Synthesis and characterization of bis(triaminoguanidinium) 5,5′-dinitrimino-3,3′-azo-1H-1,2,4-triazolate - A novel insensitive energetic material

Article abstract of DOI:10.1002/zaac.201100102

The synthesis of 5,5′-diamino-3,3′-azo-1H-1,2,4-triazole (3) by reaction of 5-acetylamino-3-amino-1H-1,2,4-triazole (2) with potassium permanganate is described. The application of the very straightforward and efficient acetyl protection of 3,5-diamino-1H-1,2,4-triazole allows selective reactions of the remaining free amino group to form the azo-functionality. Compound 3 is used as starting material for the synthesis of 5,5′-dinitrimino-3,3′-azo-1H-1,2,4-triazole (4), which subsequently reacted with organic bases (ammonia, hydrazine, guanidine, aminoguanidine, triaminoguanidine) to form the corresponding nitrogen-rich triazolate salts (5-9). All substances were fully characterized by IR and Raman as well as multinuclear NMR spectroscopy, mass spectrometry, and differential scanning calorimetry. Selected compounds were additionally characterized by low temperature single-crystal X-ray diffraction measurements. The heats of formation of 4-9 were calculated by the CBS-4M method to be 647.7 (4), 401.2 (5), 700.4 (6), 398.4 (7), 676.5 (8), and 1089.2 (9) kJ·mol^-1. With these values as well as the experimentally determined densities several detonation parameters were calculated using both computer codes EXPLO5.03 and EXPLO5.04. In addition, the sensitivities of 5-9 were determined by the BAM drophammer and friction tester as well as a small scale electrical discharge device. Copyright

Full text of DOI:10.1002/zaac.201100102

ARTICLE
DOI: 10.1002/zaac.201100102
Synthesis and Characterization of Bis(triaminoguanidinium) 5,5'-
Dinitrimino-3,3'-azo-1H-1,2,4-triazolate – A Novel Insensitive Energetic
Material
Alexander Dippold,[a] Thomas M. Klapötke,*[a] and Franz A. Martin[a]
Keywords: Energetic materials; High nitrogen containing compounds; Nitamines; Sensitivities; Triazoles
Abstract. The synthesis of 5,5'-diamino-3,3'-azo-1H-1,2,4-triazole (3) mass spectrometry, and differential scanning calorimetry. Selected
by reaction of 5-acetylamino-3-amino-1H-1,2,4-triazole (2) with potas- compounds were additionally characterized by low temperature single-
sium permanganate is described. The application of the very straight- crystal X-ray diffraction measurements. The heats of formation of 4–
forward and efficient acetyl protection of 3,5-diamino-1H-1,2,4-tria- 9 were calculated by the CBS-4M method to be 647.7 (4), 401.2 (5),
zole allows selective reactions of the remaining free amino group to 700.4 (6), 398.4 (7), 676.5 (8), and 1089.2 (9) kJ·mol–1. With these
form the azo-functionality. Compound 3 is used as starting material for values as well as the experimentally determined densities several deto-
the synthesis of 5,5'-dinitrimino-3,3'-azo-1H-1,2,4-triazole (4), which nation parameters were calculated using both computer codes EX-
subsequently reacted with organic bases (ammonia, hydrazine, guani- PLO5.03 and EXPLO5.04. In addition, the sensitivities of 5–9 were
dine, aminoguanidine, triaminoguanidine) to form the corresponding determined by the BAM drophammer and friction tester as well as a
nitrogen-rich triazolate salts (5–9). All substances were fully character- small scale electrical discharge device.
ized by IR and Raman as well as multinuclear NMR spectroscopy,
energy density materials (HEDM) mostly derive their energy
Introduction
In recent years, the synthesis of energetic, heterocyclic com-
of ring or cage strain as well as of a high heat of formation, a
lot of research was done on explosives containing the azo-
pounds has attracted an increasing amount of interest, since
functionality. Several heterocyclic compounds like 4,4'-diam-
heterocycles generally offer a higher heat of formation, density,
ino-3,3'-azofurazane (a) and 3,3'-azobis(6-amino-1,2,4,5-tetra-
and oxygen balance than their carbocyclic analogues.[1] In
zine) (b) were reported in literature so far (Scheme 1).[6]
combination with the advantages of a high nitrogen content
such as the high average two electron bond energy associated
with the nitrogen–nitrogen triple bond,[2] those compounds are
of great interest for investigations. The current widely used
nitro-explosives TNT, RDX, or HMX per se as well as their
transformation products are toxic due to the presence of nitro
(–NO2), nitroso (–NO), or nitrito (–ONO) groups either in the
Scheme 1. Structures of some heterocyclic compounds containing the
azo-functionality.
explosives itself or their degradation products.[3] The develop-
ment of new energetic materials therefore focuses – besides
high performance and stability – on environmentally friendly
The combination of a high nitrogen content with a high heat
compounds. Nitrogen-rich compounds mainly generate envi-
of formation led to the development of azole-based compounds
ronmentally friendly molecular nitrogen as end-product of pro-
containing the azo-functionality. The recently reported 5,5'-
pulsion or explosion, therefore they continue to be the focus
azotetrazolate anion (Scheme 2a) is such an energetic com-
of energetic materials research across the globe.[4] A prominent
pound with a very high nitrogen content and therefore suitable
family of compounds regarding the properties mentioned
for the synthesis of energetic materials. There has been in-
above are azole-based energetic materials, because they are
creased interest in the synthesis of energetic salts based on the
generally highly endothermic compounds with relatively high
5,5'-azotetrazolate anion, since the neutral compound decom-
densities and a high nitrogen content.[5] Since modern high
poses at room temperature.[7] Many 5,5'-azotetrazolate salts
have found practical application in combination with nitrogen-
* Prof. Dr. T. M. Klapötke
rich bases (e.g. guanidinium, triaminoguanidinium, hydrazi-
Fax: +49-89-2180-77492
nium) as propellants,[8] in gas generators for airbags as well as
E-Mail: tmk@cup.uni-muenchen.de
in fire extinguishing systems.[9] Heavy metal salts were used
[a] Energetic Materials Research, Department of Chemistry
Ludwig-Maximilian University Munich
as initiators[10] and derivatives of 5,5'-azotetrazole are utilized
Butenandtstr. 5–13
81377 München, Germany
as additives in solid rocket propellants.[11]
Z. Anorg. Allg. Chem. 2011, 637, 1181–1193
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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A. Dippold, T. M. Klapötke, F. A. Martin
ARTICLE
zole (1) in yields of about 98 %. The desired 5-acetylaminotri-
azole (2) is obtained in nearly quantitative yields with thermal
isomerization by heating a suspension of 1 in decaline
(Scheme 3) as it is described by Pevzner et al.[16]
As shown in Scheme 3, the synthesis of 5,5'-diamino-3,3'-
azo-1H-1,2,4-triazole (3) (DAAT) was performed with a stoi-
chiometric amount of potassium permanganate, which was
added at 0 °C. After removal of the ice bath, the mixture was
allowed to warm to room temperature. Subsequent heating to
100 °C for 3 hours completes the formation of the azo-bridge,
transforms the remaining permanganate to manganese(IV) ox-
ide and leads to a complete deprotection of both amine groups.
After the removal of the generated manganese oxide by filtra-
tion, acidifying the solution to pH 7 leads to the precipitation
of compound 3 as an orange solid. Drying at 110 °C overnight
provides DAAT as elemental analysis pure orange powder. The
synthesis of the novel 5,5'-dinitrimino-3,3'-azo-1H-1,2,4-tria-
zole (4) was accomplished in good yields via nitration of 5,5'-
diamino-3,3'-azo-1H-1,2,4-triazole (3) as it is described for 3-
amino-1H-1,2,4-triazole by Licht et al.[17] using a volume ratio
H2SO4/HNO3 of 6:1 and two equivalents of nitric acid per
amine group (Scheme 4).
Scheme 2. Structures of the 5,5'-azotetrazolate anion (a) and 3,3'-dini-
tro-5,5'-azo-1H-1,2,4-triazole (b).
Since triazole derivatives often tend to be thermally and ki-
netically more stable than their tetrazole analogous, research
in this field of azo-bridged azoles shows great promise for
energetic materials. For example, 5,5'-dinitro-3,3'-azo-1H-
1,2,4-triazole (Scheme 2b) and its nitrogen-rich salts are in the
focus as potential insensitive high nitrogen compounds and
propellant burn rate modifiers.[12]
The literature known 5,5'-dinitro-3,3'-azo-1H-1,2,4-triazole
was first synthesized at Los Alamos National Laboratories by
Naud and co-workers in 2003.[13] Since this molecule and se-
lected nitrogen-rich salts like the triaminoguanidinium com-
pound reveal
a high stability and attractive explosive
properties,[14] our goal was the preparation of the correspond-
ing nitrimino compound, as this substituent is known for its
performance enhancing characteristics.
Results and Discussion
Synthesis
Scheme 4. Synthesis of 5,5'-dinitrimino-3,3'-azo-1H-1,2,4-triazole (4)
via nitration of 3.
The starting material used for nitration, 5,5'-diamino-3,3'-
azo-1H-1,2,4-triazole (3), is not yet known in literature, since
it is not accessible using 3,5-diamino-1H-1,2,4-triazole as a
starting material. The formation of the azo-bridge works appar-
ently only with a unique amino group in the molecule, which
necessitates the protection of one amino group first. The acetyl
protecting group is suitable due to the fact that it is stable even
in concentrated acids/bases at room temperature and the amine
is not deprotected until using elevated temperatures. Theoreti-
cally, acylation of 3,5-diamino-1H-1,2,4-triazole can proceed
both at the heterocyclic nitrogen atoms and at the two amino
groups.[15] The treatment of 3,5-diamino-1H-1,2,4-triazole
with acetic anhydride in water provides 1-acetyl-diaminotria-
DNAAT immediately precipitates as a yellow solid, while
pouring the nitration mixture on ice and can easily be isolated
by filtration. After drying at 60 °C, the desired elemental anal-
ysis pure nitrimino compound (4) was obtained in yields of
about 80 %. The synthesis of the nitrogen-rich salts (5–9) was
accomplished as shown in Scheme 5 by adding two equiva-
lents of an organic base (ammonia, hydrazine, guanidine, ami-
noguanidine, triaminoguanidine) to a suspension of the neutral
compound in water.
Scheme 5. Synthesis of nitrogen-rich salts 5–9 of DNAAT.
The energetic salts of the dianion DNAAT2– were obtained
in good yields as yellow powder, while storing the mixture at
5 °C overnight. All energetic compounds were fully character-
ized by IR and Raman as well as multinuclear NMR spectro-
scopy, mass spectrometry, and differential scanning calorime-
try. Selected compounds were additionally characterized by
low temperature single-crystal X-ray spectroscopy.
Scheme 3. Reaction pathway towards 5,5'-amino-3,3'-azo-1H-1,2,4-
triazole starting from 3,5-diamino-1H-1,2,4-triazole.
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Bis(triaminoguanidinium) 5,5'-Dinitrimino-3,3'-azo-1H-1,2,4-triazolate
Table 1. NMR signals of compounds 1, 2, 2a, and 3a.
Compound
1H NMR
13C{1H} NMR
CH3
C=O
C–NH2
C–NHAca)
CH3
1
2.33
1.99
2.03
–
170.5
169.8
174.1
–
162.2, 157.0
161.6
23.6
22.9
22.7
–
2
156.4
154.1
170.0
2a
3a
162.5
165.0
a) C–azo in the case of 3a.
Table 2. NMR signals of compounds 4–9.
Compound
DNAAT2–
cation
1H
1H
13C{1H}
14N{1H}
14N{1H}
4
5
6
/
159.7, 153.8
167.7, 158.3
166.9, 157.8
–19
–14
–16
/
/
13.58
13.51
7.23
7.28
–359
–359
13C{1H}
7
8
9
13.53
13.61
13.48
167.1, 157.9
167.0, 157.7
167.3, 157.8
–14
–15
–14
7.03
7.89, 4.71
8.59, 4.49
157.7
158.9
159.0
NMR Spectroscopy
The complete deprotection of the amine groups during the
synthesis of 3 can easily be monitored by the missing C=O
vibration band at around 1700 cm–1 as well as the missing C–
H valence vibrations at 2800–3100 cm–1 in the IR and Raman
spectra. The latter is dominated by the absorption of the azo-
moiety at 1348 cm–1,[7c,18] the infrared spectrum by the defor-
mation mode of the amino groups at 1624 cm–1.
Due to the low solubility of compounds 2 and 3 in common
NMR solvents (but good solubility in bases), NMR spectro-
scopy was performed in D2O adding a stoichiometric amount
of sodium hydroxide. The NMR signals given in Table 1 corre-
spond to the sodium salts of 2a and 3a and present as well the
neutral compounds 1 and 2 in [D6]DMSO.
The Raman spectra of 4 are dominated by the vibration of
the azo-moiety at 1436 cm–1, the absorption of the amine
groups in the infrared spectrum at 1624 cm–1 has disappeared.
The N–NO2 groups result in a strong absorption at 1620–
1560 cm–1 [νasym(NO2)] and 1300–1240 cm–1 [νsym(NO2)].
The symmetric and N=O valence vibrations of all nitrogen-
rich salts 5–9 can be found at 1530 cm–1 [νsym(NO2)] and
1335 cm–1 [νasym(NO2)] in the IR spectrum, accompanied by
the fundamental frequencies of the triazole ring in the range of
1300–1500 cm–1.[19] The N–H stretch modes of the amine
group of the cations appear in the range of 3350 cm–1 to
3100 cm–1 and the –NH2 deformation vibration at 1630–
1680 cm–1. The very intense band of the azo-moiety at
1463 cm–1 in the Raman spectrum shows only a marginal shift
in comparison to the neutral compound 4.
In the case of compound 2 (2a), two different NMR signals
for the triazole carbon atoms could be obtained due to the rear-
rangement of the acetyl protecting group. The NMR signals of
the two carbon atoms of compound 3a can be found at 170.0
and 165.0 ppm in the 13C NMR spectra. The signals of the
acetyl protecting group at 2.03 ppm (1H NMR) and 22.7 ppm
(13C NMR) could not be obtained anymore, indicating full de-
protection of the amine groups. The signals in the NMR spec-
tra for compounds 4–9 were recorded in [D6]DMSO and are
compiled in Table 2. The neutral compound 4 shows two sig-
nals for the different carbon atoms at δ = 159.7 and 153.8, the
nitrimino group is visible at –19 ppm in the 14N NMR spectra.
As expected in the case of compounds 5–9, all NMR signals
are nearly identical. The single proton localized at the triazole
ring appears at chemical shifts between 13.5–13.6 ppm in the
1H NMR spectra, whereas the signals of the two triazole car-
bon atoms can be found in the range between 166.9–
167.7 ppm and 157.7–158.3 ppm. The nitrimino group is iden-
tified by a broad signal at around –15 ppm in the 14N NMR
spectra.
Structural Characterization
The single-crystal X-ray diffraction data of 4, 5, and 9 were
collected with an Oxford Xcalibur3 diffractometer equipped
with a Spellman generator (voltage 50 kV, current 40 mA) and
a Kappa CCD detector. The data collection was undertaken
using the CRYSALIS CCD software,[20] while the data reduc-
Vibrational Spectroscopy
The isomerization reaction can easily be monitored by IR tion was performed with the CRYSALIS RED software.[21]
spectroscopy and is indicated by the shift of the C=O band The structures were solved with SIR-92[22] or SHELXS-97[23]
from 1709 cm–1 (1) to 1683 cm–1(2).
and refined with SHELXL-97[24] implemented in the program
Z. Anorg. Allg. Chem. 2011, 1181–1193
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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A. Dippold, T. M. Klapötke, F. A. Martin
ARTICLE
Table 3. Crystallographic data and parameters.
4·DMSO
4·THF
5·DMSO
9
Formula
FW /g·mol–1
Crystal system
Space group
Color / Habit
Size /mm
a /Å
C4H4N12O4·4 DMSO
596.70
C4H4N12O4·4THF
572.6
C4H10N14O4·2DMSO
474.52
C6H24N24O6
528.49
monoclinic
P21/c
monoclinic
P21/n
triclinic
monoclinic
P21/c
¯
P1
Yellow plate
0.13 × 0.12 × 0.03
17.2749(6)
15.8671(8)
9.7594(4)
90
Yellow rod
0.55 × 0.08 × 0.05
5.9430(6)
15.3647(17)
15.2456(16)
90
Yellow plate
0.14 × 0.05 × 0.05
7.7810(9)
8.2010(9)
9.0610(10)
86.453(9)
81.497(9)
68.331(10)
531.42(10)
1
Yellow rod
0.22 × 0.08 × 0.02
9.7903(11)
3.6340(5)
29.233(4)
90
b /Å
c /Å
α /°
β /°
100.068(4)
90
96.237(10)
90
96.424(11)
90
γ /°
V /Å3
2633.88(19)
4
1383.9(3)
2
1033.5(2)
2
Z
ρcalcd /g·cm–3
1.505
1.374
1.483
1.698
.
μ /mm–1
0.422
0.108
0.308
0.145
F(000)
1248
608
248
552
λMo-Kα /Å
0.71073
0.71073
173
0.71073
0.71073
173
T /K
173
173
Theta min-max /°
Dataset h
4.2–28.80
–20; 22
4.2–26.50
–7; 7
4.55–26.50
–6; 9
4.15–26.50
–12; 12
Dataset k
Dataset l
–19; 18
–17; 19
–6; 10
–3; 4
–7; 13
–8; 19
–8; 11
–36; 36
Reflections collected
Independent reflections
Observed reflections
No. parameters
Rint
12529
6392
3720
4163
5979
2827
2179
2129
2609
1284
1122
1272
437
205
141
190
0.055
0.045
0.038
0.033
R1, wR2 (I>σI0)
R1, wR2 (all data)
S
0.0386; 0.0440
0.1190; 0.0509
0.663
0.058; 0.143
0.132; 0.161
0.856
0.0406; 0.0549
0.0999; 0.0611
0.742
0.0510; 0.1275
0.0881; 0.1381
0.899
Resd. dens. /e·Å–3
Device type
Solution
–0.375, 0.312
Oxford Xcalibur3 CCD
SIR-92
–0.313, 0.282
Oxford Xcalibur3 CCD
SHELXS-97
SHELXL-97
multi-scan
807481
–0.241;0.245
Oxford Xcalibur3 CCD
SHELXS-97
SHELXL-97
multi-scan
807482
–0.217; 0.693
Oxford Xcalibur3 CCD
SHELXS-97
SHELXL-97
multi-scan
807483
Refinement
Absorption correction
CCDC
SHELXL-97
multi-scan
807480
package WinGX[25] and finally checked using PLATON.[26] presented. The structure of the title compound 9 is discussed
Further information regarding the crystal-structure determina- in detail.
tion have been deposited with the Cambridge Crystallographic
The DMSO adduct of 5,5'-dinitrimino-3,3'-azo-1H-1,2,4-tria-
Data Centre.[27] Crystallographic data and parameters as well zole (4) crystallizes in the monoclinic space group P21/c with
as the crystal morphology are compiled in Table 3. four molecular moieties in the unit cell, whereas the THF ad-
The crystallization of azo-bridged triazole compounds is duct crystallizes in the monoclinic space group P21/n with only
very difficult due to the completely planar configuration of the two molecular moieties in the unit cell. Pycnometer measure-
molecules and a lack of possibilities for hydrogen bonding. We ments of 4 stated a density of 1.85 g·cm–3, whereas the densi-
were finally able to crystallize 4 from DMSO and also THF, ties derived from the crystallographic measurements are very
but were not able to record a crystal structure of the neutral low with 1.505 g·cm–3 for 4·DMSO and 1.374 g·cm–3 for
compound without incorporated solvent molecules. The same 4·THF, respectively, owed to the solvent incorporation. The
problem occurred with the ionic compounds. Only the ammo- asymmetric units for both adducts are displayed in Figure 1
nium salt (5) and the triaminoguanidinium salt (9) could be and Figure 2 together with the numbering scheme and selected
crystallized after a number of tries with different solvents and bond lengths and angles.
crystallization conditions. Whereas 5 could only be crystallized
The DNAAT molecule is nearly planar in both structures,
with incorporated solvent molecules (DMSO), 9 crystallized indicating the presence of a delocalized π-electron system, as
with two molecules of crystal water per formula unit. Due to anticipated for these compounds. Bond lengths and angles are
this circumstances, the structures of 4·DMSO, 4·THF and also as expected for this kind of compounds.[28] The bond
5·DMSO will not be discussed in detail since no results can be length of the azo moiety is in the same range as for the azotet-
drawn from the discussion of the structure, thus only selected razole compounds investigated by Hammerl,[7c, 29] while the
parameters and the asymmetric units of the compounds are nitraminogroups also exhibit regular geometrical parameters.
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Z. Anorg. Allg. Chem. 2011, 1181–1193

Bis(triaminoguanidinium) 5,5'-Dinitrimino-3,3'-azo-1H-1,2,4-triazolate
up the hydrogen bond for 4·THF. Even though, the D–H···A
angles are pretty small with 102.15(16)° (N1–H1···O1,
4·DMSO), 105.8(1)° (N7–H7···O4, 4·DMSO) and 108.21(23)°
(N1–H1···O1, 4·THF), the D–A distances are very small, ran-
ging between 2.587(1) Å (N1–O1, 4·THF) and 2.606(4) Å
(N1–O1, 4·DMSO). The hydrogen bonds are considered to be
of electrostatic nature rather than being directed.[30] The build-
up of a six-membered ring between the nitrimino group and
the triazole ring, is making the backbone of the molecule more
stable, which is also indicated by the very high thermal stabili-
ties, unusual for this class of compounds. In addition the hy-
drogen atom can only be deprotonated with the use of earth
alkaline bases, not with the bases used to form the di-anion.
Further, the incorporated solvent molecules take their space
due to the formation of hydrogen bonds with each of the four
N–H hydrogen atoms. Thus both structures show the mutual
number of solvent molecules surrounding each DNAAT mole-
cule.
Figure 1. Molecular moiety of 4·DMSO. Thermal ellipsoids represent
the 50 % probability level. Selected bond lengths /Å: O1–N6 1.243(3),
O2–N6 1.242(3), N1–C2 1.340(3), N1–N2 1.370(3), N1–H1 0.90(2),
N2–C1 1.307(3), N3–C2 1.352(3), N3–C1 1.355(3), N3–H3 0.913(16),
N4–N10 1.280(3), N4–C1 1.397(3), N5–C2 1.341(3), N5–N6
1.343(3); selected bond angles /°: C2–N1–N2 111.9(2), C2–N1–H1
132.8(16), N2–N1–H1 115.2(16), C1–N2–N1 103.1(2), C2–N3–C1
106.3(2), C2–N3–H3 119.7(15), C1–N3–H3 133.8(16), N10–N4–C1
111.8(2), C2–N5–N6 115.7(2), O2–N6–O1 122.0(2), O2–N6–N5
115.7(3), O1–N6–N5 122.3(3), C4–N7–N8 112.46(19), C4–N7–H7
128.8(15), N2–C1–N3 112.9(2), N2–C1–N4 119.3(3), N3–C1–N4
127.4(2), N1–C2–N5 135.9(2), N1–C2–N3 105.8(2), N5–C2–N3
118.2(3).
Bis(ammonium) 5,5'-dinitrimino-3,3'-azo-1H-1,2,4-triazolate
¯
(5·DMSO) crystallizes in the triclinic space group P1, formally
with only one molecular moiety occupying the unit cell. The
density is as expected very low with only 1.483 g·cm–3 due
to the formation of the DMSO adduct. One molecular moiety
together with selected bond length and angles is presented in
Figure 3.
Figure 3. Molecular moiety of 5. Thermal ellipsoids represent the
50 % probability level. Selected bond lengths /Å: O1–N6 1.270(2),
O2–N6 1.260(2), N1–C2 1.345(3), N1–N2 1.368(2), N1–H1
0.917(15), N2–C1 1.327(3), N3–C2 1.335(3), N3–C1 1.356(3), N4–N4
1.278(3), N4–C1 1.413(3), N5–N6 1.322(2), N5–C2 1.381(3); selected
bond angles /°: C2–N1–N2 110.46(19), C2–N1–H1 133.0(14), N2–
N1–H1 116.5(14), C1–N2–N1 101.00(19), C2–N3–C1 102.0(2), N4–
N4–C1 112.0(2), N6–N5–C2 116.8(2), O2–N6–O1 120.4(2), O2–N6–
N5 123.6(2), O1–N6–N5 116.1(2), N2–C1–N3 116.5(2), N2–C1–N4
117.4(2), N3–C1–N4 126.2(2), N3–C2–N1 110.1(2), N3–C2–N5
117.9(2), N1–C2–N5 132.0(2).
Figure 2. Molecular moiety of 4·THF. Thermal ellipsoids represent
the 50 % probability level. Selected bond lengths /Å: C4–C3 1.406(5),
C4–C5 1.424(6), N6–1.244(3), N1–C2 1.356(4), N1–N2 1.368(3), N1–
H1 0.88(3), N2–C1 1.308(3), N5–C2 1.339(4), N5–N6 1.356(3), N4–
N4 1.272(4), N4–C1 1.392(3), N3–C2 1.346(3), N3–C1 1.368(4), N3–
H4 0.94(3), N6–O2 1.239(3); selected bond angles /°: C2–N1–N2
111.8(3), C2–N1–H1 129(2), N2–N1–H1 119(2), C1–N2–N1 103.6(2),
C2–N5–N6 115.6(3), N4–N4–C1 112.2(3), C2–N3–C1 106.8(2), C2–
N3–H4 125(2), C1–N3–H4 128(2), O2–N6–O1 121.5(3), O2–N6–N5
116.0(3), O1–N6–N5 122.4(2), N5–C2–N3 119.8(3), N5–C2–N1
134.8(3), N3–C2–N1 105.5(3), N2–C1–N3 112.3(2), N2–C1–N4
120.8(2), N3–C1–N4 127.0(2).
The dianion is completely planar within the ionic structures
with only very slight deviations. The N1–H1···O2 hydrogen
bond builds up the six membered ring again, as seen for the
neutral compound, keeping the nitrimino group perfectly in
plane with the triazole ring. Since the thermal decomposition
The interesting aspect of both structures is the presence of temperature differs only by 3 °C when compared with 4
moderately strong intramolecular hydrogen bonds. N1 and N7 [209 °C (4) compared to 212 °C (5)] the formation of this sta-
are utilized as donor atoms with O1 and O4 function as ac- ble configuration seems to have a very important impact on
ceptor atoms respectively for 4·DMSO, while N1 and O1 build the stability of these compounds. The structure itself is build
Z. Anorg. Allg. Chem. 2011, 1181–1193
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1185

A. Dippold, T. M. Klapötke, F. A. Martin
ARTICLE
Table 4. Hydrogen bonds present in the crystal structure of 5. Since the N–H bonds of the ammonium ion had to be set as restraint, no standard
deviation is presented.
Atoms D–H–A
Dist D–H /Å
Dist. H–A /Å
Dist. D–A /Å
Angle D–H–A /°
N1–H1–O3i
N7–H7a–O1ii
N7–H7b–O3
N7–H7c–N3
0.917(15)
0.96
1.937(18)
2.00
2.786(3)
2.929(2)
2.811(2)
2.872(3)
153.0(19)
163.8
0.92
1.91
167.1
0.92
1.98
164.3
Symmetry operators: (i) x, y–1, z; (ii) x+1, y, z; (iii) –x+1, –y+1, –z.
Table 5. Hydrogen bonds present in the crystal structure of 9. H7, H8 and H9 had to be set restraint, thus no standard deviations are given for
the D–H and H–A distances as well as for the D–H–A angles.
Atoms D–H–A
Dist. D–H /Å
Dist. H–A /Å
Dist. D–A /Å
Angle D–H–A /°
N1–H1–O1
0.770(4)
0.77(3)
0.88
2.256(37)
1.98(4)
2.34
2.579(9)
2.733(3)
2.995(3)
2.954(3)
3.186(3)
3.075(4)
3.198(4)
3.126(3)
3.142(5)
3.147(3)
3.176(4)
3.189(3)
3.000(3)
3.197(9)
3.000(3)
2.922(3)
106.2(9)
165(4)
130.9
N1–H1–O3
N7–H7–O1i
N8–H8–O2ii
0.88
2.18
146.3
N9–H9–N5iii
0.88
2.37
153.7
N10–H10a–O1
N10–H10b–N10ii
N10–H10b–O2i
N11–H11a–N11iv
N11–H11a–O2iii
N11–H11b–N5v
N12–H12a–N4vi
N12–H12b–N3iii
N12–H12a–O3
O3–H3a–N12vii
O3–H3b–N2vi
0.96(4)
0.83(4)
0.83(4)
0.827(19)
0.827(19)
0.82(4)
0.82(4)
0.87(4)
0.82(4)
0.73(4)
0.91(4)
2.14(4)
2.52(4)
2.57(4)
2.63(3)
2.54(3)
2.37(4)
2.46(4)
2.20(4)
2.71(3)
2.31(4)
2.04(4)
163(3)
140(3)
125(3)
121(3)
131(3)
168(3)
148(3)
154(3)
119.6(3)
159(4)
163(4)
Symmetry operators: (i) x, y+1, z; (ii) –x+1, y+1/2, –z+1/2; (iii) x–1, y+1, z; (iv) –x, y+1/2, –z+1/2; (v) x–1, y, z; (vi) –x+1, –y+1, –z; (vii) x,
y–1, z.
up from four moderately stable hydrogen bonds, all four of nometer measurement). The molecular moiety of 9, as well as
them involving the ammonium cation. An illustration of the the numbering scheme and selected bond lengths and angles
surrounding of one ammonium cation is presented in Figure 4, are presented in Figure 5.
whereas the parameters of the hydrogen bonds are compiled in
Table 4.
Figure 4. Chemical surrounding of the ammonium cation in 5, display- Figure 5. Molecular moiety of 9. Thermal ellipsoids represent the
ing the hydrogen bonds. Thermal ellipsoids represent the 50 % proba- 50 % probability level. Selected bond lengths /Å: O1–N6 1.264(3),
bility level.
O2–N6 1.255(3), N1–N2 1.351(3), N1–C2 1.354(3), N1–H1 0.77(3),
N2–C1 1.323(3), N3–C2 1.336(3), N3–C1 1.344(3), N4–N4 1.277(4),
N4–C1 1.407(3), N5–N6 1.310(3), N5–C2 1.368(3), N7–C3 1.313(3),
N7–N10 1.431(3), N8–C3 1.316(4), N8–N11 1.406(3), N9–C3
1.331(4), N9–N12 1.419(3); selected bond angles /°: N2–N1–C2
110.2(2), N2–N1–H1 116(3), C2–N1–H1 134(3), C1–N2–N1 101.8(2),
C2–N3–C1 102.5(2), N4–N4–C1 111.9(3), N6–N5–C2 117.7(2), O2–
N6–O1 120.8(2), O2–N6–N5 116.9(2), O1–N6–N5 122.2(2), N2–C1–
N3 116.2(2), N2–C1–N4 116.7(2), N3–C1–N4 127.1(2), N3–C2–N1
109.4(2), N3–C2–N5 118.2(2), N1–C2–N5 132.4(2), C3–N7–N10
The dihydrate of the bis(triaminoguanidinium) 5,5'-dinitri-
mino-3,3'-azo-1H-1,2,4-triazolate (9) crystallizes in the mono-
clinic space group P21/c with two formula units in the unit
cell. The density is in the same range as other guanidinium
salts of nitrimino compounds with 1.698 g·cm–3. The density
is also in good agreement with the experimentally determined
density of the anhydrous compound being 1.72 g·cm–3 (pyc- 118.3(2), C3–N8–N11 121.9(3), C3–N9–N12 119.0(2).
1186
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Z. Anorg. Allg. Chem. 2011, 1181–1193

Bis(triaminoguanidinium) 5,5'-Dinitrimino-3,3'-azo-1H-1,2,4-triazolate
As seen in the structure of 5, the DNAAT2– anion is com- bonds formed between the triaminoguanidinium cations and
pletely planar. The structural motive of two six-membered
rings, stabilizing the nitrimino groups is also evident in this
structure. The donor acceptor distance is in the same range as
for 4 and 5 with 2.579(9) Å and with the D–H···A angle of
106.22(31)° of strong electrostatic nature. The complete struc-
ture is build up by a strong hydrogen network including 15
non-equivalent hydrogen bonds. All hydrogen bonds are com-
piled in Table 5.
interactions from the triaminoguanidinium cation with the ni-
tramino groups, to form zigzag layers presenting an angle of
133.99° between the individual bands. The hydrogen bonds
involved are namely N11–H11a···N11iv and N10–H10b···N10ii,
only involving the triaminoguanidinium cations, whereas N8–
H8···O2ii presents the interaction between the NH group of the
triaminoguanidinium cation in one layer with the nitrimino
group of the DNAAT2– anion in the tilted layer. The layer
scheme of the structure is displayed in Figure 7 along the a
axis.
The structure consists of coplanar bands, build up from
DNAAT2– anions, water molecules and triaminoguanidinium
cations located approximately 1 Å below and above the layer
spanned up by DNAAT2– anions. The water molecules are lo-
cated between the DNAAT2– molecules forming strong and di-
rected hydrogen bonds with the triazole rings, namely N1–
H1···O3 and O3–H3b···N2vi. These hydrogen bonds are well
below the sum of van der Waals radii [rw(N) + rw(O) =
3.10 Å].[31] The third hydrogen bond is formed by the water
molecule as donor, whereas N12vii functions as the donor.
Again, the D–A distance is much shorter than the sum of van
der Waals radii and the D–H···A angle is 159°, which again
indicates a rather directed than only electrostatic interaction.
The only weak hydrogen bond build up by the H2O is N12–
H12a···O3, with a donor acceptor distance of 3.197(9) Å and
therefore longer than the sum of van der Waals radii and an
D–H···A angle of only 119.6(3)°. All other hydrogen bonds
formed are using the nitrogen atoms of the triaminoguanidi-
nium cation as donor atoms. The two hydrogen bonds utilizing
nitrogen atoms of the DNAAT2– anion as acceptors all show
D–A distances smaller than the sum of van der Waals radii
[rw(N) + rw(N) = 3.2 Å] at 3.186 Å (N9–H9–N5iii) and
3.000 Å (O3–H3a–N12vii), respectively. The corresponding D–
H···A angles (around 150°) indicate the bonds being moder-
ately strong but mostly of electrostatic nature. The three hydro-
gen bonds using oxygen atoms as acceptors are moderately
strong with D–A distances between 2.954 and 3.147 Å and
with D–H···A angles between 125° and 131° they are rather of
electrostatic nature. The complete hydrogen bonding scheme
within the bands is presented in Figure 6.
Figure 7. Layer structure of 9, showing the connectivity of the individ-
ual bands along the a axis. Thermal ellipsoids represent the 50 % prob-
ability level.
The angle between the bands is due to the connectivity over
hydrogen bonds formed by the triaminoguanidinium cations.
The N10–H10b···N10ii and N11–H11a···N11iv hydrogen bonds
are rather long with D–A distances of 3.142 and 3.198 Å, re-
spectively, but shorter than the sum of van der Waals radii. D–
H···A angles of only 121° and 140°, respectively, indicate
mostly electrostatic interactions. Since the donor atoms are the
two amine groups, the angle between the bands is given. The
third band connecting hydrogen bond N8–H8···O2ii is rather
short with a D–A distance of 2.954 Å. The bond is mainly of
electrostatic nature, but also directed with a D–H···A angle of
Figure 6. Hydrogen bonding scheme within the band structures of 9.
Thermal ellipsoids represent the 50 % probability level.
Figure 8. Surrounding of one triaminoguanidinium cation in 9, show-
ing the connectivity of the structural motive. Non participating atoms
are set transparent, molecules are partially omitted for better clarity.
The distance between the bands is 3.280 Å, whereas they are
stacked along the b axis. The bands are connected by hydrogen Thermal ellipsoids represent the 50 % probability level.
Z. Anorg. Allg. Chem. 2011, 1181–1193
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1187

A. Dippold, T. M. Klapötke, F. A. Martin
Table 8. Enthalpies of the gas-phase species M.
ARTICLE
146.43°. The surrounding of one triaminoguanidinium cation
is displayed in Figure 8, presenting the complete three dimen-
sional hydrogen bonding network. Three moderately strong hy-
drogen bonds connect the bands towards the next layer, namely
N11–H11b···N5v, N12–H12a···N4vi, and N10–H10a···O1.
M
M
ΔfH°(g, M) /kcal·mol–1
DNAAT
DNAAT2–
A
C4H4N12O42–
743.6
446.5
151.9
184,9
136.6
160.4
184.5
208.8
C4H2N12O4
+
NH4
+
Hy
N2H5
+
Theoretical Calculations
G
CH6N3+
AG
CH7N4+
CH8N5+
CH7N4
Due to the highly energetic character of 4–9, bomb calori-
metric measurements could only be performed with small
amounts; consequently doubtful combustion energies were ob-
tained. Therefore an extensive computational study was ac-
complished for 4–9, which is presented in the following sec-
tion. All calculations were carried out using the Gaussian
G03W (revision B.03) program package.[32] The enthalpies (H)
and free energies (G) were calculated using the complete basis
set (CBS) method of Petersson and co-workers in order to
obtain very accurate energies. The CBS models use the known
asymptotic convergence of pair natural orbital expressions to
extrapolate from calculations using a finite basis set to the esti-
mated complete basis set limit. CBS-4 begins with a HF/3-
21G(d) geometry optimization; the zero point energy is com-
puted at the same level. Subsequently, it uses a large basis set
SCF calculation as a base energy, and a MP2/6-31+G calcula-
tion with a CBS extrapolation to correct the energy through
second order. A MP4(SDQ)/6-31+(d,p) calculation is used to
approximate higher order contributions. In this study we ap-
plied the modified CBS-4M method (M referring to the use of
Minimal Population localization), which is a re-parameterized
version of the original CBS-4 method and also includes some
additional empirical corrections.[33] The enthalpies of the gas-
phase species M were computed according to the atomization
energy method [Equation (1)] (Table 6, Table 7, and
Table 8).[34]
DAG
TAG
The solid state energy of formation of DNAAT was calcu-
lated by subtracting the gas-phase enthalpy with the heat of
sublimation (22.5 kcal·mol–1) obtained by Trouton’s rule
(ΔHsub = 188 Tm) (Tm = 204 °C).[36] In the case of the salts,
the lattice energy (UL) and lattice enthalpy (ΔHL) were calcu-
lated from the corresponding molecular volumes (Table 9 and
Table 10) according to the equations provided by Jenkins et
al.[37] With the calculated lattice enthalpy (Table 9) the gas-
phase enthalpy of formation (Table 8) was converted into the
solid state (standard conditions) enthalpy of formation. These
molar standard enthalpies of formation (ΔHm) were used to
calculate the molar solid state energies of formation (ΔUm)
according to Equation (2) (Table 7).
ΔUm = ΔHm – Δn RT
(2)
(Δn being the change of moles of gaseous components)
Detonation Parameters and Thermal Properties
The calculation of the detonation parameters was performed
with the program package EXPLO5 (version 5.03 and 5.04).[38]
The program is based on the chemical equilibrium, steady-state
model of detonation. It uses the Becker–Kistiakowsky–Wilson
equation of state (BKW EOS) for gaseous detonation products
and the Cowan–Fickett equation of state for solid carbon. The
calculation of the equilibrium composition of the detonation
products is done by applying a modified White–Johnson–Dan-
tzig free energy minimization technique. The program is de-
signed to enable the calculation of detonation parameters at the
CJ point. The BKW equation in the following form was used
with the BKWN set of parameters (α, β, κ, θ) as stated below
the equations and Xi being the mol fraction of i-th gaseous
product, ki is the molar co-volume of the i-th gaseous
product:[39]
ΔfH°(g,M,298) = H(Molecule,298) – ∑H°(Atoms,298) + ∑ΔfH°(Atoms,298)
(1)
Table 6. Results obtained from theoretical calculations at the CBS-4M
level of theory.
point group
–H298 /a.u.
NIMAG
DNAAT
C1
Cs
Td
Cs
C1
C1
C3
1111.064789
1110.009835
56.796608
112.030523
205.453192
260.701802
371.197775
0.500991
37.786156
54.522462
74.991202
459.674576
0
0
0
0
0
0
0
0
0
0
0
0
DNAAT2–
A+
Hy+
G+
AG+
TAG+
H
C
N
pV / RT = 1 + xeβx x = (κ Σ Xiki) / [V (T + θ)]α
α = 0.5, β = 0.176, κ = 14.71, θ = 6620.
O
Cl
Table 7. Literature values for atomic ΔHf298 /kcal·mol–1.
The detonation parameters calculated with the EXPLO5 ver-
sions V5.03 and V5.04 using the experimentally determined
densities (X-ray) are summarized in Table 11.
The neutral compound 4 already shows a remarkably high
thermal stability of 209 °C, but a quite high sensitivity towards
friction and impact. Since salts of energetic compound tend to
be more stable as the neutral compound, the nitrogen-rich salts
NIST[35]
H
C
N
O
Cl
52.1
171.3
113.0
59.6
29.0
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Z. Anorg. Allg. Chem. 2011, 1181–1193

Bis(triaminoguanidinium) 5,5'-Dinitrimino-3,3'-azo-1H-1,2,4-triazolate
Table 9. Lattice energies and lattice enthalpies.
VM /nm3
UL /kJ·mol–1
ΔHL /kJ·mol–1
ΔHL / kcal·mol–1
(NH4)2DNAAT (5)
(N2H5)2DNAAT (6)
(G)2DNAAT (7)
(AG)2DNAAT (8)
(TAG)2DNAAT (9)
298
312
388
464
472
1306.1
1283.5
1181.0
1102.3
1095.0
1317.0
1294.4
1191.9
1113.2
1105.9
314.5
309.2
284.7
265.9
264.1
Table 10. Solid state energies of formation (ΔfU°).
ΔfH°(s) /kcal·mol–1 ΔfH°(s) /kJ·mol–1 Δn
ΔfU°(s) /kJ·mol–1
M /g·mol–1
ΔfU°(s) /kJ·kg–1
DNAAT (4)
154.7
95.8
647.7
401.2
700.4
398.4
676.5
1089.2
10
14
16
18
20
24
672.5
435.9
740.1
443.0
726.1
1148.7
248.2
2366.3
1369.6
2124.6
1101.0
1679.2
2332.3
(NH4)2DNAAT (5)
(N2H5)2DNAAT (6)
(G)2DNAAT (7)
(AG)2DNAAT (8)
(TAG)2DNAAT (9)
318.3
167.3
95.2
348.32
402.4
432.42
492.50
161.6
260.1
Table 11. Physico-chemical properties of 4–9 in comparison with hexogen (RDX).
DNAAT (4) (NH4)2
DNAAT (5)
(N2H5)2
DNAAT (6)
(G)2 DNAAT (7) (AG)2 DNAAT (TAG)2 DNAAT RDX*
(8)
(9)
Formula
Molecular mass /g·mol–1 284.16
Impact sensitivity /Ja)
C4H4N12O4 C4H10N14O4
C4H12N16O4 C6H14N18O4
C6H16N20O4
432.17
> 40
C6H20N24O4
492.38
> 40
C3H6N6O7
222.12
7
318.21
> 40
348.12
10
402.14
> 40
2
Friction sensitivity /Nb) 20
> 360
0.15
> 360
0.05
> 360
0.35
> 360
0.2
160
120
ESD-test /J
0.1
0.2
–
37.8
N /%c)
59.15
–33.78
209
61.62
–45.25
212, 257
1.70
401.2
1369.6
64.35
–45.94
154, 228
1.70
62.67
–59.65
261
64.80
–59.21
177
68.27
–58.48
219
Ω /%d)
–21.6
204 (mp)
1.80
Tdec /°Ce)
ρ /g·cm–3 f)
1.85
647.7
2366.3
1.70
398.4
1101.0
1.70
1.70
ΔfHm° /kJ·mol–1 g)
ΔfU° /kJ·kg–1 h)
EXPLO5 values: V5.03
(V5.04)
700.4
2124.6
676.5
1679.2
1089.2
2332.3
70
417
–ΔEU° /kJ·kg–1 i)
TE /Kj)
5268 (5339) 4473 (4461)
4237 (4089) 3362 (3234)
5055 (5026) 3731 (3690)
3583 (3475) 2855 (2732)
4202 (4147)
3048 (2944)
267 (262)
4681 (4602)
3213 (3087)
300 (290)
6038 (6125)
4368 (4236)
341 (349)
pC–J /kbark)
337 (298)
259 (267)
290 (294)
242 (241)
V
Det./m s–1 l)
8784 (8723) 8156 (8229)
8609 (8575) 8034 (7944)
8391 (8244)
8890 (8596)
8906 (8748)
Gas vol. /L·kg–1 m)
732 (708) 809 (798)
832 (816) 801 (781)
820 (797)
852 (822)
793 (739)
a) BAM drophammer, grain size (75–150 μm). b) BAM friction tester, grain size (75–150 μm). c) Nitrogen content. d) Oxygen balance.[40] e)
Temperature of decomposition by DSC (β = 5 °C, Onset values). f) Estimated density based on X-ray data from 7 and 9, Pycnometer for
DNAAT. g) Molar enthalpy of formation. h) Energy of formation. i) Energy of Explosion. j) Explosion temperature. k) Detonation pressure. l)
Detonation velocity. m) Assuming only gaseous products; * values based on reference[41] and the EXPLO5 database; n.d.: not determined.
of DNAAT are expected to show an improved stability. The
decomposition temperatures of the compounds 5–9 are in the
range of the neutral compound, those of the ammonium and
guanidinium as well as the triaminiguanidinium salt are even
higher and appear in the range from 212 °C up to 261 °C. The
ammonium and the hydrazinium salts show two decomposition
points in the DSC with the first decomposition starting at
212 °C and 154 °C, respectively. As expected, the sensitivity
values of all nitrogen-rich salts are considerably lower in com-
parison to the neutral compound. Nearly all compounds are
insensitive towards friction, impact and electrostatic discharge,
only the hydrazinium salt is slightly sensitive towards impact
(10 J) and the triaminoguanidium salt towards friction
(160 N).
The nitrogen-rich salts of DNAAT exhibit positive heats and
energies of formation. The detonation velocities were calcu-
lated in the range of 7944 m·s–1 (7) to 8596 m·s–1 (9). The best
performance was calculated for the triaminoguanidinium salt
(9) with a detonation velocity of 8596 m·s–1, which is only
slightly lower than the performance of RDX. With the excel-
lent sensitivity values for friction (160 N), impact (<40 J), and
ESD (0.2 J) in addition to the remarkable high temperature
of decomposition (219 °C) and a very low solubility in water
(2.5 g·L–1, 25 °C), the triaminoguanidinium salt (9) seems to
be the best choice in terms of performance and sensitivity and
makes this compound suitable as a potential new high explo-
sive. Additionally, the DSC curves of the 5,5'-dinitrimino-3,3'-
Z. Anorg. Allg. Chem. 2011, 1181–1193
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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1189

A. Dippold, T. M. Klapötke, F. A. Martin
ARTICLE
azo-1H-1,2,4-triazole (4) and the corresponding bis(triamino- different densities, but we can state an overall increase in per-
guanidinium) salt (9) are displayed in Figure 9.
formance. At a density of 1.58 g·cm–3 TAG2 DNAT shows a
detonation velocity of 8200 m·s–1 and a detonation pressure at
the Chapman–Jouguet point of 230 kbar, whereas 9 exhibits a
detonation pressure of 8596 m·s–1 paired with a dentonation
pressure of 290 kbar at a density of 1.70 g·cm–3.
Conclusions
From this combined experimental and theoretical study the
following conclusions have been drawn:
The application of the very straightforward and efficient ace-
tyl protection of 3,5-diamino-1H-1,2,4-triazole allows selective
reactions of the remaining free amine group and establishes a
basis to a multitude of potential new energetic compounds that
are now accessible. The synthesis of 5,5'-diamino-3,3'-azo-1H-
1,2,4-triazole (3) by reaction of 5-acetylamino-3-amino-1H-
1,2,4-triazole (2) with potassium permanganate is described.
Compound 3 acts as starting material for other new high ener-
getic materials, since several modifications of the amine
groups are possible. The subsequent nitration of 3 leads to the
formation of 5,5'-dinitrimino-3,3'-azo-1H-1,2,4-triazole (4),
which was fully characterized in terms of sensitivity and ener-
getic properties as well as by single-crystal X-ray diffraction.
The molecule reveals promising energetic properties but quite
high sensitivities towards friction (20 N), impact (2 J), and
electrostatic discharge (0.1 J). Therefore, nitrogen rich salts
were synthesized by reaction with high-nitrogen bases (ammo-
Figure 9. Differential scanning calorimetry (DSC) curves for the neu-
tral nitrimino compound 4 and the bis(triaminoguanidinium) salt of 4 nia, hydrazine, guanidine, aminoguanidine, and triaminoguani-
(9).
dine). All salts were fully characterized by NMR-, IR-, and
Raman spectroscopy. Special attention was turned on the ther-
Since 3,5-diamino-1H-1,2,4-triazole was used previously as
a starting material resulting in 3,3'-dinitro-5,5'-azo-1,2,4-tria-
zole (DNAT) and its triaminoguanidinium salt,[13, 14] we want
to put the results obtained for these compounds in relation to
the advances we were able to make. DNAT, synthesized by
Naud et al., as mentioned in the introduction, shows a much
lower sensitivity towards impact and friction with 12.5 J and
250 N, respectively, than the neutral nitrimino compound
DNAAT (4), while the density is in the same region as ob-
served for 4 (1.85 g·cm–3). DNAT as a neutral compound is
mal stabilities and sensitivities values. The triaminoguanidi-
nium salt (9) exhibits a remarkable high temperature of decom-
position (219 °C) and detonation velocity (8596 m·s–1) and
therefore turned out to be the most promising compound in
terms of performance and stability. The performance character-
istics of 9 exceed the ones of TAG2 DNAT, which served us as
a starting point regarding performance and stability, especially
when comparing the detonation pressure and sensitivity values.
therefore much more stable regarding outer stimuli, but shows Experimental Section
lower performance characteristics than DNAAT with a detona-
Caution: Although all 3,5-diamino-1,2,4-triazole derivatives reported
tion velocity of 8500 m·s–1 (4: 8723 m·s–1). Hence we were
able to increase the performance of the molecule with the ex-
change of the nitro group with the nitrimino group, but the
sensitivity values are much to high which prohibits the use as
an energetic material (other than for primary explosives). This
relation changes, when comparing the triaminoguanidinium
salts of DNAT and DNAAT. In this case TAG2 DNAAT (9) is
exceeding the properties of TAG2 DNAT in every respect: the
decomposition temperature of 9 is higher (219 °C compared to
202 °C) together with the sensitivity values being much better
in respect to the impact sensitivity (DNAT: 9.3 J, 9: > 40 J)
and close to equal with respect to the friction sensitivity
(DNAT: 157 N, 9: 160 N). The performance characteristics of
in this publication are rather stable against friction, impact, and electric
discharge, proper safety precautions should be taken when handling
these compounds. The derivatives are energetic materials and tend to
explode under certain conditions, especially under physical stress. Lab-
oratories and personnel should be properly grounded, and safety equip-
ment such as Kevlar gloves, leather coats, face shields, and ear plugs
are recommended.
General: All chemical reagents, except 3,5-diamino-1,2,4–1H-triazole
and solvents were obtained from Sigma–Aldrich Inc. or Acros Organ-
ics (analytical grade) and were used as supplied. 3,5-Diamino-1,2,4-
1H-triazole was obtained from ABCR. 1H, 13C{1H}, and 14N NMR
spectra were recorded with a JEOL Eclipse 400 instrument in
[D6]DMSO at or near 25 °C. The chemical shifts are given relative to
9 cannot be compared directly, since they were calculated at tetramethylsilane (1H, 13C) or nitromethane (14N) as external standards
1190
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1181–1193

Bis(triaminoguanidinium) 5,5'-Dinitrimino-3,3'-azo-1H-1,2,4-triazolate
and coupling constants are given in Hertz (Hz). Infrared (IR) spectra 2.0 g, 14.2 mmol) in sodium hydroxide (32 %, 15 mL) at 0 °C. The
were recorded with a Perkin–Elmer Spectrum BX FT-IR instrument mixture was allowed to warm to room temperature and subsequently
equipped with an ATR unit at 25 °C. Transmittance values are qualita- heated to reflux for 3 h after addition of sodium hydroxide (5 mL,
tively described as “very strong” (vs), “strong” (s), “medium” (m) and 2m). The generated manganese oxide was removed by filtration and
“weak” (w). Raman spectra were recorded with a Bruker RAM II spec- the filtrate acidified with concentrated hydrochloric acid to pH = 6.
trometer equipped with a Nd:YAG laser (1064 nm) and a reflection The precipitate was filtered off and 5,5'-diamino-3,3'-azotriazole (3)
angle of 180°. The intensities were reported as percentages of the most was obtained as an orange solid (0.93 g, 4.8 mmol, 68 %). 13C NMR
intense peak and are given in parentheses. Elemental analyses were (D2O, NaOH): δ = 170.2 (C–N=N), 165.3 (C–NH2). IR (ATR, 25 °C):
performed with a Netzsch Simultaneous Thermal Analyzer STA 429. ν = 3452 (s), 3351 (s), 2677 (m), 1624 (vs), 1490 (m), 1465 (m), 1413
˜
Melting points were determined by differential scanning calorimetry (w), 1349 (m), 1142 (m), 1102 (m), 1051 (m), 880 (w), 799 (w), 759
(Setaram DSC141 instrument, calibrated with standard pure indium (w), 708 (vw), 676 (vw) cm–1. Raman (200 mW, 25 °C): 3349(1),
and zinc). Measurements were performed at a heating rate of 1658(2), 1520(4), 1448(42), 1388(24), 1347(100), 1139(35), 1103(7),
5 °C·min–1 in closed aluminum sample pans with a 1 μm hole in the 1056(9), 927(2), 912(3) cm–1. Elemental analysis C4H10N10O2 dihy-
top for gas release in a nitrogen flow of 20 mL·min–1 with an empty drate: calcd: C 20.87, H 4.38, N 60.85 %; found C 21.58, H 3.85,
identical aluminum sample pan as a reference.
N 59.05 %.
For initial safety testing, the impact and friction sensitivities as well
as the electrostatic sensitivities were determined. The impact sensitiv-
ity tests were carried out according to STANAG 4489,[42] modified
according to instruction[43] using a BAM[44] drophammer. The friction
sensitivity tests were carried out according to STANAG 4487[45] and
modified according to instruction[46] using the BAM friction tester. The
electrostatic sensitivity tests were accomplished according to STANAG
4490[47] using an electric spark testing device ESD 2010EN (OZM
Research) operating with the “Winspark 1.15 software package”.
5,5'-Dinitrimino-3,3'-azo-1H-1,2,4-triazole (4): 5,5'-Diamino-3,3'-
azotriazole (0.35 g, 1.8 mmol) was dissolved in sulfuric acid (conc.,
1.75 mL) and nitric acid (conc., 0.30 mL, 7.2 mmol) was added at
0 °C. After stirring at 0 °C for 30 minutes, the mixture was allowed
to warm to room temperature, stirred for 1 h and poured on ice (10 g).
The precipitate was filtered off, washed with water, and dried at 60 °C
to obtain 4 as a yellow solid. DSC (Onset, 5 °C·min–1): TDec. = 209 °C.
13C{1H} NMR ([D6]DMSO, 25 °C): δ = 159.7 (C–N=N), 153.8 (C–
N–NO2). 14N NMR ([D6]DMSO, 25 °C): δ = –19 (NO2). IR (ATR,
25 °C): ν = 3066 (s), 1695 (w), 1586 (vs), 1542 (m), 1522 (s), 1493
˜
1-Acetyl-3,5-diamino-1H-1,2,4-triazole
(1):
According
to
(m), 1436 (m), 1273 (s), 1238 (s), 1139 (m), 1075 (m), 1039 (m),
979 (m), 845 (w), 770 (w), 721 (w) cm–1. Raman (200 mW, 25 °C):
1538(16), 1493(10), 1436(100), 1354(11), 1307(16), 1145(21),
1091(7), 994(11), 905(4), 847(3), 754(2) cm–1. Elemental analysis
C4H4N12O4: calcd: C 16.91, H 1.42, N 59.15 %; found: C 18.27,
H 1.83, N 58.25 %. Sensitivities (grain size: 100–500 μm): FS: 20 N,
IS: 2 J, ESD: 0.1 J.
literature,[16] acetic anhydride (40.8 mL, 1.2 equiv.) was added drop-
wise under vigorous stirring to a solution of 3,5-diamino-1,2,4-triazole
(36.0 g, 0.36 mol) in 130 mL water at room temperature. After stirring
for 1 h, the precipitate was filtered off, washed with water, and dried
at room temperature to yield 1 as a colorless powder (48.3 g, 0.34 mol,
1
95 % 1-acetyl-3,5-diamino-1H-1,2,4-triazole). H NMR ([D6]DMSO,
25 °C): δ = 7.35 (s, 2 H, NH2), 5.64 (s, 2 H, NH2), 2.33 (s, 3 H, CH3).
13C NMR ([D6]DMSO, 25 °C): δ = 170.5 (C=O), 162.2, 157.0, 23.6
General Synthesis of Nitrogen-rich Salts of DNAAT: The free nitro-
gen-rich base (2 equiv., 22.8 mmol) was added to a suspension of 5,5'-
dinitrimino-3,3'-azo-1H-1,2,4-bistriazole (4, 3.24 g, 11.4 mmol) in wa-
ter (75 mL) at 60 °C. After cooling to 5 °C, the precipitate was filtered
off, washed with cold water and dried at 60 °C to yield the correspond-
ing nitrogen-rich salt of 5,5'-dinitrimino-3,3'-azo-1H-1,2,4-triazole (5–
9) as a yellow solid.
(CH ). IR (ATR, 25 °C): ν = 3414 (m), 3388 (vs), 3295 (m), 3127 (s),
˜
3
1709 (s), 1640 (vs), 1568 (s), 1448 (m), 1393 (s), 1365 (vs), 1336 (s),
1178 (m), 1116 (m), 1066 (m), 1043 (m), 973 (m), 839 (w), 757 (w),
699 (w), 669 (w) cm–1. Raman (200 mW, 25 °C): 3418(4), 3403(5),
3220(10), 3183(9), 3132(9), 3022(35), 2989(16), 2934(68), 1711(100),
1641(40), 1568(44), 1549(25), 1459(9), 1425(21), 1396(41), 1375(39),
1340(43), 1182(37), 1155(80), 1118(25), 1037(42), 972(21), 840(25),
767(8), 719(11), 668(49), 590(15), 577(17), 445(50), 399(15), 385(15),
345(39), 245(13), 224(18) cm–1.
(NH4)2 DNAAT (5): Yield 50 %; DSC (onset, 5 °C·min–1): TDec
=
.
212 °C, 257 °C. 1H NMR ([D6]DMSO,25 °C): δ = 13.58 (s, 2 H,
Nring–H), 7.23 (NH4+). 13C NMR ([D6]DMSO, 25 °C): δ = 167.7 (C–
3-Acetylamino-5-amino-1H-1,2,4-triazole (2): A mixture of 1-acetyl-
3,5-diamino-1,2,4-triazole (1) (10.0 g, 70.9 mmol) and decaline
(100 mL) was heated to reflux without stirring at 187–190 °C for 6 h.
The solid was filtered off, washed with petroleum ether (100 mL) and
diethyl ether (100 mL) and dried in air to yield 2 as a colorless powder
(9.6 g, 68.0 mmol, 96 %). 1H NMR (D2O, NaOH, 25 °C): δ = 2.03
(s, 3 H, CH3). 13C NMR ([D2O, NaOH, 25 °C): δ = 174.1 (C=O),
N=N), 158.3 (C–N–NO2). 14N NMR ([D6]DMSO, 25 °C): δ = –14 (–
+
NO ), –359 (NH ). IR (ATR, 25 °C): ν = 3171 (s), 1692 (w), 1641
˜
2
4
(w), 1594 (m), 1530 (s), 1474 (s), 1432 (s), 1380 (s), 1316 (vs), 1168
(m), 1078 (s), 1035 (w), 1004 (m), 861 (w), 770 (m), 733 (w) 698
(w) cm–1. Raman (200 mW, 25 °C): 1544(25), 1466(100), 1403(53),
1352(84), 1167(30), 1099(17), 1044(8), 1002(41), 924(12), 860(8),
748(6), 397(7) cm–1. Sensitivities (grain size: 100–500 μm): FS:
>360 N, IS: >40 J, ESD: 0.15 J.
162.5 (C–NH ), 154.1 (C–NHAc), 22.7 (CH ). IR (ATR, 25 °C): ν =
˜
2
3
3426 (m), 3251 (s), 1682 (vs), 1597 (vs), 1581 (vs), 1451 (s), 1295
(m), 1269 (m), 1080 (m), 1026 (w), 1010 (w), 816 (w), 714 (m) cm–1.
Raman (200 mW, 25 °C): 3243(5), 2933(39), 1684(100), 1647(12),
1586(52), 1537(11), 1456(13), 1366(24), 1296(10), 1261(8), 1084(47),
1027(45), 970(28), 818(11), 793(12), 694(4), 590(38), 493(12),
363(12), 324(24) cm–1. Elemental analysis C4H7N5O: calcd: C 34.04,
H 5.00, N 49.62 %; found: C 34.11, H 4.86, N 49.12 %.
(N2H5)2 DNAAT (6): Yield 54 %. DSC (onset, 5 °C·min–1): TDec
=
.
154 °C, 228 °C. 1H NMR ([D6]DMSO,25 °C): δ = 13.51 (s, 2 H,
Nring–H), 7.28 (N2H5 ). 13C NMR ([D6]DMSO, 25 °C): δ = 166.9 (C–
+
N=N), 157.8 (C–N–NO2). 14N NMR ([D6]DMSO, 25 °C): δ = –16 (–
+
NO ), –359 (N H ). IR (ATR, 25 °C): ν = 3103 (s), 1631 (m), 1528
(s), 1472 (m), 1426 (s), 1385 (m), 1315 (vs), 1260 (s), 1168 (m), 1080
˜
2
2
5
5,5'-Diamino-3,3'-azo-1H-1,2,4-triazole (3): Potassium permanga- (s), 996 (m), 859 (w), 769 (w), 732 (vw), 705 (w) cm–1. Raman
nate (2/3 equiv., 1.54 g, 9.7 mmol) was added over a period of 10 mi- (200 mW, 25 °C): 1541(9), 1461(100), 1403(36), 1353(54), 1258(3),
nutes to a solution of 3-acetylamino-5-amino-1H-1,2,4-triazole (2, 1162(19), 1100(10), 1000(20), 924(7), 859(4), 747(2), 399(2) cm–1.
Z. Anorg. Allg. Chem. 2011, 1181–1193
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1191

A. Dippold, T. M. Klapötke, F. A. Martin
ARTICLE
Sensitivities (grain size: 100–500 μm): FS: >360 N, IS: 10 J, ESD: and inspired discussions and support of our work. We are also indebted
0.05 J.
to and thank Dr. Jörg Stierstorfer for performing quantum mechanical
and performance calculations.
G2 DNAAT (7): Yield 73 %. DSC (onset, 5 °C·min–1): TDec. = 261 °C.
1H NMR ([D6]DMSO,25 °C): δ = 13.53 (s, 2 H, Nring–H), 7.03 (s,
G+). 13C NMR ([D6]DMSO, 25 °C): δ = 167.1 (C–N=N), 157.9 (C–
N–NO2), 157.7 (G+). 14N NMR ([D6]DMSO, 25 °C): δ = –14 (–NO2).
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AG2 DNAAT (8): Yield 87 %. DSC (onset, 5 °C·min–1): TDec
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177 °C. 1H NMR ([D6]DMSO,25 °C): δ = 13.61 (s, 2 H, Nring–H),
7.89 (s, AG+), 7.12 (s, AG+), 4.71 (s, AG+). 13C NMR ([D6]DMSO,
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(m), 1164 (w), 1086 (s), 1009 (m), 864 (w), 770 (m), 730 (w), 692
(w) cm–1. Raman (200 mW, 25 °C): 1534(16), 1488(12), 1463(100),
1409(22), 1367(51), 1156(20), 1096(12), 1041(5), 1008(29), 918(9),
861(5), 746(4), 403(5) cm–1. Elemental analysis C6H16N20O4: calcd.:
C 16.67, H 3.73, N 64.80 %; found: C 16.87, H 3.73, N 61.97 %
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0.20 J.
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=
.
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˜
6
2
1682 (s), 1526 (s), 1466 (m), 1435 (s), 1315 (vs), 1250 (m), 1133 (m),
1073 (s), 1003 (m), 857 (w), 771 (w), 728 (w), 656 (w) cm–1. Raman
(200 mW, 25 °C): 1534(16), 1488(12), 1463(100), 1409(22),
1367(51), 1156(20), 1096(12), 1041(5), 1008(29), 918(9), 861(5),
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Acknowledgement
Financial support of this work by the Ludwig-Maximilian University
of Munich (LMU), the U.S. Army Research Laboratory (ARL), the
Armament Research, Development and Engineering Center (ARDEC),
the Strategic Environmental Research and Development Program
(SERDP), and the Office of Naval Research (ONR Global, title: “Syn-
thesis and Characterization of New High Energy Dense Oxidizers
(HEDO) - NICOP Effort”) under contract nos. W911NF-09-2-0018
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knowledged. The authors acknowledge collaborations with Dr. Mila
Krupka (OZM Research, Czech Republic) in the development of new
testing and evaluation methods for energetic materials and with Dr.
Muhamed Sucesca (Brodarski Institute, Croatia) in the development
of new computational codes to predict the detonation and propulsion
parameters of novel explosives. We are indebted to and thank Drs.
Betsy M. Rice and Brad Forch (ARL, Aberdeen, Proving Ground, MD)
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1192
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1181–1193

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Z. Anorg. Allg. Chem. 2011, 1181–1193
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