1,3,4,5-Tetraamino-1,2,4-triazolium Cation: An Energetic Moiety

Article abstract of DOI:10.1021/acs.inorgchem.1c00877

The amination of 3,4,5-triamino-1,2,4-triazole with O-tosylhydroxylamine yielded the nitrogen-rich 1,3,4,5-tetraamino-1,2,4-triazolium cation as its tosylate salt. Subsequent metathesis reactions produced energetic salts with various energetic anions, inc

Full text of DOI:10.1021/acs.inorgchem.1c00877

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1
,3,4,5-Tetraamino-1,2,4-triazolium Cation: An Energetic Moiety
Sebastian R. Yocca, Joseph Yount, Matthias Zeller, Edward F. C. Byrd, and Davin G. Piercey*
Cite This: Inorg. Chem. 2021, 60, 9645−9652
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sı Supporting Information
ABSTRACT: The amination of 3,4,5-triamino-1,2,4-triazole with
O-tosylhydroxylamine yielded the nitrogen-rich 1,3,4,5-tetraamino-
1
,2,4-triazolium cation as its tosylate salt. Subsequent metathesis
reactions produced energetic salts with various energetic anions,
including perchlorate, nitrate, nitrotetrazolate, and bistetrazolate
diolate. All energetic salts possess relatively high heats of
formation, thermal sensitivities, and detonation velocities and
pressures. The prepared energetic salts were characterized
chemically using single-crystal X-ray crystallography, elemental
analysis, and H NMR, C NMR, and IR spectroscopy and
energetically by measuring their thermal, impact, and friction
sensitivities. N NMR was carried out on the tosylate salt.
Energetic performances were determined by a combined
1
13
1
5
experimental-computational method using calculated heats of formation and experimental crystal densities.
1
. INTRODUCTION
Nitro, nitramino, and azido groups have shown to improve
11−13
azole detonation characteristics.
However, there is also a
Novel energetic materials are a subject of continuous
investigation to improve upon legacy molecules. This is done
to produce higher performing materials that have less
environmental impact and are insensitive to undesired stimuli.
There are multiple design strategies for contributing energy
content to an energetic molecule. First, a molecule can feature
ring or cage strain, which releases a significant amount of
energy when its structure is broken.
contain oxidizer and fuel components within itself. This is
common within many energetic legacy materials such as 2,4,6-
limit as to the number and identity of substituents which can
be added to an azole. Adding multiple explosophoric groups
could cause the product to become too thermally unstable or
14
too shock or friction sensitive for practical use. Alternatively,
adding substituents may also limit energetic performance, such
as azide groups, because the density decreases compared to
15
1
−3
what is possible with denser functional groups. Therefore,
there is an incentive to generate new energetic compounds by
the addition of these groups to both well-known and relatively
new energetic materials and to characterize these new
products’ performances.
A molecule can also
4
,5
trinitrotoluene (TNT) and the popular secondary explosive
6
1
,3,5-trinitro-l,3,5-triazinane (RDX). Moving to modern
One means to do this is by formation of energetic salts. The
salt’s overall energetic performance and stability can be readily
fine-tuned by the exchanging of cations or anions. Energetic
salts have been shown to be capable of possessing high
energetic performances while also having lowering sensitivities
to thermal and mechanical stimuli than their neutral
counterparts. In addition, salts generally possess a very low
vapor pressure, making them low inhalation risk and can be
achieved using conventionally “green” methods. Lastly, an
energetic salt may have a higher crystal density than its neutral
alternatives, a nitrogen-rich molecule could be designed to
have an inherently large heat of formation. During decom-
position of such a molecule, the nitrogen atoms will come
together forming nitrogen gas and release significant energy.
These strategies are often combined, and many energetic
materials derive energy content from multiple design strategies.
Recently, more developmental focus has been centered on
high heat of formation energetic materials because of their
relatively nontoxic postdetonation products and their ease of
7
−9
synthesis.
A family of energetic materials that show great
16
parent species.
promise is the nitrogen rich azoles, due to their high heat of
formation resultant from their high nitrogen content within
their five-membered heterocyclic ring. Specifically, both
triazole and tetrazole structures have shown acceptable thermal
stability and large heats of formations. However, neither
molecular structure is inherently energetic and, as a result,
requires the incorporation of explosophoric functionalities to
Received: March 26, 2021
Published: June 11, 2021
1
0
be interesting.
©
2021 American Chemical Society
https://doi.org/10.1021/acs.inorgchem.1c00877
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Incorporation of N-amines is an effective means for
developing high performing energetic materials without relying
on traditional methods of functionalization (i.e., wasteful and
Scheme 2. Synthesis of Ethyl O-(p-
Tolylsulfonyl)acetohydroximate and Fresh O-
Tosylhydroxylamine
hazardous mixed acid nitration). The formation of the N−NH
2
bond increases the molecule’s heat of formation due to the
thermodynamic driving force to produce stable N gas. The
2
presence of N-amines can dramatically improve the energetic
performance of materials as seen with comparison of 5-amino
tetrazole, 1-amino tetrazole, and 2-amino tetrazole. For the
most part, 5-amino tetrazole is considered nonenergetic,
whereas 1-amino tetrazole and 2-amino tetrazole are both
17
much more energetic. Additionally, the presence of N-amines
acts as a powerful scaffold for further molecular modification,
18,19
such as azo coupling and nitramino generation.
Scheme 3. Synthesis of 1,3,4,5-Tetraamino-1,2,4-triazolium
Tosylate Salt (1)
In this paper, we report on the amination of the known
nitrogen-rich heterocycle 3,4,5-triamino-1,2,4-triazole (guana-
zine) to the novel 1,3,4,5-tetraamino-1,2,4-triazolium cation
using O-tosylhydroxylamine. This is the only known instance
of a triazole possessing four amines on the backbone and offers
a unique high nitrogen cation to be considered in energetic
salts. The novel 1,3,4,5-tetraamino-1,2,4-triazolium tosylate
(
1) was then used as the precursor for metathesis reactions to
Scheme 4. Synthesis of Intermediate 1,3,4,5-Tetraamino-
obtain the 1,3,4,5-tetraamino-1,2,4-triazolium cation paired
with the more energetic nitrate, perchlorate, nitrotetrazolate,
and bistetrazole diolate anions.
1
,2,4-triazolium Bromide Salt (2) from 1
Each energetic salt was characterized chemically by
1
13
elemental analysis, X-ray crystallography, and H NMR,
NMR, and IR spectroscopy. The tosylate salt was characterized
C
1
5
by N NMR as well. Additionally, the salts’ energetic
properties, including their thermal decomposition temperature,
friction sensitivity, and impact sensitivity, were determined.
Lastly, detonation parameters for each energetic salt were
calculated using an experimental-computational method
involving calculated heats of formation and experimental
crystal densities.
Equal mole amounts of 2 and a corresponding silver salt of
an energetic anion were combined in aqueous solution and
stirred in the dark overnight at 40 °C in minimal water
(Scheme 5). The resulting solution was filtered, and the
Scheme 5. Synthesis of Energetic 1,3,4,5-Tetraamino-1,2,4-
triazolium Salts (3−6) from 2
2
. RESULTS AND DISCUSSION
.1. Synthesis. 3,4,5-Triamino-1,2,4-triazole (guanazine)
2
20
was prepared using a modified procedure outlined by Child
in which anhydrous hydrazine and dimethylcyanamide were
refluxed overnight in 2-methoxyethanol (Scheme 1). Once
Scheme 1. Synthesis of 3,4,5-Triamino-1,2,4-triazole
filtered and collected, guanazine was dissolved in minimal
water due to insolubility in acetonitrile. Freshly prepared O-
tosylhydroxylamine was derived from ethyl O-(p-tolylsulfonyl)-
energetic crystals of the nitrate (3), perchlorate (4), nitro-
tetrazolate (5), and bistetrazole diolate (6) salts were collected
by slow evaporation of the filtrate. Both salts 5 and 6 were
isolated as hydrates, as determined from their crystal
structures. Both of these salts were heated at 80 °C under
vacuum (>1 mbar) overnight and crystallized from methanol.
This procedure removed the water of crystallization from 5 but
not 6.
2
1
acetohydroximate (Scheme 2) in dichloromethane and
combined with the guanazine solution along with an equal
volume of acetonitrile and stirred for 48 hr (Scheme 3).
The reaction solution was then evaporated under vacuum
yielding the crude tosylate salt. The salt was recrystallized in
hot 2-propanol to remove impurities and residual guanazine,
yielding pure 1 as fine light-salmon needles. Recrystallized 1
was then dissolved in minimal hot ethanol, and 1 equivalent of
hydrobromic acid was added. The solution was removed from
heat and quenched with diethyl ether yielding a beige
precipitate of 1,3,4,5-tetraamino-1,2,4-triazolium bromide (2)
2.2. Spectroscopy. The 1,3,4,5-tetraamino-1,2,4-triazo-
lium cation was extensively characterized with multinuclear
NMR spectroscopy. The cation contains two different carbons
which are represented by two well-defined resonances in the
1
3
(Scheme 4).
C NMR spectra (147.4 and 148.9 ppm). The more shielded
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carbon at 147.4 ppm corresponds to the carbon closer to the
recently aminated nitrogen due to additional crowding.
Guanazine only has one 13C resonance at 151.3 ppm due to
its symmetry. Therefore, the ring N-amination slightly shields
the carbon atoms by approximately 2 to 4 ppm.
groups were assigned using XPREP within the SHELXTL suite
25,26 26
of programs
and solved by direct methods using ShelXS
2
and refined by full matrix least-squares against F with all
27
reflections using Shelxl2018 using the graphical interface
28
Shelxle. H atoms attached to carbon, boron, and nitrogen
atoms as well as hydroxyl hydrogens were positioned
geometrically and constrained to ride on their parent atoms.
C−H bond distances were constrained to 0.95 Å for aromatic
The cation also exhibits four distinguishable hydrogens,
which is identified with four separate singlet resonances in the
1
H NMR spectra (7.8, 6.4, 6.0, 5.6 ppm). The 7.8 and 6.4 ppm
hydrogens represent the N-amines, while the 6.0 and 5.6 ppm
and alkene C−H and to 0.98 Å for CH moieties, respectively.
3
1
hydrogen correspond to the C-amines. Guanazine’s H NMR
Amine and water H atom positions were refined. For
compound 6, N−H and O−H distances were restrained to
target values of 0.88(2) and 0.84(2) Å, respectively. For
compound 3, Uiso(H) values were freely refined. For all other
structures, they were set to a multiple of Ueq(C/N) with 1.5 for
spectrum displays two unique singlet resonances at 5.15 ppm
(
N-amine) and 5.06 ppm (2 × C-amines).
Using a saturated solution of salt 1, 15N NMR spectroscopy
identified seven unique peaks corresponding to the 1,3,4,5-
tetraamino-1,2,4-triazolium cation which contains seven nitro-
gen atoms, shown in Figure 1. The azolium nitrogen atom
CH and OH and 1.2 or 1.5 for NH units, respectively.
3
2
Complete crystallographic data, in CIF format, have been
deposited with the Cambridge Crystallographic Data Centre.
CCDC 2063169, 2063170, 2063171, 2063172, and 2063173
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif.
Figures 2−6 show the novel crystal structures containing the
,3,4,5-tetraamino-1,2,4-triazolium cation. Densities of all
1
Figure 1. 15N NMR spectrum of the 1,3,4,5-tetraamino-1,2,4-
triazolium cation.
without an attached N-amine (N ) and its adjacent nitrogen
a
(
N ) corresponds to −156.2 and −218.8 ppm, respectively.
b
The third azolium nitrogen (N ) is well resolved at −242.9
ppm. For the amines, the least shielded nitrogen corresponds
c
to N-3 (N ) of the 1,3,4,5-tetraamino-1,2,4-traizolium cation,
d
resonating at −335.0 ppm. N-1, N-4, and N-5 amines
unfortunately are indistinguishable; however, they resonated
at −308.2, −321.4, and −322.1 ppm. Darwich et al. conducted
1
5
N spectroscopy on the precursor 3,4,5-triamino-1,2,4-triazole
2
2
in 2007. Due to the symmetry of the molecule, they found
Figure 2. Molecular unit of 1,3,4,5-tetraamino-1,2,4-triazolium
tosylate (1). Ellipsoids are drawn at the 50% probability level.
four unique nitrogen resonances at −156.5 (azole, N-1 and N-
2
), −238.1 (azole, N-4), −326.3 (amine, N-4), and −340.7
(
amine, N-3, N-5) ppm. By comparing the chemical shifts
before and after the amination, one can see that the newly
aminated ring nitrogen exhibited the largest chemical shift of
over 60 ppm, while all other nitrogen exhibited much lower
shifts (<20 ppm).
crystals were determined at 150 K (Table 1) and at ambient
temperature (Table 2). Each salt crystal was colorless. Tosylate
salt 1 (Figure 2) and nitrate salt 3 (Figure 3) both crystallized
Using mass spectrometry, the 1,3,4,5-tetraamino-1,2,4-
in the monoclinic space group P2 /c with 4 formula units in
1
+
−3
triazolium cation (C N H ) for all salts appeared at 130.2
the unit cell. 1 exhibited a density of 1.469 g-cm at 150 K
and 1.434 g-cm at ambient temperature. 3 featured a density
of 1.632 g-cm at 150 K and 1.600 g-cm at ambient
2
7
8
+
−3
m/z (ESI ). The salts respective anions or anionic complexes
appeared at 171.1 (1, C H SO ), 289.8 (2, C N H Br ),
2.0 (3, NO ), 328.1 (4, C N H (ClO ) ), 114.0 (5,
−
−
−3
−3
7
7
3
2
7
8
2
−
−
6
temperature. Perchlorate salt 4 (Figure 4) crystallized in a
3
2
7
8
4 2
−
−
−
CN O ), and 169.0 (6, C N O ) m/z (ESI ).
monoclinic space group P2 /n with 4 formula units in the unit
5
2
2
8
2
1
−
3
2
.3. Single-Crystal X-ray Analysis. Single crystals of the
cell. 4 had the highest densities of all the salts, 1.808 g-cm at
−
3
investigated compounds 1, 3, 4, 5, and 6 were coated with a
trace of Fomblin oil and were transferred to the goniometer
head of a Bruker Quest diffractometer with kappa geometry, a
Cu Kα wavelength (λ = 1.54178 Å) I-μ-S microsource X-ray
tube, a laterally graded multilayer (Goebel) mirror for
monochromatization, and a Photon III C14 area detector.
The instrument was equipped with an Oxford Cryosystems
low temperature device, and examination and data collection
were performed at 150 K. Data were collected, reflections were
indexed and processed, and the files were scaled and corrected
150 K and 1.763 g-cm at ambient temperature. Nitro-
tetrazolate salt 5 (Figure 5) crystallized in the monoclinic
space group C2/c with 8 formula units per unit cell and a
−
3
−3
density of 1.694 g-cm at 150 K and 1.606 g-cm at ambient
temperature. Lastly, the bistetrazole diolate salt 6 (Figure 6)
crystallized in the triclinic space group P1 with 1 formula unit
per unit cell and two waters of hydration. This dihydrated salt
featured a density of 1.680 g-cm at 150 K and 1.651 g-cm
at ambient temperature. None of the produced salts yielded
−
3
−3
−
3
densities close to RDX (1.82 g-cm at ambient temper-
23
24
29
for absorption using APEX3 and SADABS. The space
ature).
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Table 1. Crystallographic Data and Structure Refinement Details for Salts 1, 3, 4, 5, and 6
1
3
4
5
6
formula
FW [g mol−1]
crystal system
space group
a [Å]
b [Å]
c [Å]
α [deg]
β [deg]
γ [deg]
V [Å3]
Z
ρ [g cm−3]
T [K]
C H N SO
301.34
monoclinic
C H N O
192.16
monoclinic
C H N ClO
229.60
monoclinic
C H N O
244.21
C H N O
4
9
15
7
3
2
8
8
3
2
8
7
4
3
8
12
2
6
20 22
464.44
triclinic
P1
6.5034 (4)
7.9023 (5)
10.1915 (7)
458.98 (4)
105.162 (3)
111.469 (3)
458.98 (5)
1
monoclinic
C2/c
24.9631 (17)
3.7996 (3)
20.8866 (14)
90
104.791 (3)
90
104.791 (3)
8
P2 /c
P2 /c
P2 /n
1
1
1
15.0951 (8)
9.6374 (6)
9.4354 (4)
90
97.114 (3)
90
1362.07 (13)
4
5.5461 (2)
8.4679 (3)
16.6593 (9)
90
90.817 (3)
90
782.30 (6)
4
1.632
5.6741 (2)
11.0488 (4)
13.4960 (5)
90
94.6549 (12)
90
843.30 (5)
4
1.808
150
1.469
150
1.694
150
1.680
150
150
crystal shape
color
crystal size (mm)
R1
wR2
S
no. of reflections
parameters
restraints
CCDC
plate
colorless
0.04 × 0.03 × 0.002
0.046
0.130
1..06
2893
207
fragment
colorless
0.25 × 0.15 × 0.11
0.040
0.117
1.09
1605
151
0
block
colorless
0.23 × 0.20 × 0.15
0.040
0.117
1.16
1786
152
plate
block
colorless
0.13 × 0.10 × 0.07
0.041
0.127
1.09
1913
176
colorless
0.21 × 0.08 × 0.03
0.034
0.096
1.05
2048
179
0
0
0
10
2063171
2063173
2063169
2063170
2063172
Table 2. Energetic Properties and Calculated Detonation Parameters for Salts 3−6 and RDX
2
9
3
4
5
6
RDX
C H N O
formula
C H N O
C H N ClO
C H N O
C H N O
2
8
8
3
2
8
7
4
3
8
12
2
6
20 22
4
3
6
6
6
FW (g/mol)
192.14
−41.64
156
1.600
1.662
61.3
229.58
−27.88
163
1.763
1.788
144.0
6.0
244.17
−32.76
137
1.606
1.656
518.0
2.0
464.39
−62.01
177
1.651
1.732
909.7
>40
222.12
−21.6
239
a
Ω
(%)
(°C)
b
T
d
c
ρ (g-cm−3)
47
1.858 (90 K)
ρcalc (g-cm−3)
d
o
e
Δ H
(kJ/mol)
92.6
7.4
120
f
m
f
IS (J)
7.0
8.4
g
FS (N)
11.2
8.0
14.4
calculated values by EXPLO5
o
h
Δ U (kJ/kg)
4034
2484
23.9
8209
0.486
4852
3150
28.9
8410
0.436
4103
2866
23.6
8198
0.486
4214.8
2436.9
27.4
8795
0.476
5355
3959
33.7
8710
0.734
Ex
i
T
(°C)
ρ (GPa)
(m/s)
Vo (cm /g)
det
j
k
V
det
l
3
a
b
c
d
e
Oxygen balance. Temperature decomposition. Density from X-ray diffraction (25 °C). Calculated density. Calculated molar enthalpy of
f
g
h
i
j
k
formation. Impact sensitivity. Friction sensitivity. Total energy of detonation. Detonation temperature. Detonation pressure. Detonation
velocity. Volume of detonation products.
l
2
.4. Thermal Behavior. All energetic salts decomposed at
decomposition point of 3,4,5-triamino-1,2,4-triazolium nitrate
to be near 220 °C. By comparing to our nitrate salt 3 (Tdec =
30
elevated temperatures between 137 and 177 °C, as shown in
Table 2. Intermediate salts 1 and 2 decomposed at 177 and
89 °C, respectively. Each salt displayed one exotherm during
157 °C), our results indicate the decomposition temperature of
the triazolium moiety drops over 60 °C with one additional N-
amine. All salts have lower decomposition temperatures than
1
incremental heating, representing the decomposition point.
The temperatures were recorded at the onset temperature of
the exothermic process. The highest energetic salt decom-
position temperature was bistetrazolate diolate 6 at 177 °C,
while the lowest was the nitrotetrazolate 3 at 137 °C. The
hydrated salt 6 also displayed an endotherm around 100 °C,
corresponding to the loss of its crystal water. The amination of
the 3,4,5-triamino-1,2,4-triazole reduces the decomposition
temperature of the salt. In 2010, Liang et. al determined the
29
RDX (205 °C).
2.5. Detonation Parameters. Only salts 3, 4, 5, and 6
were studied for energetic performance. Intermediate salts 1
and 2 were not tested for energetic performance because their
anions are not considered energetic. All calculated detonation
characteristics were calculated using the theoretical heat of
formation and experimental X-ray crystallography room
temperature density.
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Figure 3. Molecular unit of 1,3,4,5-tetraamino-1,2,4-triazolium nitrate
(3). Ellipsoids are drawn at the 50% probability level.
Figure 6. Molecular unit of 1,3,4,5-tetraamino-1,2,4-triazolium
bistetrazole diolate dihydrate (6). Ellipsoids are drawn at the 50%
probability level.
Salt 6 showed the highest heat of formation (909.7 kJ/mol)
of the 1,3,4,5-tetraamino-1,2,4-triazolium salts. This high heat
of formation can be attributed to its nitrogen-rich bistetrazole
diolate anion. Additionally, 6 displayed a calculated detonation
velocity of 8795 m/s, which surpasses RDX performance
Figure 4. Molecular unit of 1,3,4,5-tetraamino-1,2,4-triazolium
perchlorate (4). Ellipsoids are drawn at the 50% probability level.
(
8710 m/s). If the nonhydrated salt of 6 was produced,
meaning solely two tetraamino-triazolium cations per biste-
trazole diolate anion, the calculated heat of formation and
calculated density would change to 1381.6 kJ/mol and 1.655 g-
−
3
cm . This theoretical salt has a slightly larger heat of
formation and slightly smaller density than its hydrated form 6,
so it can be assumed that its performance is similar to 6’s
parameters.
The perchlorate salt 4 achieved the second best character-
istics (Vdet = 8410 m/s, Δ U° = 4852 kJ/kg, ρ = 28.9 GPa),
Ex
despite a low heat of formation (144.0 kJ/mol). 4’s higher
performance values (especially the detonation pressure) are
most likely due to its higher density and greater oxygen balance
−
3
than the other salts (1.763 g-cm ). Dense crystal formation is
46
important to achieve high energetic performance. Salts 3, 4,
and 5 do not surpass RDX detonation performance. This may
be attributable to their lower crystal density and oxygen
balance compared to RDX.
Figure 5. Molecular unit of 1,3,4,5-tetraamino-1,2,4-triazolium
nitrotetrazolate (5). Ellipsoids are drawn at the 50% probability level.
2.6. Mechanical Sensitivity. The four energetic salts
The energetic properties of each of the compounds are
shown in Table 2. The method of Byrd and Rice (based on
properties of individual energetic compounds derived from
underwent sensitivity testing, and the results are found in
Table 2. Impact sensitivity was performed according to
48
STANAG 4489 and modified according to instruction on
49
31
quantum mechanics) provided the heats of formation and
an OZM drop hammer by the BAM method. Friction
50
3
2,33
densities
of all compounds. These calculated densities
sensitivity was carried out in accordance with STANAG 4487
51
agreed within 3% with those measured via X-ray crystallog-
and modified according to instruction using a BAM friction
tester. The nitrotetrazolate salt 5 was the most sensitive for
both friction and impact (8.0 N, 2.0 J), while the hydrated
bistetrazole diolate salt 6 was the least sensitive (14.4 N, >40
J). Hydrated energetic materials are often less sensitive to
various stimuli, which most likely increased its resistance to
34
raphy at 150 K. The Gaussian09 program package and the
B3LYP spin-restricted Kohn−Sham density functional theory
3
5−38
(
set
KS-DFT)
with the 6-31G** Pople Gaussian basis
3
9−41
were used to determine gas phase geometries of
each compound. Using these geometry data, the G3MP2-
4
2
52
detonating. If the anhydrous form of salt 6 was achieved, it
(
B3LYP) electronic energy was determined which is required
43
can be predicted to be much more sensitive. Salts 3, 4, and 5
to compute the heat of formation. The Gutowski method
29
exhibited more sensitive behavior than RDX (7.4 J, 120 N).
provided the heat of sublimation as determined from the
molecular volume of each compound. The EXPLO5 V6.05.02
44,45
3. CONCLUSIONS
software package
provided the detonation performance
data from the calculated heats of formation based on observed
X-ray diffraction crystal densities at ambient temperature.
In summary, a new energetic 1,3,4,5-tetraamino-1,2,4-triazo-
lium cation was created by reacting the strong aminating agent
9
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Article
ethyl O-(p-tolylsulfonyl)acetohydroximate with nitrogen-rich
C
9
H
15
N
7
SO
3
(301.32): calcd. C 35.87, H 5.02, N 32.54; found C
35.90, H 5.02, N 32.52.
3
,4,5-triamino-1,2,4-triazole. The novel energetic cation was
4
.4. 1,2,3,4-Tetraamino-1,3,5-triazolium Bromide (2). Tosy-
then paired with other energetic anions using metathesis
reactions to form distinct energetic salts. None of the salts
exhibited remarkable energetic performance, with all salts
having detonation parameters around or below RDX. We
theorize that the low performance is mostly due to the salts’
low densities. However, the successful amination of guanazine
to the first ever 1,3,4,5-tetraamino-1,2,4-triazolium cation is
still important as a new high nitrogen moiety and will lead to
more energetic compounds in the future.
late 1 (0.486 g, 1.61 mmol) was dissolved in a minimal amount of hot
ethanol (20 mL). Hydrobromic acid (48%, 0.415 g, 5.129 mmol) was
added to the solution. The bromide salt precipitated out of solution at
RT. To further reduce solubility, diethyl ether (100 mL) was added
and placed in the fridge overnight. The solid beige product was
separated from the solution via vacuum filtration and dried to yield
0.332 g, 1.58 mmol of 2 (yield = 98%). DSC: 189 °C (dec.). IR: v
375(w), 3320 (m), 3294 (m), 3174 (m), 3121 (m), 2750 (w), 1728
m), 1650 (s), 1622 (m), 1607 (m), 1569 (m), 1445 (m), 1380 (w),
341 (w), 1311 (w), 1221 (w), 1152 (w), 1079 (m), 1009 (w), 949
s), 892 (m), 799 (w), 765 (w), 710 (m), 671 (w), 630 (m), 599 (s),
̃ =
3
(
1
(
4
−
1
1
+
4
. EXPERIMENTAL SECTION
91 (s) cm . H NMR ([D ]DMSO): δ = 7.8 (s, 2H, N −N−C−
6
+
NH ), 6.4 (s, 2H, N −C−NH ), 6.0 (s, 2H, N−NH ), 5.6 (s, 2H,
4.1. General. All reagents and solvents were used as received
2
2
2
+
13
N −NH ). C NMR ([D ]DMSO): δ = 148.9 (1C, NH −N−C−
unless otherwise specified (Sigma-Aldrich, Fluka, Acros Organics,
Fisher Scientific Co LLC). Decomposition temperatures were
acquired using a TA Instruments SDT Q600 TGA/DSC using
2
6
2
+
+
N −NH ), 147.4 (1C, NH −N−C−N). MS (ESI ): m/z 130.2
2
2
+
−
−
(C N H ); MS (ESI ): m/z = 78.9 (Br ),210.1 (C N H Br), 289.9
2 7 8 2 7 8
−
−
1
(C N H Br ). C H N Br (210.0): calcd. C 11.44, H 3.84, N 46.68;
found C 11.84, H 3.88, N 46.38.
2 7 8 2 2 8 7
heating rates of 5 °C min . Salt characterization using Elemental
Analysis was conducted using an Elementar Vario EL cube. All NMR
1
13
15
4.5. 1,2,3,4-Tetraamino-1,3,5-triazolium Nitrate (3). Silver
nitrate (0.087 g, 0.512 mmol) was dissolved in a minimal amount of
water (10 mL). Bromide salt 2 (0.105 g, 0.500 mmol) was dissolved
in a separate container in a minimal amount of water (10 mL). The
two solutions were combined and stirred overnight at 40 °C in
darkness. The solution then underwent a Celite filtration. The filtrate
was allowed to evaporate to dryness to yield 0.076 g of nitrate salt 3
(
H, C, N) spectroscopy was collected with a Bruker AV-III-500-
HD (5 mm BBFO Cryoprobe Prodigy) Avance DRX NMR
1
13
spectrometer. All chemical shifts for H and C spectra are relative
1
5
15
to TMS. Salt 1 was used for the N NMR spectrum. N chemical
shifts are relative to CH NO . Infrared spectra were measured with a
3
2
PerkinElmer Spectrum Two FT-IR spectrometer. Transmittance
values are described as “strong” (s), “medium” (m), and “weak”
(
(
1
(
yield = 79%). DSC: 156 °C (dec.). IR: v
w), 3134 (w), 2949 (w), 1728 (w), 1667 (m), 1632 (m), 1596 (w),
530 (w), 1458 (w), 1437 (w), 1371 (s), 1337 (m), 1316 (m), 1235
m), 1182 (w), 1148 (m), 1073 (m), 1054 (m), 963 (w), 903 (m),
̃ = 3320 (w), 3234 (w), 3196
(
w). Mass spectra were obtained using an Agilent 1260 Infinity II
Quaternary LC instrument. The BAM (Bundesanstalt fur Materi-
̈
alforschung) friction tester from Reichel & Partner Gmbh and the
OZM BAM Fall Hammer BFH-10 were used to acquire sensitivity
data.
8
5
25 (m), 774 (m), 720 (m), 710 (m), 670 (w), 656 (m), 630 (m),
22 (s), 463 (s) cm . H NMR ([D ]DMSO): δ = 7.8 (s, 2H, N −
−
1
1
+
6
4.2. WARNING. This paper’s salts and many of their intermediates
+
N−C−NH ), 6.4 (s, 2H, N −C−NH ), 6.0 (s, 2H, N−NH ), 5.6 (s,
2
2
2
are considered energetic materials that could be detonated by various
stimuli. During our experiments, we did not encounter issues while
handling the materials. However, personal protective equipment (face
shield, body armor, Kevlar gloves, grounded equipment) should be
used at all times.
+
13
2
H, N −NH ). C NMR ([D ]DMSO): δ = 148.9 (1C, NH −N−
2
6
2
+
+
C−N −NH ), 147.4 (1C, NH −N−C−N). MS (ESI ): m/z = 130.2
2
2
+
−
−
(C N H ); MS (ESI ): m/z = 62.0 (NO ). C H N O (192.14):
2 7 8 3 2 8 8 3
calcd. C 12.50, H 4.20, N 58.32; found C 13.20, H 4.17, N 57.40.
BAM impact: 7.0 J; BAM friction: 8.4 N.
4
.3. 1,2,3,4-Tetraamino-1,3,5-triazolium Tosylate (1). Ethyl
O-(p-tolylsulfonyl)acetohydroximate (2.2 g, 8.7 mmol) was stirred in
0% perchloric acid (40 mL) for 2 hr at RT. The solution was then
4
.6. 1,2,3,4-Tetraamino-1,3,5-triazolium Perchlorate (4).
Silver perchlorate (0.208 g, 1.00 mmol) was dissolved in a minimal
amount of water (10 mL). Bromide salt 2 (0.204 g, 0.97 mmol) was
dissolved in a separate container in a minimal amount of water (10
mL). The two solutions were combined and stirred overnight at 40
6
poured into ice water. The white aminating agent was extracted from
the water using dichloromethane. In a separate container, 3,4,5-
triamino-1,2,4-triazole (1.0 g, 8.7 mmol) was dissolved in a minimal
amount of water. The water (25 mL) and dichloromethane solutions
°
C in darkness. The solution then underwent a Celite filtration. The
filtrate was allowed to evaporate to dryness to yield 0.199 g, 0.87
mmol of perchlorate salt 3 (yield = 89%). TGA: 171 °C (dec.). IR: v
3439 (m), 3408 (m), 3376 (m), 3364 (m), 3288 (m), 3153 (w),
730 (m), 1651 (s), 1614 (m), 1463 (m) 1346 (w), 1245 (w), 1154
w), 1063 (s), 942 (m), 910 (m), 862 (m), 771 (s), 715 (s), 657 (m),
(125 mL) were combined with an equal volume acetonitrile (125
̃
mL) and stirred at RT for 24 h. The resultant aqueous layer was
evaporated to yield a purple-red solid consisting of 3,4,5-triamino-
=
1
1,2,4-triazole and 1. To increase purity, the solid was stirred in hot 2-
(
6
propanol for 2 hr. A hot vacuum filtration was performed to separate
the two compounds. Pure pink 1 (1.67 g) precipitated and was
collected via vacuum filtration and allowed to dry (yield = 64%).
−1 1
19 (s), 562 (s), 469 (m) cm . H NMR ([D ]DMSO): δ = 7.8 (s,
6
+
+
2
H, N −N−C−NH ), 6.4 (s, 2H, N −C−NH ), 6.0 (s, 2H, N−
2
2
+
13
NH ), 5.6 (s, 2H, N −NH ). C NMR ([D ]DMSO): δ = 148.9
2
2
6
̃
̃
= 3471 (w), 3316 (m), 3277 (m), 3215
+
DSC: 177 °C (dec.). IR: ν
m), 3167 (m), 2920 (w), 1726 (m), 1674 (m), 1588 (m), 1537 (w),
495 (w), 1453 (m), 1395 (w), 1361 (w), 1302 (w), 1189 (s), 1177
(
(
3
1C, NH −N−C−N −NH ), 147.4 (1C, NH −N−C−N). MS
2
2
2
(
1
+
+
−
−
ESI ): m/z = 130.2 (C N H ); MS (ESI ): m/z = 98.9 (ClO ),
2
7
8
4
−
27.9 ((C N H )(ClO ) ). C H N ClO (229.58): calcd. C 10.46,
2
7
8
4
2
2
8
7
4
(
(
s), 1122 (s), 1109 (m), 1035 (s), 1009 (s), 940 (m), 897 (m), 816
m), 799 (m), 773 (w), 711 (m), 683 (s), 631 (m), 566 (s), 514 (s)
H 3.51, N 42.71; found C 10.62, H 3.54, N 40.91. BAM impact: 6.0 J;
BAM friction: 11.2 N.
−
1
1
+
cm . H NMR ([D ]DMSO): δ = 7.8 (s, 2H, N −N−C−NH ), 7.5
6
2
4.7. 1,2,3,4-Tetraamino-1,3,5-triazolium Nitrotetrazolate
(5). Sodium nitrotetrazolate dihydrate (0.200 g, 1.16 mmol) and
silver nitrate (0.199 g, 1.17 mmol) were dissolved in water (20 mL)
and stirred for 2 h in the dark. Silver nitrotetrazolate (0.193 g, 0.87
mmol) was collected and dried via vacuum filtration (yield = 75.3%).
Bromide salt (0.166 g, 0.79 mmol) 2 was dissolved in water (10 mL).
The silver nitrotetrazolate was added slowly into the solution and
stirred overnight at 40 °C in darkness. The solution then underwent a
Celite filtration. The filtrate was allowed to evaporate to dryness to
yield the hydrated nitrotetrazolate salt 5. The hydrated salt was then
baked under vacuum for 24 h and redissolved in methanol. Anhydrous
−
+
(
d, 2H, CH−C−SO ), 7.1 (d, 2H, CH−C−CH ), 6.4 (s, 2H, N −
3
3
+
C−NH ), 6.0 (s, 2H, N−NH ), 5.6 (s, 2H, N −NH ), 2.3 (s, 3H,
CH ). C NMR ([D ]DMSO): δ = 148.9 (1C, N−C−N ), 147.4
2
2
2
13
+
3
6
−
(
(
1C, N−C−N), 146.3 (1C, C−CH ), 138.1 (1C, C−SO , 128.5
3
3
− 15
2C, CH−C−CH ), 126.0 (2C, CH−C−SO ), 21.2 (1C, CH ).
N
3
3
3
NMR ([D ]DMSO): δ = −156.2 (2N-azolium), −218.8 (1N-
6
azolium), −242.9 (4N-azolium), −308.2 (1N-amine, 4N-amine, 5C-
amine), −321.4 (1N-amine, 4N-amine, 5C-amine), −322.1 (1N-
+
amine, 4N-amine, 5C-amine), −335.0 (3C-amine). MS (ESI ): m/z =
+
−
−
1
30.2 (C N H ); MS (ESI ): m/z = 171.1 (C H SO ).
2 7 8 7 9 3
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pubs.acs.org/IC
Article
5
(0.089 g, 0.36 mmol) was obtained by letting the methanol solution
evaporate to dryness slowly (yield = 46%). DSC: 137 °C (dec.). IR: v
3360 (w), 3230 (m), 3139 (w), 2999 (w), 2951 (w), 2846 (w),
458 (w), 1722 (m), 1660 (s), 1635 (m), 1573 (w), 1532 (s), 1504
m), 1457 (w), 1439 (s), 1418 (s), 1358 (w), 1342 (w), 1317 (s),
239 (w), 1183 (m), 1168 (m), 1152 (w), 1118 (w), 1079 (w), 1051
w), 1030 (w), 946 (w), 900 (m), 839 (s), 759 (m), 735 (m), 701
Authors
̃
Sebastian R. Yocca − Department of Chemical Engineering,
Purdue University, West Lafayette, Indiana 47906, United
States; Department of Materials Engineering and Purdue
Energetics Research Center, Purdue University, West
Lafayette, Indiana 47906, United States; orcid.org/0000-
0001-8989-1273
Joseph Yount − Department of Materials Engineering and
Purdue Energetics Research Center, Purdue University, West
Lafayette, Indiana 47906, United States; orcid.org/0000-
0001-6720-9261
Matthias Zeller − Department of Chemistry, Purdue
University, West Lafayette, Indiana 47906, United States;
orcid.org/0000-0002-3305-852X
Edward F. C. Byrd − Detonation Sciences & Modeling
Branch, CCDC U.S. Army Research Laboratory, Aberdeen
Proving Ground, Maryland 21005, United States
=
2
(
1
(
(
(
−
1 1
m), 672 (m), 623 (m), 596 (s), 528 (s), 451 (m) cm . H NMR
[D ]DMSO): δ = 7.8 (s, 2H, N −N−C−NH ), 6.4 (s, 2H, N −C−
+
+
6
2
+
13
NH ), 6.0 (s, 2H, N−NH ), 5.6 (s, 2H, N −NH ). C NMR
2
2
2
(
[D ]DMSO): δ = 169.2 (1C, N−C−NO ), 148.9 (1C, NH −N−
6
2
2
+
+
C−N −NH ), 147.4 (1C, NH −N−C−N). MS (ESI ): m/z = 130.2
2
2
+
−
+
(
(
6
C N H ); MS (ESI ): m/z = 114.0 (CN O ), 228.8 (H-
2 7 8 5 2
+
CN O ) ). C H N O (244.17): calcd. C 14.76, H 3.30, N
5
2
2
3
8
12
2
8.84; found C 14.83, H 3.21, N 68.49. BAM impact: 2.0 J; BAM
friction: 8.0 N.
4.8. 1,2,3,4-Tetraamino-1,3,5-triazolium Bistetrazole Dio-
late Dihydrate (6). Diammonium bistetrazolate diolate (0.195 g,
0.96 mmol) and silver nitrate (0.327 g, 1.93 mmol) were dissolved in
water and stirred for 2 h. The resultant precipitant silver bistetrazole
diolate was collected and dried via vacuum filtration (0.260 g, 0.73
mmol). The silver bistetrazole diolate (0.242 g, 0.68 mmol) was
redissolved in hot water (50 °C). Bromide salt 2 (0.280 g, 1.33 mmol)
was dissolved in a separate container in a minimal amount of water.
The two solutions were combined and stirred overnight at 40 °C in
darkness. The solution then underwent a Celite filtration. The filtrate
was allowed to evaporate and then dried under vacuum to yield 0.243
g (0.52 mmol) of the bistetrazole diolate salt 6 (yield = 78%). TGA:
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.1c00877
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support of this work by the US Army ACC APG
Adelphi Div under grant No. W911NF2020189 “Advancing
Army Modernization Priorities through Collaborative Ener-
getic Materials Research; Task 1: CHNOF energetic materials
with higher lethality” is acknowledged. The National Science
Foundation is acknowledged through the Major Research
Instrumentation Program under Grant No. CHE 1625543 for
the single-crystal X-ray diffractometer. Financial support of our
laboratory by Purdue University, The Office of Naval Research
(ONR), and the Army Research Office (ARO) is also
acknowledged. We thank the Purdue Military Research
Initiative for graduate education funding. We acknowledge
Austin Credle for providing any artwork associated with our
work. Lastly, we would like to thank Dr. John Harwood for his
1
3
00 °C (H O removal), 186 °C (dec.). IR: v
̃
= 3334 (m), 3279 (m),
220 (m), 3113 (m), 2955 (w), 2927 (w), 2850 (w), 1740 (m), 1660
2
(
1
(
6
7
s), 1626 (m), 1524 (w), 1454 (m), 1411 (m), 1349 (m), 1266 (w),
228 (m), 1174 (m), 1130 (m), 1100 (m), 1056 (m), 997 (m), 944
w), 865 (m), 771 (m), 735 (s), 714 (m), 689 (m), 659 (m), 630 (s),
−1 1
19 (s), 562 (s), 495 (s), 468 (s) cm . H NMR ([D ]DMSO): δ =
6
+
+
.8 (s, 2H, N −N−C−NH ), 6.5 (s, 2H, N −C−NH ), 6.0 (s, 2H,
2
2
+
13
N−NH ), 5.7 (s, 2H, N −NH ). C NMR ([D ]DMSO): δ = 148.9
2
2
6
+
(
(
1C, NH −N−C−N −NH ), 147.4 (1C, NH −N−C−N) 134.4
2
2
2
+ + −
2C, N−C−C−N). MS (ESI ): m/z = 130.2 (C N H ); MS (ESI ):
2
7
8
−
m/z = 169.0 (C N HO ). C H N O (316.22): calcd. C 15.19, H
2
7
2
4
10 15
3
3.19, N 66.44; found C 16.10, H 4.32, N 67.68. BAM impact: >40 J;
BAM friction: 14.4 N.
ASSOCIATED CONTENT
■
15
N NMR expertise, Dr. Stephen Beaudoin for his continual
*
sı Supporting Information
guidance, and Dr. Jesse Sabatini (ARL) for many fruitful
discussions.
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00877.
1
13
15
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