Metal salts of dinitro-, trinitropyrazole, and trinitroimidazole

Article abstract of DOI:10.1002/zaac.201400233

The syntheses of alkali and earth alkaline dinitropyrazolate (DNP), trinitropyrazolate (TNP), and trinitroimidazolate (TNI) salts are reported. Additionally, copper trinitroimidazolate was synthesized. Their characterization by NMR spectroscopy, mass spectrometry, elemental analysis, and vibrational spectroscopy is reported as well. Crystal structures of compound Ba(DNP)₂ (9), which crystallizes with one molecule of methanol and ethyl ether as well as of compounds Sr(TNP)₂·3H₂O (12), Ba(TNP)₂·3H₂O (13), and LiTNI·3H₂O (14) were determined. The energetic and thermal properties were measured as well. Green- and red-burning pyrotechnic formulations containing barium salts 9 and 13 as well as strontium salts 8 and 12 serving as colorants are tested. Additionally, formulations using Sr(TNP)₂·3H₂O (12) and Ba(TNP)₂·3H₂O (13) as the oxidizer and colorant at the same time were examined. The formulations were investigated with regard to their combustion behavior and performances such as burn time, dominant wavelength, spectral purity, luminous intensity, and luminous efficiency. The sensitivities towards ignition stimuli and the decomposition temperatures were determined as well.

Full text of DOI:10.1002/zaac.201400233

Job/Unit: Z14233
/KAP1
Date: 13-06-14 12:01:35
Pages: 11
ARTICLE
DOI: 10.1002/zaac.201400233
Metal Salts of Dinitro-, Trinitropyrazole, and Trinitroimidazole
[
a]
[a]
[a]
Ines E. Drukenmüller, Thomas M. Klapötke,* Yvonne Morgenstern,
[a]
[a]
Magdalena Rusan, and Jörg Stierstorfer
Keywords: Nitropyrazolate salts; Trinitroimidazole; Synthesis; Nitrogen-rich compounds; Green-burning pyrotechnic formula-
tions; Red-burning pyrotechnic formulations
Abstract. The syntheses of alkali and earth alkaline dinitropyrazolate as well. Green- and red-burning pyrotechnic formulations containing
(
DNP), trinitropyrazolate (TNP), and trinitroimidazolate (TNI) salts
are reported. Additionally, copper trinitroimidazolate was synthesized. colorants are tested. Additionally, formulations using Sr(TNP)
Their characterization by NMR spectroscopy, mass spectrometry, ele- (12) and Ba(TNP) ·3H O (13) as the oxidizer and colorant at the same
mental analysis, and vibrational spectroscopy is reported as well. Crys- time were examined. The formulations were investigated with regard
tal structures of compound Ba(DNP) (9), which crystallizes with one to their combustion behavior and performances such as burn time,
molecule of methanol and ethyl ether as well as of compounds dominant wavelength, spectral purity, luminous intensity, and lumi-
Sr(TNP) ·3H O (12), Ba(TNP) ·3H O (13), and LiTNI·3H O (14) nous efficiency. The sensitivities towards ignition stimuli and the de-
were determined. The energetic and thermal properties were measured composition temperatures were determined as well.
barium salts 9 and 13 as well as strontium salts 8 and 12 serving as
2
2
·3H O
2
2
2
2
2
2
2
2
Introduction
sition product is molecular nitrogen, which also means im-
proved color brilliance. But also high performance and sta-
bility are important properties. For these reasons alkali and
earth alkali salts of 3,5-dinitropyrazolate (3,5-DNP), 3,4,5-
trinitropyrazole (TNP), and 2,4,5-trinitroimidazole (TNI) are
interesting compounds as potential coloring agents since they
may fit these requirements.
Energetic materials based on five-membered nitrogen-con-
taining heterocycles such as tetrazole and triazole have been
[1]
widely investigated. The introduction of nitro groups en-
hances the oxygen balance and density of energetic compounds
and therefore improves the detonation properties.[ Various ni-
2]
trogen-rich 3,4,5-trinitropyrazolate and 2,4,5-trinitroimidazol-
In this contribution the syntheses of alkali and earth alkaline
dinitropyrazolate, trinitropyrazolate, and trinitroimidazolate
salts are described. The characterization was performed using
NMR and IR spectroscopy as well as elemental analysis and
mass spectrometry. Crystal structures of barium bis(2,5-
dinitropyrazolate) crystallizing with one molecule of methanol
and ethyl ether, strontium bis(trinitropyrazolate) trihydrate,
barium bis(trinitropyrazolate) trihydrate, and lithium trinitro-
imidazolate trihydrate were determined. Also copper
bis(trinitroimidazolate) tetrahydrate was synthesized and char-
acterized. Green- and red-burning formulations containing se-
lected metal salts were prepared and investigated with respect
to their color performance and thermal and energetic proper-
ties. Compounds Sr(TNP) ·3H O (12) and Ba(TNP) ·3H O
ate salts are reported in literature.[
2,3]
3,5-Dinitropyrazole as
well as salts of 3,4,5-trinitropyrazole and 2,4,5-trinitroimida-
zole with nitrogen-rich cations are reported to be insensitive
and reveal good oxygen balance, high thermal stability, and
high positive molar enthalpies of formation.[
2,3]
Although
metal 3,4,5-trinitropyrazolate salts are mentioned in patents,[
their full characterization and energetic properties are not de-
scribed. The synthesis of potassium 2,4,5-trinitroimidazolate is
reported by Duddu et al.[ Nitrogen-rich compounds based on
4]
5]
3,5-dinitropyrazole, 3,4,5-trinitropyrazole, and 2,4,5-trinitro-
imidazole are investigated as potential energetic materials and
propellants, respectively,[
2,3]
but the corresponding metal salts
could also be of interest for the use as colorants in pyrotechni-
cal applications. The development of environmentally friendly
pyrotechnics, which is of high relevance, requires a smokeless
or smoke-reduced combustion as well as the formation of less
toxic decomposition products. Nitrogen-rich compounds are
considered to be suitable candidates since their main decompo-
2
2
2
2
(13) were tested in pyrotechnic formulations serving as the
oxidizer and colorant at the same time.
Results and Discussion
*
Prof. Dr. T. M. Klapötke
Syntheses
Fax: +49-89-2180-77492
E-Mail: tmk@cup.uni-muenchen.de
[
a] Department of Chemistry
Energetic Materials Research
Ludwig-Maximilian University
Butenandtstr. 5–13 (D)
The first starting material 3,5-dinitropyrazole (1) was syn-
thesized according to literature procedures by stepwise ni-
tration of commercially available pyrazole.[
6,7]
The second
81377 München, Germany
starting material 3,4,5-trinitropyrazole (2) was synthesized by
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. M. Klapötke et al.
ARTICLE
nitration of compound 1 with concentrated HNO /H SO (Fig-
The synthesis of potassium 2,4,5-trinitroimidazolate was re-
3
2
4
ure 1). The third starting compound 2,4,5-trinitroimidazole (3) ported by Duddu et al.[ The herein reported compounds 14–
5]
was obtained by nitration of 4-nitroimidazole with concen- 20 were obtained by the reacting of a solution of compound 3
trated HNO and glacial acetic acid obtaining 2,4-dinitroimid- in ethyl ether with the corresponding metal carbonates (Fig-
3
azole as intermediate compound followed by a second nitration ure 5). After removing the solvent and recrystallization from
reaction with concentrated HNO /H SO yielding compound 3 ethyl acetate the products were gained.
3
2
4
(Figure 2).
Figure 1. Synthesis of compounds 1 and 2.
Figure 5. Synthesis of metal 2,4,5-trinitroimidazolate salts.
IR Spectroscopy
All product compounds were characterized by infrared spec-
troscopy. The assignment of absorptions is based on the values
given in the literature.[ The 3,5-dinitropyrazole salts exhibit
Figure 2. Synthesis of compound 3.
8]
symmetrical and asymmetrical nitro groups stretching vi-
The alkali and earth alkaline salts of 3,5-dinitropyrazole brations between 1282–1284 cm–1 and 1608–1636 cm . The
–1
were obtained by the reaction of compound 1 with the corre- C–NO stretching vibrations are observable in the regions of
2
sponding metal hydroxides in water at room temperature (Fig- 1333–1351 cm–1 and 1528–1555 cm . The 3,4,5-trinitro-
–1
ure 3). After removing the solvent products 4–9 were obtained pyrazole salts show C–C valence vibration in the region be-
–1
–1
as yellow solids. Estimation of the amount of crystal water is tween 1454 cm and 1668 cm . The ring vibrations appear in
the range between 841 cm–1 and 850 cm . The symmetrical
and asymmetrical valence vibrations of the nitro groups are
visible between 1318–1328 cm–1 and 1512–1540 cm . The vi-
–1
based on elemental analysis.
–1
–1
brations of the crystal water were detected at 3582 cm and
512 cm . The ring vibrations of the 2,4,5-trinitroimidazolate
salts are visible in the range between 650 cm and 690 cm .
The symmetrical and asymmetrical vibrations of the nitro
groups as well as the crystal water vibrations appear in at the
same range like that of the 3,4,5-trinitropyrazole salts.
–1
3
–1
–1
Figure 3. Synthesis of metal 3,5-dinitropyrazolate salts.
The synthesis of 3,4,5-trinitropyrazolate salts was reported
in a patent but no analytical data was provided.[ The alkali Crystal Structures
4]
and earth alkaline salts of 3,4,5-trinitropyrazolate were synthe-
In order to round out characterization low temperature sin-
sized by deprotonating compound 2 with the corresponding
metal carbonates in ethanol at room temperature (Figure 4).
Removing the solvent resulted in the formation of products
gle-crystal X-ray diffraction was carried out and the results are
described in the following. Selected data and parameter of the
measurements and solutions are gathered in Table 1. Salts of
10–13 as slightly yellow solids.
3
,5-dinitropyrazole do not tend to form single crystals. Up to
[9]
now only the gold complex DNP-Au-PPh3 has been submit-
ted to the CCDC database. Also barium dinitropyrazolate (9)
could only be obtained single crystalline with inclusion of the
two solvent molecules methanol and diethyl ether, which is
shown in Figure 6. The compound crystallizes in the mono-
clinic space group P2 /c with (due to the solvent inclusion) a
1
relatively low density of 1.86 g·cm–3 at 173 K in comparison
to other barium salts. Both pyrazolate anions are arranged al-
most planar. The nitro groups are twisted only very little out
Figure 4. Synthesis of metal 3,4,5-trinitropyrazolate salts.
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2
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Metal Salts of Dinitro-, Trinitropyrazole, and Trinitroimidazole
Table 1. Crystallographic data of 9, 12, 13, and 14.[12–18]
9
12
13
14
Formula
FW /g·mol–1
Crystal system
Space group
Color / habit
Size /mm
a /Å
C
11
557.65
H
16BaN
8
O
10
C
6
H
6
N
10
O
15Sr
C
6
H
6
BaN10
595.54
orthorhombic
Fdd (No. 43)
O
15
3 6 5 9
C H LiN O
545.83
orthorhombic
Fdd (No. 43)
263.07
monoclinic
P2
triclinic
¯
P1 (No. 2)
1
/c (No. 14)
2
2
colorless plate
0.09ϫ0.18ϫ0.34
10.1288(3)
9.4139(2)
21.4156(8)
90
colorless block
colorless block
0.08ϫ0.13ϫ0.22
28.6910(8)
28.8940(9)
8.8301(2)
90
colorless plate
0.08ϫ0.15ϫ0.32
7.3642(9)
8.2851(10)
9.1092(12)
94.148(11)
104.721(11)
108.607(11)
502.25(12)
2
0.14ϫ0.15ϫ0.20
28.5318(8)
b /Å
28.4016(8)
c /Å
8.5108(2)
α /°
90
β /°
103.197(3)
90
90
90
90
γ /° 3
90
V /Å
1988.08(11)
4
6896.7(3)
16
7320.1(3)
16
Z
–
3
ρ
calcd. /g·cm
1.863
2.103
2.162
1.740
–1
μ /mm
F(000)
λ Mo-K
T /K
2.066
3.238
2.275
0.172
1096
4320
4608
268
α
/Å
0.71073
173
0.71073
173
0.71073
100
0.71073
173
θ min-max /°
Dataset h; k; l
Reflect. coll.
Independ. refl.
4.2, 26.0
–12:12; –11:11; –26:26
19502
4.4, 26.0
–35:26; –34:32; –7:10
8806
4.3, 27.0
–36: 36; –36:36; –11:11
19700
4.3, 26.0
–8: 9; –10:10; –11:11
3859
3892
3059
3977
1963
R
int
0.048
0.028
0.029
0.025
Reflection obs.
No. parameters
3283
2898
3827
1640
283
313
313
187
R
wR
S
1
(obs)
(all data)
0.0254
0.0225
0.0165
0.0335
2
0.0580
0.0504
0.0384
0.0881
1.03
1.04
1.04
1.04
–3
Resd. dens. /e·Å
Device type
Solution
Refinement
Absorpt. corr.
CCDC
–0.41, 0.61
Oxford Xcalibur3 CCD
SIR-92
–0.35, 0.50
Oxford Xcalibur3 CCD
SIR-92
–0.25, 0.57
Oxford Xcalibur3 CCD
SHELXS-97
SHELXL-97
multi-scan
1002138
–0.24, 0.24
Oxford Xcalibur3 CCD
SIR-92
SHELXL-97
multi-scan
1002135
SHELXL-97
multi-scan
1002137
SHELXL-97
multi-scan
1002136
of the ring plane. Including coordination up to a distance of
Å, the barium cations are surrounded by the atoms N5, N2,
3
i
i
ii
O4, O8, N1 , O1 , O6 , and O9 (symmetry codes: (i) –x, 0.5+y,
0.5–z, (ii) x, –1+y, z).
In contrast to dinitropyrazole, structures of 3,4,5-trinitropyr-
azole and derivatives have been described in the literature
more often. Prominent examples are neutral 3,4,5-trinitropyra-
zole[ and its ammonium salt.
10]
[11]
It was possible to obtain
single crystals of strontium as well as barium trinitropyrazolate
both as their trihydrates. Interestingly, both salts crystallize iso-
typically (see Table 1) in the non-centrosymmetric orthorhom-
bic space group Fdd with 16 anion/cation pairs in the unit
2
cell. The density of the barium salt is only slightly higher
–
3
(
(
2.162 g·cm at 100 K) than that of the strontium salt
2.103 g·cm–3 at 173 K). The molecular moieties are depicted
in Figure 7 and Figure 8. Also the coordination distances are
in the same range. The structure of the trinitropyrazolate anion
[
11]
is comparable to that observed for the ammonium salt,
in
which the inner nitro group significantly is twisted out of the
planar ring plane due to steric reasons.
Figure 6. Representation of the molecular unit of 9, showing the atom-
labeling scheme. Thermal ellipsoids represent the 50% probability
level and hydrogen atoms are shown as small spheres of arbitrary ra-
Lithium 2,4,5-trinitroimidazolate trihydrate (14) crystallizes
¯
–3
dius. Selected anion bond lengths /Å: O1–N3 1.238(3), O2–N3 in the triclinic space group P1 with a density of 1.740 g·cm .
1
1
1
1
.227(3), O3–N4 1.224(4), O4–N4 1.242(4), N1–C3 1.347(4), N1–N2
.355(3), N2–C1 1.352(4), N3–C3 1.439(4), N4–C1 1.431(4), C1–C2
.373(5), C2–C3 1.372(4); selected anion bond angles /°: O2–N3–O1
24.0(3), O2–N3–C3 117.3(3) O1–N3–C3 118.7(3); selected anion tor-
The structure of the anions is comparable to the structure pub-
lished for dimethylammonium 2,4,5-trinitro-imidazolate.
The nitro group bonded to carbon atom C3 follows the planar
ring structure. The adjacent nitro groups are slightly rotated
[3]
sion angles /°: N1–C3–N3–O1 6.8(5), C2–C1–N4–O3 11.4(5).
Z. Anorg. Allg. Chem. 0000, 0–0
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T. M. Klapötke et al.
ARTICLE
Table 2. Thermal properties of compounds 4–9.
4
5
6
7
8
9
FS /N
IS /J
ESD /J
Ͼ360
Ͼ40
0.7
Ͼ360
Ͼ40
0.5
216
20
0.1
360
8
0.5
Ͼ360
Ͼ40
0.2
72
30
0.1
Grain size /μm
Ͻ100
78
145
Ͻ100
98
295
100–500
–
–
306
100–500
120
–
100–500
89
–
500–1000
150
–
T
T
T
dehydro /°C
m
/°C
dec /°C
325
324
Ͼ400
398
361
Figure 7. Molecular unit of 12, showing the atom-labeling scheme.
Thermal ellipsoids represent the 50% probability level and hydrogen
atoms are shown as small spheres of arbitrary radius. Selected stron-
tium coordination distances /Å: O1–Sr 2.863(2), N–Sr 2.704(2), Sr–
O17 2.531(2), Sr–O16 2.691(2), Sr–O15 2.816(2), Sr1–N6 2.840(2).
Figure 9. Illustration of the dimeric lithium coordination and two trini-
troimidazolate anions in the crystal structure of LiTNI (14). Thermal
ellipsoids represent the 50% probability level and hydrogen atoms are
shown as small spheres of arbitrary radius. Lithium-oxygen distances
i
/Å: : Li–O7 1.916(3), Li–O8 1.910(3), Li–O9 2.064(3), Li–O9
1.999(3); symmetry codes (i) 1–x, 1–y, 1–z; (ii) 1–x, –y, 1–z.
tetrahedrally by four water molecules. A dimeric dicationic
motive is formed by two bridging water molecules, which is
shown in Figure 9.
Thermal and Energetic Properties
Table 2, Table 3, and Table 4 show the dehydration
(
Tdehydro), melting (T ) and decomposition (Tdec) temperatures
m
of compounds 4–9 (dinitropyrazolate salts), compounds 10–13
trinitropyrazolate salts), and compounds 14–20 (trinitro-
(
imidazolate salts) measured by differential scanning calorime-
try (DSC). The friction (FS) and impact (IS) sensitivities as
well as the sensitivity towards electrostatic discharge (ESD)
were determined and are summarized in Table 2, Table 3, and
Table 4.
Figure 8. Representation of the molecular unit of 13, showing the
atom-labeling scheme. Thermal ellipsoids represent the 30% prob-
ability level and hydrogen atoms are shown as small spheres of arbi-
trary radius. Selected barium coordination distances /Å: Ba–O15
Table 3. Thermal properties of compounds 10–13.
10
11
12
13
2.700(2), Ba–O13 2.874(2), Ba–N1 2.898(2), Ba–N6 2.913(2), Ba–
FS /N
IS /J
ESD /J
96
40
0.2
80
25
0.2
80
40
0.2
144
5
0.1
100–500
115
158
302
O14 2.943(2), Ba–O1 3.052(2).
out of the ring system [torsion angles: N1–C1–N3–O1 28.2(2)°
and C1–C2–N4–O3 14.1(3)°]. A O2–N3–N4–O3 bent angle of
Grain size /μm 100–500
100–500
–
–
254
100–500
121
–
T
T
T
dehydro /°C
104
–
274
m
/°C
43.9(1)° is observed due to steric repulsion. The anions do
not coordinate to the lithium cations, which are coordinated
dec /°C
193
4
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Metal Salts of Dinitro-, Trinitropyrazole, and Trinitroimidazole
Table 4. Thermal properties of compounds 14–20.
14
15
16
17
18
19
20
FS /N
IS /J
ESD /J
Ͼ360
Ͼ40
0.5
Ͼ360
Ͼ40
0.6
120
25
0.2
Ͼ360
Ͼ40
0.7
Ͼ360
Ͼ40
0.7
Ͼ360
Ͼ40
0.6
80
3
0.1
Grain size /μm
Ͻ100
79
152
Ͻ100
–
–
100–500
–
–
231
100–500
110
–
Ͻ100
104
–
100–500
98
123
100–500
107
–
T
T
T
dehydro /°C
m
/°C
dec /°C
252
249
188
239
166
170
The 3,5-dinitropyrazolate salts (4–9) are predominantly fric- Red-Burning Formulations
tion insensitive. Only the potassium (6) and barium (9) salts
are friction sensitive. The impact sensitivities vary from insen-
sitive to very sensitive (compound 7). All salts 4–9 show high
decomposition temperatures and the DSC curves reveal endo-
thermic peaks between 78 °C and 150 °C, which can be as-
signed to the loss of crystal water (Table 2).
The strontium control M126A1 was mixed in a small-scale
0.6 g) and the color properties as well as thermal and ener-
getic properties were measured and are summarized in Table 5,
Table 6, and Table 7.
(
Table 5. US ArmyЈs composition M126A1 /wt-%.
3
,4,5-Trinitropyrazolate salts are friction and impact sensi-
Sr(NO
Sr-control 39.9
3
)
2
KClO
9.8
4
Mg
PVC
14.7
VAAR
6.8
tive. The DSC curves reveal peaks between 104 °C and 121 °C
corresponding to the crystal water loss (Table 3). As can been
seen in Table 4 the 2,4,5-trinitroimidazolate salts are impact
and friction insensitive. Only the potassium (16) and copper
20) salts are impact and friction sensitive.
The DSC curves of compounds 14 and 17–20 show endo-
thermic peaks between 79 °C and 110 °C, which can be as-
signed to the loss of crystal water. All salts show high decom-
position temperatures ranging from 166 °C to 252 °C
29.4
Table 6. US ArmyЈs composition M126A1.
Burn time /s Dw /nm Sp /% LI /cd LE /cdsg–1
Sr-control 4 617 91 992 6613
(
Table 7. US ArmyЈs composition M126A1.
(
Table 4).
Impact /J Friction /N
10 360
Grain size /μm
Ͻ100
T
dec /°C
Sr-control
266
Pyrotechnical Formulations
In Table 8 the content of formulation SrDNP_1 containing
The investigation of perchlorate-free formulations is per- compound 8, ammonium nitrate, magnesium, and poly(vinyl
formed. The barium compounds 9 and 13 and the strontium chloride) serving as colorant, the oxidizer, fuel and chlorine
compounds 8 and 12 were tested as nitrogen-rich colorants donor is summarized. The content of formulations SrDNP_2
in pyrotechnic formulations. Several formulations containing and SrDNP_3 consisting of compound 8, ammonium dinitram-
besides the metal salts ammonium nitrate and ammonium dini- ide, and magnesium is shown in Table 9. Formulation
tramide (ADN) as oxidizer were prepared and compared to SrDNP_3 contains additionally PVC.
the US ArmyЈs in-service green (M125A1) and red (M126A1)
Table 8. Formulation /wt-% SrDNP_1.
formulations. Formulations without additional NH NO3 or
4
ADN but containing compounds 12 and 13, which served as
the oxidizer and colorant, were prepared and investigated. SrDNP_1
Magnesium was used as fuel. The pyrotechnical compositions
were prepared by mixing all substances, except the binder, in
8
NH
4
NO
3
Mg
13
PVC
3
VAAR
4
13
67
Table 9. Formulations /wt-% SrDNP_2 and SrDNP_3.
a mortar. Then the binder, a solution of 25% vinyl alcohol
acetate resin (VAAR), was added. After drying in high vacuum
for 3 h the mixtures were grinded again. Pellets of 0.6 g each
8
ADN
Mg
PVC
VAAR
SrDNP_2
15
10
72
62
8
13
–
10
5
5
were pressed using a consolidation dead load of 2000 kg. The SrDNP_3
pellets were dried overnight at ambient temperature. The per-
formance of each composition has been evaluated with respect
All three formulations burned smokeless with a red flame
to color emission, smoke generation, and the amount of solid color. In Table 11 the burn time and the color performance
residues. The dominant wavelength and spectral purity was values are summarized. While formulations SrDNP_2 and
measured based on the 1931 CIE method using illuminant C SrDNP_3 show comparable spectral purities to the strontium
as the white reference point. Five samples were measured for control, formulation SrDNP_1 exhibits a lower spectral purity
each formulation and all given values are averaged based on (Table 6 and Table 11). The luminous intensities of all three
the full burn of the mixture.
formulations are lower than that of the strontium control for-
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de 5

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T. M. Klapötke et al.
ARTICLE
mulation (Table 6 and Table 11). In Table 12 the impact and Table 13. US ArmyЈs composition M125A1 /wt-%.
friction sensitivities as well as the decomposition temperatures
Ba(NO
46
3
)
2
Mg
33
PVC
16
VAAR
5
are shown. Formulation SrDNP_1 containing NH NO instead
4
3
Ba-control
ADN is neither friction nor impact sensitive and reveals a
higher decomposition temperature than formulations SrDNP_2
and SrDNP_3, which are also friction and impact sensitive.
Two formulations containing compound 12 as the oxidizer
and colorant were tested. Both formulations do not contain
any additional oxidizer. Magnesium was used as fuel and only
composition SrTNP_1 contains PVC. The content of these for-
mulations is summarized in Table 10.
Table 14. US ArmyЈs composition M125A1.
Burn time /s Dw /nm Sp /% LI /cd LE /cdsg–1
Ba-control 3 558 75 390 1950
Table 15. US ArmyЈs composition M125A1.
Impact /J
15
Friction /N
360
Grain size /μm
Ͻ100
Tdec /°C
Table 10. Formulations /wt-% SrTNP_1 and SrTNP_2.
Ba-control
258
12
Mg
PVC
VAAR
SrTNP_1
SrTNP_2
68
68
20
25
5
–
7
7
Two formulations containing compound 9 as colorant and
ammonium nitrate (Table 16) and ammonium dinitramide
(
Table 17) as the oxidizer are shown. Both formulations con-
Both formulations revealed a smokeless burn down. An in-
tensive-red flame color and no remaining residues could be
observed. Compared to the Sr-control formulation both compo-
sitions showed long burn times of 8.5 s and 9 s. The spectral
purity of SrTNP_1 is 89% and hence lower than that of the
Sr-control, whereas SrTNP_2 shows a spectral purity of 94%
exceeding that of the control. The luminous intensities are 370
cd (SrTNP_1) and 390 cd (SrTNP_2), respectively. Addition-
ally, it is worth to mention that formulation SrTNP_2 does not
contain PVC, but shows better color properties than SrTNP_1
containing PVC (Table 11). Both formulations show high de-
composition temperatures and are relatively less impact and
friction sensitive (Table 12).
tain additionally magnesium as fuel and PVC as the chlorine-
source. Both formulations burned smokeless with a green
flame color. The color properties are summarized in Table 19.
The spectral purities are in the same range like the barium
control formulation; however, lower luminous intensities were
observed (Table 14 and Table 19). Whereas formulation
BaDNP_1 is rather less impact and friction sensitive, formula-
tion BaDNP_2 shows a high impact sensitivity of 5 J
(Table 20).
Table 16. Formulation /wt-% BaDNP_1.
9
NH
4
NO
3
Mg
8
PVC
5
VAAR
4
BaDNP_1 13
70
Table 11. Color properties of Sr-formulations.
Sp /wt-
%
Table 17. Formulation /wt-% BaDNP_2.
Burn time /s Dw /nm
LI /cd LE /cdsg–1
9
ADN
62
Mg
8
PVC
10
VAAR
5
SrDNP_1
SrDNP_2
SrDNP_3
SrTNP_1
SrTNP_2
4
5
5
8
5
605
610
610
608
603
68
90
90
89
94
90
600
BaDNP_2 15
192
150
390
390
1600
1250
5200
3250
Three formulations using compound 13 as colorant were in-
vestigated. Two formulations (BaTNP_1 and BaTNP_2) con-
tain compound 13, ammonium nitrate, magnesium, and PVC.
Formulations BaTNP_3 and BaTNP_4 do not contain any ad-
ditional oxidizer (Table 18). Formulations BaTNP_1,
BaTNP_3, and BaTNP_4 burned smokeless with an intensive
green flame color. Formulation BaTNP_2 burned with a pale-
green flame color. As can be seen in Table 19 formulations
BaTNP_1 and BaTNP_2 show lower spectral purities com-
pared to the barium control formulation, whereas the spectral
purities of formulations BaTNP_3 and BaTNP_4 exceed that
of the control formulation. Formulation BaTNP_3 exhibits the
Table 12. Energetic and thermal properties of Sr-formulations.
Impact /J
Friction /N
Grain size /μm
Tdec /°C
SrDNP_1
SrDNP_2
SrDNP_3
SrTNP_1
SrTNP_2
Ͼ40
30
Ͼ360
168
Ͻ 100
Ͻ 100
Ͻ 100
Ͻ 100
Ͻ 100
214
159
161
201
196
30
144
40
120
40
180
Table 18. Formulations /wt-% containing compound 13.
Green-Burning Formulations
The barium control M125A1 was mixed in a small-scale
1
3
NH
4
NO
3
Mg
PVC
VAAR
BaTNP_1 35
40
40
–
13
15
30
20
5
–
10
15
7
7
7
7
(
0.6 g) and the color properties as well as thermal and ener- BaTNP_2 38
BaTNP_3 53
BaTNP_4 58
getic properties were measured and are summarized in
Table 13, Table 14, and Table 15.
–
6
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Metal Salts of Dinitro-, Trinitropyrazole, and Trinitroimidazole
highest luminous intensity among the investigated formula- friction, heat or electrostatic discharge. While no issues in the handling
of these materials were encountered, appropriate precautions and
tions, which is also in the range of the barium control formula-
proper protective measures (safety glasses, face shields, leather coat,
tion (Table 14 and Table 19). The BaTNP formulations reveal
Kevlar gloves and ear protectors) should be taken when preparing and
manipulating these materials.
rather less impact and friction sensitivities and show high de-
composition temperatures (Table 20).
Table 19. Color properties of Ba-formulations.
General: All reagents and solvents were purchased from Sigma-Ald-
rich, Fluka and Acros Organics. Melting and decomposition points
were measured with a Linseis PT10 DSC using heating rates of 5 °C
–
Burn time /
s
1LE /cdsg
Dw /nm Sp /wt% LI /cd
–
1
min , which were checked with a Büchi Melting Point B-450 appara-
BaDNP_1
BaDNP_2
BaTNP_1
BaTNP_2
BaTNP_3
BaTNP_4
4
3
3
3
6
5
560
559
552
497
558
559
75
79
66
46
80
79
159
189
169
109
359
278
1060
945
845
545
3590
2317
1
13
14
tus. H, C and N NMR spectra were measured with a JEOL Eclipse
00, JEOL Eclipse 270 or JEOL EX400 instrument at an ambient tem-
perature of 25 °C if not stated otherwise. All chemical shifts are quoted
4
1
13
14
in ppm relative to TMS ( H, C), nitromethane ( N) or boron tri-
11
fluoro etherate ( B) as external standards. Infrared spectra were mea-
sured using a Perkin-Elmer Spectrum BX-FTIR spectrometer with a
Smiths DuraSampl IR-ATR unit. Elemental analyses were performed
with an Elementar Vario EL or an Elementar Vario EL micro cube.
Mass spectra were measured with a JEOL MS station JMS 700 instru-
Table 20. Energetic and thermal properties of Ba-formulations.
Impact /J Friction /N Grain size /μm
T
dec /°C
ment. The impact and friction sensitivity was determined with a BAM
BaDNP_1
BaDNP_2
BaTNP_1
BaTNP_2
BaTNP_3
BaTNP_4
30
5
40
30
40
35
360
168
192
324
Ͼ360
360
Ͻ 100
Ͻ 100
Ͻ 100
Ͻ 100
Ͻ 100
Ͻ 100
194
170
165
186
210
234
[19]
drophammer and a BAM friction tester.
The sensitivities of the
compounds are indicated according to the UN Recommendations on
[
19]
the Transport of Dangerous Goods (+):
impact: insensitive Ͼ 40 J,
less sensitive Ͼ 35 J, sensitive Ͼ 4 J, very sensitive Ͻ 4 J; friction:
insensitive Ͼ 360 N, less sensitive = 360 N, sensitive Ͻ 360 N Ͼ
80 N, very sensitive Ͻ 80 N, extreme sensitive Ͻ 10 N. The controlled
The investigation of SrTNP- and BaTNP-containing formu- burn down of the pyrotechnic formulations was filmed with a digital
video camera recorder (SONY, DCR-HC37E). Spectrometric measure-
lations revealed that brilliant flame colors and good color prop-
ments of the formulations were performed with a HR2000+ES spec-
erties can be achieved without the use of additional oxidizer.
trometer with an ILX511B linear silicon CCD-array detector and in-
In addition, formulation SrTNP_2 showed that PVC, which is
cluded software from Ocean Optics with a detector-sample distance of
used as chlorine-source to generate the red-light-emitting spe-
1
meter.
cies SrCl, is not necessary to produce intensive red-burning
flame colors.
Metal 3,5-Dinitropyrazolate Salts: 3,5-Dinitropyrazolate salts were
synthesized by the reaction of 3,5-dinitropyrazole
[
6,7]
(1) and the corre-
sponding metal bases in stoichiometric amounts in water at room tem-
perature. After stirring overnight the solvent was evaporated and the
Conclusions
Alkali and earth alkaline salts of 3,5-dinitropyrazole (DNP), obtained solids were recrystallized from hot ethanol.
,4,5-trinitropyrazole (TNP), and 2,4,5-trinitroimidazole (TNI)
3
Lithium 3,5-Dinitropyrazolate Trihydrate (4): Slightly brown crys-
tals (97%) were obtained as product. IR (ATR): ν˜ = 3156 (w), 1738
as well as copper 2,4,5-trinitroimidazolate were synthesized
and fully characterized. Crystal structures of Ba(DNP) (9)
2
(
(
m), 1641 (m), 1531 (m), 1470 (m), 1443 (s), 1353 (s), 1318 (m), 1273
crystallizing with one molecule of methanol and ethyl ether
–
1
m), 1171 (m), 1016 (m), 997 (m), 821 (m), 749 (m), 681 (w) cm .
as well as of Sr(TNP) ·3H O (12), Ba(TNP) ·3H O (13), and
2
2
2
2
1
H NMR ([D
6
]acetone): δ = 4.07 (s, H
]acetone): δ = 97.6 (C–H), 156.4 (C–NO
]acetone): δ = –18 (C–NO ) ppm. EA C HN
2
O), 7.26 (s, 1 H, CH) ppm.
LiTNI·3H O (14) were determined. Energetic and thermal
2
13
14
C NMR ([D
NMR ([D
6
2
) ppm.
Li·3 H
N
O
analysis of all compounds were performed and revealed pre-
dominantly low friction and impact sensitivities and high de-
6
2
3
4
O
4
2
(
218.05): calcd. C 16.53, H 3.24, N 25.69%; found C 16.97, H 3.12,
): m/z for Li : calculated 7.02, found 7.0. MS
Sr(DNP) ·6H O (8), Ba(DNP) ·H O (9), Sr(TNP) ·3H O (12), (FAB ): m/z for C HN O : calculated 157.00; found 156.9. IS: Ͼ40
composition temperatures. Pyrotechnic formulations using N 25.84%. MS (FAB
+
+
–
–
2
2
2
2
2
2
3
4 4
and Ba(TNP) ·3H O (13) as red and green colorants were in- J (grain size Ͻ 100 μm). FS: 360 N (grain size Ͻ 100 μm). ESD: 0.7
2
2
J (grain size Ͻ 100 μm). DSC: 325 °C (dec.).
vestigated. Especially formulations based on Sr(TNP) ·3H O
2
2
(
12) and Ba(TNP) ·3H O (13) showed good color properties
2 2
Sodium 3,5-Dinitropyrazolate Dihydrate (5): As product a brownish
solid was gained (99%). IR (ATR): ν˜ = 3570 (m), 3156 (m), 2362
as well as low friction and impact sensitivities and high de-
composition temperatures. The best performance values were
observed for the red-burning formulation SrTNP_2 and the
green-burning formulation BaTNP_3 revealing the highest
spectral purities and the highest luminous intensities.
(
m), 2337 (m), 1683 (m), 1645 (m), 1560 (w), 1532 (m), 1507 (m),
1
1
472 (s), 1443 (s), 1355 (s), 1316 (s), 1272 (m), 1166 (m), 1072 (w),
–1
1
012 (m), 994 (m), 837 (s), 820 (s), 750 (s), 686 (w) cm . H NMR
13
(
(
(
(
[D
[D
[D
6
6
6
]acetone): δ = 3.42 (s, H
]acetone): δ = 97.8 (C–H), 156.4 (C–NO
]acetone): δ = –18 (C–NO ) ppm. EA C
2
O), 7.30 (s, 1 H, CH) ppm. C NMR
1
4
2
) ppm. N NMR
HN Na·2 H
2
3
4
O
4
2
O
Experimental Section
216.09): calcd. C 16.67, H 2.33, N 25.92%; found C 16.61, H 2.43,
+
+
CAUTION! The compounds described in this work are potential ex-
plosives, which are sensitive to environmental stimuli such as impact,
N 25.23%. MS (FAB ): m/z for Na : calculated 22.99; found 23.0.
MS (FAB ): m/z for C
–
–
3
HN
4
O
4
: calculated 157.00; found 157.0. IS:
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Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. M. Klapötke et al.
ARTICLE
Ͼ40 J (grain size Ͻ 100 μm). FS: 360 N (grain size Ͻ 100 μm). ESD:
.5 J (grain size Ͻ 100 μm). DSC: 324 °C (dec.).
Lithium 3,4,5-Trinitropyrazolate Tetrahydrate (10): A yellow solid
(86%) was obtained as product. IR (ATR): ν˜ = 3620 (m), 3582 (w),
0
3
512 (m), 3343 (w), 3209 (w), 2628 (w), 1668 (m), 1630 (w), 1540
Potassium 3,5-Dinitropyrazolate (6): Yellow crystals were obtained
as product (99%). IR (ATR): ν˜ = 3156 (w), 2596 (w), 2294 (w), 1738
(
(
m), 1522 (s) 1456 (s), 1351 (s), 1325 (s), 1299 (s), 1172 (w), 1133
m), 1024 (m), 850 (s), 806 (m), 763 (m), 731 (m), 680 (m) cm . H
–1
1
(
(
w), 1539 (m), 1476 (s), 1443 (s), 1378 (m), 1353 (s), 1338 (s), 1310
s), 1270 (m), 1151 (m), 1064 (w), 1003 (s), 993 (m), 830 (s), 754 (s)
13
NMR ([D
δ = 145.9 ppm. N NMR ([D
Li·4 H O (281.06): calcd. C 12.82, H 2.87, N 24.92%; found
C 12.98, H 2.80, N 24.45%. MS (FAB ): m/z for Li : calculated 7.02,
6
]acetone): δ = 3.37 (s, H
2
O) ppm. C NMR ([D
6
]acetone):
14
6
]acetone): δ = –22 (C–NO ) ppm. EA
2
–1
1
13
cm . H NMR ([D
(
(
6
]acetone): δ = 7.21 (s, 1 H, CH) ppm. C NMR
C
3
N
5
O
6
2
4
[D
[D
6
]acetone): δ = 97.8 (C–H), 156.9 (C–NO
]acetone): δ = –17 (C–NO ) ppm. EA C HN
2
) ppm. 1 N NMR
+
+
6
2
3
4
O
4
K (196.16): calcd.
–
3 5 6
found 7.0. MS (FAB ): m/z for C N O
2
5
–
: calculated 201.98; found
02.0. IS: 40 J (grain size 100–500 μm). FS: 96 N (grain size 100–
00 μm). ESD: 0.2 J (grain size 100–500 μm). DSC: 274 °C (dec.).
C 18.37, H 0.51, N 28.56%; found C 18.42, H 0.62, N 27.96%. MS
+
+
–
(
FAB ): m/z for K : calculated 38.96; found 39.0. MS (FAB ): m/z for
–
3 4 4
C HN O : calculated 157.00; found 156.9. IS: 20 J (grain size 100–
5
1
00 μm). FS: 216 N (grain size 100–500 μm). ESD: 0.1 J (grain size
00–500 μm). DSC: 306 °C (dec.).
Sodium 3,4,5-Trinitropyrazolate (11): As product (96%) yellow
crystals were gained. IR (ATR): ν˜ = 3638 (w), 1605 (w), 1560 (w),
1
546 (m), 1512 (s), 1456 (m), 1357 (m), 1319 (s), 1296 (w), 1170 (w),
Calcium Bis(3,5-dinitropyrazolate) Tetrahydrate (7): As the prod-
uct yellow-brownish crystals were obtained (77%). IR (ATR): ν˜ =
–1
1132 (w), 1024 (w), 850 (s), 808 (m), 762 (w), 682 (w) cm . EA
3 5 6
C N O
Na (225.05): calcd. C 16.01, N 31.12%; found C 16.15, N
3638 (m), 3549 (m), 3166 (m), 1636 (m), 1540 (m), 1511 (m), 1483
13
14
3
0.85%.
[D ]acetone): δ = –22 (C–NO
lated 22.99; found 23.0. MS (FAB ): m/z for C
01.98; found 202.0. IS: 25 J (grain size 100–500 μm). FS: 80 N
grain size 100–500 μm). ESD: 0.2 J (grain size 100–500 μm). DSC:
54 °C (dec.).
6
C NMR ([D ]acetone): δ = 146.8 ppm. N NMR
(
s), 1450 (m), 1344 (s), 1318 (s), 1280 (m), 1204 (w), 1175 (m), 1017
+
+
(
6
2
) ppm. MS (FAB ): m/z for Na : calcu-
–1 1
(s), 998 (m), 842 (s), 818 (w), 748 (s) cm . H NMR ([D
6
]acetone):
]acetone): δ
]acetone): δ = –18
2
O (426.27): calcd. C 16.91, H
–
–
3 5 6
N O : calculated
13
δ = 3.91 (s, H
=
2
O), 7.29 (s, 1 H, CH) ppm. C NMR ([D
) ppm. 14N NMR ([D
Ca·4 H
.36, N 26.29%; found C 17.05, H 2.34, N 25.72%. MS (FAB ): m/z
6
2
(
2
97.6 (C–H), 156.3 (C–NO
2
6
(C–NO ) ppm. EA C
2
6
H
2
N
8
O
8
+
2
+
–
for C
3
HN
4
–
O
4
Ca : calculated 196.96; found 197.0. MS (FAB ): m/z for
Strontium Bis(3,4,5-trinitropyrazolate) Trihydrate (12): As product
yellow crystals were obtained (74%). IR (ATR): ν˜ = 3616 (w), 3139
C HN O : calculated 157.00; found 156.9. IS: 8 J (grain size 100–
3 4 4
5
1
00 μm). FS: 360 N (grain size 100–500 μm). ESD: 0.5 J (grain size
00–500 μm). DSC: Ͼ400 °C (dec.).
(
m), 2924 (m), 1596 (w), 1518 (s), 1493 (m), 1454 (m), 1358 (m) 1328
–1
1
(
s), 1131 (m), 1025 (s), 841 (m), 787 (w), 760 (m), 672 (w) cm . H
1
3
NMR ([D
6
]acetone): δ = 3.06 (s, H
2
O) ppm. C NMR ([D
]acetone): δ = –22 (C–NO ) ppm. EA
2
O (545.79): calcd. C 13.20, H 1.11, N 25.66%; found
6
]acetone):
Strontium Bis(3,5-dinitropyrazolate) Hexahydrate (8): Yellow-
brownish crystals were gained as product (98%). IR (ATR): ν˜ = 2971
1
4
δ = 146.1 ppm. N NMR ([D
12Sr·3H
C 12.99, H 1.14, N 25.10%. MS (FAB ): m/z for C
6
2
C
6
N
10
O
(w), 2170 (w), 1739 (s), 1618 (m), 1540 (m), 1475 (m), 1443 (m),
–
–
3 5 6
N O : calculated
1
9
=
9
(
354 (s), 1322 (m), 1279 (w), 1229 (m), 1217 (m), 1073 (w), 1017 (m),
–1
1
201.98; found 202.0. IS: 40 J (grain size 100–500 μm). FS: 80 N
(grain size 100–500 μm). ESD: 0.2 J (grain size 100–500 μm). DSC:
193 °C (dec.).
99 (w), 835 (m), 826 (m), 749 (m) cm . H NMR ([D
6
]acetone): δ
]acetone): δ =
]acetone): δ = –18
2
O (509.84): calcd. C 14.14, H
13
3.68 (s, H
8.3 (C–H), 157.0 (C–NO
C–NO ) ppm. EA C
.77, N 21.98%; found C 14.43, H 2.68, N 21.71%. MS (FAB ): m/z
2
O), 7.27 (s, 1 H, CH) ppm. C NMR ([D
) ppm. 14N NMR ([D
Sr·6H
6
2
6
2
6
H
2
N
8
O
8
+
Barium Bis(3,4,5-trinitropyrazolate) Trihydrate (13): As product
yellow crystals were obtained (55%). IR (ATR): ν˜ = 3582 (m), 1619
(m), 1540 (s), 1514 (s), 1457 (m), 1354 (m), 1322 (s), 1303 (m), 1132
2
+
–
for C
3
HN
4
–
O
4
Sr : calculated 244.91; found 245.0. MS (FAB ): m/z for
C HN O : calculated 157.00; found 157.0. IS: Ͼ40 J (grain size 100–
3 4 4
–
1 1
(
m), 1028 (w), 850 (s), 806 (m), 766 (w) cm . H NMR ([D
6
]ace-
]acetone): δ = –23 (C–
2
O (595.56): calcd. C 12.10, H 1.02,
5
1
00 μm). FS: 360 N (grain size 100–500 μm). ESD: 0.2 J (grain size
00–500 μm). DSC: Ͼ400 °C (dec.).
1
4
tone): δ = 2.99 (s, H
2
O) ppm. N NMR ([D
12Ba ·3 H
N 23.52%; found C 12.13, H 1.04, N 23.10%. MS (FAB ): m/z for
6
NO
2
) ppm. EA C
6
N
10
O
–
Barium Bis(3,5-dinitropyrazolate) Hydrate (9): Brownish crystals
were obtained as product (86%). IR (ATR): ν˜ = 3610 (w), 3156 (w),
–
3 5 6
C N O : calculated 201.98; found 202.0. IS: 5 J (grain size 100–
5
1
00 μm). FS: 144 N (grain size 100–500 μm). ESD: 0.1 J (grain size
00–500 μm). DSC: 302 °C (dec.).
2
1
8
2
9
361 (w), 1739 (m), 1611 (m), 1548 (s), 1494 (s), 1444 (m), 1369 (m),
342 (s), 1321 (s), 1230 (w), 1172 (m), 1070 (w), 1010 (m), 1000 (w),
–1 1
40 (s), 821 (w), 744 (s), 669 (w) cm . H NMR ([D
6
]acetone): δ =
]acetone): δ =
6
]acetone): δ = –19
13
Metal 2,4,5-Trinitroimidazolate Salts: To a solution of trinitroimida-
zole
added in stoichiometric amounts and the solutions were stirred over-
night at room temperature. Evaporation of the solvent and recrystalli-
zation from ethyl acetate resulted in the formation of the products.
.88 (s, H
8.6 (C–H), 157.3 (C–NO
) ppm. EA C
.86, N 23.84%; found C 15.36, H 0.92, N 23.18%. MS (FAB ): m/z
2 6
O), 7.28 (s, 1 H, CH) ppm. C NMR ([D
[
21]
) ppm. 14N NMR ([D
(3) in ethyl ether the corresponding metal carbonates were
2
(C–NO
2
6 2 8 8 2
H N O Ba H O (469.47): calcd. C 15.32, H
+
0
+
–
6 2 8 8
for C H N O Ba : calculated 451.90; found 448.0. MS (FAB ): m/z
for C
–
3 4 4
HN O : calculated 157.00; found 157.0. IS: 30 J (grain size
Lithium 2,4,5-Trinitroimidazolate Trihydrate (14): A yellow-
orange solid (79%) was obtained as product. IR (ATR): ν˜ = 3563 (m),
500–1000 μm). FS: 72 N (grain size 500–1000 μm). ESD: 0.1 J (grain
size 500–1000 μm). DSC: 361 °C (dec.).
3321 (w), 1648 (m), 1538 (s), 1467 (s), 1426 (m), 1328 (s), 1301 (s),
–
1 1
Metal 3,4,5-Trinitropyrazolate Salts: All metal 3,4,5-trinitropyrazol-
1111 (m), 868 (s), 832 (m), 812 (s), 755 (w), 650 (m) cm . H NMR
1
4
ate salts were obtained by the same synthesis procedure. To a solution ([D
6
]DMSO): δ = 3.37 (s, H
) ppm. EA C
carbonates were added in stoichiometric amounts. The solutions were 2.30, N 26.62%; found C 14.01, H 2.25, N 26.67%. MS (FAB ): m/z
2
O) ppm. N NMR ([D
6
]DMSO): δ =
[
20]
of 3,4,5-trinitropyrazole
(2) in ethanol the corresponding metal –21 (C–NO
2
3
N
5
O
6
Li·3H O (263.05): calcd. C 13.70, H
2
+
+
–
stirred overnight at room temperature. After removing the solvent the
products were obtained as solids.
for Li : calculated 7.02, found 7.0. MS (FAB ): m/z for
C N O : calculated 201.98; found 201.9. IS: Ͼ40 J (grain size
3 5 6
–
8
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

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/KAP1
Date: 13-06-14 12:01:35
Pages: 11
Metal Salts of Dinitro-, Trinitropyrazole, and Trinitroimidazole
–
Ͻ 100 μm). FS: Ͼ360 N (grain size Ͻ 100 μm). ESD: 0.5 J (grain
size Ͻ 100 μm). DSC: 252 °C (dec.).
H 1.49, N 25.95%; found C 13.49, H 1.49, N 25.92%. MS (FAB ):
m/z for C
–
3 5 6
N O : calculated 201.98; found 201.9. IS: 3 J (grain size
1
00–500 μm). FS: 80 N (grain size 100–500 μm). ESD: 0.1 J (grain
Sodium 2,4,5-Trinitroimidazolate (15): As product a yellow-orange
solid (80%) was obtained. IR (ATR): ν˜ = 3600 (w), 2978 (w), 1693
size 100–500 μm). DSC: 170 °C (dec.).
(
s), 1545 (s), 1470 (s), 1425 (m), 1378 (m), 1325 (s), 1297 (s), 1170
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Na Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
(w), 1111 (s), 1035 (s), 867 (s), 835 (m), 810 (s), 753 (m), 645 (m)
–1 14
cm . N NMR ([D
6
]DMSO): δ = –21 (C–NO
2
) ppm. EA C
3
N
5
O
6
(
(
225.05): calcd. C 16.01, N 31.12%; found C 16.45, N 30.67%. MS of the data can be obtained free of charge on quoting the depository
+
+
–
FAB ): m/z for Na : calculated 22.99; found 23.0. MS (FAB ): m/z numbers CCDC-1002135, CCDC-1002137, CCDC-1002138, and
–
for C
3
N
5
O
6
: calculated 201.98; found 201.9. IS: Ͼ40 J (grain size
CCDC-1002136 for 9, 12, 13, and 14 (Fax: +44-1223-336-033;
Ͻ 100 μm). FS: N (grain size Ͻ 100 μm). ESD: 0.6 J (grain size E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Ͻ 100 μm). DSC: 249 °C (dec.).
Potassium 2,4,5-Trinitroimidazolate (16): As product a yellow crys- Acknowledgements
tals (83%) were obtained. IR (ATR): ν˜ = 2629 (w), 1530 (s), 1465 (s),
1
8
426 (m), 1315 (s), 1302 (s), 1280 (m), 1110 (m), 869 (s), 832 (m), Financial support of this work by the Ludwig-Maximilian University
–1 14
12 (s), 764 (m), 758 (m), 690 (w) cm . N NMR ([D
–21 (C–NO ) ppm. EA C K (241.16): calcd. C 14.94, N
9.04%; found C 14.93, N 28.67%. MS (FAB ): m/z for K : calcu-
6
]DMSO): δ of Munich (LMU), the U.S. Army Research Laboratory (ARL) under
=
2
3
N
5
O
6
grant no. W911NF-09–2-0018, the Armament Research, Development
and Engineering Center (ARDEC) under grant no. W911NF-12–1-
0467, and the Office of Naval Research (ONR) under grant nos.
+
+
2
–
–
3 5 6
lated 38.96; found 39.0. MS (FAB ): m/z for C N O : calculated
2
01.98; found 201.9. IS: 25 J (grain size 100–500 μm). FS: 120 N ONR.N00014–10–1-0535 and ONR.N00014–12–1-0538 is gratefully
(
2
grain size 100–500 μm). ESD: 0.2 J (grain size 100–500 μm). DSC:
31 °C (dec.).
acknowledged. The authors acknowledge collaborations with Dr. Mila
Krupka (OZM Research, Czech Republic) in the development of new
testing and evaluation methods for energetic materials and with Dr.
Calcium Bis(2,4,5-trinitroimidazolate) Dihydrate (17): Orange Muhamed Suceska (Brodarski Institute, Croatia) in the development
crystals (78%) were obtained as product. IR (ATR): ν˜ = 3582 (m), of new computational codes to predict the detonation and propulsion
3
347 (w), 1643 (w), 1619 (m), 1535 (s), 1468 (s), 1422 (w), 1327 (s),
parameters of novel explosives. The authors are indebted to and thank
304 (s), 1109 (m) 865 (s), 830 (w), 808 (s), 752 (m), 672 (m) cm . Drs. Betsy M. Rice and Brad Forch (ARL, Aberdeen, Proving Ground,
–
1
1
1
14
H NMR ([D
]DMSO): δ = –20 (C–NO
calcd. C 15.01, H 0.84, N 29.17%; found C 15.12, H 1.01, N 28.18%.
6
]DMSO): δ = 3.18 (s, H
2
O) ppm.
N NMR MD) for many inspired discussions. The Cusanuswerk is gratefully
([D
6
2
) ppm. EA C
6
N
10
O
12Ca·2H
2
O (480.24):
acknowledged for the award of a Ph.D. scholarship (M. Rusan).
–
–
3 5 6
MS (FAB ): m/z for C N O : calculated 201.98; found 201.9. IS:
Ͼ40 J (grain size 100–500 μm). FS: Ͼ360 N (grain size 100–500 μm). References
ESD: 0.7 J (grain size 100–500 μm). DSC: 188 °C (dec.).
[
[
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4
Strontium Bis(2,4,5-trinitroimidazolate) Hydrate (18): A yellow-
orange solid (78%) was gained as product. IR (ATR): ν˜ = 3616 (w),
1
2
1
988 (w), 1693 (s), 1545 (s), 1470 (s), 1425 (m), 1378 (m), 1321 (s),
297 (s), 1189 (w), 1111 (s), 1041 (s), 867 (s), 833 (m), 810 (s), 753
1
–1 1
(
m), 650 (m) cm . H NMR ([D
6
]DMSO): δ = 3.47 (s, H
]DMSO): δ = –20 (C–NO ) ppm. EA C
509.76): calcd. C 14.14, H 0.39, N 27.48%; found C 14.11, H 0.50,
2
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4
N NMR ([D
6
2
6
N
10
O
2
12Sr·H O
(
[3] H. Gao, C. Ye, O. D. Gupta, J.-C. Xiao, M. A. Hiskey, B. Twam-
–
–
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N
5
O
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: calculated 201.98; found
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[
[
4] G. Hervé, US Pat. US 0186931, 2009.
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201.9. IS: Ͼ40 J (grain size Ͻ 100 μm). FS: Ͼ360 N (grain size
Ͻ 100 μm). ESD: 0.7 J (grain size Ͻ 100 μm). DSC: 239 °C (dec.).
8153786, 2012.
[
[
6] R. Hüttel, F. Büchele, Chem. Ber. 1955, 88, 1586.
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Barium Bis(2,4,5-trinitroimidazolate) Dihydrate (19): Orange crys-
tals (73%) were obtained as product. IR (ATR): ν˜ = 3229 (w), 1589
(
(
s), 1413 (m), 1306 (s), 1222 (w), 1184 (w), 1130 (w), 855 (m), 769
[
8] a) G. Socrates, Infrared and Raman Characteristic Group Fre-
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Methoden in der Organischen Chemie, 6. Auflage, Thieme, Stutt-
gart, 2002.
–1
1
14
m), 692 (m) cm . H NMR ([D
6
]DMSO): δ = 3.52 (s, H
) ppm. EA C
2
O) ppm.
12Ba·2H
N
NMR ([D
6
]DMSO): δ = –20 (C–NO
2
6
N
10
O
2
O
(
577.48): calcd. C 12.48, H 0.70, N 24.25%; found C 12.23, H 0.82,
–
–
3 5 6
N 23.98%. MS (FAB ): m/z for C N O : calculated 201.98; found
[
9] R. Galassi, A. Burini, S. Ricci, M. Pellei, M. P. Rigobello, A.
Citta, A. Domella, V. Gandin, C. Marzano, Dalton Trans. 2012,
2
1
01.9. IS: Ͼ40 J (grain size 100–500 μm). FS: Ͼ360 N (grain size
00–500 μm). ESD: 0.6 J (grain size 100–500 μm). DSC: 166 °C
4
1, 5307.
10] G. Herve, C. Roussel, H. Graindorge, Angew. Chem. 2010, 122,
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2659.
(dec.).
[
[
3
Copper Bis(2,4,5-trinitroimidazolate) Tetrahydrate (20): A tur-
quoise solid (65%) was obtained as product. IR (ATR): ν˜ = 2745 (w),
1
1
8
610 (s), 1469 (s), 1400 (m), 1315 (s), 1302 (s), 1280 (m), 1143 (m),
[
[
12] CrysAlisPro, Oxford Diffraction Ltd., version 171.33.41, 2009.
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1993, 26, 343.
–1 1
69 (s), 832 (m), 824 (s), 764 (m), 758 (m), 680 (w) cm . H NMR
]DMSO): δ = 3.17 (s, H ]DMSO): δ =
O) ppm. 14N NMR ([D
20 (C–NO ) ppm. EA C 12Cu · 4 H O (539.73): calcd. C 13.35,
([D
6
2
6
–
2
6
N
10
O
2
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
9

Job/Unit: Z14233
/KAP1
Date: 13-06-14 12:01:35
Pages: 11
T. M. Klapötke et al.
ARTICLE
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14] a) A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi,
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19.
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Received: May 13, 2014
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Published Online: ᭿
1
0
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z14233
/KAP1
Date: 13-06-14 12:01:35
Pages: 11
Metal Salts of Dinitro-, Trinitropyrazole, and Trinitroimidazole
I. E. Drukenmüller, T. M. Klapötke,* Y. Morgenstern,
M. Rusan, J. Stierstorfer ................................................. 1–11
Metal Salts of Dinitro-, Trinitropyrazole, and Trinitroimidazole
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
11