Synthesis, Structure, and Energetic Properties of 1,5-Diaminotetrazolium Sulfate Salts

Article abstract of DOI:10.1002/jhet.2579

1,5-diaminotetrazolium chloride (DATC) and 1,5-diaminotetrazolium sulfate (DATS) were synthesized in this work. The structures of DATS and DATC were characterized. The single crystal of DATS was first cultured, and its structure was analyzed. The thermal behavior of DATS was investigated. The activation energy and pro-exponential factor were calculated, E_k = 120.86 KJ/mol, A_k = 10^12.96 s^-1. The density, heat of formation, detonation pressure, and detonation velocity of DATS were first calculated. The detonation pressure and detonation velocity of DATS are P = 11.877 GPa, D = 5.617 km s^-1, which are smaller than those of 1,5-diaminotetrazolium nitrate (DATN) (P = 33.3GPa, D = 8.77 km s^-1).

Full text of DOI:10.1002/jhet.2579

March 2016
Synthesis, Structure, and Energetic Properties of 1,5-Diaminotetrazolium
Sulfate Salts
651
a
a
a
a
a
a
b
*
Yao Qian, Zhiyue Han, Yinghao Zhang, Zhiming Du, Yan Zhao, Yuezhen Yang, and Jingchang Zhang
aState Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, 5 South Zhongguancun
Street, Haidian District, Beijing 100081, China
bHainan Institute of Science and Technology, Haikou 571126, China
*
E-mail: hanzhiyue@bit.edu.cn
Additional Supporting Information may be found in the online version of this article.
Received September 4, 2015
DOI 10.1002/jhet.2579
Published online 22 December 2015 in Wiley Online Library (wileyonlinelibrary.com).
1,5-diaminotetrazolium chloride (DATC) and 1,5-diaminotetrazolium sulfate (DATS) were synthesized in
this work. The structures of DATS and DATC were characterized. The single crystal of DATS was first cul-
tured, and its structure was analyzed. The thermal behavior of DATS was investigated. The activation energy
and pro-exponential factor were calculated, Ek = 120.86 KJ/mol, Ak = 1012.96 ꢀ1. The density, heat of forma-
s
tion, detonation pressure, and detonation velocity of DATS were first calculated. The detonation pressure
and detonation velocity of DATS are P = 11.877 GPa, D = 5.617 km sꢀ1, which are smaller than those of
1,5-diaminotetrazolium nitrate (DATN) (P = 33.3GPa, D = 8.77 km sꢀ1).
J. Heterocyclic Chem., 53, 651 (2016).
INTRODUCTION
chloride [10], 1-amino-5-methyltetrazolium iodide [11],
2-amino -5-methyltetrazolium perchlorate [12], and so
forth. About 1,5-diaminotetrazole (DAT) inorganic acid
salts, there are DATN and DATC were reported, but there
is no introduction about the other structure and performance
characterization of DATS.
Nitrogen-rich compounds, which have good potential
applications in the military chemistry field, are a new type
of energetic material [1–4]. The thermal decomposition
products of these energetic ionic salts are mostly nitrogen,
with low vapor pressure [5–7] and high density, so they are
friendly to the environment.
The introduction of amino group to energetic ionic salt is
conducive to form strong hydrogen bonding, improve the
stability, and reduce the sensitivity [8]. Now, some ener-
getic ionic salts with amino group were reported, such
as: 5-aminotetrazolium nitrate [9], 5-aminotetrazolium
In this study, DATC was synthesized with DAT and hy-
drochloric acid. DATS was first synthesized with DATC
and silver sulfate. The structure was characterized by ele-
1
mental analysis, IR, HNMR, and MS. The single crystal
of DATS was cultivated, and the single crystal structure
was analyzed. The density, heat of formation, detonation
pressure, and detonation velocity were first calculated. The
© 2015 HeteroCorporation

652
Y. Qian, Z. Han, Y. Zhang, Z. Du, Y. Zhao, Y. Yang, and J. Zhang
Vol 53
kinetic parameters including activation energy and pro-
exponential factor were calculated by the Kissinger equation.
MEASUREMENTS
German vario EL elemental analyzer, U.S. companies
Nicolet FT-IR4700 infrared spectroscopy, Switzerland
ARX400 Bruker NMR spectrometer, AZB-HS mass spec-
trograph, Rigaku 742+ single crystals diffractometer.
RESULTS AND DISCUSSION
Structure Characterization. 1,5-diaminotetrazolium Chloride.
Elemental analysis (CH5N6Cl,136.5g·molꢀ1): calculated
value, C 17.71,H 3.69,N 61.99; measured value, C 17.73,H
3.58,N 61.86.
Figure 1. Crystal structure of DATS. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]
IR (cmꢀ1,KBr):3313, 3163 and 1578 cmꢀ1 (5-NH2),
3277 cmꢀ1 (4-N–H), 3251, 3068 and 1620 cmꢀ1 (1-NH2),
1724 cmꢀ1 (C1–N5), 1117–1039 cmꢀ1 (tetrazole ring).
1H NMR (DMSO-d6,δ): 7.84
Bond lengths become average, so there are aromaticity
and big π conjugated system in the DAT+.
Space group of DATS crystal has 2-m point group of
monoclinic system, each crystal contains four molecules
DATS. The anion and cation form stable structure by elec-
trostatic forces in the compound. Seen from Figure 2, the
dihedral angle of ring 1 (N1,N2,N3,N4,C1) and ring 2
(N7,N8,N9,N10,C2) is 74.99°. The distance from center
of the ring 2 to ring 1 plane is 3.638Å. There is side to face
π–π interaction between ring 1 and 2 and there are two
kinds of hydrogen bond N–H…O and N–H…N in the mol-
ecule. Hydrogen bond N5–H5A· ·· N2iii (symmetric code:
(iii) ꢀ x, ꢀy, ꢀz) connected the tetrazole cationic rings to-
gether in the same plane. R4, 4 (18) is a 18 atomic ring
composed of four donors and receptors. It connects the
tetrazole cationic rings in the different plane together.
The hydrogen bonds make crystal structure form three-
dimensional network structure (Figure 3).
MS (EI,70eV): m/z 100 (DAT molecular peak), m/z 36
(HCl+ ion peak).
DATS. Elemental analysis (C2H10N12SO4,298g·Mꢀ1):
calculated value, C 8.05,H 3.36,N 56.38; measured value,
C 8.12,H 3.23,N 56.39.
IR (cmꢀ1,KBr):3338 and 3194cmꢀ1 (5-NH2), 3294cmꢀ1
(4-N–H), 3085 and 1619 cmꢀ1 (1-NH2), 1720 cmꢀ1 (C1–N5),
1107–1039 cmꢀ1 (tetrazole ring).
1H NMR (DMSO-d6,δ): 6.98
MS (EI,70eV): m/z 100 (DAT molecular peak), m/z 64
(SO2 ion peak), m/z 48 (SO ion peak).
Crystal Structure of 1,5-diaminotetrazolium Sulfate. Crystal
structure of DATS is shown in Figure 1. The view of
the 3D structure of DATS is shown in Figure 2. The
crystal data, the bond and angle date, and hydrogen
bonding data of DATS are listed in Supplementary
Information.
Thermal Analysis.
TG–DSC.
Thermogravimetry
technology is measuring the relationship between the
Seen from Figure 1, the hydrogen atom connected to N4
atom, tetrazole ring and the two nitrogen atoms of amino
are in the same plane, N11 atom deviated from tetrazole
ring for the furthest distance of 0.014 Å. The two nitrogen
atoms outside the ring connected to the N and C atoms are
sp3 and sp2 hybridization, respectively. Bond lengths of
N–N in tetrazole ring are longer than N= N double bond
(Bond length of N= N in HN = NH is 1.252 Å [14]), and
shorter than N–N single bond (Bond length of N–N in
H2N–NH2 is 1.449 Å [14]). Bond lengths of C–N in tetra-
zole ring are longer than C = N double bond (Bond length
of C = N in H2C =NH is 1.273 Å [14]), and shorter than
C–N single bond (Bond length of C–N in H3C–NH2 is
1.471 Å [14]). Bond length of C–N bond of the amino con-
nected with C atom outside the ring is also between C = N
and C–N, and it is in the same plane with tetrazole ring.
Figure 2. The view of the 3D structure for DATS. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.com.]
Journal of Heterocyclic Chemistry
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Synthesis, Structure, and Energetic Properties of DATS
653
Figure 3. The coordination environment (hydrogenbonds) for DTAS. [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
change of material quantity and the change of temperature
under the process temperature. The TG–DSC curves of
DATS with the heating rate 20 Cminꢀ1 are shown in
Figure 4 and 5. There are two exothermic peaks during the
entire thermal decomposition process in the DSC curve, the
first temperature peak is 214.70C, and the thermal
decomposition enthalpy is 720.79 J gꢀ1, there is mass loss
in the process. The decomposition process contains two
processes, corresponding to two mass loss platforms. The
mass loss rate of the first platform in the TG curve is
43.59%, corresponding to that the one peak temperature is
214.70C. The mass loss rate of the second platform in the
TG curve is 25.58%, corresponding to that the second peak
temperature is 296.73C, and the thermal decomposition
enthalpy is 5.88Jgꢀ1. The total mass loss rate is 70.17% in
the entire thermal decomposition process.
The Calculation of Activation Energy.
Differential
scanning calorimetry curves of DATS with the
heating rate 2, 5, 10, 15 and 20 C minꢀ1 are shown in
Figure 6.About DATS (Figure 6), it has two
endothermic peaks. The thermal decomposition kinetics
data of DATS treated by Kissinger method [15] are
shown in Table 1. The Kissinger equation is listed as
follows:
βi
Ti
AKR EK
In
¼ In
ꢀ
;
2
EK
RTi
where β is heating rate (Kminꢀ1), Tp is peak temperature
(K), Ak is pre-exponential factor (sꢀ1), Ek is activation
energy (kJmolꢀ1), R is gas constant (Jminꢀ1 Kꢀ1).
Figure 4. DSC curve of DATS with heating rate 20 C minꢀ1. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
Journal of Heterocyclic Chemistry
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Y. Qian, Z. Han, Y. Zhang, Z. Du, Y. Zhao, Y. Yang, and J. Zhang
Vol 53
Figure 5. TG curve of DATS with heating rate 20 C minꢀ1. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
According to Kissinger equation, the pre-exponential factor
and activation energy of these two compounds were calcu-
lated by the slope and intercept of the straight line,
respectively. We can get Figure 7 (detailed calculations are
showed in support materials), in the stage, the activation
energy is 120.86 KJmolꢀ1, the pre-exponential factor is
in Table 1. The activation energy of DATN is biggest,
the date of DATC between DATN and DATS, in this view,
DATS is more stable.
THEORETICAL CALCULATION
1012.96 ꢀ1, and linear equation is y=20.25–14.54x, R=0.995.
s
Density.
In 2007, the density prediction method of
Meanwhile, authors have performed some works about
DATN and DATC and obtained some dates that are show
energetic ionic salts and compounds at room temperature
was reported by Shreeve [16,17]. The molecular volume
Figure 6. DSC curves of DATS with the heating rate 2, 5, 10, 15, 20 C minꢀ1. [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
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Synthesis, Structure, and Energetic Properties of DATS
655
Table 1
Activation energy and pre-exponential factor of DATN,
DATC and DATS
Material
EK (KJ/mol)
AK (sꢀ1
)
DATN
DATC
DATS
194.78
149.64
120.86
1020.26
1014.79
1012.96
isodesmic reaction (ΔH°r298) was obtained by combining
the MP2/6-311++G** energy difference for the reaction,
the scaled zero-point energies (B3LYP/6-31+ G**), and
other thermal factors.
The heat of formation for DATS was calculated by
Born-Haber energy cycles through the formula
ΔHf 0 ðionic salt; 298KÞ ¼ ΔHf 0 ðcation; 298KÞ
Figure 7. The activation energy of linear fitting equation of DATS.
[Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
þ ΔHf 0 ðanion; 298KÞ-ΔHL:
(1)
The lattice energy of ionic salt ΔHL could be predicted
by Jenkins’ method [formula (2)] [22] where UPOT is the
lattice potential energy, nM and nX depend on the nature
of the ions M+p and Xqꢀ, respectively, and are equal to 3
for monatomic ions, 5 for linear polyatomic ions, and 6
for nonlinear polyatomic ions.
can be estimated through this method, and then the density
of compounds can be rapidly estimated. The molecular
volumes of tetrazolium, H bonded to C, H bonded to N,
NH2 are 66, 5, 7, and 20, respectively [14,15]. Isodesmic
reactions were designed to obtain the density of DAT+ as
follows in Figure 8.
V (DAT+) = V (tetrazolium)-V (H bonded to C)-V (H
bonded to N) +2 V (NH2) = 66ꢀ5ꢀ7 + 2*20= 94 (Å3).
The molecular volume of NOꢀ3 , Clꢀand SO42ꢀare64, 47
and 91Å3 respectively from Jenkins’ research [18]. It is as-
sumed that the molecular volume of ionic salts: V= V (+)
+ V (). The density of DATN, DATC, and DATS can be
calculated according to the molecular molar mass as fol-
lows: ρ = M/0.6022 V. The calculated density of DATS is
listed in Table 2. It is close to the crystalline density (the
X-ray density value is 1.796).
Heat of Formation. The heat of formation is one of the
important characteristics for the energetic salts [19]. All ab
initio calculations were carried out by using the program
package Gaussian 98 [20]. The single-point energies
were calculated at the MP2 (full)/6-311++G** level.
Heats of formation of the simple cations or anions were
determined using atomization energies at G2 level.
Isodesmic reactions were designed to obtain the heats
of formation of cations and anions [21]. The enthalpy of
ΔHL ¼ UPOT þ ½pðnM =2 ꢀ 2Þ þ qðnx=2 ꢀ 2ÞꢁRT (2)
The lattice potential energy, UPOT, can be calculated
using equation:
ꢀ
ꢁ
1=3
-1
UPOT KJmol ¼ γðρm=MmÞ þ δ;
(3)
in which ρ is the density (gcmꢀ3), M is the chemical for-
mula mass of the ionic material (g), and the coefficients γ
(kJ molꢀ1 cm) and δ (kJ molꢀ1) were assigned literature
values [20]. The calculated thermochemical values of
DATS were presented in Table 2.
Detonation Pressure and Detonation Velocity. In order
to assess the expected detonation properties of DATS, the
expected detonation pressure and detonation velocity
were calculated using the semi-empirical equations [23]
(eq. 4, 5, and 6).
P ¼ Kρ2φ
(4)
(5)
(6)
d ¼ Aφ1=2ð1 þ BρÞ
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
φ ¼ N MðꢀΔEHÞ
With: P = detonation pressure GPa;
D = detonation velocity km/s;
ρ = density (g/cm3);
Figure 8. Isodesmic reactions of DAT+
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Vol 53
Table 2
The calculated density and thermochemical values of DATS.
Materials
DATS
ρcryl (g/cm3)
△f Hcation
△f Hanion
ꢀ585.0
△fHL
△fH (298 K)
+144.36
1.808
+1042.56
1355.76
Note: detailed calculations are showed in support materials.
Table 3
The detonation pressure and detonation velocity of DATS.
Compound
DATS
ρ
cryl (g/cm3)
ΔEH0 (cal/g)
ꢀ115.73
N
M
φ
P (GPa)
D (km/s)
5.167
1.808
0.047
21.29
2.33
11.877
EXPERIMENTAL
N = moles of gas per g ofexplosive;
M = average molar mass offormed gases (g/mol);
ΔEH = estimated orguessedheat of detonation (kal/g);
A = 1.01;
B = 1.30.
Synthesis of 1,5-diaminotetrazolium Chloride According to
Ref [12]. 1,5-diaminotetrazole (DAT) was synthesized
according Ref [13]. A solution of diaminoguanidinium
chloride (25.1 g, 0.2 M) in 333 mL of water and 8.3 mL
(0.1 M) concentrated HCl (37%) was cooled to 0 C (some
solid reprecipitated). With the temperature kept at 0–2 C,
a solution of sodium nitrite (13.8 mg, 0.2 M) in 83 mL of
water was added slowly. The solution obtained was
allowed to stand in ice-water for 30 min. It was then
brought to pH 8 with solid sodium carbonate, stirred for
20 min at 40°C, and steamed out part of the water, then
cooled in the refrigerator overnight, pure 1,5-
diaminotetrazole, which was recrystallized from solution.
According to the Le-Chatelier and Brinkley-Wilson
method, the explosion and reaction equation isDATS:
C2SN12O4H10 ðSÞ→5H2 ðgÞ þ 2COðgÞ þ 6N2 ðgÞ:
The calculated detonation pressure and detonation
velocity of DATS are shown in Table 3, the detonation
pressure and detonation velocity of DATS are
P = 11.877 GPa, D = 5.617 km sꢀ1, which are smaller
1,5-diaminotetrazole (2.0043 g, 20.04 mM) suspended
in 40 mL of methanol, was reacted with 10 mL concen-
trated HCl. The reaction mixture was refluxed for 2 h,
and then the solvent was evaporated until precipitation
occurred. The concentrated solution was then placed in
the refrigerator, and the white 1,5-diaminotetrazolium
hydrochloride was obtained. The precipitate was
filtered off and washed with water. The max yield is
81.15%.
than those of DATN (P = 33.3 GPa, D = 8.77 km sꢀ1
)
[13].
CONCLUSION
1,5-diaminotetrazolium chloride was synthesized
with DAT and relevant acid. DATS was first synthe-
sized with DATC as raw material. The structure was
characterized by elemental analysis, IR, 1H NMR,
and MS. The single crystal of DATS was first culti-
vated. The density, heat of formation, detonation pres-
sure, and detonation velocity of DATS were first
calculated. Both the detonation pressure and detonation
velocity of DATS are smaller than that of DATN. The ac-
tivation energy and pre-exponential factor of DATN are
higher than those of DATC and DATS. Therefore, DATN
can be used as gas-generating agent, and DATS can be
used as low energy propellant.
Synthesis of 1,5-diaminotetrazolium Sulfate.
1,5-
diaminotetrazolium chloride (2.0183 g, 20.0 mM) and
deionized water (100 mL) were added into a three-
necked flask equipped with a stirrer and a reflux
apparatus. After stirring gently at 80C to fully dissolve, sil-
ver sulfate (3.1295g, 10mM) was added into the solution to
react for 20min under exclusion of light, because silver sul-
fate is light sensitive. The filtrate was evaporated after filtra-
tion. The white DATS was obtained. Crystals suitable for X-
ray structure determination were obtained by slow evapora-
tion of a solution in methanol at ambient room temperature.
The yield is 96.59%.
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Synthesis, Structure, and Energetic Properties of DATS
657
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Acknowledgments. Financial support of this work by the basic
research fund of Beijing Institute of Technology (20130242017),
the project fund of State Key Laboratory of Explosion Science
and Technology (Beijing Institute of Technology) (YBKT16-09),
and fund the project of State Key Laboratory of Explosion
Science and Technology (Beijing Institute of Technology)
(KFJJ12-13 M).
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