(ESI+): m/z=100.00[C H N ];
MS(ESI-): m/z=
2
6
5
-
29.00[CHN O ]. C H N O (328.13): calcd. C 18.29, H3.68,N 68.27; found C
6
2
5
12 16
2
8.33, H 3.67, N 68.15.
Di(3,4-diamino-1,2,4-triazolium) 5-dinitromethyl-tetrazolate (4). Yellow
o
solid (85%). Mp: 200.1 C. IR (KBr): ν = 3330, 3269, 3136, 1720, 1698, 1529, 1442,
-
1
+
1
1
1
359, 1133, 1018, 824 cm . MS(ESI +): m/z=100.00[C H N ]; MS(ESI -): m/z=
2 6 5
-
73.00[C HN O ]. C H N O (372.12): calcd. C 19.36, H3.25,N 60.20; found C
2
6
4
6
12 16
4
9.33, H 3.17, N 60.15.
3
,4-Diamino-1,2,4-triazolium 5-nitro-tetrazolate (5). Colorless solid (88%).
o
Mp: 140.5 C. IR (KBr): ν = 3400, 3346, 3247, 1690, 1624, 1538, 1448, 1418, 1384,
-1
+
1
017, 986, 839 cm . MS(ESI+): m/z=100.00 [C H N ]; MS(ESI-): m/z=
2 6 5
-
1
14.05[CN O ]. C H N O (214.07): calcd. C 16.83, H2.82,N 65.41; found C 16.73,
5 2 3 6 10 2
H 2.87, N 65.45.
3
,4-diamino-1,2,4-triazolium 5-nitromino-tetrazolate (6). Colorless solid
o
(
84%). Mp: 196.5 C. IR (KBr): ν = 3314, 3261, 3120, 1702, 1644, 1527, 1449, 1333,
-1
+
1
303, 1217, 1062, 998, 848 cm . MS(ESI +): m/z=100.05 [C H N ]; MS(ESI -):
2 6 5
-
m/z= 128.95[CHN O ]. C H N O (229.2): calcd. C 15.72, H 3.08, N 67.23; found
6
2
3
7
11
2
C 15.77, H 3.04, N 67.25.
13

Chemistry - An Asian Journal
10.1002/asia.201500075
3
,4-Diamino-1,2,4-triazolium 5-dinitromethyl-tetrazolate monohydrate
(
7·H O). Yellow solid (79%). IR (KBr): ν = 3421, 3345, 3252, 1696, 1620, 1573,
2
-1
+
1
407, 1216, 1138, 1073, 749cm . MS (ESI +): m/z=100.00 [C H N ]; MS(ESI -):
2 6 5
-
m/z= 173.00 [C HN O ]. C H N O (291.08): calcd. C 16.50, H3.12,N 52.91; found
2
6
4
4
9
11
5
C 16.57, H 3.16, N 52.94. The 7•H O product was dried in oven overnight to remove
2
the crystal water and obtained anhydrous salt 7. C H N O (273.17): calcd. C 17.59,
4
7
11
4
H 2.58,N 56.40; found C 17.55, H 2.56, N 56.44.
3
,4-Diamino-1,2,4-triazolium 1-hydroxyl-5-amino-tetrazolate (8). Colorless
o
solid (81%). Mp: 195.7 C. IR (KBr): ν = 3371, 3280, 3157, 1692, 1624, 1589, 1291,
-1
+
1
117, 1107, 947cm . MS (ESI +): m/z=100.10 [C H N ]; MS (ESI -): m/z= 113.00
2 6 5
-
[
CN O ]. C H N O (200.09): calcd. C 18.00, H 4.03,N 69.98; found C 17.97, H 4.09,
5 2 3 8 10
N 69.94.
Acknowledgements
We gratefully acknowledge the support of the National Natural Science
Foundation of China (10776002), and the project of State Key Laboratory of Science
and Technology (No. ZDKT12-03 and YBT16-04).
Reference:
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[
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