A simple method for the preparation of 3,5-dinitrimino-1,2,4-triazole and its salts

Article abstract of DOI:10.1007/s10593-017-2116-7

The reaction of 2-methyl-1-nitrоisothiourea with hydrazine in the presence of alkali metal bicarbonates (carbonates) resulted in the formation of 3,5-dinitrimino-1,2,4-triazole salts. The same salts were also formed by a reaction of 2-methyl-1-nitrоisothiourea with alkali metal salts of 4-nitrоsemicarbazide. This represents the first synthesis and characterization of the high-energy 3,5-dinitrimino-1,2,4- triazole, which can be readily isolated by treatment of its disodium salt with HCl.

Full text of DOI:10.1007/s10593-017-2116-7

DOI 10.1007/s10593-017-2116-7
Chemistry of Heterocyclic Compounds 2017, 53(6/7), 722–727
A simple method for the preparation of
3,5-dinitrimino-1,2,4-triazole and its salts
Alexander M. Astakhov1*, Denis V. Antishin1, Vitalii A. Revenko1,
Alexander D. Vasiliev2,3, Eduard S. Buka1
1 Reshetnev Siberian State University of Science and Technology,
31 Krasnoyarsky Rabochy Ave., Krasnoyarsk 660037, Russia;
e-mail: alexastachov@mail.ru
2 Kirensky Institute of Physics, Siberian Branch of the Russian Academy of Sciences,
Akademgorodok 50, Build. 38, Krasnoyarsk 660036, Russia; e-mail: adva@iph.krasn.ru
3 Siberian Federal University,
79 Svobodny Ave., Krasnoyarsk 660041, Russia
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2017, 53(6/7), 722–727
Submitted February 1, 2017
Accepted May 24, 2017
The reaction of 2-methyl-1-nitrоisothiourea with hydrazine in the presence of alkali metal bicarbonates (carbonates) resulted in the
formation of 3,5-dinitrimino-1,2,4-triazole salts. The same salts were also formed by a reaction of 2-methyl-1-nitrоisothiourea with alkali
metal salts of 4-nitrоsemicarbazide. This represents the first synthesis and characterization of the high-energy 3,5-dinitrimino-1,2,4-
triazole, which can be readily isolated by treatment of its disodium salt with HCl.
Keywords: 3,5-dinitramino-1,2,4-triazole, 3,5-dinitrimino-1,2,4-triazole, 1,2,4-triazoles, energetic compounds, nitramines, nitrimines,
nucleophilic substitution.
Derivatives of 1,2,4-triazole that contain various
explosophoric substituents are clearly of interest as high-
energy compounds, with applications in the roles of
explosives, components of powders and solid rocket
propellants.1 3,5-Dinitrimino-1,2,4-triazole (1) has been
considered as one of hypothetical energetic compounds for
the development in the future.2
Despite the fact that salts of 3,5-dinitrimino-1,2,4-
triazole (previously referred to as salts of 3,5-dinitramino-
1,2,4-triazole) have been known for a considerable time,3
compound 1 itself was not previously isolated as a free acid.
Unlike with other 3(5)-amino-1,2,4-triazoles, direct nitration
of 3,5-diamino-1,2,4-triazole did not result in the formation
of the desired dinitrimine, probably due to diazotation of
one of the amino groups, followed by complete destruction
of the diazonium derivative.4
The previously described attempt to obtain compound 1
from its monoammonium salt by treatment with concd
HNO3 was unsuccessful; only the solvate of this salt with
HNO3 was isolated, which decomposed upon recrystal-
lization, resulting in recovery of the starting mono-
ammonium salt.3с In order to obtain free acid 1, we
developed a method that relied on precipitation of insoluble
BaSO4 when solutions of barium salts of dinitrimine 1
(compounds 2b or 3b, Scheme 1) were treated with H2SO4.
The method was successful and enabled the first prepara-
tion of dinitrimine 1 as a free compound. It is important to
note that compound 1 has very high acidity (pKa1 −2.0,
determined by spectrophotometric and potentiometric
titration of its salt3c).
During subsequent studies aimed at the preparation of
monosodium salt 3a from disodium salt 2a by the action of
HCl, we unexpectedly isolated a precipitate with de-
composition temperature of 125°С, which was identified as
dinitrimine 1. Thus, compound 1 can be easily obtained by
treating a solution of disodium salt 2a with hydrochloric
acid (Scheme 1).
The methods used so far to prepare salts of compound 13
are not simple as they involve multiple steps. According to
these methods, the formation of 1,2,4-triazole ring occurs by
cyclization of 2,5-dinitrobiguanidine 4 in alkaline medium.
The starting compound 4, in turn, must be synthesized
separately or obtained in situ by treatment of
2-nitrоguanidine3c or 1,2-dinitrоguanidine with hydrazine.3b
We have developed a simple one-step procedure for
obtaining disodium and dipotassium salts of 3,5-dinitr-
0009-3122/17/53(6/7)-0722©2017 Springer Science+Business Media New York
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Chemistry of Heterocyclic Compounds 2017, 53(6/7), 722–727
Scheme 1
imino-1,2,4-triazole 2а,c from the readily available
2-methyl-1-nitrоisothiourea (5) (Scheme 2). The formation
of 1,2,4-triazole ring according to this method obviously
also involved the cyclization of compound 4, which was
nitrimine structure of nitroguanidine was not yet clearly
proven at that time (it was believed to exist in two possible
forms – primary nitramine and nitrimine).6 The X-ray
structural analysis results for ammonium and potassium
salts of compound 1, which were obtained in 1985, were
also interpreted according to erroneous assumptions,
leading to the assignment of a nitramine structure.7
However, that study did not experimentally determine the
positions of hydrogen atoms! The authors of that
publication7 deliberately assumed hydrogen atom positions
according to their view of compound 1 as a primary
nitramine.
formed as
a result of two sequential nucleophilic
substitution reactions. In the first step, compound 5 reacted
with hydrazine, forming 1-amino-2-nitrоguanidine (6),
which further reacted with compound 5, forming salts of
compound 4.
Scheme 2
When considering the experimental data from the earlier
study,7 we noticed that placing the hydrogen atoms at posi-
tions corresponding to primary nitramine structure (as pro-
posed in that publication7), would result in very short inter-
molecular H···H (1.25 Å) and K···Н (2.19 Å) distances
in the crystal structure (Fig. 1).8 Such distances are
obviously impossible (the typical length of H···H contacts
is 2.01–2.31 Å, while the sum of ionic radius of K+ and
the van der Waals radius of hydrogen atom is 2.76 Å).9 On
the other hand, no such problems would be encountered
when placing the hydrogen atoms at positions cor-
responding to nitrimine, leading to a network of intra- and
intermolecular hydrogen bonds, typical for nitrimines
(Fig. 2).8,10 The nitrimine structure of monosalts derived
from compound 1 was unequivocally confirmed by the
recently published structural data for the hydrazinium
salt.11
The structure of double salt 2a was established by the
method of X-ray crystallography (Fig. 3). All hydrogen
atoms were located from the difference electron density
synthesis and were freely refined (without imposing
constraints) in isotropic approximation. The hydrogen
atom position at the triazole ring nitrogen atom, as well
as the values of valence angles and bond lengths pointed
to nitrimine structure of at least one of the NNO2 groups.
We identified an alternative route leading to the salts of
compound 1 during our study of the reaction of compound 5
with potassium salt of 4-nitrоsemicarbazide (7). This
reaction was expected to result in a salt of 2,5-dinitrо-
1-ureidoguanidine 8 or products of its further cyclization –
1,2,4-triazole derivatives 9 or 2с (Scheme 3). The isolation
of salt 2с from the reaction mixture did not contradict the
proposed scheme of transformations. However, kinetic
study of the hydrolysis reaction of 4-nitrоsemicarbazide
and its salts5 indicated that also in this case the reaction
proceeded according to a route similar to Scheme 2. The
easy hydrolysis of salt 7 upon heating in aqueous solution
merely provided a source of hydrazine.
The erroneous interpretation that salts of compound 1
have primary nitramine structure originated in 1950s.3а The
Scheme 3
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Chemistry of Heterocyclic Compounds 2017, 53(6/7), 722–727
Figure 1. The crystal structures of а) ammonium salt and b) potassium salt of compound 1, reproduced from the literature.7
Figure 2. The crystal structures for а) ammonium salt and b) potassium salt of compound 1 according to corrected data from the
literature.7
The attempts to grow crystals of compound 1 suitable
for X-ray structural analysis were not successful. For this
reason, there is still no direct proof available for the nitr-
imine structure of compound 1. In principle, three different
structures are possible for compound 1: nitrimine A,
primary nitramine B, and nitramino-nitrimine C (Fig. 4).
We have previously shown that compounds known as
3(5)-nitramino-1,2,4-triazoles actually have the structure of
nitrimines.12 This fact was later confirmed by multiple
X-ray structural analyses of other similar compounds.1b,4,13
The results of quantum-chemical calculations at various
levels of theory also reliably showed that the nitrimine
Figure 4. The possible structures for compound 1.
Figure 3. Crystal structure of salt 2a.
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Chemistry of Heterocyclic Compounds 2017, 53(6/7), 722–727
structure has the lowest energy.14 However, it was found
It is interesting to note that the density of compound 1 is
lower than that of its monoammonium (1.84 g/cm3)7 and, in
particular, monohydrazinium salts (1.91 g/cm3).11 In the
majority of cases, the simplest onium salts of nitrо
compounds have lower density than the starting nitrо
compounds.1b
The calculated explosive characteristics of compound 1
were sufficiently high and were approximately at the level
of such powerful explosive as RDX17 (Table 1). In order to
evaluate the practical applicability of compound 1, its
sensitivity to thermal and mechanical initiation was
studied.17 The sensitivity to thermal initiation was
determined from the temperature dependence of time-to-
explosion, according to the standard method.18 The flash of
compound 1 was accompanied by loud bang and eruption
of flame. The impact sensitivity of compound 1 was higher
than that of RDX, and was at the level of other similar
heterocyclic nitrimines19 (Table 1).
Despite the sufficiently high energetic characteristics,
compound 1 has substantial drawbacks: high acidity, low
thermal stability, and very pronounced impact sensitivity.
At the same time, onium salts of compound 1 are clearly of
interest. For example, the velocity of detonation of
hydrazinium salt at the density of 1.8 g/cm3 reached
9.0 km/s (experimental data). This salt at the same time had
lower impact sensitivity and better thermal stability than
compound 1.11 When tested at its maximum density, this
compound had detonation parameters that were superior to
HMX.
Thus, 3,5-dinitrimino-1,2,4-triazole and its salts can be
obtained from the readily available 2-methyl-1-nitrо-
isothiourea. Salts of 3,5-dinitrimino-1,2,4-triazole have
nitrimine structures, according to X-ray crystallographic
analysis. Despite the fact that the spectral data of 3,5-dinitr-
imino-1,2,4-triazole do not allow to clearly discriminate
between the nitramine and nitrimine features, the latter is
the most likely structure.
that 5-nitramino-3-nitrо-1H-1,2,4-triazole, according to the
data of X-ray structural analysis, was a primary nitramine.15
At the same time, quantum-chemical calculations still
showed a preference for the nitrimine form of this com-
pound.14 Taking into account that the quantum-chemical
calculations were performed for an isolated molecule
(simulation of the structure in the gas phase), the difference
from results of X-ray structural analysis apparently can be
explained with the influence of intermolecular interaction
forces in the crystal structure. Strong effects of intermolecular
interactions, in particular hydrogen bonds, on the molecular
structure of nitrimines has been described in the literature.16
In our opinion, X-ray structural analysis data for the
salts of compound 1 pointed in favor of the nitrimine
structure A also for compound 1 itself, since it was unlikely
that the removal of a single proton during salt formation
reaction would result in migration of the remaining
hydrogen atoms among the nitrogen atoms.
It would seem that the selection among the various
possible structures of compound 1 would be possible by
1
relying on NMR spectra. However, Н NMR spectrum of
compound 1 featured only one broadened proton signal
(11.21 ppm), which is common in systems with rapid
exchange of protons. 13C NMR spectrum also contained
only one signal with a chemical shift of 148.3 ppm. This
provided evidence for symmetrical structure of the
molecule in solution phase. 15N NMR spectrum contained
only four signals for the seven nitrogen atoms, which can also
be explained by the molecular symmetry of compound 1.
The signal with chemical shift of −25.1 ppm belonged to
the nitrogen atoms of nitrо groups; the signal of NNO2
group appeared at −179.6 ppm, while the signal at −215.4 ppm
corresponded to the nitrogen atoms of triazole ring at
positions 1, 2, and the signal at −291.2 ppm was due to the
nitrogen atom at position 4. Thus, NMR spectra provided
evidence for symmetrical molecular structure of compound
1, but these data cannot be considered as unequivocal proof
for the nitrimine structure A, since the same result can be
observed in the case of rapid proton exchange in solutions
(on NMR timescale).
Table 1. The energetic characteristics of
compound 1 and RDX
The absorption maximum (due to n→π* transition) in
the electronic spectrum of compound 1 had the same
wavelength (318 nm) and extinction coefficient (4.21) as
those for the monosalts of compound 1, which was not
surprising, because compound 1 is a strong acid according
to its first dissociation constant and exists mostly as
monoanion in aqueous solution. When compared to UV
spectra of 1,2,4-triazoles with one nitrimine group,12 UV
spectrum of compound 1 showed a bathochromic shift,
which can be explained by the presence of conjugation
through the molecular structure of the monoanion of
compound 1.
Parameter
Molecular formula
Compound 1
RDX
C2H3N7O4
–12.7
1.83
C3H6N6O6
–21.6
Oxygen balance, %
ρ0, g/cm3
1.80
ΔHf°, kJ/mol
+194
5.55
+61.5
Qexpl., MJ/kg
5.40
V0, m3/kg
0.742
8.88
0.762
8.7720
D, km/s
The crystal lattice parameters of compound 1 were
determined from powder X-ray diffraction data obtained at
room temperature. The crystals had monoclinic syngony,
space group P21/n, unit cell parameters: a 12.028(2),
b 10.521(2), c 10.920(2) Å; β 97.70(1)°; Z 8; V 1369.5(4) Å3,
PCJ, GPa
Tflash5s, °C
34.3
36.120
26018c
25 (50%)18а
139.5*
Impact sensitivity (5 kg)
H, cm
* Ea 108.5 kJ/mol, log A 10.48.
< 4 (0%)
16 (100%)
d
calc 1.834 g/cm3.
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Chemistry of Heterocyclic Compounds 2017, 53(6/7), 722–727
Experimental
into EtOH (200 ml) and cooled to −18°С. The precipitate
that formed was filtered off and washed on filter with
EtOH. Yield 10.2 g (65%), colorless crystals, decomp. temp.
280°С (H2O). IR spectrum (KBr), ν, cm−1: 3389, 3115,
3109, 1665, 1624, 1549, 1452, 1422, 1402, 1387, 1365,
1330, 1313, 1267, 1168, 1101, 1063, 1032, 996, 880, 834,
812, 753, 706, 695, 556, 488, 452. UV spectrum, λmax, nm
(log ε): 206 (4.05), 302 (4.19). Found, %: C 8.20; H 2.42;
N 34.14. C2HN7Na2O4·3H2O. Calculated, %: C 8.37;
H 2.46; N 34.15.
Hydrate of 3,5-dinitrimino-1,2,4-triazole sodium salt
(3a). A heated solution of salt 2a (2 g, 7 mmol) in H2O
(20 ml) was treated with 68% nitric acid (1 ml, 15 mmol),
the solution was cooled to room temperature and then to
−18°С. The precipitate was filtered off and washed on filter
with EtOH. Yield 0.9 g (56%), colorless crystals, decomp.
temp. 185°С (H2O). IR spectrum (KBr), ν, cm−1: 3588,
3539, 3438, 3153, 1647, 1589, 1560, 1495, 1425, 1335,
1328, 1275, 1233, 1117, 1079, 1052, 1011, 988, 881, 855,
809, 773, 753, 722, 659, 610, 539, 479, 446. UV spectrum,
λmax, nm (log ε): 210 (4.06), 318 (4.20). Found, %:
C 10.04; H 1.78; N 42.28; C2H2N7NaO4·H2O. Calculated, %:
C 10.49; H 1.76; N 42.80.
IR spectra were recorded on a Nicolet Impact 400D FT-IR
spectrometer with the resolution of 4 cm−1. UV spectra were
recorded on a Shimadzu UV-1601 spectrophotometer for
aqueous solutions at 10−4 М concentration, with cuvette
1
thickness of 1 cm. H, 13С, and 15N NMR spectra were
acquired on a Bruker Avance III instrument (600, 150, and
60 MHz, respectively) at room temperature in acetone-d6
solution, while using TMS as internal standard (or MeNO2
standard for 15N nuclei). 15N NMR spectra were acquired by
using different pulse sequences (zgig and ineptrd). Elemental
analysis was performed on a vario EL III instrument. Melt-
ing and decomposition temperatures were determined on a
PTP apparatus. The impact sensitivity was studied on a K-44-II
fall hammer apparatus18с with a 5 kg hammer and 30 mg
samples. The methods for calculation of energetic
parameters and experimental determination of flash
temperature and impact sensitivity for compound 1 have
been described in detail previously.17
3,5-Dinitrimino-1,2,4-triazole (1). Method I. Barium
salt 2b (1.75 g, 4.2 mmol) was dissolved with heating in
H2O (50 ml) and treated with concd HCl (9 ml). Then
concd H2SO4 (0.2 ml, 3.9 mmol) was added to the solution
and the BaSO4 precipitate was removed by filtration. The
filtrate was evaporated under air flow, the residue was
treated with acetone (25 ml), filtered, and the filtrate was
evaporated. Yield 0.3 g (38%).
Hydrate of 3,5-dinitrimino-1,2,4-triazole dipotassium
salt (2c). Method I. This method was analogous to the
procedure for preparation of salt 2a, except that KHCO3
(10 g, 100 mmol) or K2CO3 (6.9 g, 50 mmol) was used
instead of NaHCO3 or Na2CO3. Yield 9.7 g (62%).
Method II. Salt 3b (5.0 g, 8.5 mmol) was dissolved with
heating in H2O (75 ml) and treated with concd HCl (9 ml).
The solution was then treated with concd H2SO4 (0.4 ml,
7.9 mmol) and the BaSO4 precipitate was removed by
filtration. The filtrate was evaporated under air flow, the
residue was treated with acetone (60 ml), then filtered and
the filtrate was evaporated. Yield 1.4 g (43%).
Method II. Compound 5 (1 g, 7.4 mmol) was dissolved
with heating in H2O (10 ml), treated by the addition of salt
7 (1.17 g, 7.4 mmol),22 and maintained for 3 h on a reflux-
ing water bath. The reaction solution was cooled to room
temperature and poured into EtOH (30 ml), then cooled to
−18°С. The precipitate was filtered off, washed with EtOH,
and air-dried. Yield 0.7 g (67%), colorless crystals,
decomp. temp. 220°С (H2O) (decomp. temp. 221°С3с).
IR spectrum (thin layer), ν, cm−1: 3537, 3168, 3019, 1649,
1525, 1481, 1431, 1386, 1354, 1321, 1257, 1155, 1101,
1058, 1015, 991, 868, 798, 760, 693. UV spectra, λmax, nm
(log ε): 206 (3.99), 305 (4.19).
Pentahydrate of 3,5-dinitrimino-1,2,4-triazole barium
salt (2b). A hot solution of Ba(NO3)2 (1.8 g, 6.9 mmol) in
H2O (5 ml) was added with stirring to a hot solution of salt
2a (1.8 g, 6.3 mmol) in H2O (10 ml). The reaction solution
was cooled to room temperature, the obtained precipitate
was filtered off, washed with H2O and EtOH. Yield 2.2 g
(86%), colorless crystals, decomp. temp. ~350°С. IR spect-
rum (KBr), ν, cm−1: 3576, 3505, 3415, 1666, 1624, 1541,
1482, 1438, 1396, 1360, 1327, 1300, 1163, 1119, 1089,
1072, 1006, 993, 880, 871, 856, 756, 732, 713, 704, 693,
625, 550, 473, 452. UV spectrum, λmax, nm (log ε): 206
(4.06), 302 (4.19). Found, %: C 5.72; H 1.92; N 24.52.
C2HBaN7O4·5H2O. Calculated, %: C 5.80; H 2.68;
N 23.66.
Method III. A solution of salt 2a (4.9 g, 17 mmol) in
H2O (15 ml) at room temperature was treated with concd
HCl (19 ml) and cooled to −18°С. The precipitate that
formed was filtered off, treated with acetone (60 ml),
filtered, and the filtrate was evaporated. Yield 1.8 g (56%),
colorless crystals, decomp. temp. 125°С (acetone). IR spect-
rum (KBr), ν, cm−1: 3337, 3082, 2973, 2916, 2849, 2775,
1640, 1619, 1581, 1532, 1477, 1420, 1401, 1329, 1279,
1246, 1128, 1102, 1045, 993, 893, 832, 774, 751, 715, 515,
471, 437. UV spectrum, λmax, nm (log ε): 213 (3.99), 318
1
(4.21). H NMR spectrum, δ, ppm: 11.21 (br. s). 13C NMR
spectrum, δ, ppm: 148.3. 15N NMR spectrum, δ, ppm: −25.1
(NO2); −179.6 (NNO2); −215.4 (N-1,2); −291.2 (N-4).
Found, %: C 12.89; H 1.60; N 51.41. C2H3N7O4.
Calculated, %: C 12.70; H 1.60; N 51.85.
Trihydrate of 3,5-dinitrimino-1,2,4-triazole disodium
salt (2a). A solution of compound 521 (14.9 g, 110 mmol)
in H2O (80 ml) was stirred and treated by the addition of
hydrazine hydrate (50 mmol), which was analyzed for
hydrazine content prior to use. The reaction mixture was
maintained at room temperature for 1 h. Then NaHCO3
(8.4 g, 100 mmol) or Na2CO3 (5.3 g, 50 mmol) was added,
the mixture was heated to 70°С, and maintained at that
temperature for 1.5 h. The reaction mixture was poured
Tetrahydrate of barium di(3,5-dinitrimino-1,2,4-tri-
azolate) (3b). Method I. A hot solution of salt 2a (5.00 g,
17.4 mmol) in H2O (50 ml) was stirred and treated by the
addition of 68% HNO3 (1.5 ml), followed by adding a hot
solution of Ba(NO3)2 (2.28 g, 8.7 mmol) in H2O (12.5 ml).
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Chemistry of Heterocyclic Compounds 2017, 53(6/7), 722–727
7. Fu, Z. J.; Chen, Z. W.; Pan, K. Z.; Gao, R. X.; Du, Z. Y.
The solution was cooled to room temperature, the
Jiegou Huaxue 1985, 3, 206.
precipitate was filtered off, washed with H2O and EtOH.
Yield 4.9 g (96%).
8. (a) Astakhov, A. M.; Vasiliev, A. D.; Molokeev, M. S.;
Stepanov, R. S. In Energetic Condensed Systems. Proceedings
of 2nd All-Russia Conference [in Russian]; Yanus-K:
Chernogolovka, 2004, p. 19. (b) Astakhov, A. M.; Revenko, V. A.;
Buka, E. S.; Vasiliev, A. D. In Chemistry of Nitro Compounds
and Related Nitrogen-Oxygen Systems [in Russian]; Institute
of Organic Chemistry, Russian Academy of Sciences:
Moscow, 2009, p. 45.
9. Zefirov, Yu. V.; Zorkiy, P. M. Usp. Khim. 1995, 446.
10. Allen, F. H. Acta Crystallogr., Sect. B: Struct. Sci., Cryst.
Eng. Mater. 2002, B58, 380.
11. Cui, K.; Meng, Z.; Xu, Z.; Xue, M.; Lin, Z.; Wang, B.; Ge, Z.;
Qin, G. J. Energ. Mater. 2014, 32, S60.
Method II. A solution of Ba(NO3)2 (0.18 g, 0.69 mmol)
in H2O (2 ml) was added to a hot stirred solution of salt 3a
(0.31 g, 1.35 mmol) in H2O (3 ml). The solution was
cooled to room temperature, the precipitate was filtered off,
washed with H2O and EtOH. Yield 0.24 g (61%), colorless
crystals, decomp. temp. >320°С. IR spectrum (KBr), ν, cm−1:
3582, 3448, 3422, 3362, 3294, 3063, 2837, 1596, 1550,
1486, 1407, 1366, 1344, 1214, 1121, 1080, 1043, 1010, 980,
873, 830, 764, 723, 672, 544, 448. UV spectrum, λmax, nm
(log ε): 210 (4.04), 315 (4.22). Found, %: C 7.91; H 1.89;
N 33.25. C4H4BaN14O8·4H2O. Calculated, %: C 8.20;
H 2.07; N 33.49.
Powder X-ray diffraction analysis was performed on a
Bruker D8 Advance diffractometer. X-ray structural
analysis of salt 2a was performed on a Bruker SMART
APEX II instrument with a Bruker AXS CCD detector at
296(2) K temperature. Crystals of salt 2a that were suitable
for X-ray structural analysis were obtained by slow
evaporation from aqueous solution. The complete X-ray
structural dataset for compound 2а was deposited at the
Cambridge Crystallographic Data Center (deposit CCDC
1535107).
12. Astakhov, A. M.; Vasil'ev, A. D.; Molokeev, M. S.;
Revenko, V. A.; Stepanov, R. S. Russ. J. Org. Chem. 2005,
41, 910. [Zh. Org. Khim. 2005, 41, 928.]
13. (a) Wang, R.; Xu, H.; Guo, Y.; Sa, R.; Shreeve, J. M. J. Am.
Chem. Soc. 2010, 132, 11904. (b) Dippold, A. A.; Feller, M.;
Klapötke, T. M. Cent. Eur. J. Energ. Mat. 2011, 8, 261.
(c) Dippold, A. A.; Klapötke, T. M.; Martin, F. A. Z. Anorg.
Allg. Chem. 2011, 637, 1181. (d) Dippold, A. A.; Klapötke, T. M.;
Oswald, M. Dalton Trans. 2013, 42, 11136. (e) Dippold, A. A.;
Izsák, D.; Klapötke, T. M. Chem.–Eur. J. 2013, 19, 12042.
14. Astakhov, A. M.; Dyugaev, K. P.; Kuzubov, A. А.; Buka, E. S.
In Energetic Condensed Systems. Proceedings of 3rd All-
Russia Conference [in Russian]; Yanus-K: Chernogolovka,
2006, p. 13.
Dehydration and hydration studies for salts of
compound 1. The content of solvated water in salts was not
only reflected in the data of elemental analysis and UV
15. Dippold, A. A.; Klapötke, T. M.; Martin, F. A.; Wiedbrauk, S.
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A
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