High-performing and thermally stable energetic 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole derivatives

Article abstract of DOI:10.1039/c7ta01111c

A family of energetic salts based on 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-2-ium were prepared by reaction of 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole (3) with corresponding energetic acids. The nitration product, 7-nitroimino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole (4), was synthesized by using 100% nitric acid. The calculated detonation performance shows that compound 10, composed of 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-2-ium and 3,3′-dinitramino-4,4′-azoxyfurazanate, has good density (1.830 g cm^?3), high decomposition temperature (201 °C) and detonation performance (9077 m s^?1, 34.4 GPa) as well as acceptable sensitivities (10 J, 240 N), which is superior to those of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX).

Full text of DOI:10.1039/c7ta01111c

View Article Online
View Journal
Journal of
M at erials Chemistry A
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. M. Shreeve, Y.
Tang, C. He, G. H. Imler and D. A. Parrish, J. Mater. Chem. A, 2017, DOI: 10.1039/C7TA01111C.
Volume
4
Number
1
7
January 2016 Pages 1–330
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Journal of
Materials Chemistry A
Accepted Manuscripts are published online shortly after
Materials for energy and sustainability
www.rsc.org/MaterialsA
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
rsc.li/materials-a

Please do not adjust margins
Journal of Materials Chemistry A
Page 1 of 6
View Article Online
DOI: 10.1039/C7TA01111C
Journal of Materials Chemistry A
PAPER
High‐performing and Thermally Stable Energetic 3,7‐Diamino‐7H‐
[
1,2,4]triazolo[4,3‐b][1,2,4]triazole derivatives
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
b
a
Yongxing Tang, Chunlin He, Gregory H. Imler, Damon A. Parrish and Jean'ne M. Shreeve*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
family of energetic salts based on 3,7‐diamino‐7H‐
[1,2,4]triazolo[4,3‐b][1,2,4]triazol‐2‐ium were prepared by reaction
of 3,7‐diamino‐7H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazole (3) with
corresponding energetic acids. The nitration product, 7‐nitroimino‐
7H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazole (4), was synthesized by using
100% nitric acid. The calculated detonation performance shows that
compound 10, composed of 3,7‐diamino‐7H‐[1,2,4]triazolo[4,3‐
b][1,2,4]triazol‐2‐ium and 3,3’‐dinitramino‐4,4’‐azoxyfurazanate,
‐
3
has good density (1.830 g cm ), high decomposition temperature
o
‐1
(
201 C) and detonation performance (9077 m s , 34.4 GPa) as well
as acceptable sensitivities (10 J, 240 N), which is superior to those
of 1,3,5‐trinitroperhydro‐1,3,5‐triazine (RDX).
Fig. 1 Mono‐, di‐ or triamino‐triazolium and tetrazolium cations and fused
Introduction
heterocylic ions.
Developing energetic compounds with high performance and
low sensitivity is an important and challenging research topic
in design and synthesis of high energy density materials.[ One
of the efficient ways to achieve such targeted properties is the
formation of energetic salts given various combinations with
tunable cations and anions.[ Favorite cores are five‐
membered heterocycles, such as tetrazole, triazole, pyrazole
and furazan and their derivatives. Beneficial examples of
aromatic nitrogen‐rich cations in energetic compounds are
mono‐, di‐ or triamino‐triazolium and tetrazolium cations[
7
H‐[1,2,4]triazolo[4,3‐b] [1,2,4]triazole (TATOT),[5] which arises
1]
from the combination of 3‐amino‐1,2,4‐triazole with 3,4‐
diamino‐1,2,4‐triazole through a shared C‐N bond, exhibits
good thermal stability and high detonation performance. 3,7‐
2]
[
6]
Diamino‐7H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazole
(
3),
which
consists of 3‐amino‐1,2,4‐triazole and 4‐amino‐1,2,4‐triazole
fused through a shared C‐N bond, should contribute positively
to the heats of formation and to enhanced densities thus
exhibiting promising properties.
3]
(Fig. 1) with high nitrogen content, high positive heat of
In this study, a series of energetic salts (
,7‐diamino‐7H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazol‐2‐ium
cation, was synthesized. In addition, the nitration product (
5‐10), based on the
formation, ring strain, and high density.
3
Compared to single ring heterocycles reported previously,
nitrogen‐rich fused heterocyclic compounds have been gaining
interest gradually as building blocks for construction of
energetic compounds due to chemical stability and high
positive heat of formation.[ A typical example, 3,6,7‐triamino‐
4)
and its hydrazinium salt (11) were also prepared. All of the
compounds are fully characterized and their energetic
properties including thermal stabilities, impact sensitivities, as
well as calculated detonation performances were determined.
4]
The structures of
4
and
7
were further confirmed by single‐
a. Department of Chemistry, University of Idaho, Moscow, Idaho, 83844‐2343 USA.
Fax: (+1) 208‐885‐9146
crystal X‐ray diffraction.
E‐mail: jshreeve@uidaho.edu
Naval Research Laboratory,
USA
b.
4555 Overlook Avenue, Washington, D.C. 20375
Results and discussion
Electronic Supplementary Information (ESI) available: [Crystal refinements,
calculation detail, X‐ray crystallographic files in CIF format for
4
and
7
[CCDC Synthesis
number: 1526400, and 1526401]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 1
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 2 of 6
View Article Online
DOI: 10.1039/C7TA01111C
Paper
Journal of Materials Chemistry A
With commercially available guanidium hydrochloride and
hydrazine monohydrate to form triaminoguanidium
hydrochloride, was obtained by heating at reflux in formic
acid for 2 h (Scheme 1). Reaction of
bromide in dilute HCl led to the formation of
yield which upon further treatment with sodium bicarbonate
generated . The energetic salts ( 10) were synthesized by
reacting with energetic acids directly. In case of and , they
could be prepared by adding in dilute nitric acid or
1
[
7]
1
with cyanogen
in moderate
2
3
5‐
3
5
6
3
perchlorate acid. Due to their good solubility in water, the
pure product could be obtained from slow evaporation of the
mother liquid. For
were prepared and
7
‐
10, ethanolic solutions of energetic acids
(two equivalents) was added. All the
3
compounds were obtained in high yield and high purity. When
o
3
was stirred with 100% nitric acid at 0 C for 1 h,
4
was
bond. Fig. 2 15N NMR spectra of compounds
3‐5 and 7.
prepared by concomitant breaking of the N‐NH
Additionally, the hydrazinium salt (11) was obtained by
reaction of with hydrazine monohydrate in ethanol.
N NMR Spectroscopy
As shown in Fig. 2, the 15N NMR spectra of selected
2
4
Crystal structures
Compound crystallizes as a monohydrate in the monoclinic
space group P2 /c with a calculated density of 1.774 g cm‐3 at
1
5
4
1
compounds (
signals were assigned by comparison with similar structures,
and analysis of H‐ N heteronuclear multiple bond correlation
3‐5 and 7) were determined in d
6
‐DMSO. The 150 K. As can be seen in Fig. 3a, it has a zwitter ionic structure
[
5] with a negative charge at N4 and a protonated nitrogen atom
1
15
N6. All of the atoms lie in the same plane with an N7‐C8‐N12‐
o
(
(
HMBC). The spectrum of
3
has only six signals at δ = ‐106.1 N11 torsion angle of 178.94(16) . As shown in Fig. 3b, there
N5), ‐136.5 (N2), ‐150.1 (N4), ‐243.9 (N3), ‐318.2 (N6), ‐341.2 are several hydrogen bonds and short interactions (C
C and N O) in the crystal structure. Additionally, the
in the HMBC spectrum (Fig. S19, ESI). Similarly, only six signals crystal structure of ∙H O consists of parallel layers along the b
are seen in the spectrum of
, (Fig. S20, ESI) while the missing axis. The layers are stacked above each other with a layer
signal (N1) at δ = ‐179.3 ppm is in the HMBC spectrum. For
and , all signals are seen. Due to the effect of the two
different anions, the chemical shifts (N4, N5 and N1) in are
found at higher field than those in . Additionally, both N6 and
N7 can be seen (N6: ‐317.0 ppm; N7: ‐323.77 ppm) in the
spectrum of while only one peak (‐317.1 ppm) was observed
in
…N, C…
ppm (N7). The missing signal (N1) was observed at ‐179.7 ppm O, C
…
…
4
2
4
5
distance of d = 3.135 Å.
7
5
7
5
7
.
Fig. 3 (a) Molecular structure of 4. Thermal ellipsoids are drawn at the 50%
Scheme 1 Synthesis of 3,7‐diamino‐7H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazole (3) and
its derivatives
probability level. (b) Packing diagram of
lines represent hydrogen bonding.
4 viewed along the b axis. Dashed
2
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
Jou Pr nl eaa ls oe fd Mo an to et r ai ad lj su s Ct hm ea mr gi isn ts ry A
View Article Online
DOI: 10.1039/C7TA01111C
Journal of Materials Chemistry A
Paper
The dihydrate of
7 crystallizes in the monoclinic space group
P2
1
/c with a density of 1.749 g cm‐3 at 150 K and four
molecules per unit cell (Fig. 4a). In the cations, the two
heterocyclic rings are in the same plane with torsion angles
o
N32‐C28‐N29‐C25 of ‐179.93(15)
and N(17)‐C(18)‐N(19)‐
o
N(20) of 179.15(15) , respectively. In the anion, the
parameters involving the bond lengths and bond angles are
consistent with those in the literature.
N(3)‐N(4)‐C(5)‐N(6) is ‐1.0 (3) , indicating that the anion is also
in the same plane. The nitrogen fused cations, the 3,4‐
dinitraminofurazanate anion and the water molecule are
linked through hydrogen bonds (Fig. 4b). The details can be
found in the ESI.
[
3a]
The torsion angle
o
Physicochemical and energetic properties
The physiochemical and energetic properties are given in
Table 1. The density is an important parameter which plays an
important role in calculation of energetic performance.
o
Densities were measured by using a gas pycnometer at 25 C.
Compound 10 is the densest of these compounds at 1.83 g
‐
3
cm , while the others exhibit moderate densities of ≥1.70 g
‐
3
cm . The thermal behavior was determined by differential
o
scanning calorimetric (DSC) measurements at a rate of 5 C
‐
1
min . The parent compound
3 shows a decomposition
o
temperature of 219 C, while the nitration product
decomposes at 169 C, which is the highest of the neutral
nitroimino compounds.[ After deprotonation of
4
o
8]
4
, the
hydrazinium salt 11 exhibits a low decomposition temperature
o
of 132 C. The energetic salts
5
‐
10 formed from the
and corresponding nitrogen rich anions show
good thermal stabilities with decomposition temperatures
monocation of
3
Fig. 4 (a) Molecular structure of
7. Thermal ellipsoids are drawn at the 50%
o
o
probability level. (b) Packing diagram of
lines represent hydrogen bonding.
7 viewed along the a axis. Dashed
over the range of 167 C (7) to 222 C (9).
T
able 1 Physicochemical and energetic properties of compounds 3–11 in comparison with RDX.
ρ[a]
Dv [b]
P[c]
[d]
[e]
T
dec
(oC)
IS[f]
FS[g]
ΔH
f
Comp
‐
3
(m s‐1)
‐1
‐1
(
g∙cm )
(GPa)
(kJ mol /kJ g )
480.3/3.45
(J)
(N)
3
1.712
1.732
1.777
1.744
1.742
1.773
1.761
1.830
1.751
1.800
8461
25.4
26.6
29.0
28.4
29.5
30.1
30.3
34.4
32.1
34.9
219
40
6
360
120
120
360
240
160
240
240
360
120
4
5
6
7
8
9
1
1
∙H
2
2
O
O
8271
8250
8590
8715
8694
8732
9077
9121
8795
174.9/0.93
364.4/1.52
83.9/0.38
169
220
191
167
221
222
201
132
204
4
∙H
15
8
1411.6/3.01
1682.9/2.98
1853.2/3.28
1882.0/3.24
618.1/3.07
70.3/0.32
8
12
10
12
7.5
0
1
RDX
[
a] Density measured by a gas pycnometer at 25 °C; [b] Calculated detonation velocity; [c] Calculated detonation pressure; [d] Calculated molar enthalpy of
formation in solid state; [e] Decomposition temperature (onset); [f] Impact sensitivity; [g] Friction sensitivity.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 3
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 4 of 6
View Article Online
DOI: 10.1039/C7TA01111C
Paper
Journal of Materials Chemistry A
The heats of formation were obtained by using the Gaussian Micromeritics AccuPyc II 1340 gas pycnometer. Decomposition
0
3 suite of programs. As expected, all of them show positive temperatures (onset) were recorded on a differential scanning
o
heats of formation. Compounds
7‐
10 with large anions exhibit calorimeter (DSC, TA Instruments Q2000) at a scan rate of 5 C
‐
1
high positive heats of formation. The calculated formation min . Elemental analyses (C, H, N) were performed on a CE‐
together with the measured densities were used to derive the 440 Elemental Analyzer. Impact and friction sensitivity
detonation performances with EXPLO 5 version 6.01 code.[
10]
measurements were made using a standard BAM Fallhammer
Compound 10 has a higher detonation velocity than RDX and a and a BAM friction tester.
‐
1
comparable detonation pressure (10: D: 9077 m s ; P: 34.4
‐
1
GPa; RDX: D: 8795 m s ; P: 34.9 GPa). In addition, the Computational Methods
‐
1
detonation velocity of 11 (9121 m s ) also exceeds that of
The gas phase enthalpies of formation were calculated by
RDX, although the detonation pressure is slightly lower (32.1 G2 method. For energetic salts, the solid‐phase enthalpies of
GPa). For the other compounds 3‐9
, the calculated detonation formation were obtained using a Born−Haber energy cycle.[
velocities lie in the range between 8250 and 8732 m s and The details are found in the ESI.
detonation pressures between 25.4 and 30.3 GPa.
11]
‐
1
The sensitivities toward friction and impact were measured X‐Ray crystallography
by using standard BAM methods. The neutral nitramino
compound and nitrate salt are sensitive towards impact (
J;
other compounds
A clear colorless plate crystal of dimensions 0.258 × 0.215 ×
4
5
4:
0.029 mm3 (
4
), and a clear colorless block crystal of dimensions
2
6
5
: 4 J), and their friction sensitivities are similar to RDX. The 0.295 × 0.081 × 0.030 mm (
7) were mounted on a MiteGen
3
and
6
‐
11 show acceptable impact and MicroMesh using a small amount of Cargille immersion oil.
friction sensitivities, which are less sensitive than those of RDX. Data were collected on a Bruker three‐circle platform
diffractometer equipped with a SMART APEX II CCD detector.
The crystals were irradiated using graphite monochromated
Conclusions
MoK

radiation (λ = 0.71073 Å). An Oxford Cobra low
temperature device was used to keep the crystals at a
constant 150(2) K during data collection.
In
conclusion,
3,7‐diamino‐7H‐[1,2,4]triazolo[4,3‐
b][1,2,4]triazole (
3) was synthesized and utilized as a precursor
Data collection was performed and the unit cell was initially
to the energetic salts (
energetic acids formed in a straightforward manner by
neutralization. In addition, the nitration product which
results from the breaking of the N‐NH bond was prepared by
nitration of using 100% nitric acid. All the compounds are
well characterized including the single crystal X‐ray diffraction
structures for and . Most of them exhibit good thermal
stability except the nitroimino compound and its
hydrazinium salt 11). Calculations show that these
5‐10) composed of anions from
[
12]
refined using APEX3 [v2015.5‐2].
Data reduction was
performed using SAINT [v8.34A][ and XPREP [v2014/2][14]
.
13]
4
Corrections were applied for Lorentz, polarization, and
absorption effects using SADABS [v2014/2].[ The structure
was solved and refined with the aid of the program SHELXL‐
2
15]
3
16]
2
2
014/7.[
The full‐matrix least‐squares refinement on F
4
7
included atomic coordinates and anisotropic thermal
parameters for all non‐H atoms. The H atoms were included
using a riding model.
(4)
(
compounds have high detonation performance; especially 10
which displays promising properties with a density of 1.830 g
cm , detonation velocity of 9077 m s , detonation pressure of
‐
3
‐1
Syntheses
Caution! Although we have encountered no difficulties during
preparation and handling of these compounds, they are
potentially explosive energetic materials, which are very
sensitive to impact and friction. Mechanical actions of these
energetic materials, involving scratching or scraping, must be
avoided. Manipulations must be carried out by using
appropriate standard safety precautions.
3
2
4.4 GPa, impact sensitivity of 10 J and friction sensitivity of
40 N, which suggests it could be used as a high energy dense
material as a replacement for RDX.
Experimental Section
General methods
All reagents were purchased from AK Scientific or Alfa Aesar
in analytical grade and were used as received. H and C NMR
spectra were recorded on a Bruker 300 MHz (Bruker AVANCE
3
,7‐Diamino‐7
hydrochloride
triazolium dichloride[
H
‐[1,2,4]triazolo[4,3‐
b
][1,2,4]triazole
1
13
(2)[
6]
3‐Hydrazinium‐4‐amino‐1H‐1,2,4‐
, 2.28 g, 20.0 mmol) was dissolved
3e, 7]
(
1
3
00) NMR spectrometer operating at 300.13 and 75.48 MHz,
in dilute hydrochloric acid (50 mL, 2 M), cyanogen bromide
respectively, and a 500 MHz (Bruker AVANCE 500) nuclear
magnetic resonance spectrometer operating at 50.69 MHz for
(4.24 g, 40 mmol) was added, and the solution was heated to
o
6
0 C for 2 h. After stirring another 3 h at reflux, the solution
15
1
13
N spectra. Chemical shifts for H, and C NMR spectra are
reported relative to (CH Si. [D ]DMSO was used as a locking
was cooled and stored in the refrigerator overnight. The
precipitate was collected as a white solid and dried in air.
3
)
4
6
solvent. IR spectra were recorded using KBr plates with an
AVATAR 370 FT‐IR (Thermo Nicolet) spectrometer. Density was
o
1
White solid (1.93 g, 55% yield). Td (onset): 221 C. H NMR: δ 8.83
s, 1H), 8.61 (s, 2H), 6.24 (br) ppm. 13C NMR: δ 152.5, 147.6,
42.1 ppm. IR (KBr): 3327, 3281, 3157, 3072, 1964, 1661,
(
1
determined at room temperature by employing
a
෤
4
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
Jou Pr nl eaa ls oe fd Mo an to et r ai ad lj su s Ct hm ea mr gi isn ts ry A
View Article Online
DOI: 10.1039/C7TA01111C
Journal of Materials Chemistry A
Paper
1
5
3
615, 1530, 1427, 1224, 1186, 1088, 1027, 949, 759, 703, 589, Bis{3,7‐diamino‐7
H
‐[1,2,4]triazolo[4,3‐
b
][1,2,4]triazol‐2‐ium}
‐
1
80 cm .
,7‐Diamino‐7
3,4‐dinitraminofurazanate (7) White solid (0.431 g, 92% yield).
o
1
H
‐[1,2,4]triazolo[4,3‐
b
][1,2,4]triazole
(3)[6]
Td(onset): 167 C. H NMR: δ 8.69 (s, 1H), 7.83 (s, 2H), 6.19 (s, 2H)
Compound
2
(1.76 g, 10.0 mmol) was dissolved in distilled ppm. 13C NMR: δ 151.8, 151.2, 148.2, 142.6 ppm. IR (KBr):
෤
water (20 mL). Sodium bicarbonate (0.84 g, 10.0 mmol) was 3300, 3209, 3126, 1697, 1655, 1617, 1537, 1476, 1420, 1374,
o
added, and after stirring 15 min at 25 C, the white solid (1.15 1281, 1217, 1097, 1059, 1009, 920, 888, 846, 808, 778, 759,
‐
1
g, 83% yield) was filtered, washed with water (15 mL × 2) and 711, 601 cm . Elemental analysis for C
8
H
12
N
20
O
5
(468.31):
dried in air. Td (onset): 219 C. H NMR: δ 8.31 (s, 1H), 5.99 (s, Calcd C 20.52, H 2.58, N 59.82 %. Found: C 20.17, H 2.34, N
H), 5.78 (s, 2H) ppm. 13C NMR: δ 149.7, 149.5, 143.6 ppm. IR 60.10 %. IS: 8 J. FS: 240 N.
KBr): 3313, 3271, 3221, 3104, 1645, 1622, 1589, 1538, 1430, Bis{3,7‐diamino‐7 ‐[1,2,4]triazolo[4,3‐
231, 1215, 1117, 1080, 1000, 960, 751 cm . IS: 40 J. FS: 360 5,5’‐dinitramino‐3,3’‐azo‐1,2,4‐oxadiazolate (8) Yellow solid
o
1
2
(
1
N.
෤
H
b][1,2,4]triazol‐2‐ium}
‐
1
o
1
(0.508 g, 90% yield). Td(onset): 221 C. H NMR: δ 8.82 (s, 1H),
8.57 (s, 2H), 6.23 (s, 2H) ppm. 13C NMR: δ 175.7, 175.1, 152.6,
(1.0 g, 7.19 mmol) was added 147.7, 142.2 ppm. IR (KBr):
7
‐Nitroimino‐7
H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazole
[
6]
monohydrate (4) Compound
3
෤
3418, 3327, 3189, 1670, 1616,
o
slowly to nitric acid (3 mL, 100%) at 0 C. The solution was 1560, 1545, 1502, 1457, 1369, 1287, 1205, 1084, 1025, 1002,
o
‐1
stirred for 1 h at 0 C. The reaction mixture was poured into 983, 970, 847, 763, 711, 605 cm . Elemental analysis for
ice‐water (50 mL), the yellow solid was precipitated and (564.36): Calcd C 21.28, H 2.14, N 59.57 %. Found:
collected by filtration, washed with cold water (30 mL) and C 21.38, H 1.92, N 58.15 %. IS: 8 J. FS: 160 N.
dried in air. Yellow solid (0.66 g, 49% yield). Td (onset): 169 C. H Bis{3,7‐diamino‐7
NMR: δ 8.78 (s, 1H) ppm. 13C NMR: δ 149.1, 148.5, 141.6 ppm. 3,3’‐dinitramino‐4,4’‐azofurazanate (9) Orange‐red solid
10 12 24 6
C H N O
o
1
H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazol‐2‐ium}
o
1
IR (KBr):
148, 1113, 1070, 1012, 951, 870, 815, 775 cm . Elemental 8.53 (s, 2H), 6.21 (br) ppm. C NMR: δ 160.0, 152.6, 152.5,
analysis for C (187.12): Calcd C 19.26, H 2.69, N 52.40 147.8, 142.2 ppm. IR (KBr): 3560, 3462, 3313, 3061, 1691,
. Found: C 19.14, H 2.41, N 51.24 %. IS: 6 J. FS: 120 N. 1655, 1605, 1542, 1454, 1374, 1321, 1282, 1231, 1217, 1056,
,7‐Diamino‐7 ‐[1,2,4]triazolo[4,3‐ ][1,2,4]triazol‐2‐ium
perchlorate (5) Compound
HClO
෤ 3136, 1655, 1589, 1518, 1465, 1420, 1292, 1248, (0.497 g, 88% yield). Td(onset): 222 C. H NMR: δ 8.81 (s, 1H),
‐
1
13
1
3
H
5
N
7
O
3
෤
%
3
‐
1
H
b
1017, 950, 806, 777, 760, 690 cm . Elemental analysis for
(564.36): Calcd C 21.28, H 2.14, N 59.57 %. Found:
[
6]
3
(0.278 g, 2 mmol) was added to
10 12 24 6
C H N O
o
4
(2 mL, 10%) and the reaction was stirred at 25 C for 1 h. C 21.16, H 1.97, N 59.62 %. IS: 12 J. FS: 240 N.
The solution was allowed to evaporate in air until a white solid Bis{3,7‐diamino‐7
H‐[1,2,4]triazolo[4,3‐b][1,2,4]triazol‐2‐ium}
was formed. The solid was collected by filtration, washed with 3,3’‐dinitramino‐4,4’‐azoxyfurazanate (10) Yellow solid (0.522
o
1
ethanol and dried in vacuum to yield
2
(
6
(0.417 g, 87% yield). T
m
:
g, 90% yield??). Td(onset): 201 C. H NMR: δ 8.81 (s, 1H), 8.55 (s,
o
o
1
13
15 C. Td(onset): 220 C. H NMR: δ 13.86 (br), 8.81 (s, 1H), 8.57 2H), 6.30 (br) ppm. C NMR: δ 155.1, 154.9, 153.9, 152.6,
s, 2H), 6.21 (s, 2H) ppm. 13C NMR: δ 152.6, 147.7, 142.2 ppm. 151.2, 147.7, 142.2 ppm. IR (KBr):
෤
3542, 3500, 3434, 3381,
IR (KBr):
෤ 3343, 3167, 3135, 1701, 1667, 1628, 1590, 1541, 1708, 1685, 1637, 1535, 1518, 1459, 1406, 1394, 1565, 1321,
1
8
C
463, 1430, 1336, 1349, 1271, 1231, 1218, 1120, 969, 935, 1282, 12262, 1234, 1191, 1034, 998, 944, 843, 829, 758, 712,
‐
1
‐1
12 24 7
99, 760, 715, 670, 625, 589 cm . Elemental analysis for 597 cm . Elemental analysis for C10H N O (580.36): Calcd C
3
H
6
ClN (239.58): Calcd C 15.04, H 2.52, N 40.92 %. Found: 20.70, H 2.08, N 57.92 %. Found: C 20.56, H 2.12, N 56.79 %. IS:
7 4
O
C 15.08, H 2.39, N 40.70 %. IS: 4 J. FS: 120 N.
,7‐Diamino‐7 ‐[1,2,4]triazolo[4,3‐ ][1,2,4]triazol‐2‐ium
nitrate monohydrate (6) Compound
10 J. FS: 240 N.
3
H
b
Hydrazinium
7‐nitramino‐7
(0.37 g, 2.0 mmol) was
3
(2 mL, 20%) and the mixture was stirred at 25 suspended in ethanol (5 mL), then hydrazine monohydrate
H‐[1,2,4]triazolo[4,3‐
[6]
3
(0.278 g, 2 mmol) was
b][1,2,4]triazolate (11) Compound 4
added to HNO
o
C for 1 h. The solution was allowed to evaporate in air until (0.11 g, 2.1 mmol) in ethanol (2 mL) was added. After stirring 2
colorless crystals formed. The crystals were collected by h at room temperature, the crude product was collected by
filtration, washed with ethanol (5 mL × 2) and dried in vacuum filtration. The product was purified by recrystallization in
o
o
1
o
to yield
6
(0.396 g, 90% yield). T
m
: 174 C. Td(onset): 191 C. H water/ethanol. Yellow solid (0.34 g, 85% yield). Td(onset): 132 C.
1
H NMR: δ 7.86 (s, 1H), 7.02 (br) ppm. 13C NMR: δ 157.9, 157.8,
NMR: δ 13.93 (br), 8.82 (s, 1H), 8.55 (s, 2H), 6.24 (s, 2H) ppm.
13
C NMR: δ 152.8, 147.9, 142.3 ppm. IR (KBr):
෤ 1764, 1710, 140.4 ppm. IR (KBr): ෤ 3299, 3173, 3093, 1621, 1510, 1481,
1
1
686, 1665, 1617, 1575, 1533, 1458, 1384, 1227, 1195, 1096, 1390, 1351, 1216, 1190, 1163, 1154, 1016, 977, 962, 933, 879,
‐
1
‐1
025, 980, 762, 691, 601 cm . Elemental analysis for C
3
H
8
N
8
O
4
3 7 9 2
828, 764, 738, 701, 635 cm . Elemental analysis for C H N O
(
3
220.15): Calcd C 16.37, H 3.66, N 50.99 %. Found: C 16.44, H (201.15): Calcd C 17.91, H 3.51, N 62.67 %. Found: C 17.77, H
.58, N 50.89 %. IS: 15 J. FS: 360 N. 3.39, N 61.80 %. IS: 12 J. FS: 360 N.
General procedure for synthesis of 7‐10
The energetic acid (1 mmol) was dissolved in ethanol (10 mL), Acknowledgements
[6]
then
3
(0.278 g, 2 mmol) was added while stirring. The This work was supported by the Office of Naval Research
o
reaction mixture was stirred for 2 h at 25 C. The precipitate (N00014‐16‐1‐2089) and the Defense Threat Reduction Agency
formed, was collected by filtration, and washed with ethanol (HDTRA 1‐15‐1‐0028). We are also grateful to the Murdock
(5 mL × 2) and dried in vacuum to give the products 7‐10
.
Charitable Trust, Vancouver, WA, Reference No.:
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 5
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 6 of 6
View Article Online
DOI: 10.1039/C7TA01111C
Paper
Journal of Materials Chemistry A
1
1
5 Bruker, SADABS v2014/5, Bruker AXS Inc., Madison,
Wisconsin, USA, 2014.
6 G. M. Sheldrick, SHELXL‐2014/7, University of Göttingen,
Germany, 2014.
2
5
014120:MNL:11/20/2014 for funds supporting the purchase a
00 MHz nuclear magnetic resonance spectrometer.
Notes and references
1
(a) V. Thottempudi, H. Gao and J. M. Shreeve, J. Am. Chem.
Soc., 2011, 133, 6464; (b) V. Thottempudi and J. M. Shreeve,
J. Am. Chem. Soc., 2011, 133, 19982; (c) T. M. Klapötke,
nd
Chemistry of High‐Energy Materials, 2 ed.Walter de
Gruyter, Berlin, 2012.
2
3
H. Gao and J. M. Shreeve, Chem. Rev., 2011, 111, 7377.
(a) Y. Tang, J. Zhang, L. A. Mitchell, D. A. Parrish and J. M.
Shreeve, J. Am. Chem. Soc., 2015, 137, 15984; (b) T. M.
Klapötke, D. G. Piercey and J. Stierstorfer, Eur. J. Inorg.
Chem., 2012, 5694; (c) T. M. Klapötke, D. G. Piercey and J.
Stierstorfer, Eur. J. Inorg. Chem. 2013, 1509; (d) J. C. Gálvez‐
Ruiz, G. Holl, K. Karaghiosoff, T. M. Klapötke, K. Löhnwitz, P.
Mayer, H. Nöth, K. Polborn, C. J. Rohbogner, M. Suter and J.
J. Weigand, Inorg. Chem., 2005, 44, 4237; (e) J. Wu, J. Zhang,
X. Yin and L. Wu, New J. Chem., 2016, 40, 5414.
4
5
(a) A. B. Sheremetev, V. L. Korolev, A. A. Potemkin, N. S.
Aleksandrova, N. V. Palysaeva, T. H. Hoang, V. P. Sinditskii
and K. Y. Suponitsky, Asian J. Org. Chem., 2016, 5, 1388; (b)
P. Yin, J. Zhang, L. A. Mitchell, D. A. Parrish and J. M. Shreeve,
Angew. Chem. Int. Ed., 2016, 55, 12895‐12897; Angew.
Chem., 2016, 128, 13087.
(a) T. M. Klapötke, P. C. Schmid, S. Schnell and J. Stierstorfer,
Chem. Eur. J., 2015, 21, 9219; (b) P. Yin, J. Zhang, D. A.
Parrish and J. M. Shreeve, J. Mater. Chem. A 2015, 3, 8606.
6
7
K. T. Potts and C. A. Hirsch, J. Org. Chem., 1968, 33, 143.
P. Cardillo, M. Dellavedova, L. Gigante, A. Lunghi, C.
Pasturenzi, E. Salatelli and P. Zanirato, Eur. J. Org. Chem.,
2
012, 1195.
T. M. Klapötke, F. A. Martin and J. Stierstorfer, Chem. Eur. J.,
012, 18, 1487.
8
9
2
Gaussian 03 (Revision E.01), M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A.
Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M.
Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M.
Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida,
T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E.
Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J.
Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J.
Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K.
Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G.
Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas,
D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J.
V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L.
Martin, D. J. Fox, T. Keith, M. A. Al‐Laham, C. Y. Peng, A.
Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian,
Inc., Wallingford CT, 2004.
1
1
0 M. Sućeska, Brodarski Institute, Zagreb, Croatia, EXPLO5
v6.01, 2013.
1 (a) M. S. Westwell, M. S. Searle, D. J. Wales and D. H.
Williams, J. Am. Chem. Soc., 1995, 117, 5013; (b) H. Gao, C.
Ye, C. M. Piekarski and J. M. Shreeve, J. Phys. Chem. C, 2007,
1
11, 10718.
1
1
1
2 Bruker, APEX3 v2015.5‐2, Bruker AXS Inc., Madison,
Wisconsin, USA, 2015.
3 Bruker, SAINT v8.34A, Bruker AXS Inc., Madison, Wisconsin,
USA, 2013.
4 Bruker, XPREP v2014/2, Bruker AXS Inc., Madison, Wisconsin,
USA, 2014.
6
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins