Preparation, crystal structure and properties of a new crystal form of diammonium 5,5′-bistetrazole-1,1′-diolate

Article abstract of DOI:10.1002/cjoc.201500512

A new crystal form of diammonium 5,5′-bistetrazole-1,1′-diolate (1) was prepared by two novel methods and fully characterized by using IR, NMR spectroscopy, elementary analysis, single crystal X-ray crystallography and thermal gravity/differential thermal analysis (TG/DTA). Crystalline 1 was found as monoclinic and space group of P21/c (14). The TG/DTA analysis showed that the decomposition temperature of 1 was 287.8°C with a mass loss of 91.2% in the range of 220-300°C at a heating rate of 5°C/min. The sensitivities test towards impact, friction of 1 indicated that 1 has much lower sensitivities than those of RDX/HMX and is comparable to those of TNT, which suggested that 1 could be used as a good candidate of new insensitive energetic compound. A new crystal form of diammonium 5,5′-bistetrazole-1,1′-diolate (1) was prepared by two different novel methods and found as monoclinic and space group of P21/c (14). The thermal decomposition analysis and sensitivities test towards impact, friction of 1 indicated that 1 has much lower sensitivities than those of RDX/HMX and comparable to those of TNT, which suggested that 1 could be used as a good candidate of new insensitive energetic compound.

Full text of DOI:10.1002/cjoc.201500512

COMMUNICATION
DOI: 10.1002/cjoc.201500512
Preparation, Crystal Structure and Properties of a New Crystal
Form of Diammonium 5,5'-bistetrazole-1,1'-diolate
a,b
a
a
a
a
,a
Xiaojun Wang, Shaohua Jin, Chunyuan Zhang, Lijie Li, Shusen Chen, and Qinghai Shu*
a
School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
Research Institute of Gansu Yin Guang Chemical Industry Group, Baiyin, Gansu 730900, China
b
A new crystal form of diammonium 5,5'-bistetrazole-1,1'-diolate (1) was prepared by two novel methods and
fully characterized by using IR, NMR spectroscopy, elementary analysis, single crystal X-ray crystallography and
thermal gravity/differential thermal analysis (TG/DTA). Crystalline 1 was found as monoclinic and space group of
P21/c (14). The TG/DTA analysis showed that the decomposition temperature of 1 was 287.8 ℃ with a mass loss
of 91.2% in the range of 220－300 ℃ at a heating rate of 5 ℃/min. The sensitivities test towards impact, friction
of 1 indicated that 1 has much lower sensitivities than those of RDX/HMX and is comparable to those of TNT,
which suggested that 1 could be used as a good candidate of new insensitive energetic compound.
Keywords energetic material, diammonium 5,5'-bistetrazole-1,1'-diolate, crystal form, thermal decomposition,
explosive performances
Introduction
Scheme 1 The structure of nitrogen-rich salts of 5,5-bistetra-
zolates and 3,3-bistriazolates
Energetic materials (explosives, propellants and py-
rotechnics) are used extensively both for civil and mili-
tary applications. Recently, research in the field of en-
ergetic materials faced a profound change because of
many catastrophic explosions resulting from uninten-
tional initiation of munitions by aboard ships, aircraft
H
2
O NN
N
N
O
N
N
N
N
N
N
N
N
2
(NH
3
OH)+
N
H
N
NNO2
N
O
N
O
H
3
N
NH
3
N
H
N
H
TKX-50
[1,2]
carriers, munitions trains, impact or shock.
Addition-
CBNT
ally, concerns about the environmental impact of ener-
getic nowadays have caused a renaissance in the syn-
thesis of so-called green energetic materials, which are
based on the high nitrogen content that release mainly
NO
2
O N
O N
2
2
N
H
N
N
O
N
NO2
N
HN
NH
N
N
[3-6]
N
N
N
N
H
environmentally benign N2 after decomposition.
O
2
O
NO
NO2
2
Whereas, traditional energetic materials decompose into
a significant amount of toxic products after degradation,
the use of nitrogen-rich azoles such as triazole and te-
2
O N
Ditrolone
5
,5'-bis(trinitromethyl)-3,3'-bi-(1,2,4-triazole)
[7]
trazole derivatives avoid such drawbacks. Meanwhile,
it can also increase the heat of formation caused by C－
N and N－N bonding in nitrogen-rich azoles mole-
Diammonium salt of 5,5'-bistetrazole-1,1'-diolate (1),
one potential nitrogen-rich azole bearing C－C con-
nected bistetrazoles was firstly reported by Klapötke et
[8]
[
15]
cules. Recent studies on C－C connected heterocycles
al. with good explosive performances, such as deno-
tation velocity 8817 m/s and thermal decomposition
temperature 290 ℃. It has appeared promising applica-
tion value in high energy explosive with low sensitivi-
ties.
like bistetrazoles revealed excellent characteristics re-
[
9-11]
garding stability and detonation properties,
as most
extensively reported by Klapötke et al. on the synthesis
and characterization of a series of nitrogen-rich salts of
[12-14]
5
,5-bistetrazolates and 3,3-bistriazolates,
such as
Hence, a new crystal form of 1 was prepared by new
synthetic procedures and the obtained crystalline was
fully characterized in this study. To evaluate its ener-
getic performances, the explosive properties and ther-
carbonic dihydrazidinium bis[3-(5-nitroimino-1,2,4-tri-
azolate)], dihydroxylammonium (TKX-50), (CBNT) etc.
(
see in Scheme 1).
*
E-mail: qhshu121@bit.edu.cn; Tel.: 0086-010-68915072; Fax: 0086-010-68918535
Received July 15, 2015; accepted September 9, 2015; published online October 28, 2015.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201500512 or from the author.
Chin. J. Chem. 2015, 33, 1229—1234
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1229

Wang et al.
COMMUNICATION
mal behavior of 1 are also presented. As expected, 1 was
believed to be an excellent candidate of new insensitive
high energetic compound.
5,5'-Bistetrazole-1,1'-diol dehydrate (5): Diazidogly-
oxime (3.0 g, 17.6 mmol) was suspended in diethyl
ether (60 mL), which was cooled to 0－5 ℃ in a salt
ice bath, HCl gas was bubbled through the reaction
mixture at 0 ℃ while stirring for 1 h and then the flask
was sealed and stirred at room temperature for 24 h. The
HCl overpressure was released carefully, then the sol-
vent was removed under vacuum on a rotary. After most
of the diethyl ether had evaporated, water (100 mL) was
added to result in a solution. A remaining colorless pre-
cipitate indicated uncompleted conversion of diazi-
doglyoxime to 5,5'-bistetrazole-1,1'-diol. The water was
evaporated again on a rotary to remove the remaining
HCl and diethyl ether, thus yielding crude as colorless
solid, which could be purified by recrystallization from
water, yield 3.4 g (16.5 mmol, 93.6%).
Experimental
Caution! Diazidoglyoxim, 1-H-5,5'-bistetrazole-
1
,1'-diol and diammonium salt of 5,5'-bistetrazole-1,1'-
diolate are energetic with increased sensitivities towards
shock and friction. Therefore, proper safer precautions
(
safety glass, face shield, earthed equipment and shoes,
gloves, and ear plugs) have to be applied when synthe-
sizing and handling the described compounds.
Infrared spectra were measured with a Bruker Spec-
1
13
trum One FTIR spectrometer as KBr. H NMR,
C
NMR were recorded with a Bruker instrument. The
chemical shifts quoted in the text refer to typical stan-
dards such as tetramethylsilane. To measure elemental
analyses, Vario EL III was employed. To determine the
thermolysis performance of target compounds, SHI-
MADZU DTG-60 (heating rate 5 ℃/min) was used.
Glyoxime (3): In a 500 mL round-bottomed-neck
flask equipped with a thermometer and a dropping fun-
nel, NaOH (55.0 g, 1.4 mol) was dissolved in water
DTA-TG (5 ℃/min): 210 ℃(dec.). IR (KBr) ν:
3
1
7
327 (m), 2439 (w), 1668 (m), 1412 (w), 1377 (w),
310 (w), 1208 (w), 1143 (m), 995 (s), 916 (w), 807 (s),
−1 1
14 (w) cm ; H NMR (300 MHz, DMSO-d
6
) δ: 7.78;
) δ: 135.6; EA (found,
＝206.12): C (11.49, 11.65), H
2.41, 2.93), N (53.82, 54.36).
Diammonium 5,5'-bistetrazole-1,1'-diolate
,5'-Bistetrazole-1,1'-diol dehydrate (4.1 g, mmol) was
1
3
C NMR (300 MHz, DMSO-d
calcd for C , M
(
6
2
H
6
N
8
O
4
r
(1):
(
150 mL) and the solution was cooled to 0－5 ℃ in a
5
salt ice bath. Hydroxylammonium chloride (139 g, 2.0
mol) was added while stirring. To the above mixed solu-
dissolved in 100 mL of water, aqueous ammonia (4
mol/L, 20 mL) was added to the above solution while
stirring. The mixture was maintained for 1 h at room
temperature, the colorless crystalline residue was then
filtered and air dried, which could be purified by re-
crystallization in water, yield 2.9 g (14.2 mmol, 71.1%).
DTA-TG (5 ℃/min): 287.8 ℃ (dec.). IR (KBr) ν:
3187 (s), 3049 (s), 2153 (w), 1818 (w), 1668 (m), 1433
(s), 1353 (s), 1310 (w), 1230 (s), 1043 (m), 997 (m),
tion, glyoxal (145 g, 1.0 mol, 40% w/w in H
added dropwise while the temperature was kept below
0 ℃ over 30 min. After complete addition of the gly-
2
O) was
1
oxal, the solution was further stirred for 4 h at room
temperature. The solid was removed by suction filtra-
tion and washed with a little ice water to remove the
remaining sodium chloride. The white residue was re-
crystallized from methanol to afford glyoxime as white
−
1 1
726 (m) cm ; H NMR (300 MHz, DMSO-d ) δ: 7.12;
6
[
18]
13
crystals (69.0 g, 78.0 %); m.p. 175－177 ℃ (lit. 172
C NMR (300 MHz, DMSO-d ) δ: 134.1; EA (found,
6
1
－
174 ℃); H NMR (300 MHz, DMSO-d
6
) δ: 11.4 (s,
calcd for C H N O , M ＝204.15): C (11.59, 11.77), H
2
8
10
2
r
13
2
1
H), 7.71 (s, 2H); C NMR (300 MHz, DMSO-d ) δ:
(3.82, 3.95), N (68.55, 68.61).
6
45.1.
Method B
Method A
Diazidoglyoxime (4): Chlorinated agent (114 mmol)
Sodium 5,5'-bistetrazole-1,1'-diolate tetrahydrate (6):
Chlorinated agent (114 mmol) was added to a stirring
solution of glyoxime (5.0 g, 57 mmol) in DMF (100 mL)
at 0 ℃. The reaction mixture was stirred at room tem-
perature for 6 h. After the reaction was complete, the
solution was cooled to 0 ℃ in a salt ice bath, sodium
azide (8.0 g, 123 mmol) was added. The suspension was
stirred for 1 h at 0 ℃. HCl gas was bubbled through the
reaction mixture at 0 to 5 ℃ while stirring for 1 h, then
the flask was sealed and stirred at room temperature for
12 h. The HCl overpressure was released carefully, and
the solution was alkalized with sodium hydroxide solu-
tion to pH＝7－8. The reaction mixture was refluxed
for 0.5 h and cooled to room temperature, the precipitate
was filtered, crude solid could be purified by recrystal-
lization from hot water, yield 4.5 g (15.6 mmol, 92%).
DTA-TG (5 ℃/min): 383 ℃ (dec.). IR (KBr) ν:
3487 (s), 3305 (s), 2193 (w), 1676 (m), 1424 (s), 1359
was added to a stirring solution of glyoxime (5.0 g, 57.0
mmol) in DMF (100 mL) at 0 ℃. The reaction mixture
was stirred at room temperature for 2 h. After the reac-
tion was complete, the solution was cooled to 0 ℃ in a
－
1
salt ice bath, 1.0 mol•L sodium azide solution was
added. The precipitate was filtered, washed with 100
mL of water and air-dried. The solid was recrystallized
from ethanol to afford diazidoglyoxime as colorless
crystals (8.1 g, 84.0 %).
DTA-TG (5 ℃/min): 170 ℃ (dec.). IR (KBr) ν:
3
1
7
210 (w), 2169 (w), 2124 (w), 1623 (w), 1402 (w),
363 (w), 1288 (m), 1013 (vs), 931 (s), 920 (s), 855 (s),
−1 1
34 (s) cm ; H NMR (300 MHz, DMSO-d
6
) δ: 12.1;
) δ: 136.2; EA (found,
＝170.09): C (14.14, 14.12), H
1.39, 1.19), N (66.15, 65.88).
1
3
C NMR (300 MHz, DMSO-d
calcd for C , M
(
6
2
H
2
N
8
O
2
r
1230
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© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2015, 33, 1229—1234

New Crystal Form of Diammonium 5,5'-bistetrazole-1,1'-diolate
(
7
＝
3
s), 1239 (s), 1178 (s), 1068 (m), 1007 (m), 997 (m),
dimensions 0.22 mm×0.21 mm×0.20 mm, was used
for crystal and intensity data collection. The crystal of 1
was measured on a Bruker-AXS smart APEX2 CCD
detector using a Mo-Kα radiation wavelength of λ＝
0.71073 Å. The structures were measured at 296 K.
Bond distances, bond angles, torsion angles, hydrogen
bond, and atomic positional parameters for non-hydro-
gen atoms are shown in Table S2－S6. The molecular
structure and packing in the crystal lattice was illus-
trated in Figures 1 and 2, respectively. Additionally, the
normalized XRD patterns of 1 measured and simulated
by single crystal data were also shown in Figure S2,
where the main sharp peak at 13.46 can be attributed to
1 crystallite based on the Debye-Scherrer equation.
−1
56 (m) cm ; EA (found, calcd for C
286.11): C (8.32, 8.40), H (2.79, 2.82), N (39.04,
9.16).
Diammonium 5,5'-bistetrazole-1,1'-diolate (1): So-
2 8 8 2 6 r
H N Na O , M
dium 5,5'-bistetrazole-1,1'-diolate tetrahydrate (2.8 g, 10
mmol) was dissolved in 100 mL of warm water, ammo-
nia chloride (1.6 g, 30 mmol) was added to the above
solution while stirring. The mixture was maintain for 1
h, the solution was cooled to room temperature, the col-
orless crystalline residue was filtered and air dried,
which could be purified by recrystallization in water,
yield 1.8 g (8.8 mmol, 88.2%).
DTA-TG (5 ℃/min): 287 ℃ (dec.). IR (KBr) ν:
3
187 (s), 3049 (s), 2153 (w), 1818 (w), 1668 (m), 1433
(
7
s), 1353 (s), 1310 (w), 1230 (s), 1043 (m), 997 (m),
−1 1
26(m) cm ; H NMR (300 MHz, DMSO-d
6
) δ: 7.12;
) δ: 134.1; EA (found,
＝204.15): C (11.59, 11.77), H
3.82, 3.95), N (68.55, 68.61).
1
3
C NMR (300 MHz, DMSO-d
calcd for C , M
6
2
H
8
N
10
O
2
r
(
Results and Discussion
Synthesis
Glyoxal (2) was converted to glyoxime (3) following
[16]
the literature procedure, while 1 was prepared by our
[17]
modified synthetic routes from Fischer et al. in two
different methods (Scheme 2). Notably, in comparison
with Fischer’s step-by-step synthetic route, much higher
yield of 6 was fulfilled in one pot from glyoxime (90%
in method B), solving the headache of isolation of high
friction and impact sensitive intermediates dichlorogly-
oxime and diazidoglyoxime. Additionally, we utilized
new chlorinated reagent to replace Cl , not only greatly
2
increasing the chlorination efficiency but also simplify-
ing the synthetic progress.
+
Figure 1 Coordination of the NH
cations in 1. Thermal ellip-
4
soids are drawn at the 50% probability level and hydrogen atoms
are shown as small spheres or arbitrary radii. Symmetry operators:
(i) −1＋x, y, z; (ii) −1＋x, 0.5－y, 0.5＋z; (iii) 1−x, −0.5＋y,
−0.5−z; (iv) −1＋x, 0.5−y, −0.5＋z; (v) x, 0.5−y, −0.5＋z. Grey C;
blue N; red O; white H.
Interestingly, 1 crystallizes as monoclinic space
group P21/c with 2 molecules in the unit cell (Figure 2),
and has density of 1.765 g/cm (at 296 K) (Table 1),
Crystal structure
3
The crystal of compound 1 was grown in methanol
solution by slow evaporation at room temperature. A
colorless crystal of 1, irregularly shaped, of approximate
which is different from the reported orthorhombic
[
15]
face-centered space group I222.
Comparing with
Scheme 2 The two synthetic methods for preparation of 1
(1) Chlorinated agent
OH
(
2) NaN , DMF
3
N
3
N OH
N
N N
HCl
O
N
N
Method A
N
N
HO
N
N
3
N
O
2
4
OH
5
.
NH
2
OH HCl
NH3.H2O
(
1) Chlorinated agent
O
O
N OH
(
2) NaN , DMF
3
N
N N
NH Cl
N
N N
N
N
4
N
Method B
HO
N
N
N
N
N
N
N
3
(3) HCl
4) NaOH
N
O
2Na+
O
2NH4
+
(
6
1
Chin. J. Chem. 2015, 33, 1229—1234
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1231

Wang et al.
Table 1 Crystal date and experimental details of 1
COMMUNICATION
Klapötke’s result, crystal 1 in our work has five bistetra-
zoles coordinating with one ammonium ion, while one
bistetrazole coordinating with two ammonium ion was
presented in literature. The different crystalline form is
possibly attributed to the polarity of recrystallization
solvent. In addition, the C-N and N-N bonds of the
tetrazole ring are in the range of formal C-N and N-N
single and double bonds (C-N: 1.47 Å, 1.22 Å; N-N:
Formula
Color
2 8 10 2
C H N O
Colorless
Crystal system
Space group
a/Å
Monoclinic
P21/c
3.6786(9)
14.506 (3)
7.3456(16)
90
b/Å
[
27]
1
.48 Å, 1.20 Å).
N-oxide has a value of 108.41(97)° as compared to
11.47(57)° for neutral compound 5. As expected, the
The C(1)-N(1)-N(2) angle of
c/Å
α/(°)
1
β/(°)
101.373[5]
90
bond length of N(1)-O(1) is shortened to 1.31 Å upon
deprotonation [1.34 Å in 5]. The tetrazole ring [torsion
angle N(1)-N(2)-N(3)-N(4) ＝ 0.12(14)°] is planar,
which is a condition of the 6π aromaticity, and oxygen
groups [O(1)-N(1)-N(2)-N(3)＝79.48(10)°] is also al-
most planar out of this ring.
γ/(°)
3
Volume/Å
384.29(15)
1.765
Density/(g•cm−3)
Z
2
μ/mm−
θ range/(°)
F(000)
1
0.150
2.81－25.12
212
Index range
R(int)
−4＜h＜3, −16＜k＜17, −8＜l＜8
0.0155
Refl. collected
Refl. unique
R , wR [I>2σ(I)]
2404
687
1
2
0.0278, 0.0816
R , wR (all data)
0.0299, 0.0845
1.068
1
2
GOOF
CCDC
1057866
Additionally, a significant mass loss of 91.2% was
found in the range over 220－300 ℃. Both studies
suggested that 1 had a high thermal stability, which
most likely could be attributed to the extensive hydro-
gen bonding observed in the crystal structures.
Figure 2 The perspective view of the unit cell of 1 along the
a-axis. Grey C; blue N; red O; white H.
Due to the planarity of both cation and anion, the
crystal structure of 1 is built up by planes that are kept
together by a strong network of hydrogen bonding, in
contrast with the highly disordered crystalline in
Sensitivities
By applying the China National Military Standard,
the impact and friction sensitivities of 1 were deter-
[18]
2
−
mined. The impact sensitivities of 1 were determined
with a fall hammer apparatus. The test was performed
after drying the sample for 6 h at 60 ℃. During the test,
the room temperature was 23 ℃ and relative humidity
was 65%. A sample of 1 (30 mg) was placed between
two steel poles and hit with a 5.0 kg drop hammer from
a starting height of 25 cm. The probability detonating of
Klapötke’s result. As shown in Figure 2, each BTO
anion is surrounded by five ammonium cations via
strong hydrogen bonds towards the N atoms of the
tetrazole ring. It is remarkable to note that all accessible
nitrogen atoms and the N-oxide O(1) act as acceptors
for hydrogen bonds, which is merely possible due to the
several N－H groups of the ammonium cations. Mean-
while, the strong π-π interactions were also found be-
tween the BTO rings, which could facilitate the mo-
lecular stability.
1
1
was 0－8%, whereas that of HMX at class 1, was
00%. The determination of the 50% firing height (h50
)
was performed with a 5.0 kg drop hammer. The results
for 1, TNT, RDX, HMX and Comp. B are 89.4, 157,
[19-21]
Characterization of thermal behavior
2
2.3±0.3, 26.1±0.1 and 48.7±0.1.
From these
The thermal behavior of 1 was studied by thermo-
data, 1 appears to be less sensitive to impact than RDX,
HMX and Comp. B. In the case of friction sensitivity
test, 1 was measured with the MGY-1 pendular friction
sensitivities apparatus according to the standard proce-
dure using 20 mg of sample. After 1 was compressed
between two steel poles with mirror surfaces at a pres-
sure of 3.92 MPa, it was then hit by 5 kg hammer at a
gravimetric differential analysis (DTA-TG) in Al O
2 3
containers with a hole in the lip for gas release and a
nitrogen flow of 20 mL/min at a heating rate of 5 ℃/
min. As shown in Figure 3, decomposition of 1 was
started at 220 ℃ and reached a peak at 287.8 ℃, in-
dicating that 1 is thermally stable at least up to 220 ℃.
1232
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© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2015, 33, 1229—1234

New Crystal Form of Diammonium 5,5'-bistetrazole-1,1'-diolate
9
0° angle relative to the horizontal, the resulting firing
excellent candidate as insensitive explosive in various
warheads and ammunitions in the future.
rate was obtained to be 0%. Therefore, 1 was proved to
be as insensitive as TNT to friction. The test results are
summarized in Table 2, which is as expected because
the extensive hydrogen bonding in the molecule benefits
Table 3 Explosive properties of 1 compared with some other
important explosives
[
22]
the stabilization of material.
e
Impact
Friction Density/ D /
T
dec
/
Explosive
Ref.
b
c
d
−3
−1
P /% 50% /cm P /% (g•cm ) (m•s ) ℃
Table 2 Hydrogen bonds for 1 (Å and deg)
1
(
.765
296K)
1.779
293K)
.684
298K)
1.806
298K)
.890
298K)
1.720
An explosive composition with 39.5% of TNT, 59.5% of RDX,
1
4±4
8±4
0
89.4
82.5
0
0
0
8762 287.8
D－H…A d(D－H)
N5-H5C-N2 0.85(1)
N5-H5B-N3 0.85(1)
N5-H5A-N4 0.85(1)
N5-H5C-O1 0.85(1)
O1-H5D-N5 0.85(1)
d(H…A)
2.61(1)
2.21(1)
2.19(1)
2.09(1)
2.52(1)
d(D－A)
3.11(2)
3.06(2)
3.01(2)
2.91(1)
3.01(2)
∠DAH
117.42
172.41
161.97
178.41
117.47
Ref.
1
8817 290 [15]
6950 285 [23]
8754 210 [24]
9100 280 [25]
(
1
(
TNT
157±0.3
RDX 80±8 23.3±0.3 76
(
1
(
HMX
100 26.1±0.3 100
a
Comp. B 36±4 48.7±0.1 32
－
－ [26]
a
b
c
d
and 1% of wax; Explosion probability; Firing height; Explo-
e
sion probability; Detonation velocity.
Acknowledgement
We acknowledge the financial support from the
Youth Innovation Fund of North Chemical Industry
Group, China (No. 3090041410054).
References
[
[
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Figure 3 DTA-TG curves of 1.
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portant explosives in Table 2, the density value meas-
3
ured from the crystal of 1 at 296 K is 1.765 g/cm ,
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slightly lower than that of RDX. The overall results in-
dicated that 1 could be used as good candidate of new
insensitive high explosives. Meanwhile, it also could get
a conclusion that different crystal form of 1 resulted in
different explosive properties, especially on the aspect
of impact sensitivities and detonation velocity (Table 3).
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Conclusions
2
The diammonium 5,5'-bistetrazole-1,1'-diolate (1)
was synthesized by two novel methods using inexpen-
sive and readily available starting materials. The new
crystal form of compound 1 was found as monoclinic
space group P21/c with 2 molecules in the unit cell from
water solution. The intensive intermolecular hydrogen
bonding and the planar structure of bistetrazole ring
resulted in the high thermal stability of the overall mol-
ecule, which was further proved by DTA-TG analysis. 1
shows the high thermal stability of 287.8 ℃ and out-
standing insensitivity towards friction (H50＝89.1 cm)
and impact (P＝0%). In conclusion, 1 could become an
[
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