Nitrogen-rich salts of 1H,1′H-5,5′-Bitetrazole-1,1′-diol: Energetic materials with high thermal stability

Article abstract of DOI:10.1002/ejic.201201192

1H,1′H-5,5′-Bitetrazole-1,1′-diol was synthesized starting from glyoxal, which is converted to glyoxime after treatment with hydroxylamine. Chlorination of glyoxime with Cl₂ gas in ethanol and following chloro/azido exchange yields diazidoglyoxime, which is cyclized under acidic conditions (HCl gas in diethyl ether) to give 1H,1′H-5,5′- bitetrazole-1,1′-diol dihydrate (1). A large variety of nitrogen-rich salts of 1 such as the diammonium (2), the dihydrazinium (3), the bis-guanidinium (4), the bis(aminoguanidinium) (5), the diaminoguanidinium salt monohydrate (6), the triaminoguanidinium salt monohydrate (7), the 1-amino-3-nitroguanidinium salt dihydrate (8), the diaminouronium salt monohydrate (9), the bis(oxalyldihydrazidinium) (10), the oxalyldihydrazidinium salt dihydrate (11), the 3,6-dihydrazino-1,2,4,5-tetrazinium (12), the 5-aminotetrazolium (13), the bis(5-amino-1-methyl-1H-tetrazolium) salt (14), the bis(5-amino-2-methyl-2H-tetrazole) adduct (15), and the 1,5-diaminotetrazolium salt (16) were synthesized by means of Bronsted acid-base or metathesis reactions. All compounds were fully characterized by vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC) measurements. The crystal structures of 1-16 could be determined by using single-crystal X-ray diffraction. The heats of formation of 1-16 were calculated by using the atomization method on the basis of CBS-4M enthalpies. With regard to their potential use as cyclotrimethylene trinitramine (RDX) or hexanitrostilbene (HNS) replacements, several detonation parameters such as the detonation pressure, detonation velocity, explosion energy, and explosion temperature were computed using the EXPLO5 code on the basis of the experimental (X-ray) densities and calculated heats of formation. In addition, the sensitivities towards impact, friction, and electrical discharge were tested using the BAM drop hammer, a friction tester, as well as a small-scale electrical discharge device. Copyright

Full text of DOI:10.1002/ejic.201201192

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
FULL PAPER
DOI:10.1002/ejic.201201192
Nitrogen-Rich Salts of 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol:
Energetic Materials with High Thermal Stability
[
a]
[a]
[a]
Niko Fischer, Thomas M. Klapötke,* Marius Reymann, and
Jörg Stierstorfer[
a]
Keywords: Energetic materials / Nitrogen heterocycles / Nitrogen-rich compounds
1
H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol was synthesized starting
from glyoxal, which is converted to glyoxime after treatment
with hydroxylamine. Chlorination of glyoxime with Cl gas
Brønsted acid–base or metathesis reactions. All compounds
were fully characterized by vibrational spectroscopy (IR and
Raman), multinuclear NMR spectroscopy, elemental analysis,
and differential scanning calorimetry (DSC) measurements.
The crystal structures of 1–16 could be determined by using
single-crystal X-ray diffraction. The heats of formation of 1–
16 were calculated by using the atomization method on the
basis of CBS-4M enthalpies. With regard to their potential
use as cyclotrimethylene trinitramine (RDX) or hexanitrostil-
bene (HNS) replacements, several detonation parameters
such as the detonation pressure, detonation velocity, ex-
plosion energy, and explosion temperature were computed
2
in ethanol and following chloro/azido exchange yields di-
azidoglyoxime, which is cyclized under acidic conditions
(HCl gas in diethyl ether) to give 1H,1ЈH-5,5Ј-bitetrazole-
1,1Ј-diol dihydrate (1). A large variety of nitrogen-rich salts
of 1 such as the diammonium (2), the dihydrazinium (3), the
bis-guanidinium (4), the bis(aminoguanidinium) (5), the di-
aminoguanidinium salt monohydrate (6), the triaminoguan-
idinium salt monohydrate (7), the 1-amino-3-nitroguanid-
inium salt dihydrate (8), the diaminouronium salt mono-
hydrate (9), the bis(oxalyldihydrazidinium) (10), the oxalyl- using the EXPLO5 code on the basis of the experimental (X-
dihydrazidinium salt dihydrate (11), the 3,6-dihydrazino-
,2,4,5-tetrazinium (12), the 5-aminotetrazolium (13), the
bis(5-amino-1-methyl-1H-tetrazolium) salt (14), the bis(5-
amino-2-methyl-2H-tetrazole) adduct (15), and the 1,5-di-
aminotetrazolium salt (16) were synthesized by means of
ray) densities and calculated heats of formation. In addition,
the sensitivities towards impact, friction, and electrical dis-
charge were tested using the BAM drop hammer, a friction
tester, as well as a small-scale electrical discharge device.
1
Introduction
caged nitramines decompose into a significant amount of
toxic reaction products such as nitro- and nitrosoamines[
after degradation, the use of nitrogen-rich azoles such as
triazole and tetrazole derivatives circumvents the draw-
backs, which are related to the use of the above-mentioned
nitramines. Not only does the high nitrogen content of tri-
azoles and especially tetrazoles bring the environmental
6]
st
From an early 21 -century point of view, the practical
design of new energetic materials has a long tradition in the
materials chemists community. Reaching back at least to
the end of the 19 century, when the energetic character
of nitrogen-rich materials was first recognized, the develop-
ment of energetic materials in the 20 century was instead
th
[1]
th
benefit of releasing mainly N after decomposition, it also
2
mainly determined by efforts to synthesize cyclic and caged
nitramines, as the most prominent examples thereof,
increases the heat of formation of the compound due to
inherently energetic C–N and N–N bonds contained in the
molecule. Along with a high heat of formation, a high den-
sity, high thermal stability, and low sensitivities towards im-
pact, friction, and electrical discharge of a new material are
also amongst the most desirable features when it comes to
the synthesis of new energetic compounds with improved
detonation performance such as the detonation pressure
and the detonation velocity, which both strongly depend
on the characteristic values of ρ and enthalpy of formation
[
2]
[3]
[4]
RDX, HMX, and CL-20, which cover a wide range
of civil and military applications, show. Recent concerns
about the environmental impact of energetic materials now-
adays have caused a renaissance in the synthesis of so-called
green energetic materials,[ which are based on a high nitro-
5]
gen content that releases mainly environmentally benign N2
after decomposition or degradation. Whereas cyclic and
[
7,8]
[
a] Department of Chemistry, Energetic Materials Research,
(Δ H°).
f
Ludwig Maximilians Universität (LMU),
The authors recently reported on the synthesis and ener-
Butenandtstrasse 5–13 (D), 81377 München, Germany
Fax: +49-89-2180-77492
E-mail: tmk@cup.uni-muenchen.de
getic characterization of a series of nitrogen-rich 5,5Ј-bi-
[9]
tetrazololates. These molecules were shown to have excel-
Homepage: http://www.cup.uni-muenchen.de/ac/klapoetke/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201201192.
lent thermal stabilities while being comparatively insensi-
tive, despite their very high nitrogen contents of up to 83%.
Eur. J. Inorg. Chem. 0000, 0–0
1
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
A further improvement of the energetic character of tetra- cyclized product 1 can be isolated as its disodium salt by
zole-containing compounds was demonstrated by the intro- filtration after removing diethyl ether and excess amounts
duction of N-oxides,[
10–12]
in that the density is increased by of HCl gas, followed by the addition of two equivalents of
further possibilities to form hydrogen bonds in the solid 2 m NaOH to the NMP-containing mixture. The free acid
state, and also the oxygen content of the molecule is better is obtained by acidifying an aqueous solution of the di-
balanced, thus ensuring a maximum energy output when sodium salt of 1 with concentrated HCl and subsequent
the compound decomposes to low heat of formation prod- extraction of the aqueous solution with diethyl ether
ucts such as CO , H O, and N .
(Scheme 1).
2
2
2
A very promising candidate that fulfils a variety of the
Starting from 1, all compounds except the diamino-, the
aforementioned desirable properties is 1H,1ЈH-5,5Ј-bi- triaminoguanidinium, and the 3,6-dihydrazino-1,2,4,5-
tetrazole-1,1Ј-diol. This dihydroxylated bitetrazole is tetrazinium salt 6, 7, and 12 were synthesized after treating
strongly acidic and bears two protons, which can be easily 1 with stoichiometric amounts of the respective free base
abstracted by nitrogen-rich bases such as ammonia, guanid- or, in the cases of guanidinium and aminoguanidinium salts
ine, or even other tetrazole derivatives. We recently de- 4 and 5, the respective carbonate (4) and hydrogen carbon-
scribed the energetic properties of its dihydroxylammonium ate (5). An overview is depicted in Scheme 2. The diamino-
salt, which shows great promise for use as an explosive filler guanidinium salt 6 was isolated from a reaction mixture
[
13]
in the future.
1
Scheme 2 gives an overview about the that contained the barium salt of 1 and diaminoguan-
H,1ЈH-5,5Ј-bitetrazole-1,1Ј-diolates discussed herein, all of idinium sulfate after removing the poorly soluble barium
which were structurally characterized by low-temperature sulfate by filtration. The triaminoguanidinium salt 7 crys-
single-crystal X-ray diffraction.
tallized from a mixture that contained the free acid 1 and
triaminoguanidinium chloride, and also for the 3,6-di-
hydrazinium-1,2,4,5-tetrazine salt 12 the respective chloride
salt was treated with 1. With regard to the stoichiometries
used in the different reaction mixtures, we anticipated the
Results and Discussion
Synthesis
The synthesis of the nitrogen-rich salts 2–16 necessarily isolation of 2:1 compounds so that 2:1 stoichiometries were
needs to start with the synthesis of the free acid 1H,1ЈH- also used in the respective reactions, except for 8, for which,
5
,5Ј-bitetrazole-1,1Ј-diol (1), which is depicted in Scheme 1. due to its low water solubility, only one equivalent of 1-
Oxidation of 5,5Ј-bitetrazole by using oxone or hypofluoric amino-3-nitroguanidine was used to avoid precipitation of
acid yields mixtures of the 1,1Ј-, 1,2Ј-, and favored 2,2Ј- the base, and for 12, since the tetrazine derivative was used
dihydroxy derivatives. Tselinskii et al.[ reported the for- as its dihydrochloride. However, what we observed was the
mation of this dihydroxylated heterocycle in 2001 upon cy- crystallization of compounds with a 2:1 stoichiometry in
clization of diazidoglyoxime, which itself is synthesized by the cases of 1–4, 10, and 15 and, unexpectedly, a 1:1 stoichi-
starting from commercially available glyoxal. Glyoxal is ometry in the cases of 5–8, 11–14, and 16, with even double-
treated with hydroxylamine to form glyoxime. Chlorination protonated cations in the cases of 7, 9, 11, and 12.
14]
of glyoxime with Cl gas in ethanol affords dichloroglyox-
Aminoguanidinium chloride was synthesized from
2
ime, which is cyclized under acidic conditions (HCl gas in aminoguanidinium hydrogen carbonate by acidification
diethyl ether) to form 1. To avoid the isolation of the highly with HCl. The resulting aminoguanidinium chloride was
sensitive diazidoglyoxime, the chloro/azido exchange is per- treated with hydrazine hydrate (2 equiv.) in 1,4-dioxane un-
formed in N-methylpyrrolidinone (NMP), whereas the en- der N2 to form the triaminoguanidinium synthon. Di-
tire mixture of NMP, the dissolved covalent diazide, and aminoguanidinium sulfate was obtained from commercially
precipitated sodium chloride is directly poured onto diethyl available diaminoguanidinium chloride after ion ex-
[
15]
[16]
[17]
ether, a safer procedure that has recently been developed by change.
Diaminourea
and oxalyldihydrazide
were
[
13]
the authors. After treating the mixture with HCl gas, the obtained from the reaction of hydrazine hydrate with di-
Scheme 1. Synthesis of 1H,1ЈH-5,5Ј-bitetrazole-1,1Ј-diol (1).
Eur. J. Inorg. Chem. 0000, 0–0
2
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
Scheme 2. Synthesis of the nitrogen-rich salts 2–16.
methylcarbonate or diethylmalonate, respectively. The first forts to crystallize 1 without crystal water resulted in the
[
13]
step in the synthesis of 3,6-dihydrazino-1,2,4,5-tetrazinium formation of a methanol adduct when recrystallized from
dichloride monohydrate was the reaction of triaminoguani- dry methanol, or the dihydrate 1 when recrystallized from
dinium chloride with pentane-2,4-dione to form 3,6- glacial acetic acid or acetonitrile.
bis[(3,5-dimethyl)pyrazol-1-yl]-1,2-dihydro-1,2,4,5-tetraz-
[
18,19]
ine,
which was subjected to a hydrazinolysis reaction
to form 3,6-dihydrazino-1,2,4,5-tetrazine. Further reaction
with hydrochloric acid in methanol yielded the dichloride.
The methylated 5-aminotetrazoles 1-methyl- and 2-methyl-
Crystal Structures
Suitable single crystals of the described compounds 1–16
5
-aminotetrazole were obtained by methylation of commer- were picked from the crystallization mixture and mounted
[20]
cially available 5-aminotetrazole.
1,5-Diaminotetrazole in Kel-F oil, transferred to the N stream of an Oxford
2
was prepared by the reaction of thiosemicarbazide and so- Xcalibur3 diffractometer with a Spellman generator (volt-
dium azide in the presence of lead(II) oxide and ammonium age 50 kV, current 40 mA) and a KappaCCD detector using
[
21]
chloride, and 1-amino-3-nitroguanidine was gained from a Mo-K radiation wavelength of λ = 0.71073 Å. All struc-
α
a hydrazinolysis reaction of nitroguanidine.[
22,23]
tures were measured at –100 °C. The data collection and
The solubility of 1 and its nitrogen-rich salts 2–16 is only data reduction was carried out with the CrysAlisPro soft-
[
24]
[25]
[26]
moderate in water, so crystals of 1–16 suitable for X-ray ware. The structures were solved with Sir-92, Sir-97,
[
27]
[28]
single-crystal measurements were obtained after filtration or SHELXS-97, refined with SHELXL-97, and finally
and slow evaporation of the aqueous mother liquors. Ef- checked using the Platon software
[
29]
integrated in the
Eur. J. Inorg. Chem. 0000, 0–0
3
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
WinGX software suite.[30] The non-hydrogen atoms were re-
fined anisotropically and the hydrogen atoms were located
and freely refined. The absorptions were corrected by a
Scale3 Abspack multiscan method.[ Data and parameters
of the measurements and refinements are gathered in
Tables S1, S2, and S3 in the Supporting Information. Exact
bond lengths, angles, and selected hydrogen bonds are also
given in the Supporting Information in Tables S3–S12.
Here, only three examples of the determined crystal
structures, which from the crystallographic point of view
appear to have interesting properties, are discussed. The dis-
cussion of the solid-state structures of the remaining com-
pounds can be found in the Supporting Information.
Despite a reactand stoichiometry of 2:1, diaminoguanid-
inium salt 6 was only obtained as its monodeprotonated 1Ј-
hydroxy-1H,1ЈH-5,5Ј-bitetrazol-1-olate salt (stoichiometry
31]
Figure 2. Molecular unit of crystalline 7 with its labeling scheme.
Ellipsoids are shown at the 50% probability level.
1:1) with the inclusion of one molecule of crystal water per
molecular unit. Compound 6 crystallizes in the triclinic
¯
space group P1 with two molecules in the unit cell and a
–
3
In the structure of 15, no proton transfer between 1 as
the acid and 2-methyl-5-aminotetrazole as the base is ob-
served. It must be described as a cocrystallization product
between the two mentioned species (Figure 3). The fact that
5-amino-2-methyl-2H-tetrazole is a weaker base than 5-
amino-1-methyl-1H-tetrazole has been demonstrated in
density of 1.729 gcm . In the structure of 6, the monode-
protonated anions build long chains along the a axis by
formation of very strong hydrogen bonds H1 ···O2 and
H1···O2 , which are nearly symmetrical and similar to those
observed in the HF2 anion (Figure 1).
i
ii
–
[
32]
similar crystal structures before.
Compound 15 crys-
tallizes in the monoclinic space group C2/c with four mole-
–3
cules in the unit cell and a density of 1.608 gcm , which is
remarkably lower than 14 owing to the lack of ionic attract-
ive forces, although the structure is stabilized by strong
hydrogen bonds. The most important, since it is the shortest
i
ii
hydrogen bond, is found between O1 –H1···N8 with a dis-
tance of 1.32(19) Å. This is only slightly longer than the O–
H bond length in 1 [1.192(19) Å]. Unlike in all ionic struc-
tures described in this work, the two tetrazole moieties in 1
are distorted as evidenced by the torsion angle (N1–C1–
i
i
C1 –N1 ) of –122.98(16)°.
Figure 1. View of a selected detail of the crystal structure of 6
i
showing the nearly symmetric hydrogen bridge O2–H2···O1 . Ellip-
soids are shown at the 50% probability level. Symmetry code: (i)
–1 + x, y, z.
In agreement with 6, triaminoguanidinium salt 7 could
be obtained in the crystalline state with one molecule of
crystal water as a compound with 1:1 stoichiometry. It crys-
¯
tallizes in the triclinic space group P1 with two molecules Figure 3. Molecular unit of crystalline 15 with its labeling scheme.
in the unit cell and a comparatively high density of Ellipsoids are shown at the 50% probability level. Symmetry codes:
–
3
(i) –x, y, 0.5 – z; (ii) –x, y, 0.5 – z.
1
.749 gcm , which could be explained by the stronger at-
tractive ionic forces between the twice positively/negatively
charged ions. The coordination geometry of a single anion
consists of interactions with four triaminoguanidinium cat-
ions and two hydrate water molecules. There are only very
few ionic examples of twice positively charged triamino-
Spectroscopy
NMR Spectroscopy
Compounds 1–16 were investigated using H and 13C
1
[
15]
15
guanidinium cations (e.g., its sulfate salt) (Figure 2).
NMR spectroscopy. Additionally, N NMR spectra of 1
Eur. J. Inorg. Chem. 0000, 0–0
4
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
as well as of its ammonium salt 2 were recorded. For better 167.7 ppm for the substituted tetrazolium cations in 13–16,
comparison, all spectra were measured using [D ]DMSO as respectively.
6
solvent and all chemical shifts are given with respect to
In the 15N NMR spectrum of the free acid 1, a set of
four signals according to the four chemically nonequivalent
1
13
15
TMS ( H, C) or nitromethane ( N).
In the proton NMR spectra of 2, 3, 10, 11, 13, 14, and nitrogen atoms of the two tetrazole moieties [C symmetry
i
15, all N-connected protons contained in the cation are vis- of the 5,5Ј-bis(tetrazole 1-oxide) molecule] can be found
ible as only one singlet, which appears between δ = 7.07 (Figure 4). A partial assignment was undertaken according
and 8.72 ppm. For the 5-aminotetrazolium salt 13, an ex- to a gauge-including atomic orbital (GIAO) NMR spectro-
[
33]
ceptionally high value of δ = 11.90 ppm is observed. Except scopic calculation with Gaussian 09, which gave the rela-
for the ammonium salt 2, a fast proton exchange causes the tive NMR spectroscopic shifts of both 1 and 2 in good ac-
coincidence of the signals of the chemically nonequivalent cordance. Thereafter, the β-nitrogen atoms N3 and N2 are
protons. For the guanidinium derivatives 4–8, the signals of shifted to the lowest field. For unsubstituted 5,5Ј-bitetraz-
chemically nonequivalent protons can be distinguished well. ole, two signals at δ = 3 and –66 ppm are observed,[ ac-
The NH2 protons of 4 are visible as a singlet at δ = cording to the β- (δ = 3 ppm) and the α-nitrogen atoms (δ
9]
7.10 ppm, whereas two singlets appear for the protons of 7 = –66 ppm). In the spectra of 1 and 2, N3 is assigned to
and 8 for NH [δ = 4.46 (7), 7.03 ppm (8)] and NH [δ = signals at δ = –2.0 ppm (1, 2) and N2 to signals at δ =
2
8.62 (7), 8.27 ppm (8)]. The amino- and diaminoguanid- –18.7 (1) and –19.8 ppm (2). A larger difference, however,
inium salts 5 and 6 reveal three separated signals for is observed for the chemical shifts of the α-nitrogen atoms
CNHNH [δ = 4.60 (5), 5.15 ppm (6)], CNH [δ = 7.01 (5), of 1 and 2, since, unlike N4, N1 is hydroxyl-substituted. For
2
2
7
.10 ppm (6)], and CNHNH [δ = 8.89 (5), 8.50 ppm (6)]. N4, signals at δ = –52.3 (1) and –53.6 ppm (2) are observed,
2
In contrast to the hydrazinium salt 3, in the spectra of the which is comparable to the chemical shift of the α-nitrogen
hydrazino-moiety-containing compounds 9 and 12, the sig- atoms in unsubstituted 5,5Ј-bitetrazole (δ = –66 ppm),
nals for NH [δ = 8.31 (9), 9.57 ppm (12)] can be distin- whereas the signal for the hydroxylated N1 are found at δ
+
guished from the signals for NH3 [δ = 7.80 (9), 6.38 ppm = –110.5 (1) and –107.5 ppm (2), respectively. In the spec-
(12)]. Furthermore, the existence of the methyl groups in trum of 2, an additional signal at δ = –359.7 ppm for the
the cations of 14 and 15 is evidenced by resonances at δ = ammonium cation is visible as a quintet due to NH cou-
1
3
1
.67 (14) and 4.07 ppm (15). For the anionic species in 2– pling ( J
= 71.6 Hz).
N,H
6, a single resonance at δ = 134.5–135.8 ppm in the 13
C
NMR spectrum is observed, which does not significantly
differ from the signal of the neutral species 1 (δ =
Vibrational Spectroscopy
135.8 ppm). However, this signal differs significantly from
The assignments of the observed absorption bands to the
the signals observed for the precursor molecules glyoxime corresponding functional groups was undertaken on the ba-
[
34]
(
δ = 145.9 ppm), dichloroglyoxime (δ = 131.2 ppm), and di- sis of values found in literature. The Raman and IR spec-
azidoglyoxime (δ =136.5 ppm), which makes NMR spec- tra of all investigated compounds show absorptions of the
troscopy the analytical procedure of choice to monitor the aromatic ring system of the 5,5Ј-bis(tetrazole 1-oxide) anion
completeness of these reactions. A second signal of the cat- at 1350–1550 and 700–1350 cm–1 [ν(NN), ν(NCN), γ(CN),
ion is visible in each carbon NMR spectrum in the range δ(aromatic tetrazole oxide ring)], which partially are in the
–
of δ = 158.6–160.2 ppm for the guanidine derivatives 4–8, fingerprint region. Furthermore, the N–O vibration can
–1
in the range of δ = 157.8–159.6 ppm for the carbohydrazide barely be observed in a range of 1550–1600 cm . In all
derivatives 9–11, δ = 162.5 ppm for 12, and δ = 154.2– cases, hydroxyl groups, which are involved in hydrogen
Figure 4. 15N NMR spectra of 1 and 2. Chemical shifts are given with respect to MeNO
.
2
Eur. J. Inorg. Chem. 0000, 0–0
5
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
bonding, can be detected as absorptions in the range of contained free acid 1 and salts 2–16 (about 1.5 mg of each
–
1
3
209–3454 cm [ν(O–H)].
energetic material) were performed in covered Al containers
In the Raman spectrum of the ammonium salt 2, an ab- with a hole (0.1 mm) in the lid for gas release and a nitrogen
–
1
+
[35]
sorption at 3075 cm
[νsym(NH )] can be observed, flow of 20 mL per minute with a Linseis PT 10 DSC
4
whereas the IR spectrum exhibits several signals in the calibrated by standard pure indium and zinc at a heating
–
1
–1
range of 3047–3180 cm , which refer to the asymmetric rate of 5 °Cmin . The decomposition temperatures are
valence vibrations of the ammonium cation.
given as absolute onset temperatures.
Vibrations of the hydrazinium cation in 3 as well as those
Except for the 1-amino-3-nitroguanidinium salt 8, the
of the hydrazino groups of diaminourea in compound 9 and nonionic compound 15, and the 1,5-diaminotetrazolium
the hydrazine moiety in the cation of 12 can be observed in salt 16, the decomposition temperatures for all remaining
–
1
+
the range of 3059–3434 cm [νasym(NH /NH )] and also salts are at or even above 180 °C, which is a necessary
2
3
–
1
+
in the range of 1535–1620 cm
δasym(NH /NH )]. Furthermore, the carbonyl moiety of decomposes at about 210 °C. The low decomposition tem-
[δsym(NH /NH ), requirement for possible RDX replacements, which itself
2 3
+
2
3
the diaminourea cation of 9 reveals a sharp absorption perature of the 1-amino-3-nitroguanidinium salt 8 is in
–
1
band at 1702 cm , whereas the stretching and deformation agreement with other energetic compounds based on this
[
23]
vibrations of the tetrazine ring (in 12) are located in the cation in the literature. Also, the low decomposition tem-
same region as those of the bitetrazole dioxide ring system perature of 16 is in agreement with other 1,5-diaminotet-
[
36]
discussed above.
razolium-based materials.
This is in contrast to the 5-
The spectra of the guanidine derivatives 4–8 show ab- aminotetrazolium salt 13, which is stable up to 224 °C. A
sorption bands of valence vibrations of the amino groups potential reason for the low decomposition temperature of
–
1
at 3000–3500 cm [νsym(NH ), ν
(NH )]. Furthermore, 15 (155 °C) is possibly the lack of ionic attractive forces in
2
asym
2
deformation vibrations of the amino groups can be found the solid state, which can be easily compared to the ionic
–
1
at 1577–1690 cm [δsym(NH ), δ
(NH )]. Moreover, va- structure of 14, the sister compound, which is methylated
2
asym
2
lence vibrations of the C–N double bonds in the guanidine at the 1-position of the tetrazole ring and is thermally stable
–
1
part of the cations appear at 1680–1470 cm [ν(C=N)]. An- up to 192 °C. The highest decomposition temperature is ob-
other characteristic absorption band of the nitroamine in served for the ammonium salt 2 (290 °C); however, the
–
1
the cation of 8 is observed at 1262 cm in the IR spectrum. hydrazinium salt 3 as well as the other hydrazino-moiety-
The spectra of both compounds 10 and 11 show the sym- containing compounds 9–12 decompose significantly earlier
metric deformation vibration of the protonated hydrazino at 220–224 °C (3, 9–11) and 180 °C (12). A comparison be-
groups, the absorption bands of which are located at tween the guanidinium salts 4–7 shows that 4 reveals by
–
1
+
1
615 cm [δsym(NH )] and are clearly visible in the Raman far that the highest decomposition temperature is 274 °C,
3
spectra.
δasym(NH )] can be assigned to the C=O valence vibration water in the hydrated compounds 6–9 and 11 can be ob-
A
further strong absorption at 1677 cm–1 whereas 5–7 decompose at 204–210 °C. The loss of crystal
+
[
3
of the carbohydrazide moiety in both compounds. More- served as endothermic steps in the cases of 6 (160 °C), 8
over, the asymmetric valence vibrations of the NH group of (140 °C, immediately before decomposition), and 11
–
1
the hydrazino moieties is observed at 3029 cm [νasym(NH), (110 °C). In 6, the hydrate water seems to be comparatively
–
1
1
0] and at 3074 cm [νasym(NH), 11]. The asymmetric C– strongly bonded by hydrogen bonds, because it cannot be
H valence vibration of the methyl group in the IR spectra removed before 160 °C. Also, melting points are observed
as well as the symmetric one in the Raman spectra of com- in the DSC traces of 5, 6, and 14–16, as evidenced by (ad-
–
1
pounds 14 and 15 can be observed at 2960 and 2966 cm
ditional) endothermic steps. In the cases of 5, 6, 14, and
–
1
[
νsym(CH )] and at 2850–2960 cm [νasym(CH )]. Also, 16, the materials melt right before decomposition, whereas
3
3
the –CH deformation vibration is visible in absorptions at adduct 15 has a melting point that is somewhat below its
3
–
1
1
439 [δasym(CH )] and 1390 cm [δsym(CH )] in the spectra decomposition temperature (T = 125 °C). For the free acid
3
3
m
of 15.
1, which crystallizes as a dihydrate, a decomposition tem-
In contrast to the aminotetrazolium salts 13–15, which perature of 214 °C and a dehydration temperature of 115 °C
have their very sharp absorption bands at 1703 (13), 1693 were recorded. By heating the compound to 140 °C for
–
1
(
(
14), and 1659 cm (15) [δasym(NH )] and 1624 (13), 1616 24 h, the crystal water could completely be removed as evi-
2
–
1
14), and 1627 cm (15) [δsym(NH )], the diamino-substi- denced by elemental analysis. However, the crystals were
2
tuted cation in 16 exhibits a broadened signal at 1577– destroyed upon dehydration, so that no crystal structure of
–
1
1
731 cm [δsym(NH ), δ
(NH )] because of the existence the water-free compound could be obtained. Due to its
2
asym
2
of two amino groups.
hygroscopicity, dehydrated 1 returns into its dihydrate after
standing for several days at ambient humidity. Further-
more, there is no risk of losing the hydrate water at room
temperature and low air humidities over time. The missing
Thermal Behavior and Sensitivities
endothermic event in the DSC curves of the hydrated salts
Differential scanning calorimetry (DSC) measurements 7 and 9 indicates that either the crystal water was lost after
to determine the melt and decomposition temperatures as standing at ambient temperatures over time or it is released
well as the dehydration temperature of the crystal water that during decomposition of the salt.
Eur. J. Inorg. Chem. 0000, 0–0
6
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
The impact sensitivity tests of compounds 1–16 were car- were determined to be the most sensitive, although it should
[
37]
ried out according to STANAG 4489
modified instruc- be mentioned that the human body can generate up to
[
38]
tion using a BAM (Bundesanstalt für Materialforschung 25 mJ of static electricity through normal activities, which
und -prüfung) drop hammer. The friction-sensitivity tests can easily set off the most sensitive explosives, but is well
were carried out according to STANAG 4487
instruction using the BAM friction tester. The classifica- presented here.
tion of the tested compounds resulted from the “UN Rec-
[39]
[40]
modified below the value found for the most sensitive compounds
[
41]
[
42]
ommendations on the Transport of Dangerous Goods.”
Additionally, all compounds were tested for their sensitivity Theoretical Calculations
towards electrical discharge with the Electric Spark Tester
ESD 2010 EN.
[
43]
Heats of Formation
First, it has to be mentioned that the precursor material
diazidoglyoxime, as one would expect for a covalent diazide,
was determined to be very impact- and extremely friction-
sensitive (IS: 1.5 J, FS: Ͻ5 N) and required extreme caution
if being isolated. In contrast, cyclized 1 as its dihydrate
proved to be impact-insensitive (Ͼ4 J) and only moderately
sensitive towards friction (216 N). However, the free acid 1,
which was dried at 140 °C for 24 h, revealed sensitivities of
Usually energetic materials tend to explode in bomb
calorimetric measurements. Consequently, doubtful com-
bustion energies are obtained. Therefore, heats of formation
of energetic materials mostly are calculated theoretically. In
our group we combine the atomization energy method
[Equation (1)] with CBS-4M electronic enthalpies (Table 1),
which has been shown to be suitable in many recently pub-
[44]
lished studies.
CBS-4M energies of the atoms, cations,
4
J (IS) and 10 ⁿ (FS) and therefore needs to be handled
and anions were calculated with the Gaussian 09 (revision
with greater care.
[33]
A1) software package
and checked for imaginary fre-
Owing to their impact sensitivity of more than 35–40 J,
compounds 2, 5, 11, and 12 can be classified as less sensi-
tive, which in the case of 11 probably can be explained by
a dihydrate formation. The guanidinium salt 4 is even insen-
sitive towards impact with a value of more than 40 J. Com-
pounds 3 and 6–10 show sensitivities in the range of 9–20 J
and therefore can be classified as sensitive towards impact.
Expectedly, the protonated tetrazolium salts 13, 14, and 16
as well as the hydrogen-bond-stabilized adduct with 2-
methyl-5-aminotetrazole (15) reveal the lowest values for
impact sensitivity and are therefore classified as sensitive
quencies. Values for Δ H° (atoms) were taken from the
NIST database.
f
[45]
f f
Δ H°(g,M,298) = H(molecule,298) – ΣH°(atoms,298) + ΣΔ H°(atoms,298) (1)
Table 1. CBS-4M results and gas phase enthalpies.
Formula
–H298[a]
Δ
H(g)[b]
f
–1
[a.u.]
[kJmol ]
1
C
C
C
NH
4
N
CH
CH
CH
CH N
CH
CH
2
2
2
H
HN O
8 2
N O
8 2
2
N
8
O
2
–
664.816722
664.334858
663.687267
56.796608
689.1
420.7
587.7
635.8
774.1
571.9
671.6
772.7
2012.3
877.0
1726.2
550.6
1553.2
2307.0
981.8
935.2
277.8
1053.4
–
BTO
BTO
2–
2–
+
+
(14, 15) or very sensitive towards impact (13, 16). Except NH
4
H
+
+
N
G
AG
2
5
2
H
5
112.030523
205.453192
260.701802
315.949896
371.348640
464.914496
335.970626
448.979375
449.181787
517.532665
313.534215
352.779155
352.445333
368.793548
for 11, no apparent desensitization of the materials is ob-
served when hydrate water is included as it is the case for
+
+
+
+
6
7
8
N
N
N
3
4
5
+
6–9.
+
DAG
2
+
+
For the friction sensitivity the same trends as for the im- TAG
pact sensitivity were observed. However, a few exceptions ANQ
were observed [e.g., bishydrazinotetrazinium salt 12, which
is friction-sensitive (80 N) but insensitive towards impact
1
6
7
0
N
N
6
+
+
5
O
2
2
+
+
DAU
4
O
Oxahy+
C
2
C
2
C
2
H
7
H
8
H
8
N
N
N
O
2
+
4
4
8
2+
2+
Oxahy
BHT
O
2
(
40 J)]. The opposite behavior is observed for 15, which is
2+
2+
insensitive towards friction (360 N) but impact-sensitive 5-AT+
+
4 5
CH N
+
1
2
1
-Me-5-AT+
-Me-5-AT
C
C
2
H
H
6
N
N
5
(8 J). Furthermore, again the guanidinium salt 4 is the least
2
5
5
+
sensitive compound (Ͼ360 N), and 2, 10, and 15 can also
be classified as less sensitive. The remaining compounds fill
the space between being less sensitive (360 N) to very sensi-
tive (80–10 N), with the 5-aminotetrazolium salt (13, 72 N)
being the most sensitive compound.
,5-DAT+
5 6
CH N
[
a] CBS-4M enthalpy at room temperature. [b] Calculated gas
phase heat of formation by the atomization equation.
The sensitivity towards electrical discharge next to the
For calculation of the solid-state energy of formation
compound itself depends on the grain size of the material, (Table 2) of 1–16, the lattice energy (U ) and lattice en-
L
whereas larger crystals tend to be less sensitive and powders thalpy (ΔH ) were calculated from the corresponding mo-
L
show enhanced sensitivity. For this reason, the grain size of lecular volumes (obtained from X-ray elucidations) accord-
the materials is given in the Experimental Section. With re- ing to the equations provided by Jenkins and Glasser et
[
46]
gard to the grain size, the guanidinium (4) as well as the 1- al. With the calculated lattice enthalpy (Table 3), the gas-
methyl-5-aminotetrazolium salt 14 were determined to be phase enthalpy of formation was converted into the solid-
the least sensitive compounds, and the hydrazinium salt 9 state (standard conditions) enthalpy of formation. In the
(0.10 J) as well as the 1-amino-3-nitroguanidinium (8) and case of the neutral compounds 1 and 15, their sublimation
the 3,6-dihydrazino-1,2,4,5-tetrazinium salt 12 (both 0.08 J) enthalpy was calculated with Trouton’s rule (ΔHsub [kJmol]
Eur. J. Inorg. Chem. 0000, 0–0
7
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
Table 2. Solid-state energies of formation (Δ
f
U°).
ΔH
[
a]
[b]
3
[c]
[d]
[e]
Δn[f]
[g]
[h]
Δ
[
f
H°(g)–
V
[nm ]
M
U
L
L
Δ
f
H°(s)
Δ
f
U°(s)
Formula
M
[gmol ]
r
f
Δ U°(s)
1
–1
–1
–1
–1
–1
–1
kJmol ]
[kJmol ]
[kJmol ]
[kJmol ]
[kJmol ]
[kJ kg ]
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
205.9
91.58#
1558.9
1458.3
1323.5
1262.3
542.1
2041.8
592.4
2093.0
1216.0
2136.9
1906.8
491.4
114.3
300.5
677.7
408.0
668.6
409.6
316.7
222.1
–20.7
472.9
–479.2
987.9
911.1
876.5
1164.2
990.6
9
136.6
325.3
707.4
442.7
708.3
443.1
352.6
259.3
11.6
517.5
–442.0
1020.1
935.9
903.8
1203.8
1017.9
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
2
2
2
4
4
3
3
3
3
6
6
4
3
4
6
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
6
N
N
8
O
4
206.12
204.15
234.18
288.28
318.31
277.27
292.27
325.10
278.23
406.33
324.26
202.18
255.20
269.18
368.34
270.22
662.8
1859.4
2136.0
1731.5
1930.9
0.188
0.225
0.292
0.331
0.242
0.253
0.255
0.232
0.365
0.237
0.290
0.230
0.254
1551.4
1450.9
1316.2
1254.8
538.7
2029.4
582.5
2080.6
1208.5
2122.1
1896.9
486.5
10
12
14
16
13.5
14.5
15
13
18
15
13
10
11
16
11
8
10
O
2
1592.9
3020.2
1535.5
2225.0
1598.2
1206.5
797.4
10
12
14
11
12
11
10
14
12
N
12
14
16
13
14
13
12
16
12
O
O
O
O
O
O
O
O
O
2
2
2
3
3
6
4
6
6
N
N
N
N
N
N
N
N
[
h]
951.8
[
h]
2358.5
[
h]
814.5
[
h]
2072.3
1688.8
1657.7
2894.7
1402.5
1355.8
1244.7
1474.0
41.6
0
1
2
3
4
5
6
1273.5
–1363.3
3266.7
3667.0
3356.8
3268.1
3766.8
[
h]
8
5
7
N
16
O
O
O
2
2
2
N
N
13
474.4
479.3
13
80.5[
i]
N
O
12
18
2
0.246
478.5
483.4
6
N
14
O
2
[
a] Gas-phase enthalpies of formation (those of the ionic compounds are taken as the respective sums of the noninteracting component
ions). [b] Molecular volume of the molecular moiety in the crystal structure. [c] Lattice energy calculated by Jenkins and Glasser equations.
d] Lattice enthalpy calculated by Jenkins and Glasser equations. [e] Solid-state molar heat of formation. [f] Change in moles of gaseous
[
components. [g] Molar energy of formation. [h] Energy of formation (mass-dependent). [h] Gas-phase enthalpy of included water has
been subtracted. [i] Sublimation enthalpy calculated by the Trouton rule.
Table 3. Energetic properties and detonation parameters of 1–8.
1
2
3
4
5
6
7
8
Formula
C
206.12
Ͼ40
216
0.50
54.4
–23.28
214
1.811
114.3
662.8
2
H
6
N
8
O
4
C
204.18
35
360
0.25
68.6
–47.02
290
1.800
300.5
1592.9
2
H
8
N
10
O
2
C
234.18
9
252
0.10
71.8
–47.82
220
1.725
677.7
3020.2
2
H
10
N
12
O
2
C
288.28
Ͼ40
Ͼ360
0.50
68.0
–66.60
274
1.639
408.0
1535.5
4
H
12
N
14
O
2
C
318.31
40
324
0.25
70.4
–65.35
228
1.596
668.6
2225.0
4
H
14
N
16
O
2
C
277.27
12
168
0.25
65.7
–49.06
204
1.729
409.6
1598.2
3
H
11
N
13
O
3
C
292.27
15
120
0.25
67.1
–49.27
210
1.749
316.7
222.1
3
H
12
N
14
O
3
C
325.10
10
192
0.08
56.0
–27.06
140
1.778
222.1
797.4
3 11 13 6
H N O
–
1
M
IS [J]
FS [N]
r
[gmol ]
[
a]
[
b]
[
c]
ESD-test [J]
[
[
d]
e]
N [%]
Ω [%]
T
dec. [°C][f]
–
3 [g]
ρcalcd. [gcm ]
–1 [h]
Δ
Δ
f
m
H ° [kJmol ]
U° [kJkg ]
–
1 [i]
f
Detonation parameters calculated with EXPLO5.05
–
1 [j]
–
Δ
E
E
U° [kJkg ]
5043
3625
331
8764
810
4213
2939
316
8817
843
5415
3433
340
9159
863
3581
2606
233
7917
806
4160
2852
243
8111
825
4439
3072
294
8598
837
2981
2342
246
8028
844
5118
3599
325
8796
840
[
k]
T
[K]
[
l]
pCJ [kbar]
–1 [m]
D [ms ]
Gas vol. [Lkg ]
–1 [n]
[
o]
Isp [s]
240
211
246
194
212
215
179
241
[
(
a] Impact sensitivity (BAM drop hammer, 1 of 6). [b] Friction sensitivity (BAM friction tester, 1 of 6). [c] Electrostatic discharge device
OZM). [d] Nitrogen content. [e] Oxygen balance.[50] [f] Decomposition temperature from DSC (β = 5 °C/min). [g] Estimated from X-ray
diffraction. [h] Calculated (CBS-4M) heat of formation. [i] Calculated energy of formation. [j] Energy of explosion. [k] Explosion tempera-
ture. [l] Detonation pressure. [m] Detonation velocity. [n] Assuming only gaseous products. [o] Specific impulse calculated at isobaric
(60 bar) rocket conditions.
=
188Tm [K]).[47] These molar standard enthalpies of for- tion for the oxalyldihydrazidinium salt 11 (–1363 kJkg–1).
mation [Δ H°(s)] were used to calculate the molar solid-state Besides 11, the diaminouronium salt 9 also reveals a com-
f
–1
energies of formation (ΔU ) according to Equation (2) (see paratively low value of 42 kJkg , which in both cases is
m
Tables 3 and 4).
due to their high lattice enthalpy (both are 1:1 compounds
with double-charged an-/cations) and hydrate formation.
The highest energies of formation are found for the tetrazol-
ium derivatives, which have a large number of inherently
m m
ΔU = ΔH – ΔnRT
(Δn is the change in moles of gaseous components)
(2)
The solid-state energies of formation range from highly energetic N–N single and double bonds in combination
–
1
positive values (Ͼ3000 kJkg ) for the hydrazinium salt (3) with a solvent-free crystallization such as for the 5-amino-
–1
as well as the bis(hydrazinotetrazinium) (12) and the tet- and 1,5-diaminotetrazolium derivatives 13 (3667 kJkg )
–1
razolium derivatives (13–16) to negative energies of forma- and 16 (3767 kJkg ).
Eur. J. Inorg. Chem. 0000, 0–0
8
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
Table 4. Energetic properties and detonation parameters of 9–16.
10 11 12
9
13
14
15
16
RDX
HMX
Formula
3 10 12 4 6 14 16 6 4 12 12 6 4 8 16 2 3 5 13 2 4 7 13 2 6 12 18 2 3 6 14 2 3 6 6 6 4 8 8 8
C H N O C H N O C H N O C H N O C H N O C H N O C H N O C H N O C H N O C H N O
–
1
M
IS [J]
FS [N]
ESD test [J]
N [%]
r
[gmol ]
278.23
20
240
406.33
20
360
324.26
40
288
202.18
40
80
255.20
4
72
269.18
6
240
368.34
8
360
270.22
2
160
222.12
296.16
[a]
[51]
[51]
7.5
7
[b]
[51]
[51]
120
112
[
c]
0.40
64.6
–40.26
220
0.40
55.2
–51.19
224
0.35
51.8
–39.48
222
0.08
71.8
–51.24
180
0.30
71.4
–40.75
224
0.50
67.6
–56.46
192
0.40
68.5
–69.50
155
0.35
65.4
–41.45
170
0.2
0.2
[d]
37.84
–21.61
205
37.84
–21.61
275
[e]
Ω [%]
T
dec. [°C][f]
–
3 [g]
ρcalcd. [gcm ]
1.800
1.847
1.885
1.787
1.839
1.762
1.608
1.828
1.858
1.944
(100 K)
116.1
[52]
[53]
(90 K)
–1
Δ
f
H
m
° [kJmol ] –20.7
472.9
–479.2
987.9
911.1
903.8
1164.2
3268.1
990.6
86.3
[
h]
Δ
f
U° [kJkg–1][i]
41.6
1273.5
–1363.3
3266.7
3667.0
3356.8
3766.8
489.0
492.5
Detonation parameters calculated with EXPLO5.05
–
1 [j]
–
T
Δ
E
U° [kJkg ]
3595
2743
277
4868
3303
333
8878
789
3072
2452
275
8203
826
4961
3527
320
8788
767
5576
4009
358
9097
760
5264
3665
313
8718
751
4828
3325
249
8090
756
5625
3970
361
9160
774
6190
4232
380
8983
734
6185
4185
415
9221
729
[k]
E
[K]
[l]
pCJ [kbar]
–1 [m]
D [ms ]
8306
–1
Gas vol. [Lkg ] 832
[n]
I
sp [s][o]
191
217
175
236
250
240
232
252
258
258
[
(
a] Impact sensitivity (BAM drop hammer, 1 of 6). [b] Friction sensitivity (BAM friction tester, 1 of 6). [c] Electrostatic discharge device
OZM). [d] Nitrogen content. [e] Oxygen balance. [f] Decomposition temperature from DSC (β = 5 °C/min). [g] Estimated from X-ray
diffraction. [h] Calculated (CBS-4M) heat of formation. [i] Calculated energy of formation. [j] Energy of explosion. [k] Explosion tempera-
ture. [l] Detonation pressure. [m] Detonation velocity. [n] Assuming only gaseous products. [o] Specific impulse calculated at isobaric
(60 bar) rocket conditions.
Detonation Parameters
handling, which is rather not the case for 3, 13, and 16. If
a material should reveal detonation parameters that exceed
those of RDX or even HMX, it is advantageous to have a
combination of a high crystal density and at the same time
a high energy of formation. Unfortunately, in this study, on
the one hand, the densest materials do not have the highest
energies of formation, and on the other hand, the com-
pounds with the highest energies of formation do not reveal
the highest densities.
The detonation parameters of 1–16 (Tables 3 and 4) were
calculated by using the program EXPLO5 V5.05.
program is based on the steady-state model of equilibrium
detonation and uses Becker–Kistiakowsky–Wilson’s equa-
[
48]
The
tion of state (BKW E.O.S) for gaseous detonation products
and Cowan–Fickett E.O.S. for solid carbon.[
49]
The pro-
gram is designed to enable the calculation of detonation
parameters at the Chapman–Jouguet point. The calcula-
tions were performed using the maximum densities accord-
ing to the crystal structures at low temperatures as well as
the solid-state energies of formation and the sum formula
of the respective compound.
Conclusion
From this combined theoretical and experimental study
The calculated detonation parameters are compared to the following conclusions can be drawn.
two prominent secondary explosives that are widely used,
Firstly, 1H,1ЈH-5,5Ј-bitetrazole-1,1Ј-diol (1) can be de-
namely, 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and protonated in aqueous media by using different nitrogen-
1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX). For rich bases. The diammonium (2), dihydrazinium (3), bis(gu-
consistency, the low-temperature densities of RDX and anidinium) (4), bis-aminoguanidinium (5), diaminoguanid-
HMX were also used. The detonation velocities reach from inium (6), triaminoguanidinium (7), 1-amino-3-nitroguan-
–
1
7
917 (4) to 9160 ms (16), whereas apart from three com- idinium (8), diaminouronium (9), bis(oxalyldihydrazidin-
pounds (3, 13, 16), the large majority do not reach the deto- ium) (10), oxalyldihydrazidinium (11), 3,6-dihydrazino-
–
1
nation velocity calculated for RDX (8983 ms ), and even 1,2,4,5-tetrazinium (12), 5-aminotetrazolium (13), 5-amino-
the best performing material in terms of its detonation 1-methyltetrazolium (14), 1,5-diaminotetrazolium (16) salts,
velocity (16) does not reach the value calculated for HMX and a bis(2-methyl-5-aminotetrazole) adduct (15) were iso-
–
1
(
9221 ms ). The same argumentation applies to the deto- lated and fully characterized. In the cases of 5, 7, 11, and
nation pressures, for which we find values that range from 12, a 1:1 stoichiometry of the salts was observed with
33 (4) up to 361 kbar (16), which is below the values calcu- double-protonated cations and double-deprotonated
2
lated for RDX as well as HMX. It has to be mentioned 1H,1ЈH-5,5Ј-bitetrazole-1,1Ј-diol. For 2–5 and 10, a cation/
that for a promising RDX replacement, not only high deto- anion ratio of 2:1 was observed, whereas in the cases of 6,
nation performance plays an important role, but also the 8, 13, and 14 a 1:1 stoichiometry with monodeprotonated
sensitivities needed to meet today’s requirements for safe anions occurs. Compound 15 is an adduct of 1 and 2-
Eur. J. Inorg. Chem. 0000, 0–0
9
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
methyl-5-aminotetrazole, which is stabilized by strong hy- tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
drogen bonds. With 7, a rare example of an ionic com-
pound that bears a twice positively charged triaminoguani-
dinium cation was isolated. In the crystal structures that Glyoxime: NaOH (27.5 g, 0.69 mol) was dissolved in water (75 mL)
contain monodeprotonated 1H,1ЈH-5,5Ј-bitetrazole-1,1Ј- and the solution was cooled to 0 °C in a salt ice bath. Hydroxyl-
ammonium chloride (69.5 g, 1.00 mol) was added while stirring.
diol, the anions are connected through very strong hydro-
gen bonds similar to those observed for the HF2 anion.
–
Glyoxal (72.5 g, 0.50 mol, 40% w/w in H O) was added to the ob-
2
tained solution while the temperature was kept below 10 °C. After
Secondly, the free acid 1, which crystallizes as a dihydrate
complete addition of the glyoxal, the solution was further chilled
in the salt ice bath until glyoxime precipitated. The solid was re-
moved by suction filtration and washed with a little ice water to
remove the remaining sodium chloride.
(
IS: Ͼ40 J, FS: 216 N), can be dehydrated at 140 °C (24 h),
thereby resulting in remarkably enhanced sensitivities (IS
J, FS: 10 ⁿ). However, water-free 1 is hygroscopic and thus
4
turns into the dihydrate over time at ambient conditions.
The dihydrate does not lose its crystal water over time, even
at low air humidities.
Thirdly, the highest thermal stability (290 °C) is observed
for the diammonium salt 2, which we call ABTOX (ammo-
nium BTO explosive). As expected, the 3-amino-1-nitrogua-
Dichloroglyoxime: Glyoxime (17.6 g, 200 mmol) was suspended in
ethanol (200 mL). Cl
2
gas was bubbled through the suspension at
–20 °C until the green suspension turned into a yellowish solution.
The solution was warmed slowly to room temperature while releas-
ing dissolved chlorine. Then the solvent was removed under vac-
uum and the remaining solid was resuspended in chloroform
nidinium salt 8 decomposes at the lowest observed tempera- (50 mL), stirred for 15 min at room temperature and filtered to
1
ture of 140 °C, which is due to the thermal instability of the yield 26.6 g (85%) of the colorless product. H NMR ([D
6
]DMSO,
]DMSO, 25 °C): δ = 131.2
(156.96): calcd. C 15.30, H 1.28, N 17.85;
found C 15.65, H 1.25, N 17.49.
-amino-1-nitroguanidinium cation.[
And finally, the most promising compounds in terms of
explosive performance are the dihydrazinium salt 3 (D =
23]
13
3
25 °C): δ = 13.10 ppm. C NMR ([D
ppm. C Cl
6
2
H
2
2 2 2
N O
–
1
9
159 ms , p = 340 kbar, I = 246 s), the 5-aminotetraz- Diazidoglyoxime: Dichloroglyoxime (3.13 g, 20 mmol) was dis-
CJ sp
–
1
olium salt 13 (D = 9097 ms , p = 358 kbar, Isp = 250 s), solved in dimethyl formamide (40 mL). At 0 °C, sodium azide
CJ
–1
(
2.93 g, 45 mmol) was added. The suspension was stirred for 20 min
and the 1,5-diaminotetrazolium salt 16 (D = 9160 ms , p
CJ
at 0 °C and water (100 mL) was added. The precipitate was filtered,
washed with water (100 mL), and air-dried to yield 2.85 g (84%) of
the colorless product. DSC (5 °Cmin ): 170 °C (dec.). IR (atr): ν˜
3209 (w), 2170 (w), 2123 (w), 1622 (w), 1400 (w), 1361 (w), 1286
m), 1013 (vs), 930 (m), 920 (s), 855 (s), 731 (s) cm . Raman
1064 nm, 300 mW, 25 °C): ν˜ = 2166 (8), 2129 (5), 2091 (3), 1621
=
361 kbar, Isp = 252 s); however, their utility as RDX re-
placements is restricted by their high sensitivities (3: IS: 9 J,
FS: 252 N; 13: IS: 4 J, FS: 72 N; 16: IS: 2 J, FS: 160 N).
–
1
=
–
1
(
(
Experimental Section
(100), 1457 (14), 1390 (12), 1216 (19), 1034 (3), 882 (20), 672 (3),
–
1
1
13
442 (6) cm . H NMR ([D
6
]DMSO, 25 °C): δ = 12.08 ppm.
C
Caution! 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol and its salts are ener-
getic materials with increased sensitivities towards shock and fric-
tion. Therefore, proper safety precautions (safety glass, face shield,
earthed equipment and shoes, Kevlar gloves, and ear plugs) have
to be applied when synthesizing and handling the described com-
pounds.
NMR ([D ]DMSO, 25 °C): δ = 136.5 ppm. C H N O
6
2 2 8 2
(170.09):
calcd. C 14.12, H 1.19, N 65.88; found C 14.38, H 1.46, N 66.01.
BAM drop hammer: 1.5 J; friction tester: Ͻ5 N; ESD: 7 mJ.
1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol Dihydrate (1): Diazidoglyoxime
(1.70 g, 10 mmol) was suspended in diethyl ether (100 mL), which
was cooled to 0 °C in a salt ice bath. HCl was bubbled through the
suspension while the temperature was maintained below 20 °C, un-
til saturation of the diethyl ether, indicated by a drop in the tem-
perature back to 0–5 °C, was reached. The flask was stoppered
tightly, and the reaction mixture was stirred overnight at room tem-
perature under a slight overpressure of HCl, which formed upon
warming the mixture to room temperature. The HCl overpressure
was released carefully, and the mixture was evaporated either over-
night at room temperature in an open dish or in 1–2 h at 50 °C.
After most of the diethyl ether had evaporated, water (20 mL) was
added to result in a clear solution. A remaining colorless precipitate
indicated uncompleted conversion of diazidoglyoxime to 1H,1ЈH-
All chemicals and solvents were employed as received (Sigma–Ald-
1
13
15
rich, Fluka, Acros). H, C, and N NMR spectra were recorded
with a JEOL Eclipse 270, JEOL EX 400, or a JEOL Eclipse 400
instrument. The chemical shifts quoted in ppm in the text refer to
1
13
typical standards such as tetramethylsilane ( H, C) or nitrometh-
15
ane ( N). To determine the melting and decomposition tempera-
tures of the described compounds, a Linseis PT 10 DSC (heating
–1
rate 5 °Cmin ) was used. Infrared spectra were measured with a
Perkin–Elmer Spectrum One FTIR spectrometer as KBr pellets.
Raman spectra were recorded with a Bruker MultiRAM Raman
Sample Compartment D418 equipped with an Nd:YAG laser
(
1064 nm) and an LN-Ge diode as detector. Mass spectra of the
described compounds were measured with a JEOL MStation JMS
00 using FAB technique. To measure elemental analyses, a Netsch
5,5Ј-bitetrazole-1,1Ј-diol. The water was evaporated again on a ro-
tary evaporator to remove the remaining HCl and diethyl ether,
thus yielding crude 1 as a colorless solid, which could be further
purified by recrystallization from hot water, yield 1.90 g (9.2 mmol,
7
STA 429 simultaneous thermal analyzer was employed. 5,5Ј-Bis(1-
hydroxytetrazole) was synthesized according to a modified litera-
–
1
9
2%). DSC (5 °Cmin ): 115 °C (dehydr.), 214 °C (dec.). IR (KBr):
[
13]
ture procedure.
CCDC-884561 (for 1), -895972 (for 2), -895963 (for 3),
895965 (for 4), -895973 (for 5), -895969 (for 6), -895970 (for 7), - 300 mW, 25 °C): ν˜ = 1608 (100), 1270 (26), 1157 (46), 1133 (38),
ν˜ = 3229 (m), 1665 (m), 1411 (w), 1375 (w), 1302 (w), 1208 (w),
–
1
1144 (m), 995 (s), 714 (w), 662 (w) cm . Raman (1064 nm,
-
–
1 1
8
-
1
95977 (for 8), -895964 (for 9), -895967 (for 10),
895975 (for 11), -895974 (for 12), -895966 (for 13), -895976 (for NMR ([D
4), -895971 (for 15), and -895968 (for 16) contain the supplemen- 25 °C): δ = 135.8 ppm. N NMR ([D
1019 (22), 766 (31), 738 (13), 693 (4), 597 (6), 402 (29) cm . H
1
3
6
]DMSO, 25 °C): δ = 6.80 ppm. C NMR ([D
6
]DMSO,
1
5
6
]DMSO, 25 °C): δ = –2.0
Eur. J. Inorg. Chem. 0000, 0–0
10
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
(
(
N3), –18.7 (N2), –52.3 (N4), –110.5 (N1) ppm. C
206.12): calcd. C 11.65, H 2.93, N 54.36; found C 12.18, H 2.81,
2
H
6
N
8
O
4
suspended in a few milliliters of water. After two equivalents of
aminoguanidinium hydrogen carbonate (2.72 g, 20 mmol) were
added, the mixture was heated until boiling for 10 min, and the hot
solution was filtered. The solvent was slowly evaporated from the
filtrate to yield 1.94 g (6.09 mmol, 61%) of 5 as colorless crystals.
N 54.04. BAM drop hammer: Ͼ40 J; friction tester: 216 N; ESD:
.5 J.
0
Diammonium 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diolate (2): 1H,1ЈH-5,5Ј-
Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol) was suspended in
aqueous ammonia (2 molL , 10 mL). The mixture was heated af-
ter adding water (90 mL). After boiling, the mixture became clear.
The solution was cooled to room temperature, the colorless crystal-
line residue was filtered, and 1.14 g (5.57 mmol, 56% yield) was
obtained. DSC (5 °Cmin ): 290 °C (dec.). IR (KBr): ν˜ = 3180 (s),
3
1
–
1
DSC (5 °Cmin ): 208 °C (m.p.), 228 °C (dec.). IR (KBr): ν˜ = 3432
(s), 3308 (s), 3180 (s), 2344 (w), 1678 (vs), 1416 (m), 1424 (s), 1384
–1
(
(
m), 1352 (w), 1234 (m), 1208 (w), 1176 (w), 1101 (w), 994 (m), 957
w), 730 (w), 712 (w), 677 (w), 643 (w), 515 (w), 494 (w) cm .
–
1
Raman (1064 nm, 300 mW, 25 °C): ν˜ = 3302 (2), 3245 (3), 3184 (4),
1673 (2), 1613 (100), 1590 (32), 1452 (2), 1292 (2), 1241 (23), 1214
–1
(
(
2), 1147 (10), 1133 (6), 1114 (9), 1009 (7), 968 (10), 778 (10), 736
2), 637 (1), 612 (4), 512 (4), 423 (2), 339 (1), 289 (11), 177 (10),
047 (s), 2851 (s), 2150 (w), 1817 (w), 1668 (w), 1433 (s), 1400 (vs),
352 (s), 1231 (s), 1165 (s), 1046 (m), 997 (m), 727 (m), 501 (m)
–
1 1
–1
6
145 (10), 95 (23) cm . H NMR ([D ]DMSO, 25 °C): δ = 8.89 (s,
cm . Raman (1064 nm, 300 mW, 25 °C): ν˜ = 3075 (1), 1605 (100),
1
6
1
2 2 2 2
H, CNHNH ), 7.01 [s, 4 H, C(NH ) ], 4.60 (s, 2 H, NHNH )
463 (3), 1278 (2), 1245 (23), 1118 (8), 1000 (7), 774 (8), 740 (3),
1
3
–1
1
ppm. C NMR ([D ]DMSO, 25 °C): δ = 159.4 [C(NH ) NHNH ],
134.7 (CN O) ppm. MS (FAB ): m/z = 75.1 [CH N ]; MS (FAB ):
m/z = 169.0 [C HN O ]. C H N O (318.26): calcd. C 15.10, H
16 (3), 408 (4), 281 (3), 120 (14), 102 (18), 81 (16) cm . H NMR
6
2 2
2
–
+
+
+
13
(
[D
DMSO, 25 °C): δ = 134.8 (CN
5 °C): δ = –2.0 (N3), –19.8 (N2), –53.6 (N4), –107.5 (N1) ppm.
6
]DMSO, 25 °C): δ = 7.07 (s, NH
4
) ppm. C NMR ([D
6
]-
4
7
4
–
O) ppm. 15N NMR ([D
]DMSO,
2
8
2
4
14 16
2
4
6
4.43, N 70.42; found C 15.41, H 4.24, N 69.46. BAM drop hammer:
2
–
–
+
40 J; friction tester: 324 N; ESD: 0.25 J.
MS (FAB ): m/z = 169.0 [C
2
N
8
O
2
]; MS (FAB ): m/z = 18.1
+
[NH ]. C H N O (204.15): calcd. C 11.77, H 3.95, N 68.61;
4 2 8 10 2
Diaminoguanidinium
1Ј-Hydroxy-1H,1ЈH-5,5Ј-bitetrazol-1-olate
found C 12.14, H 3.69, N 68.18. BAM drop hammer: 35 J; friction
tester: 360 N; ESD: 0.25 J.
Monohydrate (6): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate
(
2.06 g, 10 mmol) was suspended in a few milliliters of water.
Dihydrazinium 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diolate (3): 1H,1ЈH-
Ba(OH) ·8H O (3.16 g, 10 mmol) was added to the clear solution,
2
2
5
,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol) was sus-
pended in a few milliliters of water, and hydrazine hydrate (1.00 g,
0 mmol) was added to the clear solution. The mixture was heated
and filtered. Compound 3 was obtained as small colorless crystal-
and the mixture was heated until boiling to obtain a white, poorly
soluble deposit. The white barium salt was filtered off under vac-
uum and dried. The substance was proved to be anhydrous by ele-
mental analysis. Afterwards, the white powder was suspended in
water to mix it with diaminoguanidinium sulfate (5.72 g, 20 mmol).
2
–
1
line needles to yield 0.95 g (4.05 mmol, 41%). DSC (5 °Cmin ):
2
2
1
20 °C (dec.). IR (KBr): ν˜ = 3434 (w), 3322 (s), 3294 (s), 3189 (s),
958 (s), 2864 (s), 2743 (s), 2642 (s), 2133 (m), 1832 (w), 1620 (s),
578 (m), 1529 (m), 1511 (m), 1420 (s), 1408 (s), 1347 (m), 1232 (5 °C min °C): 160 °C (dehydr.), 200 °C (m.p.), 204 °C (dec.). IR
BaSO
4
was filtered off and 6 precipitated from the filtrate as clear
crystalline agglomerates to yield 1.52 g (5.48 mmol, 55%). DSC
–
1
(
(
s), 1170 (s), 1117 (s), 1096 (s), 1046 (w), 1038 (w), 998 (m), 970
vs), 732 (m), 712 (w), 523 (w), 495 (w) cm . Raman (1064 nm,
(KBr): ν˜ = 3437 (s), 3338 (vs), 3301 (s), 2302 (w), 1690 (s), 1670
(s), 1628 (m), 1602 (m), 1458 (w), 1408 (w), 1369 (s), 1340 (w), 1269
–1
3
00 mW, 25 °C): ν˜ = 3294 (1), 3196 (2), 2006 (1), 1605 (100), 1476 (m), 1179 (s), 1148 (s), 1085 (s), 1022 (s), 867 (s), 758 (s), 710 (m),
–
1
(1), 1458 (2), 1399 (2), 1241 (21), 1139 (7), 1109 (8), 1007 (7), 974
692 (m), 631 (s), 491 (w) cm . Raman (1064 nm, 300 mW, 25 °C):
]DMSO, ν˜ = 3338 (3), 3290 (2), 3237 (2), 1615 (100), 1469 (2), 1250 (33),
–
1 1
(6), 782 (9), 739 (3), 613 (3), 406 (6) cm . H NMR ([D
6
+
13
2
2
5 °C): δ = 7.20 (s, NH
5 °C): δ = 134.9 (CN
2
NH
3
) ppm. C NMR ([D
O) ppm. MS (FAB ): m/z = 33.1 [N
6
]DMSO,
1180 (2), 1122 (9), 1150 (15), 1132 (16), 1009 (6), 924 (5), 763 (3),
+
+
–1
1
4
2
H
5
];
739 (3), 695 (2), 540 (3), 411 (5) cm . H NMR ([D
6
+
]DMSO,
–
–
MS (FAB ): m/z = 169.0 [C
C 10.26, H 4.30, N 71.77; found C 10.71, H 3.97, N 71.17; BAM
drop hammer: 9 J; friction tester: 252 N; ESD: 0.1 J.
2
HN
8
O
2
]; C
2
H
10
N
12
O
2
(234.18): calcd.
25 °C): δ = 8.50 [s, 2 H, C(NH)
4 H, (NHNH
] ppm. 13C NMR ([D
), 135.7 (CN O) ppm. MS (FAB ): m/z = 90.1 [CH
2
], 7.10 (s, 2 H, C=NH ), 5.15 [s,
2
2
)
2
6
]DMSO, 25 °C): δ = 160.2
+
+
+
(C=NH
2
4
8
N
5
];
–
–
MS (FAB ): m/z = 169.0 [C HN O ]. C H N O (277.20): calcd.
2 8 2 3 11 13 3
Bis(guanidinium) 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diolate (4): 1H,1ЈH-
C 13.00, H 4.00, N 65.69; found C 13.79, H 3.31, N 67.46. BAM
drop hammer: 12 J; friction tester: 168 N; ESD: 0.25 J.
5
,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol) was sus-
pended in a few milliliters of water, and guanidinium carbonate
1.08 g, 12 mmol) was added. The mixture was heated to reflux for
(
Triaminoguanidinium
Monohydrate (7): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate
2.06 g, 10 mmol) was suspended in a few milliliters of water, and
triaminoguanidinium chloride (2.81 g, 20 mmol) was added to the
clear solution. The mixture was briefly heated to reflux and filtered.
1Ј-Hydroxy-1H,1ЈH-5,5Ј-bitetrazol-1-olate
1
4
0 min and filtered. After cooling the filtrate to room temperature,
precipitated as colorless crystalline needles, yield 2.00 g
(
–1
(6.94 mmol, 69%). DSC (5 °Cmin ): 274 °C (dec.). IR (KBr): ν˜ =
3
1
454 (s), 3376 (s), 3089 (s), 2192 (w), 1652 (vs), 1583 (m), 1424 (s),
385 (m), 1347 (m), 1289 (w), 1234 (m), 1169 (m), 1139 (m), 1068
From the filtrate, 7 crystallizes as small crystalline needles to give
(m), 1014 (w), 999 (m), 744 (m), 595 (w), 543 (w), 530 (w), 513 (m),
–1
2
.43 g (8.32 mmol, 83%). DSC (5 °Cmin ): 210 °C (dec.). IR
–1
–1
4
90 (w) cm . Raman (1064 nm, 300 mW, 25 °C, cm ): ν˜ = 3197
(
(
KBr): ν˜ = 3364 (m), 3320 (s), 3209 (s), 2994 (m), 1683 (vs), 1615
m), 1585 (m), 1508 (w), 1410 (s), 1384 (m), 1338 (m), 1235 (m),
(2), 1603 (100), 1458 (4), 1233 (17), 1152 (12), 1120 (6), 1017 (33),
791 (9), 739 (2), 621 (2), 545 (5), 422 (3), 409 (4), 292 (6), 179 (4),
1
202 (m), 1150 (m), 1128 (m), 1057 (m), 1013 (m), 989 (m), 949
–
1 1
128 (18), 100 (18) cm . H NMR ([D
6
]DMSO, 25 °C): δ = 7.10 [s,
–1
(m), 779 (w), 733 (m), 638 (m), 567 (m), 496 (w) cm . Raman
(1064 nm, 300 mW, 25 °C): ν˜ = 3362 (3), 3270 (7), 3171 (7), 1680
(5), 1657 (5), 1602 (100), 1456 (4), 1374 (2), 1232 (25), 1171 (2),
13
C(NH
2
)
3
] ppm.
C NMR ([D
6
]DMSO, 25 °C): = 158.6
δ
+
+
[C(NH
2
)
3
], 134.6 (CN
4
O) ppm. MS (FAB ): m/z = 60.1 [CH
6
N
3
];
–
–
MS (FAB ): m/z = 169.0 [C
C 16.67, H 4.20, N 68.03; found C 16.95, H 3.94, N 67.45; BAM
drop hammer: Ͼ40 J; friction tester: Ͼ360 N; ESD: 0.5 J.
2
HN O ]; C H N O (288.23): calcd.
8 2 4 12 14 2
1
6
135 (13), 1110 (14), 1002 (8), 890 (11), 779 (14), 740 (4), 646 (3),
13 (5), 424 (9), 406 (6), 289 (6), 143 (24), 118 (15), 100 (41), 83
–1
1
(
34) cm . H NMR ([D
], 4.46 [s, 6 H, C(NHNH
25 °C): δ = 159.7 [C(NHNH ], 134.5 (CN
4
6
]DMSO, 25 °C): δ = 8.62 [s, 3 H,
1
3
Bis(aminoguanidinium) 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diolate (5): C(NH)
H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol) was
3
2
)
3
] ppm. C NMR ([D
6
]DMSO,
1
2
)
3
O) ppm. MS (FAB+):
Eur. J. Inorg. Chem. 0000, 0–0
11
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
+
–
–]. 327 (2), 296 (3), 271 (3), 158 (38), 98 (11), 67 (6) cm . H NMR
–1 1
m/z = 105.1 [CH
9
N
6
]; MS (FAB ): m/z = 169.0 [C
2
HN
8
O
2
1
3
C
3
H
12
N
14
O
3
(292.22): calcd. C 12.33, H 4.14, N 67.10; found C
3.17, H 4.51, N 73.36. BAM drop hammer: 15 J; friction tester:
20 N; ESD: 0.25 J.
([D
6 6
]DMSO, 25 °C): δ = 7.74 (s) ppm. C NMR ([D ]DMSO,
+
1
1
25 °C): δ = 135.7 (CN O), 158.1 (C=O) ppm. MS (DEI ): m/z =
4
+
·
–
–
118.1 [C
2
H
6
N
4
O
2
]; MS (FAB ): m/z = 169.1 [C
2 8 2
HN O ].
C H N O (406.28): calcd. C 17.74, H 3.47, N 55.16; found C
6 14 16 6
1
-Amino-3-nitroguanidinium 1Ј-Hydroxy-1H,1ЈH-5,5Ј-bitetrazol-1-
17.80, H 3.24, N 54.41. BAM drop hammer: 20 J; friction tester:
60 N; ESD: 0.4 J.
olate Dihydrate (8): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate
0.59 g, 2.87 mmol) was dissolved in warm water (5 mL), and a
3
(
solution of 1-amino-3-nitroguanidine (0.34 g, 2.87 mmol) in hot Oxalyldihydrazidinium 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diolate Dihy-
water (10 mL) was added. After boiling and stirring the mixture
for a few minutes, 8 precipitated as thin, colorless plates upon cool-
ing the solution to room temperature. Single crystals suitable for
X-ray crystallography in this case were grown from a 40% aqueous
solution of HF. DSC (5 °Cmin ): 138 °C (dehydr.), 140 °C (dec.).
IR (KBr): ν˜ = 3494 (m), 3373 (s), 3285 (m), 3197 (m), 3097 (s),
drate (11): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (1.03 g,
5 mmol) was suspended in a few milliliters of water, and oxalyldihy-
drazide (0.59 g, 5 mmol) was added. The mixture was briefly heated
to reflux and filtered. After cooling to room temperature, 11 was
obtained as small crystalline needles to give 1.41 g (4.35 mmol,
–1
–
1
87%). DSC (5 °Cmin ): 110 °C (dehydr.), 222 °C (dec.). IR (KBr):
2677 (m), 1644 (m), 1577 (m), 1469 (m), 1377 (s), 1262 (vs), 1248 ν˜ = 3871 (w), 3428 (s), 3074 (s), 2837 (s), 2730 (s), 2043 (m), 1676
(
(
(
(
(
s), 1166 (w), 1153 (w), 1116 (m), 1074 (m), 1024 (w), 1002 (w), 910 (vs), 1585 (m), 1523 (s), 1431 (s), 1415 (s), 1358 (m), 1265 (m), 1241
w), 820 (m), 763 (s), 729 (m), 646 (s), 460 (w) cm . Raman (s), 1209 (m), 1173 (m), 1040 (m), 1000 (m), 811 (m), 735 (m), 715
–1
–
1
1075 nm, 300 mW, 25 °C): ν˜ = 3092 (1), 1628 (100), 1491 (3), 1475
(w), 616 (w), 532 (m), 471 (w) cm . Raman (1064 nm, 300 mW,
25 °C): ν˜ = 1706 (5), 1660 (2), 1615 (100), 1591 (4), 1555 (2), 1478
]- (2), 1334 (3), 1287 (1), 1248 (18), 1216 (3), 1139 (6), 1116 (9), 1008
2), 1392 (2), 1257 (30), 1152 (13), 1015 (5), 913 (9), 799 (7), 738
–1 1
3), 621 (7), 445 (3), 404 (4), 361 (7), 282 (7) cm . H NMR ([D
OH), 8.27 (s, 1 H, NHNH
) ppm. 13C NMR ([D
)(NHNH )(NNO )], 135.7 (CN
FAB ): m/z = 120.1 [CH
6
DMSO, 25 °C): δ = 9.34 (s, 1 H, CN
.03 (s, 4 H, NHNH , NH
δ = 160.0 [C(NH
4
2
),
(5), 929 (5), 779 (4), 744 (3), 631 (2), 520 (2), 416 (4), 397 (3), 322
6
]DMSO, 25 °C): (1), 287 (4), 266 (2), 162 (12), 151 (15), 124 (20), 88 (17), 66 (5)
7
2
2
–
1
1
+
2
2
2
4
O) ppm. MS
]; MS (FAB ): m/z = 169.0
(325.20): calcd. C 11.08, H 3.41, N
5.99; found C 11.54, H 3.27, N 55.96. BAM drop hammer: 10 J;
cm . H NMR ([D
6
]DMSO, 25 °C): δ = 7.53 [s, (NHNH
3
)
2
] ppm.
O)
2 6 4 2
ppm. MS (DEI ): m/z = 118.1 [C H N O ]; MS (DCI ): m/z =
+
+
–
13
(
6
N
5
O
2
C NMR ([D
6
]DMSO, 25 °C): δ = 157.8 (C=O), 135.7 (CN
4
–
+
+·
+
[C
2
HN
8
O
2
]. C
3
H
11
N
13
O
6
+
·
–
–
5
119.14 [C
2
H
7
N
4
O
2
]; MS (FAB ): m/z = 169.1 [C
2 8 2
HN O ].
friction tester: 192 N; ESD: 0.08 J (at grain size 100–500 μm).
4 12 12 6
C H N O (324.21): calcd. C 14.82, H 3.73, N 51.84; found C
1
2
5.14, H 3.52, N 51.32. BAM drop hammer: 40 J; friction tester:
88 N; ESD: 0.35 J.
Diaminouronium 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diolate Monohydrate
(
9): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol)
was suspended in a few milliliters of water. Diaminourea (1.81 g,
0 mmol) was added to the clear solution. The mixture was briefly
3,6-Bishydrazino-1,2,4,5-tetrazinium 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-
diolate (12): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (0.37 g,
1.8 mmol) was suspended in a few milliliters of water, and 3,6-dihy-
drazino-1,2,4,5-tetrazinium dichloride monohydrate (0.41 g,
1.8 mmol), previously dissolved in a few milliliters of water was
added. The mixture was heated until boiling to obtain a clear solu-
tion. After cooling to 10 °C, 12 precipitated as a red flaky deposit,
which was filtered and washed with a little cold water, yield 0.36 g
2
heated to reflux and filtered. After cooling to room temperature, 9
precipitated as crystalline needles, yield 2.56 g (9.20 mmol, 92%).
–1
DSC (5 °Cmin ): 220 °C (dec.). IR (KBr): ν˜ = 3617 (m), 3545 (m),
3
1
1
5
274 (s), 2964 (s), 2659 (s), 2126 (w), 2049 (w), 1702 (m), 1608 (s),
535 (vs), 1427 (s), 1413 (s), 1385 (m), 1356 (w), 1269 (w), 1233 (s),
171 (s), 1048 (m), 1006 (w), 996 (w), 978 (w), 729 (m), 565 (w),
–1
–1
04 (w) cm . Raman (1064 nm, 300 mW, 25 °C): ν˜ = 1709 (2), 1616
(1.15 mmol, 64%) of small, orange crystals. DSC (5 °Cmin ):
(
100), 1474 (5), 1289 (2), 1246 (18), 1202 (4), 1144 (11), 1122 (9),
008 (7), 1000 (4), 980 (4), 778 (8), 744 (3), 614 (4), 411 (3) cm . (m), 2857 (m), 2657 (m), 2005 (w), 1620 (m), 1573 (m), 1535 (s),
180 °C (dec.). IR (KBr): ν˜ = 3424 (m), 3259 (s), 3059 (m), 2923
–
1
1
1
H NMR ([D
] ppm. 13C NMR ([D
O), 159.6 [C(NHNH ] ppm. MS (FAB ): m/z = 91.1
6
]DMSO, 25 °C): δ = 8.31 [s, C(NHNH
2
)
2
], 7.80 [s,
1495 (s), 1426 (vs), 1359 (w), 1327 (w), 1242 (s), 1175 (m), 1159
C(NHNH
CN
CH
2
)
2
6
]DMSO, 25 °C): δ = 135.7 (m), 1098 (w), 1053 (m), 1000 (w), 939 (m), 856 (m), 730 (m), 706
+
–1
(
4
2
)
2
(m), 595 (m), 508 (w), 464 (w) cm . Raman (1064 nm, 300 mW,
+
–
–
[
(
7
N
4
]; MS (FAB ): m/z = 169.0 [C
2
HN
8
O
2
]. C
3
H
10
N
12
O
4
25 °C): ν˜ = 3260 (2), 1907 (1), 1615 (100), 1550 (2), 1515 (3), 1490
(7), 1314 (3), 1286 (2), 1247 (21), 1221 (2), 1165 (2), 1141 (10), 1115
(8), 1077 (2), 1008 (7), 876 (8), 816 (2), 777 (7), 740 (3), 702 (1),
671 (3), 613 (4), 467 (4), 435 (3), 415 (3), 293 (9), 198 (3), 157 (7),
278.19): calcd. C 12.95, H 3.62, N 60.42; found C 13.29, H 3.28,
N 60.21. BAM drop hammer: 20 J; friction tester: 240 N; ESD:
.4 J.
0
–
1 1
1
6
27 (18), 115 (47), 105 (54), 90 (34) cm . H NMR ([D ]DMSO,
Bis(oxalyldihydrazidinium)
10): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol)
was suspended in a few milliliters of water, and oxalyldihydrazide
2.36 g, 20 mmol) was added. The mixture was briefly heated to
1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diolate
+
+
2
5 °C): δ = 9.57 (s, 2 H, NHNH
3
), 6.38 (s, 6 H, NHNH
]DMSO, 25 °C): δ = 162.5 (C ), 135.7 (CN
(312.21):
3
) ppm.
(
13
C NMR ([D
6
2
N
4
4
O)
–
–
2 8 2 4 8 16 2
ppm. MS (FAB ): m/z = 169.1 [C HN O ]. C H N O
(
calcd. C 15.39, H 2.58, N 71.78; found C 15.79, H 2.49, N 70.58.
BAM drop hammer: 40 J; friction tester: 80 N; ESD: 0.08 J.
reflux and filtered. After cooling to room temperature, 10 precipi-
tated as small crystalline needles to yield 3.57 g (8.79 mmol, 88%).
DSC (5 °Cmin ): 224 °C (dec.). IR (KBr): ν˜ = 3423 (m), 3316 (m),
3
1
1
7
3
–1
5-Aminotetrazolium
(13): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol)
429 (s), 1412 (s), 1348 (m), 1290 (m), 1256 (m), 1239 (s), 1175 (m), was suspended in a few milliliters of water, and 5-aminotetrazole
148 (m), 1077 (m), 971 (m), 927 (m), 831 (m), 780 (w), 730 (m), (1.70 g, 20 mmol) was added. The mixture was briefly heated to
1Ј-Hydroxy-1H,1ЈH-5,5Ј-bitetrazol-1-olate
269 (s), 3029 (s), 2340 (w), 1677 (vs), 1607 (s), 1579 (s), 1512 (s),
–1
12 (w), 636 (w), 536 (m), 498 (m), 479 (m) cm . Raman (1064 nm, reflux and filtered. After cooling to room temperature, 13 crys-
00 mW, 25 °C): ν˜ = 3318 (1), 3259 (2), 2017 (1), 1715 (4), 1674 tallized as colorless needles, yield 2.31 g (9.05 mmol, 91%). DSC
–
1
(2), 1615 (100), 1542 (9), 1471 (2), 1320 (12), 1285 (4), 1245 (13),
(5 °Cmin ): 224 °C (dec.). IR (KBr): ν˜ = 3407 (s), 3325 (s), 3281
1
7
211 (2), 1139 (12), 1119 (8), 1071 (1), 1003 (4), 977 (3), 932 (6),
76 (5), 744 (4), 617 (1), 525 (1), 503 (1), 433 (2), 407 (5), 363 (2), 1703 (vs), 1594 (m), 1489 (m), 1451 (w), 1407 (w), 1370 (m), 1322
(m), 3167 (m), 2965 (m), 2837 (m), 2720 (s), 2565 (m), 2508 (m),
Eur. J. Inorg. Chem. 0000, 0–0
12
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
(
(
1
m), 1281 (m), 1140 (m), 1080 (m), 1056 (m), 999 (s), 809 (s), 522 3325 (s), 3225 (s), 3153 (s), 2791 (w), 2692 (w), 2439 (w), 2241 (w),
–1
m), 456 (w) cm . Raman (1064 nm, 300 mW, 25 °C): ν˜ = 1698 (1),
624 (100), 1592 (3), 1496 (17), 1322 (3), 1297 (1), 1260 (26), 1143
1731 (m), 1655 (vs), 1577 (m), 1487 (w), 1470 (w), 1368 (w), 1329
(s), 1134 (w), 1109 (m), 1077 (m), 1002 (m), 931 (m), 745 (m), 687
–
1
(
6), 1130 (11), 1063 (10), 1018 (3), 819 (1), 787 (2), 743 (8), 653 (1), (m), 605 (m), 486 (w) cm . Raman (1064 nm, 300 mW, 25 °C): ν˜
4
11 (3), 403 (2), 295 (5), 173 (9), 129 (18), 121 (18), 111 (15), 97
= 3322 (7), 3247 (8), 3157 (9), 1671 (8), 1618 (20), 1547 (30), 1498
–1
1
(45), 77 (25) cm . H NMR ([D
6
]DMSO, 25 °C): δ = 11.90 [s, (6), 1328 (23), 1306 (32), 1250 (5), 1135 (6), 1106 (26), 1079 (10),
+
] ppm. 13C NMR ([D
CNH
CH
2
, (NH)
2
6
]DMSO, 25 °C): δ = 155.7 1000 (4), 957 (3), 792 (100), 698 (20), 497 (2), 322 (34), 231 (16),
+
+
+
–1 1
(
4
N
5
), 135.8 (CN
4
O) ppm. MS (FAB ): m/z = 86.1 [CH
4
N
5
];
138 (22), 105 (44), 92 (37), 78 (62) cm . H NMR ([D
6
]DMSO,
), NH ] ppm. 13C NMR ([D
]-
O) ppm. MS
–
–
+
MS (FAB ): m/z = 169.0 [C
C 14.12, H 1.98, N 71.36; found C 14.50, H 1.91, N 70.90. BAM
drop hammer: 4 J; friction tester: 72 N; ESD: 0.3 J.
2
HN
8
O
2
]. C
3
H
5
N
13
O
2
(255.16): calcd.
25 °C): δ = 7.87 [s, CNH
2
, N(NH
2
6
+
DMSO, 25 °C): δ = 154.2 (CH
5
N
6 4
), 135.8 (CN
]; MS (FAB ): m/z = 169.1
[C HN O ]. C H N O (270.17): calcd. C 13.34, H 2.24, N 72.58;
+
+
–
(FAB ): m/z = 101.1 [CH
5
N
6
–
2 8 2 3 6 14 2
1
-Methyl-5-aminotetrazolium 1Ј-Hydroxy-1H,1ЈH-5,5Ј-bitetrazol-1-
found C 13.95, H 2.23, N 75.97. BAM drop hammer: 2 J; friction
tester: 160 N; ESD: 0.35 J.
olate (14): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol (2.06 g, 10 mmol) was
suspended in a few milliliters of water, and 5-amino-1-methyl-1H-
tetrazole (1.98 g, 20 mmol) was added. The mixture was heated and
filtered. After cooling to room temperature, 14 crystallized as col-
Supporting Information (see footnote on the first page of this arti-
cle): Description of crystal structures of compounds 1–5, 8–14 and
16; tables of crystallographic details (mesurements and refinements,
bond lengths, bond angles and hydrogen bonds.
–
1
orless blocks to yield 1.07 g (3.98 mmol, 40%). DSC (5 °Cmin ):
88 °C (m.p.), 192 °C (dec.). IR (KBr): ν˜ = 3496 (m), 3398 (s), 3296
m), 3126 (m), 3061 (m), 2950 (m), 2850 (m), 2752 (m), 2676 (m),
693 (vs), 1514 (w), 1465 (w), 1424 (w), 1367 (m), 1273 (m), 1240
w), 1138 (m), 1116 (m), 1084 (m), 1042 (m), 1007 (w), 963 (m),
1
(
1
(
Acknowledgments
–
1
847 (m), 779 (w), 759 (m), 713 (m), 661 (w), 621 (m) cm . Raman
Financial support of this work by the Ludwig-Maximilians Uni-
versität (LMU), Munich, the U.S. Army Research Laboratory
(
(
(
1075 nm, 300 mW, 25 °C): ν˜ = 3032 (4), 3012 (2), 2960 (9), 2822
2), 1712 (1), 1616 (100), 1513 (1), 1464 (2), 1422 (4), 1366 (2), 1275
5), 1252 (34), 1131 (15), 1112 (10), 1063 (1), 1039 (5), 1013 (4),
(
ARL) under grant no. W911NF-09-2-0018, the Armament Re-
search, Development and Engineering Center (ARDEC) under
grant no. R&D 1558-TA-01, and the Office of Naval Research
9
2
69 (2), 781 (25), 741 (5), 671 (5), 623 (1), 475 (2), 412 (4), 314 (5),
–1 1
92 (5), 231 (6) cm . H NMR ([D
, OH), 3.67 (s, CH
) ppm. 13C NMR ([D
5 °C): δ = 155.6 (CN ), 135.8 (CN O), 32.2 (CH ) ppm. MS
]; MS (FAB ): m/z = 169.0
(269.08): calcd. C 17.85, H 2.62, N 67.64;
6
]DMSO, 25 °C): δ = 8.72 (br.
(
ONR) under grant numbers ONR.N00014-10-1-0535 and
s, NH, NH
2
2
3
6
]DMSO,
ONR.N00014-12-1-0538 is gratefully acknowledged. The authors
acknowledge collaborations with Dr. Mila Krupka (OZM Re-
search, 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 pa-
rameters of novel explosives. We are indebted to and thank Drs.
Betsy M. Rice and Brad Forch (ARL, Aberdeen, Proving Ground,
MD). Stefan Huber is acknowledged for measuring the sensitivities
of all compounds. Furthermore, the authors thank Mr. Dennis Fi-
scher for many helpful discussions as well as Mr. Andreas Preim-
esser for supplying 3,6-dihydrazino-1,2,4,5-tetrazinium dichloride
monohydrate.
4
4
3
+
–
–
2 6 5
(FAB ): m/z = 100.0 [C H N
–
[C
2
HN
8
O
2
]; C
4
H
7
N
13
O
2
found C 18.27, H 2.60, N 67.09. BAM drop hammer: 6 J; friction
tester: 240 N; ESD: 0.50 J (at grain size 500–1000 μm).
1
H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol·2 (5-Amino-2-methyl-2H-tetraz-
ole) (15): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g,
1
2
was briefly heated to reflux and filtered. After cooling to room
temperature, 15 precipitated as clear crystals to yield 0.98 g
0 mmol) was suspended in a few milliliters of water, and 5-amino-
-methyl-2H-tetrazole (1.98 g, 20 mmol) was added. The mixture
–1
(
2.66 mmol, 27%). DSC (5 °Cmin ): 125 °C (m.p.), 155 °C (dec.).
IR (KBr): ν˜ = 3403 (s), 3344 (s), 3212 (m), 2743 (w), 2400 (w),
659 (vs), 1596 (s), 1439 (m), 1287 (m), 1159 (s), 1130 (m), 1064 [1] J. Thiele, Justus Liebigs Ann. Chem. 1898, 203, 57–75.
[2] W. E. Bachmann, J. C. Sheehan, J. Am. Chem. Soc. 1949, 71,
842–1845.
1
–
1
(
m), 896 (m), 781 (m), 748 (m), 710 (m), 653 (m), 487 (m) cm .
Raman (1064 nm, 300 mW, 25 °C): ν˜ = 3220 (7), 3047 (9), 3029
14), 2966 (49), 1847 (4), 1771 (4), 1714 (4), 1671 (7), 1627 (100),
438 (18), 1414 (8), 1390 (16), 1328 (4), 1268 (27), 1150 (18), 1091
1
[
[
3] H. Fischer, Chem. Ber. 1949, 82, 192–193.
(
1
4] A. T. Nielsen, A. P. Chafin, S. L. Christian, D. W. Moore, M. P.
Nadler, R. A. Nissan, D. J. Vanderah, R. D. Gilardi, C. F.
George, J. L. Flippen-Anderson, Tetrahedron 1998, 54, 11793–
(
(
(
10), 1065 (11), 1015 (24), 807 (5), 768 (18), 724 (10), 647 (51), 562
10), 493 (18), 409 (19), 324 (15), 305 (6), 276 (7), 207 (21), 138
71) cm . H NMR ([D
.07 (s, 3 H, NCH
) ppm. 13C NMR ([D
), 135.8 (CN O), 39.4 (NCH ) ppm. MS (FAB ): m/z =
1
1812.
–1 1
6
]DMSO, 25 °C): δ = 7.26 (s, 2 H, CNH
2
),
[5] a) H. Gao, J. M. Shreeve, Chem. Rev. 2011, 111, 7377–7436; b)
R. Haiges, S. Schneider, T. Schroer, K. O. Christe, Angew.
Chem. 2004, 116, 5027; Angew. Chem. Int. Ed. 2004, 43, 4919–
4924; c) D. E. Chavez, M. A. Hiskey, D. L. Naud, D. Parrish,
Angew. Chem. 2008, 120, 8431; Angew. Chem. Int. Ed. 2008,
4
3
6
]DMSO, 25 °C): δ = 167.7
+
(CNH
2
4
3
+
–
–
100.1 [C
2
H
6
N
5
]; MS (FAB ): m/z
2 8 2
= 169.1 [C HN O ].
C
6
H
12
N
18
O
2
, (368.28): calcd. C 19.57, H 3.28, N 68.46; found C
47, 8307–8309; d) M. B. Talawar, R. Sivabalan, T. Mukundan,
2
3
0.08, H 3.24, N 68.50. BAM drop hammer: 8 J; friction tester:
60 N; ESD: 0.4 J.
H. Muthurajan, A. K. Sikder, B. R. Gandhe, A. Subhan-
anda Rao, J. Hazard. Mater. 2009, 161, 589–607; e) O. S. Bu-
shuyev, P. Brown, A. Maiti, R. H. Gee, G. R. Peterson, B. L.
Weeks, L. J. Hope-Weeks, J. Am. Chem. Soc. 2012, 134, 1422–
1,5-Diaminotetrazolium 1Ј-Hydroxy-1H,1ЈH-5,5Ј-bitetrazol-1-olate
(16): 1H,1ЈH-5,5Ј-Bitetrazole-1,1Ј-diol dihydrate (2.06 g, 10 mmol)
1
425.
was suspended in a few milliliters of water, and 1,5-diaminotetra-
zole (2.04 g, 20 mmol) was added. The mixture was heated and
filtered. After cooling to room temperature, 16 crystallized from
the aqueous solution to give 2.60 g (9.62 mmol, 96%) of 16. DSC
[
6] S. A. Meyer, A. J. Marchand, J. L. Hight, G. H. Roberts, L. B.
Escalon, L. S. Inouye, D. K. MacMillan, J. Appl. Toxicol. 2005,
25, 427–434.
[7] T. M. Klapötke, in: High Energy Density Materials, Springer,
Berlin, Heidelberg, 2007.
–1
(5 °Cmin ): 160 °C (m.p.), 170 °C (dec.). IR (KBr): ν˜ = 3322 (s),
Eur. J. Inorg. Chem. 0000, 0–0
13
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
[
[
[
[
[
[
[
[
[
[
8] D. E. Chavez, M. A. Hiskey, R. D. Gilardi, Angew. Chem. 2000,
J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M.
Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Ad-
amo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Mar-
tin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador,
J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B.
Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09,
revision A.1, Gaussian, Inc., Wallingford CT, 2009.
112, 1861; Angew. Chem. Int. Ed. 2000, 39, 1791–1793.
9] N. Fischer, D. Iszak, T. M. Klapötke, S. Rappenglück, J. Stier-
storfer, Chem. Eur. J. 2012, 18, 4051–4062.
10] M. Göbel, K. Karaghiosoff, T. M. Klapötke, D. G. Piercey, J.
Stierstorfer, J. Am. Chem. Soc. 2010, 132, 17216–17226.
11] T. M. Klapötke, D. G. Piercey, J. Stierstorfer, Chem. Eur. J.
2
011, 17, 13068–13077.
12] A. M. Churakov, V. A. Tartakovsky, Chem. Rev. 2004, 104,
601–2616.
[
34] M. Hesse, H. Meier, B. Zeeh, in: Spektroskopische Methoden in
der organischen Chemie, Vol. 6, Thieme, Stuttgart, New York,
2
2002.
13] N. Fischer, D. Fischer, T. M. Klapötke, D. Piercey, J. Stier-
[
[
35] http://www.linseis.com.
storfer, J. Mater. Chem. 2012, 22, 20418–20422.
14] I. V. Tselinskii, S. F. MelЈnikova, T. V. Romanova, Russ. J. Org.
Chem. 2001, 37, 430–436.
15] T. M. Klapötke, P. Mayer, J. Stierstorfer, Phosphorus Sulfur
Silicon Relat. Elem. 2009, 184, 2393–2407.
16] Z. Li, W. Zhu, J. Yu, X. Ma, Z. Lu, S. Xiao, Synth. Commun.
36] T. M. Klapötke, F. A. Martin, J. Stierstorfer, Chem. Eur. J.
2012, 18, 1487–1501.
[
[
37] NATO standardization agreement (STANAG) on explosives,
impact sensitivity tests, no. 4489, 1st ed., Sept. 17, 1999.
38] WIWEB-Standardarbeitsanweisung 4-5.1.02, Ermittlung der
Explosionsgefährlichkeit, hier der Schlagempfindlichkeit mit
dem Fallhammer, Nov. 8, 2002.
2
006, 36, 2613–2619.
17] T. Curtius, K. Hochschwender, J. Prakt. Chem. 1915, 91, 415–
41.
[
[
39] a) http://www.bam.de; b) www.reichel&partner.de.
40] NATO standardization agreement (STANAG) on explosive,
friction sensitivity tests, no. 4487, 1st ed., Aug. 22, 2002.
[41] WIWEB-Standardarbeitsanweisung 4-5.1.03, Ermittlung der
Explosionsgefährlichkeit oder der Reibeempfindlichkeit mit
dem Reibeapparat, Nov. 8, 2002.
[42] Impact: insensitive Ͼ40 J, less sensitive Ͼ35 J, sensitive Ͼ4 J,
very sensitive Ͻ3 J. Friction: insensitive Ͼ360 N, less sensitive
= 360 N, sensitive Ͼ80 ⁿ, very sensitive Ͼ10 N, extremely sensi-
tive Ͻ10 N. According to the UN Recommendations on the
Transport of Dangerous Goods, (+) indicates not safe for
transport.
4
[
[
18] K. Y. Lee, M. D. Coburn, US 4733610, 1988, 28, 1–2.
19] M. D. Coburn, G. A. Buntain, B. W. Harris, J. Heterocycl.
Chem. 1991, 28, 2049–2050.
[
[
[
[
20] R. A. Henry, W. G. Finnegan, J. Am. Chem. Soc. 1954, 76, 923–
926.
21] P. N. Gaponik, V. P. Karavai, Chem. Heterocycl. Compd. 1984,
683–1686.
22] J. A. Castillo-Melendez, B. T. Golding, Synthesis 2004, 10,
655–1663.
23] N. Fischer, T. M. Klapötke, J. Stierstorfer, Z. Naturforsch. B
012, 67, 573–588.
1
1
2
[43] http://www.ozm.cz.
[
[
24] CrysAlisPro Oxford Diffraction Ltd., Version 171.33.41, 2009.
25] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J.
Appl. Crystallogr. 1993, 26, 343.
[44] E. F. C. Byrd, B. M. Rice, J. Phys. Chem. A 2006, 110, 1005–
1013.
[45] P. J. Linstrom, W. G. Mallard (Eds.), in: NIST Chemistry Web-
Book, NIST Standard Reference Database Number 69,
National Institute of Standards and Technology, Gaithersburg
MD, 20899, http://webbook.nist.gov (retrieved October 27,
2011).
[46] a) H. D. B. Jenkins, H. K. Roobottom, J. Passmore, L. Glasser,
Inorg. Chem. 1999, 38, 3609–3620; b) H. D. B. Jenkins, D. Tud-
ela, L. Glasser, Inorg. Chem. 2002, 41, 2364–2367.
[47] a) M. S. Westwell, M. S. Searle, D. J. Wales, D. H. Williams, J.
Am. Chem. Soc. 1995, 117, 5013–5015; b) F. Trouton, Philos.
Mag. 1884, 18, 54–57.
[48] M. Su c´ eska, EXPLO5.05 program, Zagreb, Croatia, 2012.
[49] M. Su c´ eska, Propellants Explos. Pyrotech. 1991, 16, 197–202.
[50] Calculation of oxygen balance: Ω [%] = (wO – 2xC – 1/2yH –
2zS)1600/M (w: number of oxygen atoms, x: number of carbon
atoms, y: number of hydrogen atoms, z: number of sulfur
atoms, M: molecular weight).
[
26] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R.
Spagna, J. Appl. Crystallogr. 1999, 32, 115–119.
[
[
[
27] G. M. Sheldrick, SHELXS-97, Program for Crystal Structure
Solution, University of Göttingen, 1997.
28] G. M. Sheldrick, SHELXL-97, Program for the Refinement of
Crystal Structures, University of Göttingen, Germany, 1997.
29] A. L. Spek, PLATON, A Multipurpose Crystallographic Tool,
Utrecht University, Utrecht, The Netherlands, 1998.
[
[
30] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837–838.
31] Empirical absorption correction using spherical harmonics, im-
plemented in SCALE3 ABSPACK scaling algorithm (CrysAli-
sPro, Oxford Diffraction Ltd., v. 171.33.41, 2009).
[
32] N. Fischer, T. M. Klapötke, J. Stierstorfer, Z. Anorg. Allg.
Chem. 2009, 635, 271–281.
33] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B.
Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li,
H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Son-
nenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hase-
[
[51] R. Mayer, J. Köhler, A. Homburg, in: Explosives, vol. 5, Wiley-
VCH, Weinheim, Germany, 2002.
[52] P. Hakey, W. Ouellette, J. Zubieta, T. Korter, Acta Crystallogr.,
Sect. E 2008, 64, o1428/1–o1428/6.
gawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, [53] J. R. Deschamps, M. Frisch, D. Parrish, J. Chem. Crystallogr.
T. Vreven, J. A. Montgomery Jr, J. E. Peralta, F. Ogliaro, M.
Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Starov-
erov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell,
2011, 41, 966–970.
Received: October 2, 2012
Published Online: ᭿
Eur. J. Inorg. Chem. 0000, 0–0
14
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I21192
/KAP1
Date: 12-02-13 10:20:15
Pages: 15
www.eurjic.org
FULL PAPER
Energetic Materials
Fifteen nitrogen-rich energetic salts of
H,1ЈH-5,5Ј-bitetrazole-1,1Ј-diol were syn-
N. Fischer, T. M. Klapötke,* M. Reymann,
J. Stierstorfer .................................. 1–15
1
thesized and characterized. The energetic
investigation partly showed candidates that
performed very well with respect to deton-
ation and combustion applications. They
combine good thermal and chemical stab-
ilities with acceptable sensitivities and syn-
thetic costs.
Nitrogen-Rich Salts of 1H,1ЈH-5,5Ј-Bi-
tetrazole-1,1Ј-diol: Energetic Materials
with High Thermal Stability
Keywords: Energetic materials / Nitrogen
heterocycles / Nitrogen-rich compounds
Eur. J. Inorg. Chem. 0000, 0–0
15
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim