Energetic salts based on 1-methoxy-5-nitroiminotetrazole

Article abstract of DOI:10.1039/c3nj41117f

Eight new energetic salts based on 1-methoxy-5-nitroiminotetrazole, which was obtained by nitration of 1-methoxy-5-aminotetrazole, were synthesized. Guanidinium (5), aminoguanidinium (6), diaminoguanidinium (7), triaminoguanidinium (8), carbohydrazidinium (9), 3-amino-1,2,4-triazolium (10), 4-amino-1,2,4-triazolium (11), and 3,5-diamino-1,2,4-triazolium (12) salts were characterized by vibrational spectroscopy (IR, Raman), multinuclear spectroscopy (¹H, ¹³C, ¹⁵N), elemental analysis, and single crystal X-ray diffraction analysis. Salts 5·1/3H₂O and 7-9 crystallize in the triclinic space group P1, whereas compounds 6 and 10 crystallize in the monoclinic space groups C2/c and P2(1)/n, respectively. Compound 11 is in orthorhombic group P2(1)2(1)2(1). In addition, the heats of formation (ΔH_f), and detonation properties (pressure and velocity) were calculated using Gaussian 03 and EXPLO5 programs, respectively. Thermal stabilities were obtained by DSC measurements and the sensitivities toward impact and friction were determined by BAM methods.

Full text of DOI:10.1039/c3nj41117f

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Energetic salts based on 1-methoxy-5-nitroiminotetrazole†
a
b
b
b
Young-Hyuk Joo,* Jin Hyuk Chung, Soo Gyeong Cho and Eun Mee Goh
Cite this: DOI: 10.1039/c3nj41117f
Eight new energetic salts based on 1-methoxy-5-nitroiminotetrazole, which was obtained by nitration
of 1-methoxy-5-aminotetrazole, were synthesized. Guanidinium (5), aminoguanidinium (6),
diaminoguanidinium (7), triaminoguanidinium (8), carbohydrazidinium (9), 3-amino-1,2,4-triazolium
(
10), 4-amino-1,2,4-triazolium (11), and 3,5-diamino-1,2,4-triazolium (12) salts were characterized by
1
13
15
vibrational spectroscopy (IR, Raman), multinuclear spectroscopy ( H, C, N), elemental analysis, and
single crystal X-ray diffraction analysis. Salts 5ꢀ1/3H
O and 7–9 crystallize in the triclinic space group P1%,
whereas compounds 6 and 10 crystallize in the monoclinic space groups C2/c and P2(1)/n, respectively.
Compound 11 is in orthorhombic group P2(1)2(1)2(1). In addition, the heats of formation (DH ), and
Received (in Montpellier, France)
2
9
th December 2012,
Accepted 24th January 2013
f
detonation properties (pressure and velocity) were calculated using Gaussian 03 and EXPLO5 programs,
respectively. Thermal stabilities were obtained by DSC measurements and the sensitivities toward impact
and friction were determined by BAM methods.
DOI: 10.1039/c3nj41117f
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tetrazole species positively enhances both thermal stability and
insensitivity.
Introduction
Energetic tetrazole derivatives are predicted to be reasonably
A few years ago, the Klap o¨ tke group reported the synthesis of
powerful high explosive molecules with thermal and shock alkali salts of 1-methyl-5-nitroiminotetrazole and their
stabilities which are considerably greater than those of many derivatives, which can be used as brilliant coloring agents in
1
other known energetic materials. Recently, a considerable modern pyrotechnics. Both high performance in coloring and
amount of research has been directed toward synthesizing producing greener gases are attributed to their alkali metal
6
new energetic materials to replace current primary explosives cations combined with high nitrogen content heterocycles.
containing heavy metal elements including highly toxic lead.
2
The copper(II) salt of 1-methyl-5-nitroiminotetrazole, whose
One of the typical approaches for developing green explosives is sensitivities to impact and friction are almost the same as
to develop novel high energy density molecules (HEDMs) based those of primary explosives, was suggested as a low toxic
3
7
on the tetrazole moiety. In the case of 1-substituted tetrazole explosive molecule for initiation devices. In addition,
derivatives, the heterocyclic ring may confer high density and synthesis and characterization of various guanidinium 5-nitro-
4
thermal stability on the molecules. The high nitrogen content iminotetrazolate salts, which can be prepared from silver
gives rise to a high volume of detonation products and low 5-nitroiminotetrazolate by metathesis and which are forecasted
sensitivity to external stimuli. A combination of amino, nitro, or to be HEDMs, were also reported by the Klap o¨ tke group.8
9
nitroimino groups results in inter- and intra-molecular hydro-
Recently, we extended our research scope to develop mono-,
5
9
9,10
gen bonding, leading to improved stability and density. In methylene bridged, and ethylene bridged
oxy-5-aminotetra-
particular, the anionic species with nitrogen-rich cations zole compounds utilizing an excellent in situ method which
usually provide excellent thermal and explosive properties to be involved the reactions of cyanogen azide and primary oxy-
3
used in future high explosive formulations. The deprotonation of amines. Nitration of these aminotetrazoles using 100% nitric
acid was shown to form oxy nitroiminotetrazole derivatives I
a
and II, which were good candidates for high explosives because
they combined both the strongly oxidizing nitroimino-group
and the energetic nitrogen-rich backbone in one molecule
Department of Energetic Materials & Pyrotechnics, Hanwha Corporation Defence
R&D Center, Daejeon, 305-156, Korea. E-mail: joo2011@hanwha.co.kr;
Fax: +82 42 829 2623
b
10
Defense Advanced R&D Center, Agency for Defense Development, Daejeon,
(
Scheme 1). Ethylene bis(oxy)-5-nitroiminotetrazole (II, I-10)
3
05-600, Korea
Electronic supplementary information (ESI) available: IR, H, C, and N NMR
O), 899438 (6), 899439 (7), 899440 (8), 899441 (9),
99442 (10) and 861470 (11). For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/c3nj41117f
ꢁ3
exhibits a high density of 1.81 g cm , and is calculated to
have a heat of formation of 3.58 kJ g . It is also predicted to
have a detonation pressure of 38.19 GPa, and a detonation
1
13
15
†
ꢁ
1
spectra. CCDC 899437 (5ꢀ1/3H
2
8
ꢁ
1
10
velocity of 9329 m s , which approach those of HMX. Impact
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1-methoxy-5-nitroiminotetrazolate and silver nitrate, with the
corresponding chloride salts. After stirring for three hours,
silver chloride was filtered and the filtrate was dried slowly in
air (yield: 90–99%). The energetic salts 9–12 were obtained by
the acid–base reaction between 3 and energetic bases in aqu-
eous solutions (yield: 97–98%). Compound 12 precipitated
rapidly as a white powder, when 3,5-diamino-1,2,4-triazole
was added to the solution of 3 in water. The structures of the
Scheme 1 Oxy-nitroiminotetrazoles.
1
13
energetic salts 5–12 are supported by IR, Raman, and H, C,
sensitivity measurements indicate that II is quite sensitive to
1
5
and N NMR spectroscopic data as well as elemental analysis.
The molecular structures of guanidinium 1-methoxy-5-nitroi-
shock. In order to make nitroiminotetrazole derivatives which
1
1
are less sensitive, we previously reported the synthesis of
1
0
minotetrazolate (5ꢀ1/3H
O), aminoguanidinium 1-methoxy-5-
2
new energetic salts of II and energetic bases. In the current
work, we focused on the synthesis and characterization of
new ionic energetic materials based on the 1-methoxy-5-
nitroiminotetrazolate anion.
nitroiminotetrazolate (6), diaminoguanidinium 1-methoxy-5-
nitroiminotetrazolate (7), triaminoguanidinium 1-methoxy-5-
nitroiminotetrazolate (8), carbohydrazidinium 1-methoxy-5-
nitroiminotetrazolate (9), 3-amino-1,2,4-triazolium 1-methoxy-
5
1
-nitroiminotetrazolate (10), and 4-amino-1,2,4-triazolium
-methoxy-5-nitroiminotetrazolate (11) were confirmed by single
Results and discussion
Synthesis
crystal X-ray diffraction analysis.
The Raman spectra are dominated by the vibrations of
1
-Methoxy-5-aminotetrazole (2) was obtained by the cyclization 1-methoxy-5-nitroiminotetrazolate and the IR spectra are better
of cyanogen azide with methoxyamine (obtained by neutraliza- suited for the characterization of the energetic cations. All salts
tion of commercially available 1 with sodium hydroxide) in show a set of strong absorption bands in IR spectra and weak
ꢁ
1
acetonitrile–water solution according to the literature bands in Raman between 2800–3500 cm corresponding to N–H
1
2
(
Scheme 2). At ambient temperature, nitration of 2 using stretching modes. The absorption band of the CQN stretching
1
00% nitric acid without solvent was shown to give 1-methoxy- vibration is the most significant peak in the Raman spectrum of 3
9
ꢁ1
5
-nitroiminotetrazole (3) in good yield (84%). Guanidinium and lies in the range between 1564 and 1600 cm . This absorp-
ꢁ
1
salts 5–8 were synthesized using silver 1-methoxy-5-nitroimino- tion band is shifted to lower wave numbers (1509–1513 cm
)
tetrazolate (4), which was obtained by the metathesis of sodium in deprotonated molecules (6, 8, 9, and 12) (Fig. 1).
Scheme 2 Synthesis of 1-methoxy-5-nitroiminotetrazole (3) and its salts (5–12).
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Crystal structure analysis
Compounds 5ꢀ1/3H O–11 were characterized by single crystal
X-ray structure determination (Fig. 2). Hydrogen bond geo-
O–11 are included
2
metric parameters for compounds 5ꢀ1/3H
2
in Table 1. Selected data and parameters of the X-ray determi-
nation are given in Table 2. Further information on the crystal
structure determination is presented in the ESI.† CCDC 899437
(
8
5ꢀ1/3H O), 899438 (6), 899439 (7), 899440 (8), 899441 (9),
2
99442 (10), and 899443 (11). Compounds 5ꢀ1/3H O and 7–9
2
crystallize in the triclinic space group P1%, whereas compounds 6
and 10 crystallize in the monoclinic space groups C2/c and
P2(1)/n, respectively. Compound 11 is orthorhombic
P2(1)2(1)2(1). In this work, energetic salts (5ꢀ1/3H
2
O–11) are
discussed based on 1-methoxy-5-nitroiminotetrazole. The
nitroiminotetrazolate ring is nearly planar, building an aro-
Fig. 1 Selected Raman spectra of 3, 6, 8, 9, and 12.
matic system. The ring moieties of 5ꢀ1/3H O–11 are in good
2
agreement with the geometry observed for 5-nitroiminotetra-
Next strong intense signals in the Raman spectra are observed in
6
–11
ꢁ1
zoles and their salts.
The N3–N4 bond lengths of all
the range 1030–1092 cm
Those signals correspond to N–NO
for the different compounds.
symmetric stretching
structures of 5ꢀ1/3H
2
O–11 lie between 1.287 and 1.292 Å, which
are typical values observed for the nitroiminotetrazolate
2
modes. These assignments are based on the values of
wave numbers reported for nitroiminotetrazolate salts in the
anions. The N3–N4 bond length in neutral compound 3
6
–8
(1.279 Å) is slightly shorter than those of its salts. The bond
literature.
Fig. 2 Single-crystal X-ray diffraction analysis of 5ꢀ1/3H
2
O–11 (thermal displacement set at 50% probability).
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Table 1 Selected hydrogen bonding in the structure of 5ꢀ1/3H
2
O–11
NMR spectroscopy
1
Compd
D–Hꢀ ꢀ ꢀA
D–H
Hꢀ ꢀ ꢀA
2.178(18)
2.17(2)
2.04(3)
1.91(3)
D–Hꢀ ꢀ ꢀA
2.9746(17)
1-Methoxy-5-nitroiminotetrazole salts were characterized by H,
1
3
15
C, and N NMR spectroscopy. The chemical shifts are given
5
ꢀ1/3H
2
O
N14–H14Bꢀ ꢀ ꢀO8
N15–H15Bꢀ ꢀ ꢀN5
O46–H46Aꢀ ꢀ ꢀO8
N13–H13ꢀ ꢀ ꢀO9
N15–H15Aꢀ ꢀ ꢀO8
N16–H16Bꢀ ꢀ ꢀN4
N25–H25ꢀ ꢀ ꢀO8
N26–H26Aꢀ ꢀ ꢀO9
N28–H28Aꢀ ꢀ ꢀN17
N13–H13ꢀ ꢀ ꢀN4
N13–H13ꢀ ꢀ ꢀN5
N17–H17Aꢀ ꢀ ꢀN5
N17–H17Aꢀ ꢀ ꢀO8
N15–H15ꢀ ꢀ ꢀN5
N15–H15ꢀ ꢀ ꢀO8
0.871(18)
0.85(2)
0.91(3)
0.93(3)
0.93(3)
0.919(16)
0.842(18)
0.89
1
13
15
3.0183(19) with the respect to TMS (for H, C) and CH
3 2
NO (for N) as
external standards. The NMR shifts corresponding to the
cations and anions in this study are in good agreement with
2.914(2)
2.843(2)
3.071(2)
6
2.19(3)
8
9
2.623(16)
2.494(17)
2.02(2)
3.5331(15) previously recorded shifts for the relevant cations and
9
,10
13
3.0581(17)
2.9076(16)
2.8437(16)
anions.
In the C NMR spectra of the salts 5–12, the
resonance of the carbon atom in tetrazole is observed at lower
2.9368(17) field (d = B150 ppm) than that of 3 (d = 146 ppm) as a
0.89
1.99(2)
1
0
1
0.883(16)
0.883(16)
0.855(18)
0.855(18)
1.077(17)
1.077(17)
2.079(16)
2.511(16)
2.131(18)
2.355(17)
1.593(17)
2.407(18)
3.1603(16)
2.9100(19)
3.0361(17)
2.657(2)
1
2.9465(19)
lengths in 1-methoxy-5-nitriminotetrazolate are very similar to
9
the value found and discussed in the literature.
The packing of 5ꢀ1/3H O is influenced by medium strong
2
hydrogen bonds between the water molecule and 5. Only one
hydrogen atom of the water participates in the formation of the
layers. These extensive hydrogen-bonding interactions between
oxygen atom O46 from water and O8 [O46–H46Aꢀ ꢀ ꢀO8 2.914(2)]
are given in ESI† (Table 1). As in 8, the nitrogen atom N4 of the
tetrazolate ring with N16 of the triaminoguanidine cation parti-
cipates in a weak hydrogen bond [N16–H16Bꢀ ꢀ ꢀN4 3.5331(15)]. In
contrast to the structures 5ꢀ1/3H O–10, the packing structure of
2
11 is strongly influenced by strong hydrogen bonds between N15
of 4-aminotriazolium and N5 of 1-methoxy-5-nitroiminotetrazo-
late [N15–H15ꢀ ꢀ ꢀN5 2.657(2)].
15
Fig. 3
N NMR spectra of 3, 7–9, and 12.
Table 2 Crystallographic data for 5ꢀ1/3H
2
O–11
5
ꢀ1/3H
2
O
6
7
8
9
10
11
Chemical formula
Formula mass
Crystal system
C
9
H
29
N
27
O
l0
C
3
H
10
N
10
O
3
C
3
H
11
N
11
O
3
C
3
H
12
N
12
O
3
C
5
H
14
N
16
O
7
C
4
H
8
N
10
O
3
4 8 10 3
C H N O
244.20
675.59
Triclinic
7.5920(4)
13.7908(8)
15.7389(9)
114.474(2)
234.21
249.23
Triclinic
264.25
Triclinic
6.93360(10)
7.97080(10)
10.6766(2)
103.9800(10) 101.616(3)
97.668(3) 97.4510(10)
100.9850(10) 94.214(5)
552.022(15)
296(2)
P1%
410.32
Triclinic
7.37150(10)
7.44260(10)
15.3365(3)
244.20
Monoclinic
17.1247(6)
9.7122(3)
13.4618(8)
90
Monoclinic Orthorhombic
a/Å
b/Å
c/Å
6.5764(12)
9.2377(17)
9.8647(18)
105.849(4)
100.993(4)
103.370(4)
539.86(17)
296(2)
P1%
2
Mo-K
0.131
1.533
6313
1964
3.8294(3)
27.714(2)
9.5787(8)
90
97.7960(10) 90
90 90
1007.18(14) 1001.6(13)
296(2)
P2(1)/n
4
Mo-K
0.137
1.610
5.437(4)
11.969(9)
15.391(10)
90
o
a/
o
b/
100.4090(10) 119.073(2)
o
g/
90.831(5)
1467.75(14)
296(2)
P1%
2
Mo-K
0.133
1.529
28 334
7254
90
3
Unit cell volume/Å
Temperature/K
Space group
No. of formula units per unit cell, Z
Radiation type
1956.84(15)
296(2)
C2/c
812.91(2)
296(2)
P1%
296(2)
P2(1)2(1)2(1)
4
8
2
2
a
Mo-K
0.137
1.590
23 975
2422
a
a
M0-K
0.136
1.590
14 907
2746
a
Mo-K
0.149
1.676
21 966
4040
a
a
Mo-K
0.138
1.619
a
ꢁ1
Absorption coefficient/m mm
ꢁ
3
Densitycalcd/g cm
No. of reflections measured
No. of independent reflections
15 247
2489
15 459
2496
R
int
0.0432
0.0413
0.1192
0.0598
0.1287
1.077
0.0722
0.0411
0.1044
0.0859
0.1241
0.985
0.0289
0.0495
0.1561
0.0531
0.1601
1.068
0.0576
0.0333
0.0988
0.0408
0.1032
1.115
0.0533
0.0374
0.0954
0.0575
0.1032
0.964
0.0595
0.0364
0.0765
0.0674
0.0850
0.861
0.0469
0.0286
0.0613
0.0346
0.0638
0.965
a
Final R
Final wR
Final R
Final wR
Goodness of fit on F
CCDC number
1
values (I 4 2s(I))
2
b
values (I 4 2s(I))
values (all data)
values (all data)
1
2
2
c
899437
899438
899439
899440
899441
899442
899443
n
h
i.
h
io
P
P
P
ꢀ
ꢁ2
P
ꢀ
ꢁ2
1=2
a
b
w Fo 2 ꢁ Fc 2
2
c
R1 ¼
jjFoj ꢁ jFcjj= jFoj. wR2 ¼
w Fo
. CCDC numbers contain the supplementary crystallographic data
for this paper.†
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Table 3 Physical properties of energetic salts 5–12
oc
o
c
o
c
oc
oc
DH
L
DHcation
DHanion
DH
[kJ mol
f
DH
f
a
a
b
ꢁ3
ꢁ1
ꢁ1
ꢁ1
ꢁ1
ꢁ1
d
e
ꢁ1
f
g
Compd
T
m
[1C]
T
dec [1C] Density [g cm
]
[kJ mol
]
[kJ mol
]
[kJ mol
]
]
[kJ g
] P [GPa] vD [m s ] IS [J] FS [N]
h
3
—
116
179
167
134
139
151
174
134
159
295
230
1.660
1.596
1.587
1.556
1.594
1.709
1.613
1.649
1.597
1.650
1.816
—
—
—
504.28
405.04
484.98
566.16
699.43
1374.67
645.95
774.94
621.99
ꢁ295.0
92.6
3.15
31.4
24.9
25.2
24.7
27.0
34.2
25.1
27.7
24.1
19.5
35.2
8690
8141
8210
8187
8479
9065
8107
8408
8013
6881
8977
5
13
4.1
—
4360
89
5
6
7
8
9
177
141
118
112
—
—
131
—
492.74
483.63
473.58
469.39
1461.23
480.48
483.27
463.94
—
575.85
646.68
717.81
846.89
2192.04
804.50
936.28
764.00
—
321.93
321.93
321.93
321.93
321.93
321.93
321.93
321.93
—
1.85
2.07
2.27
2.65
3.35
2.64
3.17
2.24
ꢁ1.38
0.42
4.7
8.2
5.5
4.4
4.6
11
15
7.4
51
20
13
83
1
1
1
0
1
2
59
102
353
120
i
TNT
RDX
80
206
i
—
—
—
a
ꢁ1
b
c
Melting and thermal decomposition temperature under nitrogen gas (DSC, 10 1C min ). Gas pycnometer (25 1C). Heat of formation
d
e
f
(
calculated via Gaussian 03). Calculated detonation pressure (EXPLO5 V5.05). Calculated detonation velocity (EXPLO5 V5.05). Impact
sensitivity (BAM drop hammer). Friction sensitivity (BAM friction tester). Ref. 9. Ref. 16.
g
h
i
consequence of the deshielding effect produced by the deloca- of the energetic salts, the detonation pressures (P) and detona-
1
5
lization of the negative charge. Shown in Fig. 3 are the N NMR tion velocities (vD) were calculated using the program EXPLO5
1
4
spectra of 3 and salts 7–9, 12 measured in deuterated dimethyl V5.05. In Table 3 it is observed that all 1-methoxy-5-nitroimi-
sulfoxide solution. The signals for the primary amine of the notetrazole salts are highly endothermic. All of the energetic
triazole or guanidine system appear at the highest field salts exhibit positive heats of formation with compound 9
ꢁ1
between ꢁ328 and ꢁ304 ppm. The nitrogen anion (N4) having the highest value at 3.35 kJ g (Table 3). The densities
of tetrazolate is shifted to a lower field (between ꢁ83 and of salts 5–12, which are one of governing physical properties in
ꢁ
73 ppm) than the neutral NH of 3. Assignment of the signals determining explosive performance, range from 1.556 to
ꢁ
3
ꢁ3
of the other nitrogen atoms in the tetrazole ring is given based 1.649 g cm . Except for compound 9 (1.709 g cm ), densities
ꢁ
3
on the values of the chemical shift of the oxy-5-nitroiminote- are slightly lower than that of 3 (1.660 g cm ). The detonation
trazolate system in the literature.
9
,10
pressures of these energetic salts are calculated to lie in a range
The thermal stabilities of all compounds were studied by between P = 24.1 and P = 34.2 GPa. These values are higher than
differential scanning calorimetry (DSC) at a heating rate of that of TNT (19.5 GPa) and lower than that of RDX (35.2 GPa).
ꢁ
1
1
0 1C min . DSC measurements were made on samples of Detonation velocities are calculated to lie between D = 8013 and
ꢁ1
B0.5 mg of each energetic compound. Five compounds (5–8, 11) D = 9065 m s . When the latter values are compared with those
melted before decomposing, whereas the compounds 9, 10, and of TNT and RDX, the results appear to be more promising than
11 decomposed at 151, 174, and 159 1C, respectively, without those based on the detonation pressure. The detonation
melting (Table 3). Compound 5 has the highest thermal stability velocities of all the energetic salts are substantially higher than
ꢁ
1
at 179 1C. All energetic salts show higher decomposition that of TNT (6881 m s ). Most of the energetic salts have lower
ꢁ
1
temperatures than the corresponding neutral compound 3, detonation velocities than RDX (8977 m s ), except compound
ꢁ1
which agrees well with the comparison of the decomposition 9, which has the detonation velocity of 9065 m s . Impact and
temperatures between oxy-nitroiminotetrazoles and their friction sensitivity measurements were made using a standard
8
–11
15
corresponding oxy-nitroimino-tetrazolates.
These studies BAM drop hammer and BAM friction tester, respectively.
show that the 1-methoxy-5-nitroimino-tetrazole salts 5–12 Since the sensitivity data are known to strongly depend on
presented here have high thermal stabilities, which is probably the particle size and shape, fine crystalline materials (grain
attributable to the extensive hydrogen bonding as observed in sizes lower than 500 mm) are used. In Table 3 a range of impact
the crystal structures.
sensitivities of the relatively sensitive 1-methoxy-5-nitroimino-
Calculations were carried out using the Gaussian 03 tetrazole salts 5–12 (5–13 J) compared to TNT (15 J) or RDX
1
3
(
Revision D.01) suite of programs at the B3LYP/6-31+G**// (7.4 J) are listed. The friction sensitivities are found between 12
MP2/6-311++G** level. All of the optimized structures were and 108 N for salts 6–12, which are higher than RDX (120 N),
characterized to be true local energy minima on the potential- except 5 (4360 N).
energy surface without having imaginary frequencies. The
heats of formation of the cations and anions are computed
Conclusions
using isodesmic reactions (see ESI†). The enthalpy of an
o
r298
isodesmic reaction (DH ) is obtained by combining the In the present work energetic nitrogen-rich salts based on the
MP2/6-311++G** energy difference for the reaction, the scaled 1-methoxy-5-nitroiminotetrazolate anion and guanidinium,
zero-point energies (B3LYP/6-31+G**), and other thermal aminoguanidinium, diaminoguanidinium, triamino-guanidinium,
factors (B3LYP/6-31+G**). Thus, the heats of formation of the carbohydrazidinium, 3-amino-1,2,4-triazolium, 4-amino-1,2,4-tria-
cations and anions being investigated can be extracted readily zolium, 3,5-diamino-1,2,4-triazolium cations were synthesized in
(see ESI†). With the values of the heats of formation and density good yield and characterized using IR, Raman and multinuclear
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1
13
15
NMR ( H, C, N) spectroscopy as well as elemental analysis. to which was added 61.0 g (0.938 mol) of dry sodium azide. The
O–11 were determined reaction mixture was stirred at 0 1C for 4 hours. The inorganic
The structures of the compounds 5ꢀ1/3H
2
by single crystal X-ray crystallography. Although all of the salt was filtered off (after filtering, the salt must be dissolved in
energetic salts except 9 exhibit relatively lower densities (1.556– cold water quickly). The cyanogen azide solution is added to a
ꢁ3
ꢁ3
1
.649 g cm ) than the neutral nitroiminotetrazole 3 (1.660 g cm ), solution containing 6.06 g (0.0727 mol) of methoxyamine
they have better thermal stabilities than 3. Most of the compounds hydrochloride (1), for 2.91 g (0.0727 mol) of NaOH was required
decompose at temperatures in a range of 134–179 1C. Some of the for the neutralization in 25 mL of water at 0 1C. After stirring for
oxy nitroiminotetrazolate salts, namely 8, 9, and 11, are shown to four hours at ambient temperature, the solvent was removed by
ꢁ
1
ꢁ1
have high heats of formation (2.65 kJ g for 8, 3.35 kJ g for 9, blowing air over the liquid surface. The product was purified by
3
ꢁ
1
.17 kJ g for 11), good detonation pressures (27.0 GPa for 8, washing with water and acetonitrile. Yellow crystal 2 was
3
4.2 GPa for 9, 27.7 GPa for 11), and good detonation velocities obtained in a yield of 74% (6.16 g, 0.0536 mol). Yellow crystal;
ꢁ1
ꢁ1
ꢁ1
(8479 m s for 8, 9065 m s for 9, 8408 m s for 11). All of these Tm 166 1C. dH (300 MHz; DMSO[d ]) 4.07 (3H, s, CH ), 7.05
6 3
new energetic salts have high thermal stabilities in comparison to (2H, s, NH ). d (75.5 MHz; DMSO[d ]) 67.0, 149.0.
2
C
6
the corresponding neutral compound 3. We are expecting to report
1-Methoxy-5-nitroiminotetrazole (3). At 0 1C, 2.00 g (0.0174
novel explosive formulations based on these energetic salts in the mol) of 1-methoxy-5-aminotetrazole (2) was added in small
near future.
3
portions to 6 mL 100% HNO . The reaction mixture was stirred
at ambient temperature for 18 hours. The solution was poured
into ca. 20 g of ice. Water and excess nitric acid should be
removed by blowing air over the liquid surface. (Caution! Must
be carried out in a hood behind a safety shield.) The product was
Experimental section
Safety precautions
While we have experienced no difficulties with the impact precipitated, filtered, and washed with a small amount of cold
instability of all energetic salts, manipulations must be carried water. Colorless crystals 3 were obtained in a yield of 84%
out in a hood behind a safety shield. Eye protection and leather (2.33 g, 0.0146 mol). Caution! Nitration of compound 2 should be
gloves must be worn. Extreme caution should be exercised at all carried out on a less than 2.00 g scale. Colorless crystals; Tdec.
times during the synthesis, characterization, and handling of 116 1C. d
any of these materials, especially compound 3 (must be pre- H-tetrazole). d
pared on a less than 2.00 g scale), and mechanical actions (532 nm, 50 mW) n/cm 3020, 2961, 1600, 1584, 1564, 1441,
H
(300 MHz; DMSO[d
6
]) 4.19 (3H, s, CH
3
), 11.12 (1H, s,
C
(75.5 MHz; DMSO[d
6
]) 68.0, 145.9. Raman
ꢁ
1
involving scratching or scraping must be avoided.
1412, 1261, 1220, 1037, 1024, 979, 759, 685, 485. Found C,
1
5.05; H, 2.67; N, 52.50%. Calc. for C H N O : C, 15.00; H, 2.52;
2 4 6 3
General methods
N, 52.50%.
1
13
15
H, C and N NMR spectra were recorded on 300 MHz (Bruker
AVANCE 300) and 600 MHz (Varian INOVA) Nuclear Magnetic (4.87 g, 0.0287 mol) was dissolved in 25 mL of water and added
Resonance spectrometers using DMSO[d ] as solvent. The melt- to a solution of sodium 1-methoxy-5-nitroiminotetrazolate,
Silver 1-methoxy-5-nitroiminotetrazolate (4). Silver nitrate
6
ing and decomposition points were obtained on a Differential which was obtained from 4.59 g (0.0287 mol) of 1-methoxy-5-
Scanning Calorimeter (METTLER TOLEDO DSC1) at a scan rate nitroiminotetrazole (3) and 1.15 g (0.0287 mol) of sodium
ꢁ
1
of 10 1C min . The onset temperatures reported herein corre- hydroxide in 75 mL of water. The white silver salt precipitated
spond to the first positive deviation from the working base line. immediately. The suspension was stirred for 30 min at ambient
IR spectra were recorded using ATR for solids on a Nicolet model temperature. The product was filtered and dried in air over-
iS10 spectrometer. Raman spectra were recorded with a confocal night. White powder 4 was obtained in a yield of 96% (7.32 g,
ꢁ
1
Raman microscope, which used an Nd:YAG laser with a wave- 0.0274 mol). White solid; Tdec. 193 1C. IR n/cm 2960, 1514,
length of 532 nm. Densities of the 1-methoxy-5-nitroiminotetra- 1442, 1412, 1375, 1321, 1255, 1223, 1211, 1109, 1014, 942, 871,
ꢁ1
zole salts were determined at 25 1C by employing
Micromeritics AccuPyc 1340 gas pycnometer. Elemental analyses 1513, 1321, 1109, 1009, 751, 693. Found C, 9.53; H, 1.14; N,
were carried out using a Thermo Fisher Scientific model Flash 32.96%. Calc. for C AgN : C, 9.00; H, 1.13; N, 31.48%.
EA 1112 series elemental analyzer. Details of the X-ray diffraction
Caution! During elemental analysis, DSC analysis, and Raman
analysis of compounds 5ꢀ1/3H
O–11 are provided. Data were measurements the compound exploded.
collected on a Bruker SMART APEX-II CCD detector using Guanidinium 1-methoxy-5-nitroiminotetrazolate (5). To an
a
752, 715, 694, 667. Raman (532 nm, 50 mW) n/cm 3041, 2966,
H
2
O
6 3
3
2
graphite monochromated MoKa radiation (l = 0.71073). Struc- aqueous solution of 1.79 g (0.0187 mol) of guanidine hydro-
tures were solved by applying direct methods using SHELXS- chloride in 100 mL of water was added 7.72 g (0.0289 mol) of
1
7
2
9
7. The full-matrix least-squares refinement on F included silver 1-methoxy-5-nitroiminotetrazolate (4). After stirring at
atomic coordinates and anisotropic thermal parameters for all ambient temperature for 3 hours, the silver chloride was
non-H atoms. The H atoms were included using a riding model. removed by filtering the solution three times, and the solvent
was removed under a stream of air. A 3.94 g portion (0.0180 mol,
Compound synthesis
9
6%) of white crystalline 5 was obtained. White crystals; T
m
ꢁ1
1
-Methoxy-5-aminotetrazole (2). At 0 1C, 23.1 g (0.218 mol) of 177 1C. Tdec. 179 1C. IR n/cm 3558, 3432, 3396, 3250, 3167,
cyanogen bromide was dissolved in 260 mL of dry acetonitrile 2953, 2809, 1660, 1576, 1516, 1445, 1427, 1417, 1374, 1327, 1288,
New J. Chem.
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Paper
1
236, 1143, 1093, 1028, 968, 945, 884, 772, 728. Raman (532 nm, of colorless crystals 8 was obtained. Colorless crystals; T
m
112 1C.
dec. 139 1C. IR n/cm 3380, 3337, 3324, 3205, 3180, 3119, 3036,
2965, 1692, 1675, 1592, 1449, 1419, 1298, 1279, 1197, 1178, 1131,
75.5 MHz; DMSO[d ]) 67.0, 150.4, 158.3. d (60.8 MHz; 1088, 1024, 986, 950, 902, 879, 775, 731, 665, 638. Raman (532 nm,
ꢁ
1
ꢁ1
50 mW) n/cm 2953, 1518, 1334, 1295, 1099, 1029, 754. d
H
T
(
(
300 MHz; DMSO[d ]) 4.09 (3H, s, CH ), 6.98 (6H, s, NH ). d
6 3 2 C
6
N
ꢁ
ꢁ1
DMSO[d ]) ꢁ304.7, ꢁ159.0, ꢁ122.2, ꢁ75.5 ( N), ꢁ28.8, ꢁ14.6, 50 mW) n/cm 3380, 3327, 3293, 3231, 3039, 2969, 1511, 1284,
6
ꢁ
6.9. Found C, 16.50; H, 4.25; N, 57.33%. Calc. for C
3
ꢁ
H
9
3
N O
9 3
: C, 1087, 1022, 886, 746. d
6.44; H, 4.14; N, 57.52%. Density: 1.596 g cm . Impact 4.48 (6H, s, NH ), 8.57 (3H, s). d
(60.8 MHz; DMSO[d
]) ꢁ328.3, ꢁ287.7, ꢁ159.3, ꢁ121.3,
H
(300 MHz; DMSO[d
6
]) 4.08 (3H, s, CH
3
),
1
2
C
(75.5 MHz; DMSO[d
6
]) 66.5, 150.4,
sensitivity: 12.7 J, friction sensitivity: 4360 N. The structure of 159.1. d
N
6
ꢁ
5ꢀ1/3H
2
O is supported by single crystal X-ray diffraction analysis. ꢁ72.9 ( N), ꢁ28.6, ꢁ13.1, ꢁ5.8. Found C, 13.64; H, 4.93; N,
3 12 12 3
Aminoguanidinium 1-methoxy-5-nitroiminotetrazolate (6). 63.73%. Calc. for C H N O : C, 13.64; H, 4.58; N, 63.62%. Density:
ꢁ
3
To an aqueous solution of 2.07 g (0.0187 mol) of aminoguani- 1.594 g cm . Impact sensitivity: 8.2 J. Friction sensitivity: 20 N. The
dine hydrochloride in 100 mL of water was added 5.00 g structure of 8 is supported by single crystal X-ray diffraction
(0.0187 mol) of silver 1-methoxy-5-nitroiminotetrazolate (4). analysis.
After stirring at ambient temperature for 3 hours, the silver Carbohydrazinium 1-methoxy-5-nitroiminotetrazolate (9).
salt was removed by filtering the solution three times, and the The reaction of 3.00 g (0.0188 mol) of 1-methoxy-5-nitroimino-
solvent was removed under a stream of air. A 4.20 g portion tetrazole (3) with 0.844 g (0.00938 mol) carbohydrazide in
(
0.0179 mol, 96%) of colorless crystals 6 was obtained. Color- 50 mL of water at ambient temperature for 10 min stirring
ꢁ
1
m
less crystal; T 141 1C. Tdec. 167 1C. IR n/cm 3417, 3376, 3342, gave a colorless crystal solid 9 (2.30 g, 0.00920 mol, 98%) after
ꢁ1
3
1
6
2
315, 3160, 3080, 3011, 2952, 2870, 1687, 1660, 1514, 1448, slowly air drying. Colorless crystals; Tdec. 151 1C. IR n/cm
414, 1341, 1315, 1276, 1233, 1090, 1024, 960, 878, 775, 728, 3299, 3120, 3087, 2959, 2854, 2677, 1737, 1599, 1589, 1561,
ꢁ
1
71, 622. Raman (532 nm, 50 mW) n/cm 3319, 3248, 3017, 1550, 1513, 1459, 1446, 1420, 1316, 1276, 1238, 1209, 1155,
950, 1509, 1309, 1292, 1092, 1025, 967. d (300 MHz; 1087, 1024, 946, 887, 878, 773, 740, 726, 661. Raman (532 nm,
]) 4.09 (3H, s, CH ), 4.68 (2H, s, NH ), 6.83 (2H, br, s), 50 mW) n/cm 3127, 3051, 2961, 1742, 1523, 1464, 1437, 1375,
.20 (2H, br, s), 8.56 (1H, s, NH). d (75.5 MHz; DMSO[d ]) 66.9, 1290, 1200, 1160, 1030, 980, 949, 877. d (300 MHz; DMSO[d ])
50.4, 159.0. d (60.8 MHz; DMSO[d (75.5 MHz;
(60.8 MHz; DMSO[d
]) ꢁ323.4,
H
ꢁ
1
DMSO[d
7
1
ꢁ
6
3
2
C
6
H
6
+
N
6
]) ꢁ324.6, ꢁ312.5 (br), 4.08 (6H, s, CH
3
3 C
), 9.72 (6H, br. s, NH and NH ). d
ꢁ
306.1 (br), ꢁ282.7, ꢁ159.2, ꢁ121.7, ꢁ74.0 ( N), ꢁ28.6, ꢁ13.8, DMSO[d
6
]) 67.0, 150.2, 156.9. d
N
ꢁ
6
ꢁ
6.2. Found C, 15.36; H, 4.36; N, 59.46%. Calc. for C H N O : ꢁ284.2, ꢁ159.6, ꢁ122.7, ꢁ79.4 ( N), ꢁ29.3, ꢁ14.3, ꢁ7.4. Found
3
ꢁ
10 10 3
3
C, 15.39; H, 4.30; N, 59.81%. Density: 1.587 g cm . Impact C, 14.76; H, 3.44; N, 54.37. Calc. for C H N O : C, 14.64; H,
5
14 16 7
ꢁ3
sensitivity: 4.1 J. Friction sensitivity: 89 N. The structure of 6 is 3.44; N, 54.62%. Density: 1.709 g cm . Impact sensitivity: 5.5 J.
supported by single crystal X-ray diffraction analysis. Friction sensitivity: 13 N. The structure of 9 is supported by
Diaminoguanidinium 1-methoxy-5-nitroiminotetrazolate (7). single crystal X-ray diffraction analysis.
To an aqueous solution of 3.43 g (0.0273 mol) of diaminoguani-
3-Amino-1,2,4-triazolium 1-methoxy-5-nitroiminotetrazolate
dine hydrochloride in 100 mL of water was added 7.30 g (10). The reaction of 2.56 g (0.0160 mol) of 1-methoxy-5-nitroi-
(0.0274 mol) of silver 1-methoxy-5-nitroiminotetrazolate (4). After minotetrazole (3) with 1.35 g of (0.0161 mol) 3-amino-1,2,4-
stirring at ambient temperature for 3 hours, the silver salt was triazole in 50 mL of water at ambient temperature for 10 min
removed by filtering the solution three times, and the solvent stirring gave colorless crystals 10 (3.82 g, 0.0157 mol, 98%) after
ꢁ1
was removed under a stream of air. A 6.81 g portion (0.0273 mol, slowly air drying. Colorless crystals; Tdec. 175 1C. IR n/cm
9
1
1
3
9%) of colorless crystals 7 was obtained. Colorless crystals; T
m
3347, 3227, 3142, 3082, 3017, 2956, 2779, 1698, 1598, 1522,
18 1C. Tdec. 134 1C. IR n/cm 3404, 3316, 2954, 1659, 1514, 1437, 1411, 1339, 1269, 1240, 1189, 1148, 1125, 1097, 1047,
447, 1423, 1325, 1227, 1174, 1090, 1006, 945, 773, 730. Raman 1028, 944, 913, 885, 794, 746, 730, 672, 611. d (300 MHz;
359, 3292, 3026, 3012, 2950, 1518, 1296, 1092, 1020, 749. DMSO[d ]) 2.28 (2H, br. s, NH ), 4.08 (3H, s, CH ), 8.29 (1H, s,
]) 4.08 CH), 8.42 (1H, br. s, NH), 12.44 (1H, br. s, NH). d (75.5 MHz;
ꢁ1
H
6
2
3
ꢁ
1
Raman (532 nm, 50 mW) n/cm
d
H
(300 MHz; DMSO[d
6
C
(
3H, s, CH ), 4.56 (4H, s, NH ), 7.12 (2H, s, NH), 8.52 (2H, br, s, DMSO[d ]) 66.7, 139.2, 150.3, 150.7. d (60.8 MHz; DMSO[d ])
3 2 6 N 6
+
ꢁ
NH ). d (75.5 MHz; DMSO[d ]) 66.5, 150.4, 159.8. d (60.8 MHz; ꢁ322.3, ꢁ232.2, ꢁ203.6, ꢁ159.2, ꢁ122.6, ꢁ109.5, ꢁ77.4 ( N),
2
C
6
N
ꢁ
DMSO[d ]) ꢁ326.5, ꢁ311.3, ꢁ286.4, ꢁ159.2, ꢁ121.5, ꢁ73.5 ( N), ꢁ29.3, ꢁ14.7, ꢁ7.2. Found C, 19.45; H, 3.22; N, 57.09%. Calc.
6
ꢁ
3
ꢁ
28.6, ꢁ13.5, ꢁ5.9. Found C, 14.39; H, 4.49; N, 61.69%. Calc. for for C
4
H
8
N
O
10 3
: C, 19.68; H, 3.30; N, 57.36%. Density: 1.613 g cm
Impact sensitivity: 4.4 J. Friction sensitivity: 83 N. The structure of
Impact sensitivity: 4.7 J. Friction sensitivity: 58 N. The structure 10 is supported by single crystal X-ray diffraction analysis.
of 7 is supported by single crystal X-ray diffraction analysis. 4-Amino-1,2,4-triazolium 1-methoxy-5-nitroiminotetrazolate
.
ꢁ
3
3 11 11 3
C H N O : C, 14.46; H, 4.45; N, 61.83%. Density: 1.556 g cm .
Triaminoguanidinium 1-methoxy-5-nitroiminotetrazolate (8). (11). The reaction of 2.52 g (0.0158 mol) of 1-methoxy-5-nitro-
To an aqueous solution of 4.37 g (0.0311 mol) of triaminogua- iminotetrazole (3) with 1.32 g of (0.0157 mol) 4-amino-1,2,4-
nidine hydrochloride in 100 mL of water was added 8.31 g triazole in 50 mL of water at ambient temperature for 10 min
(0.0311 mol) of silver 1-methoxy-5-nitroiminotetrazolate (4). After stirring gave a white solid 11 (3.78 g, 0.0155 mol, 98%) after
stirring at ambient temperature for 3 hours, the silver salt was slowly air drying. Colorless crystals; T 131 1C. Tdec. 134 1C. IR
m
ꢁ
1
removed by filtering the solution three times, and the solvent was n/cm 3275, 3140, 3106, 3059, 1519, 1456, 1427, 1386, 1323,
removed under a stream of air. A 7.05 g portion (0.0280 mol, 90%) 1280, 1253, 1207, 1074, 953, 918, 879, 778, 758, 724, 664, 629.
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ꢁ
1
Raman (532 nm, 50 mW) n/cm 3284, 3152, 3142, 3051, 2955,
557, 1521, 1324, 1076, 1025, 949, 878, 757. d (300 MHz;
DMSO[d ]) 4.10 (3H, s, CH ), 8.50 (3H, br. s, NH and NH ), 9.44
2006, 103, 5409; (e) T. M. Klap o¨ tke, J. Stierstorfer and
B. Weber, Inorg. Chim. Acta, 2009, 362, 2311.
3 Reviews: (a) H. Gao and J. M. Shreeve, Chem. Rev., 2011,
111, 7377; (b) G. Steinhauser and T. M. Klap o¨ tke, Angew.
Chem., Int. Ed., 2008, 47, 3330.
4 (a) T. Abe, G.-H. Tao, Y.-H. Joo, Y. Huang, B. Twamley and
J. M. Shreeve, Angew. Chem., Int. Ed., 2008, 47, 7087;
(b) Y.-H. Joo, B. Twamley, S. Garg and J. M. Shreeve, Angew.
Chem., Int. Ed., 2008, 47, 6236; (c) T. M. Klap ¨o tke, C. Mir ´o
Sabat ´e and A. Penger, Eur. J. Inorg. Chem., 2009, 880;
(d) T. M. Klap ¨o tke and S. M. Sproll, Eur. J. Org. Chem.,
2009, 4284; (e) V. Hartdegen, T. M. Klap o¨ tke and
S. M. Sproll, Inorg. Chem., 2009, 48, 9549;
( f ) T. M. Klap o¨ tke, C. Mir o´ Sabat ´e and J. Stierstorfer, New
J. Chem., 2009, 33, 136.
1
H
+
6
3
2
(
2H, s, CH). d (75.5 MHz; DMSO[d ]) 66.9, 144.0, 149.6. d (60.8
C 6 N
MHz; DMSO[d ]) ꢁ327.7, ꢁ244.4, ꢁ198.3, ꢁ159.3, ꢁ122.2,
6
ꢁ
ꢁ
76.7 ( N), ꢁ29.0, ꢁ14.4, ꢁ7.8. Found C, 20.13; H, 3.37; N,
5
4 8 10 3
9.22%. Calc. for C H N O : C, 19.68; H, 3.30; N, 57.36%.
ꢁ
3
Density: 1.649 g cm . Impact sensitivity: 4.6 J. Friction sensi-
tivity: 59 N. The structure of 11 is supported by single crystal
X-ray diffraction analysis.
,5-Diamino-1,2,4-triazolium 1-methoxy-5-nitroiminotetra-
zolate (12). The reaction of 2.75 g (0.0172 mol) of 1-methoxy-
-nitroiminotetrazole (3) with 1.71 g (0.0172 mol) of 3,5-dia-
mino-1,2,4-triazole in 80 mL of water at ambient temperature
for 10 min stirring gave a white solid 12 (4.31 g, 0.0166 mol,
7%) after air drying. White solid; Tdec. 159 1C. IR n/cm 3419,
308, 3124, 3011, 2959, 2812, 2762, 1694, 1666, 1519, 1439,
419, 1373, 1333, 1289, 1239, 1094, 1070, 1030, 1009, 952, 881,
3
5
ꢁ
1
9
3
1
7
1
5 T. M. Klap o¨ tke, in High Energy Density Materials, ed.
T. M. Klap o¨ tke, Springer, Berlin, 2007, p. 85.
6 (a) T. M. Klap ¨o tke, H. Radies and J. Stierstorfer, Z. Natur-
forsch., B: Chem. Sci., 2007, 62, 1343; (b) R. Damavarapu,
T. M. Klap ¨o tke, J. Stierstorfer and K. R. Tarantik, Propellants,
Explos., Pyrotech., 2010, 10, 395.
ꢁ
1
00, 665. Raman (532 nm, 50 mW) n/cm 3031, 2962, 1513,
295, 1099, 1073, 1025, 950, 885, 754, 689, 663. dH (300 MHz;
DMSO[d ]) 4.08 (3H, s, CH ), 7.07 (5H, br, s, NH and NH ).
+
6
3
2
d
C
(75.5 MHz; DMSO[d
6
]) 66.7, 150.4, 151.5. d
N
(60.8 MHz;
7 G. Geisberger, T. M. Klap o¨ tke and J. Stierstorfer, Eur. J.
Inorg. Chem., 2007, 4743.
8 (a) T. M. Klap ¨o tke, J. Stierstorfer and A. U. Wallek, Chem.
Mater., 2008, 20, 4519; (b) N. Fischer, T. M. Klap o¨ tke,
D. Piercey, S. Scheutzow and J. Stierstorfer, Z. Anorg. Allg.
Chem., 2010, 636, 2357.
DMSO[d
6
ꢁ
]) ꢁ307.4, ꢁ188.0, ꢁ159.8, ꢁ123.1, ꢁ120.5,
ꢁ
83.1 ( N), ꢁ29.5, ꢁ14.3, ꢁ9.2. Found C, 17.43; H, 4.08; N,
5
5.74%. Calc. for C : C, 17.33; H, 4.00; N, 55.58%.
4 11 11 4
H N O
ꢁ3
Density: 1.597 g cm . Impact sensitivity: 11 J. Friction
sensitivity: 102 N.
9
Y.-H. Joo and J. M. Shreeve, Angew. Chem., Int. Ed., 2010,
9, 7320.
4
Acknowledgements
10 Y.-H. Joo and J. M. Shreeve, J. Am. Chem. Soc., 2010,
The authors gratefully acknowledge the support of the Agency
for Defense Development (Korea).
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New J. Chem.
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15 (a) www.bam.de; (b) A portion of 30 mg of 1-methoxy-5-
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nitroiminotetrazolate salts was subjected to a drop-hammer
test using a 1 or 5 kg weight dropped. A range in impact and 16 H. H. Krause, in Energetic Materials, ed. U. Teipel, VCH,
extremely sensitive: r10 N).
friction sensitivities according to the UN recommendations
Weinheim, 2005, p. 1.
(impact: insensitive 440 J, less sensitive Z35 J, sensitive 17 G. M. Sheldrick, Acta Crystallogr., Sect. A: Fundam. Crystal-
Z4 J, very sensitive r3 J; friction: insensitive 4360 N, less
logr., 2008, 64, 112.
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New J. Chem.