FULL PAPER

DOI: 10.1002/chem.200802203

New Energetic Materials: Functionalized 1-Ethyl-5-aminotetrazoles and

1-Ethyl-5-nitriminotetrazoles

Jçrg Stierstorfer, Karina R. Tarantik, and Thomas M. Klapçtke*[a]

Abstract: Alkylation of 5-aminotetra-
zole (1) with 2-chloroethanol leads to a
mixture of the N-1 and N-2 isomers of
(2-hydroxyethyl)-5-aminotetrazole.
Treatment of 1-(2-hydroxyethyl)-5-ami-
notetrazole (2) with SOCl2 yielded 1-
(2-chlorethyl)-5-aminotetrazole (3). 1-
(2-Azidoethyl)-5-aminotetrazole (4)
was generated by the reaction of 3 with
sodium azide. Nitration of 2, 3, and 4
with HNO3 (100 %) yielded in the case
of 2 and 3 1-(2-hydroxyethyl)-5-nitrimi-
notetrazole (5) and 1-(2-chloroethyl)-5-
nitriminotetrazole (6). In the case of 4,
1-(2-nitratoethyl)-5-nitriminotetrazole
monohydrate (7) was obtained. 1-(2-
Azidoethyl)-5-nitriminotetrazole (8)
could be obtained by nitration of 4
with NO2BF4 via the formation of po-
tassium 1-(2-azidoethyl)-5-nitriminote-
trazolate (9). The reaction of 6 with
NaN3 resulted in the formation of the
salt sodium 1-(2-chloroethyl)-5-nitrimi-
notetrazolate (10 a). The deprotonation
reaction of 6 was further investigated
by the formation of the ammonium salt
(10 b). The protonation of 2 and 4 with
dilute nitric acid led to 1-(2-hydrox-
yethyl)-5-aminotetrazolium nitrate (11)
and 1-(2-azidoethyl)-5-aminotetrazoli-
um nitrate (12), respectively. Similarly,
protonation of 4 with perchloric acid
led to 1-(2-azidoethyl)-5-aminotetrazo-
lium perchlorate monohydrate (13).
Since 5-nitrimino-tetrazoles can be
used as bidentate ligands, the coordina-
tion abilities of 5, 6, and 8 were tested
by the reaction with copper nitrate tri-
hydrate, yielding the copper complexes
trans-[diaquabis{1-(2-hydroxyethyl)-5-
nitriminotetrazolato-k2N4,O5}copper(II)]
(14), trans-[diaquabis{1-(2-chloroethyl)-
5-nitriminotetrazolato-
Keywords: azides · energetic
materials · nitrogen heterocycles ·
structure elucidation
k2N4,O5}copper(II)] dihydrate (15), and
[diaquabis{1-(2-azidoethyl)-5-nitrimino-
tetrazolato-k2N4,O5}copper(II)] (16).
All compounds were characterized by
low-temperature single-crystal X-ray
diffraction. In addition, comprehensive
characterization (IR, Raman, and mul-
tinuclear NMR spectroscopy (1H, 13C),
elemental analysis, mass spectrometry,
DSC) was performed. The heats of for-
mation of selected compounds were
computed by using heats of combustion
obtained by bomb calorimetry or calcu-
lated by the atomization method. With
these values and the densities deter-
mined from X-ray crystallography, sev-
eral detonation parameter were calcu-
lated by the EXPLO5 program. Finally,
the sensitivities towards impact and
friction were determined using a BAM
drop hammer and friction tester.

Introduction ic materials (EMs) is by their performance and use. Accord-

The development of nitrogen-rich high-energy-density mate-
rials (HEDMs)[1] is an ongoing area of interest in our re-
search group.[2] The most suitable way of classifying energet-
[a] Dr. J. Stierstorfer, Dipl.-Chem. K. R. Tarantik,
Prof. Dr. T. M. Klapçtke
Department Chemistry and Biochemistry
Energetic Materials Research
Ludwig-Maximilian University of Munich
Butenandtstrasse 5–13, 81377 Munich (Germany)
Fax: (+ 49) 89-2180-77492
E-mail: tmk@cup.uni-muenchen.de
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200802203.
ing to this classification system, EMs are divided into three
classes (Figure 1): 1) explosives, 2) propellants, and 3) pyro-
technics.
The class of explosives can be divided into primary explo-
sives and secondary explosives, also called high explosives.
Compounds considered to be in the class of primary explo-
sives are mostly highly sensitive towards friction, impact,
and electrical sparks. They usually detonate with velocities
of between 3500 and 5500 m s1. Secondary explosives show
detonation velocities greater than 7000 m s1. Primary explo-
sives differ from secondary explosives in that they undergo
a very rapid transition from burning to detonation. The det-
onation is often used for ignition of less sensitive explosives.
Some examples of the class of explosives are shown in

Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 5775

Figure 1. Classification of energetic materials.
Figure 2. Example of compounds classified as explosives: a) lead azide; b) mercury fulminate; c) TATB (1,3,5-
triamino-2,4,6-trinitrobenzene); d) RDX (hexogen); e) HMX (octogen); f) CL-20 (hexanitrohexaazaisowurzi-
tane); g) PETN (pentaerythritol tetranitrate).
Figure 2. Modern explosives derive most of their energy
either a) from oxidation of the carbon backbone (traditional
energetic materials),[3] or b) from their high positive heats of
formation. Examples for the first class are explosives such
as TNT (1,3,5-trinitrotoluene),[4] RDX (cyclo-1,3,5-trimethy-
lene-2,4,6-trinitramine),[5] and HMX (cyclo-1,3,5,7-tetra-
methylene-2,4,6,8-tetranitramine).[6] Modern nitro com-
pounds such as CL-20,[7] TEX,[8] or the hepta- and octanitro-
cubanes[9] possess very high densities and have enhanced en-
ergetic properties owing to their substantial cage strain.
Propellants are combustible materials containing within
themselves all the oxygen needed for combustion. There-
fore, mostly mixtures containing a fuel and an oxidizer are
used. They differ from primary and secondary explosives in
that their prime objective is to deflagrate.
Pyrotechnics are mixtures or compounds designed to pro-
duce effects such as heat, light, sound, gas, or smoke. Un-
fortunately, most of the commonly used substances are
strongly polluting.
Nitrogen-rich molecules are one approach in the develop-
ment of new “green” energetic materials,[10] since molecular
nitrogen is the main component (78 %) in the earths atmos-
phere. Nitrogen occurs in all living organisms. Exceptionally,
5-N substituted tetrazoles, for example, 5-aminotetrazoles,[11]
[12]
5,5’-azotetrazolates, bis(1H-tetrazolyl)amine (H2BTA),
5776 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5,5’-bis(1H-tetrazolyl)hydrazine (BTH),[14] and 5-azido-1H-
tetrazole[15] have nitrogen contents above 82 %. Tetrazoles
have the outstanding property of often combining high ni-
trogen content and high positive heat of formation with
good thermal stability, owing to their aromatic ring system.
Of particular interest are tetrazoles, which exhibit energetic
nitrogen–oxygen-containing functional groups, such as nitro
groups (R-NO2),[16, 17] nitrate esters (RONO2),[18] or nitra-
mine functionalities (R2NNO2).[19, 20] Also, the formation of
tetrazolium salts with oxygen-rich counteranions such as
NO3[21, 22] or NACHTUNGRE(NO2)2[23, 24] are the focus of research be-
cause these compounds have
balanced oxygen contents. 5-Ni-
triminotetrazoles have been
known for a long time, as they
can be obtained by facile syn-
thetic routes.[25] 1-Substituted 5-
nitriminotetrazoles, such as 1-
methyl-5-nitriminotetrazole and
1-ethyl-5-nitriminotetrazole,
were first described in 1957.[26]
1-Methyl-5-nitriminotetrazole
(1 MeHAtNO2) is synthesized
by methylation of 5-aminotetra-
zole (5-At) to form 1-methyl-5-
aminotetrazole (1 MeAt) and
subsequent nitration of the pri-
mary amine.
Herein, we present the syn-
theses of several new 1-func-
tionalized 5-nitriminotetrazoles
and derivatives, which are also
accessible by nitration of the corresponding 5-aminotetra-
zoles.[27, 28] The compounds belong to all classes of energetic
materials. Thus, 1-(2-azidoethyl)-5-aminotetrazole represents
a nitrogen-rich fuel for propellant charges, 1-(2-azidoethyl)-
5-nitriminotetrazole represents a powerful secondary explo-
sive, and the copper complexes can be used as colorants
(green and blue) in modern smokeless pyrotechnical compo-
sitions.
Results and Discussion
Synthesis: The functionalized 1-ethyl-5-aminotetrazoles and
1-ethyl-5-nitriminotetrazoles were synthesized according to
Scheme 1. The N-alkylation of 5-aminotetrazole using 1-
chloroethanol was performed as described by Henry and
Finnegan.[27] The alkylation reaction produces the isomers 1-
(2-hydroxyethyl)-5-aminotetrazole (2) and 2-(2-hydroxyeth-
yl)-5-aminotetrazole in 32 % and 58 % yields, respectively.
The 1-isomer was separated by recrystallization from etha-
nol. The 2-isomer, which shows a long crystallization-delay,
is not described in this work. Single crystals were obtained
from water. Treatment of 2 with SOCl2 gave 1-(2-chloroeth-
yl)-5-aminotetrazole (3) in 75 % yield.[28] Single crystals
[13]
were also obtained by recrystallization from hot water. The
Chem. Eur. J. 2009, 15, 5775 – 5792
Energetic Materials
Scheme 1. Synthesis of 1-functionalized 5-amino- and 5-nitriminotetrazoles.
substitution of chlorine with azide was tried in different sol-
vents (MeCN, acetone, H2O, DMF) using different azide
sources (NaN3, Me3SiN3, AgN3). Only the reaction of 3 with
NaN3 in DMF as the solvent yielded 1-(2-azidoethyl)-5-ami-
notetrazole (4) in good yields (76 %). Two different kinds of
single crystals (polymorphs 4 a and 4 b), both suitable for X-
ray diffraction, could be obtained by recrystallization from
hot water and hot ethanol. The nitration of 2–4 using 100 %
nitric acid yielded the products 1-(2-hydroxyethyl)-5-nitrimi-
notetrazole (5), 1-(2-chloroethyl)-5-nitriminotetrazole (6),
and 1-(2-nitratoethyl)-5-nitriminotetrazole monohydrate (7).
The reactions were performed simply by adding 2–4 to an
ice-cooled excess of 100 % nitric acid and stirring the mix-
ture for 12 h. Afterwards the reaction mixtures were poured
onto ice and the solvent was removed under high vacuum.
Single crystals of 5–7 were obtained by evaporation of aque-
ous solutions in air at ambient temperature. In the case of 2,
the hydroxy group could not be nitrated by using fuming
nitric acid. Interestingly, nitration of 4 did not yield 1-(2-azi-
doethyl)-5-nitriminotetrazole (8) since the azide group was
substituted by an ONO2 group. Compound 7 could be ob-
tained in solid form only as its monohydrate. Compound 8
could be synthesized by NO2BF4 as a mild nitration agent.
Unfortunately, the yields were low (38 %) and the purifica-
tion is difficult, because HBF4 has to be removed. There-
fore, potassium hydroxide was added to an ethanolic solu-
tion of the nitration mixture, first precipitating KBF4 and
then potassium 1-(2-azidoethyl)-5-nitriminotetrazolate (9),
Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
which both were isolated by filtration. The starting material
can be easily removed, since it cannot be deprotonated and
it is soluble in ethanol. Other attempts to synthesize 8 under
the same reaction conditions as for 6 failed because of the
formation of the sodium salt, which cannot be substituted by
the azide anion. The deprotonation of 6 was also proved by
the formation of the ammonium salt 10 b by using aqueous
ammonia solution. Furthermore, protonation of 1-substitut-
ed 5-aminotetrazoles was performed using diluted nitric acid
on 2 and 4, and perchloric acid on 4. From this reaction, 1-
(2-hydroxyethyl)-5-aminotetrazolium nitrate (11), 1-(2-azi-
doethyl)-5-aminotetrazolium nitrate (12), and 1-(2-azidoeth-
yl)-5-aminotetrazolium perchlorate monohydrate (13) were
obtained in nearly quantitative yields and recrystallized
from water/ethanol mixtures.
In a recently published work, we presented several copper
complexes of 1-methyl-5-nitriminotetrazole, in which two
tetrazole moieties act as bidentate ligands.[29] One of the
complexes was shown to be a promising alternative to toxic
lead azide as a new primary explosive. Therefore, 5, 6, and 8
were treated with copper(II) nitrate in hot aqueous solu-
tions to yield the complexes trans-[diaquabis{1-(2-hydroxy-
ethyl)-5-nitriminotetrazolato-k2N4,O5}copper(II)] (14), trans-
[diaquabis{1-(2-chloroethyl)-5-nitriminotetrazolato-k2N4,O5}-
copper(II)] dihydrate (15), and [diaquabis{1-(2-azidoethyl)-
5-nitriminotetrazolato-k2N4,O5}copper(II)] (16) (Scheme 2).
Blue-green single crystals of complexes 14–16 precipitated
from concentrated aqueous solutions overnight.
www.chemeurj.org 5777
 T. M. Klapçtke et al.

3. Further details of the crystal-

Scheme 2. Synthesis of the copper complexes 14–16.
Molecular structures: Suitable single crystals were picked
from the crystallization mixture, mounted in Kel-F oil on a
glass fiber, and transferred to the N2 stream of an Oxford
Xcalibur3 diffractometer with a Spellman generator (voltage
50 kV, current 40 mA) and a KappaCCD detector. The data
collection was undertaken using the CrysAlis CCD soft-
ware[30] and the data reduction was performed with the Crys-
Alis Red software.[31] The structure was solved with SIR-
92[32] and refined with SHELXL-97[33] implemented in the
program package WinGX[34] and finally checked using
PLATON.[35] Selected data and parameters from the X-ray
data collection and refinement are given in Tables 1, 2, and
structure determination have
been deposited with the Cam-
bridge Crystallographic Data
Centre.[36]
The molecular structures of
2–16 are shown in Figures 3–20.
A detailed description of the
packing and hydrogen bonding as well as geometry tables
(bond length and angles) are given in the Supporting Infor-
mation. In general, all tetrazole rings follow the geometries
observed for other tetrazole derivatives in the CCDC data-
base. The five-membered ring is planar, building an aromat-
ic system. The ring moieties of 2, 3, 4 a, 4 b, and 11–13 are in
agreement with the geometry observed for 5-amino-1H-tet-
razole monohydrate[37] and 1-phenyl-5-aminotetrazole.[38]
The nitrated 5-aminotetrazoles 5, 6, 7, and 8 are in agree-
ment with both the structure of 1-methyl-5-nitriminotetrazo-
le[19a] and of 1-(2-nitro-2-azapropyl)-5-nitriminotetrazole
monohydrate.[39] Compound 2 crystallizes in the monoclinic

Table 1. Crystallographic data for 2–6.

2 3 4a 4b 5 6
formula C3H7N5O C3H6ClN5 C 3 H 6 N8 C3H6N8 C3H6N6O3 C3H5ClN6O2
form. weight 129.14 147.58 154.16 154.16 174.14 192.58
[g mol1]
crystal system monoclinic triclinic monoclinic triclinic triclinic orthorhombic
space group P21/c (14) P1̄ (2) P21/c (14) P1̄ (2) P1̄ (2) P212121 (19)
color/habit colorless rods colorless rods colorless needles colorless rods colorless blocks colorless rods
size [mm3] 0.15  0.20  0.25 0.15  0.21  0.25 0.10  0.10  0.12 0.10  0.10  0.16 0.30  0.22  0.12 0.10  0.13  0.20
a [] 7.006(5) 4.6620(6) 6.0263(6) 4.8512(3) 7.129(1) 5.207(5)
b [] 6.0570(7) 5.3220(7) 7.8546(6) 5.9583(4) 7.130(1) 7.197(5)
c [] 13.864(2) 13.42(2) 14.559(1) 12.3508(9) 7.922(1) 19.804(5)
a [8] 90 96.15(1) 90 92.037(5) 66.21(2) 90
b [8] 103.17(2) 90.75(1) 98.303(7) 94.938(6) 89.24(1) 90
g [8] 90 106.66(1) 90 105.130(6) 66.86(2) 90
V [3] 572.86(14) 316.81(7) 681.9(1) 342.72(4) 333.7(1) 742.2(9)
Z 4 2 4 2 2 4
1calcd [g cm3] 1.497 1.547 1.502 1.494 1.733 1.724
m [mm1] 0.118 0.514 0.114 0.114 0.152 0.484
FACHTUNGRE(000) 272 152 320 160 180 392
lMoKa [] 0.71069 0.71073 0.71073 0.71073 0.71073 0.71073
T [K] 200 200 200 200 200 200
q min/max [8] 4.5, 26.0 4.1, 26.0 4.3, 26.0 3.8, 26.0 4.6, 26.5 4.1, 25.5
dataset 8:8; 7:7; 17:17 5:5; 6:6 ; 7:7; 9:9; 17:17 5:5; 7:7; 15:15 8:8; 8:8; 9:9 6:6; 8:8 ; 23:
16:16 14
reflections collected 5524 3237 6660 3331 3516 3737
independent reflec- 1127 1249 1343 1329 1367 1382
tions
Rint 0.033 0.024 0.030 0.022 0.023 0.071
observed reflections 1070 1191 1343 909 1210 949
No. parameters 110 106 124 124 133 129
R1 (obs) 0.0582 0.0305 0.0305 0.0349 0.0359 0.0529
wR2 (all data) 0.1266 0.0776 0.0776 0.1048 0.0921 0.0692
S 1.22 1.05 1.14 1.02 1.05 0.93
resd. dens. [e 3] 0.17, 0.29 0.25, 0.23 0.19, 0.14 0.18, 0.30 0.28, 0.19 0.20, 0.26
device type Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3
CCD CCD CCD CCD CCD CCD
solution SIR-92 SIR-92 SIR-92 SIR-92 SIR-92 SIR-92
refinement SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97
absorption correc- multi-scan multi-scan multi-scan multi-scan multi-scan multi-scan
tion
CCDC 704303 704306 704301 705303 704309 704302

5778 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2009, 15, 5775 – 5792
Energetic Materials
FULL PAPER
Table 2. Crystallographic data for 7–11.
7 8 9 10 a 10 b 11
formula C3H7N7O6 C3H5N9O2 C3H4KN9O2 C3H4ClN6NaO2 C3H8ClN7O2 C3H8N6O4
form. weight 237.16 199.16 237.25 214.56 209.61 192.15
[g mol1]
crystal system triclinic monoclinic triclinic monoclinic monoclinic monoclinic
space group P1̄ (2) P21/n (14) P1̄ (2) P21/c (14) P21/c (14) P21/c (14)
color/habit colorless plates colorless rods colorless plates colorless rods colorless blocks colorless rods
size [mm3] 0.03  0.10  0.10 0.05  0.11  0.12 0.02  0.10  0.15 0.13  0.18  0.19 0.15  0.16  0.23 0.01  0.09  0.10
a [] 6.324(1) 6.2652(7) 6.8683(4) 10.239(1) 10.1928(9) 10.599(1)
b [] 7.198(1) 7.9142(9) 10.8930(7) 9.4797(9) 9.9612(9) 5.3468(5)
c [] 10.711(2) 16.026(2) 18.178(1) 8.3739(9) 8.7198(8) 14.945(1)
a [8] 82.99(2) 90 96.491(5) 90 90 90
b [8] 82.73(2) 90.204(9) 97.054(5) 109.65(1) 106.092(8) 109.86(1)
g [8] 66.52(2) 90 96.038(5) 90 90 90
V [3] 442.22(15) 794.63(16) 1331.22(14) 765.4(2) 850.7(1) 796.56(14)
Z 2 4 6 4 4 4
1calcd [g cm3] 1.781 1.665 1.776 1.862 1.637 1.602
m [mm1] 0.168 0.140 0.599 0.530 0.530 0.144
FACHTUNGRE(000) 244 408 720 432 432 400
lMoKa [] 0.71073 0.71073 0.71073 0.71073 0.71073 0.71073
T [K] 200 200 200 200 200 150
q min/max [8] 4.4, 26.0 4.2, 25.5 3.8, 26.5 4.2, 26.0 4.2, 26.0 4.1, 25.7
dataset 7:7; 8:8; 13:13 7:7; 6:9; 18:19 8:8; 13:13; 12:12; 11:11; 12: 12 ; 12: 12; 11:12; 4:6;
22:22 10:10 10: 10 18:17
reflections collect- 4503 3849 14 218 7497 8074 3733
ed
independent reflec- 1723 1487 5503 1507 1576 1519
tions
Rint 0.040 0.036 0.036 0.026 0.032 0.100
observed reflec- 1293 824 2921 1418 1463 499
tions
No. parameters 173 247 406 134 150 150
R1 (obs) 0.0658 0.0332 0.0418 0.0348 0.0444 0.0560
wR2 (all data) 0.1971 0.0755 0.1065 0.0892 0.0999 0.1486
S 1.14 0.88 0.90 1.09 1.16 0.81
resd. dens. [e 3] 0.61, 1.13 0.20, 0.15 0.70, 0.94 0.31, 0.28 0.23, 0.22 0.24, 0.52
device type Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3 Oxford Xcalibur3
CCD CCD CCD CCD CCD CCD
solution SIR-92 SIR-92 SIR-92 SIR-92 SIR-92 SHELXS-97
refinement SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97
absorption correc- multi-scan multi-scan multi-scan multi-scan multi-scan multi-scan
tion
CCDC 704310 704312 705304 704307 704308 704315

space group P21/c with four molecules in the unit cell and a
density of 1.497 g cm3. Its molecular structure (Figure 3)
can be compared with that of 1-(2-hydroxyethyl)-tetrazole
described 2007 by Lyakhov et al.[40] The intensive hydrogen
bonding is explained in the Sup-
porting Information.
1-(2-Chloroethyl)-5-aminote-
trazole (3) crystallizes with a
density of 1.547 g cm3 and two
molecules in a triclinic unit cell
with the space group P1̄. The
molecular structure (Figure 4)
Figure 3. Molecular structure
of 3 can be compared with that
of 2. Thermal ellipsoids repre- of 1-(2-chloroethyl)-tetrazole[41]
sent the 50 % probability level. and also with that of 1-ethyl-tet-
razole, which also has been described as ligands in copper
complexes.[42] The packing is very similar to that observed
for 2 and can be found in Supporting Information.
Interestingly, two polymorphs of 4 were obtained. Recrys-
tallization from water yielded
the structure 4 a, shown in
Figure 5, whereas recrystalliza-
tion from ethanol yielded the
molecular structure 4 b, shown
in Figure 6. Single-point calcu-
lations at the experimentally
observed structures (X-ray) of
4 a and 4 b showed that latter Figure 4. Molecular structure
molecule is approximately of 3. Thermal ellipsoids repre-
32 kJ mol1 lower in electronic sent the 50 % probability level.

Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 5779
 T. M. Klapçtke et al.

Table 3. Crystallographic data for 12–16.

12 13 14 15 16
formula C3H7N9O3 C3H9ClN8O5 C6H14CuN12O8 C6H16Cl2CuN12O8 C6H12CuN18O6
form. weight [g mol1] 217.18 272.63 445.84 518.75 495.83
crystal system monoclinic monoclinic monoclinic monoclinic monoclinic
space group P21/c (14) P21/c (14) P21/c (14) P21/c (14) P21/n (14)
color/habit colorless rods colorless rods blue rods light blue rods blue rods
size [mm3] 0.03  0.13  0.29 0.05  0.09  0.12 0.08  0.12  0.14 0.10  0.13  0.17 0.01  0.10  0.10
a [] 11.639(2) 7.748(2) 7.5380(4) 6.0251(3) 12.5699(6)
b [] 5.2940(11) 25.801(3) 8.4400(4) 21.7937(9) 6.5342(3)
c [] 14.827(3) 5.900(2) 12.7970(6) 7.0960(4) 22.792(1)
a [8] 90 90 90 90 90
b [8] 108.33 (3) 111.899(5) 92.974(4) 98.856(4) 94.291(4)
g [8] 90 90 90 90 90
V [3] 867.2(3) 1094.3(5) 813.06(7) 920.66(8) 1866.75(15)
Z 4 4 2 2 4
1calcd [g cm3] 1.663 1.655 1.821 1.871 1.764
m [mm1] 0.144 0.379 1.415 1.545 1.244
FACHTUNGRE(000) 448 560 454 526 1004
lMoKa [] 0.71073 0.71073 0.71073 0.71073 0.71073
T [K] 200 200 200 200 200
q min/max [8] 3.7, 26.0 3.7, 26.0 4.0, 26.0 4.2, 26.5 3.8, 26.0
dataset 14:14; 6:6; 18:18 9:8; 31:30; 7: 6 9:9; 10:10; 15:15 7:7; 27:27; 8: 8 15:14; 8:8; 20:28
reflections collected 3151 5666, 7897 9620 8800
independent reflections 1715 2149 1584 1908 3624
Rint 0.014 0.032 0.020 0.022 0.084
observed reflections 1426 1324 1563 1885 1687
No. parameters 165 190 152 165 328
R1 (obs) 0.0612 0.0361 0.0275 0.0268 0.0585
wR2 (all data) 0.2018 0.0920 0.0754 0.0627 0.1653
S 1.12 0.92 1.09 1.07 0.94
resd. dens. [e 3] 0.52, 0.45 0.39, 0.32 0.39, 0.33 0.35, 0.45 0.54, 0.99
device type Oxford Xcalibur3 CCD Oxford Xcalibur3 CCD Oxford Xcalibur3 CCD Oxford Xcalibur3 CCD Oxford Xcalibur3 CCD
solution SIR-92 SIR-92 SIR-92 SIR-92 SIR-92
refinement SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97 SHELXL-97
absorption correction multi-scan none multi-scan multi-scan multi-scan
CCDC 704314 704311 704304 704305 704313

lizes in the triclinic space group P1̄ with two molecules in

Figure 5. Molecular structure of 4 a (crystals from water). Thermal ellip-
soids represent the 50 % probability level.
Figure 6. Molecular structure of 4 b (crystals from ethanol). Thermal el-
lipsoids represent the 50 % probability level.
energy (B3LYP/cc-pVDZ). Compound 4 a crystallizes in the
monoclinic space group P21/c with four molecules in the
unit cell and a density of 1.50 g cm3. In contrast, 4 b crystal-
the unit cell and a calculated density of 1.49 g cm3. The mo-
lecular structures are similar, and a comparison of the bond
lengths is given in Table 4. There are no differences between
the bond lengths within the standard deviations. The great-
est difference is observed in the bond angles C1-N1-C2 and
N2-N1-C2, which are responsible for displacement of the 2-
azidoethyl substituent. The structures can be compared with
the complex bis{1-(2-azidoethyl)-tetrazole-kN4}copper(II)
chloride described in 2001 by Ivashkevich et al.[43] A neutral
1-(2-azidoethyl)tetrazole moiety cannot be found in the lit-
erature.
The hydrogen-bond motif of 4 a is depicted in Figure 7.
However, the same motifs are observed in the structure of
polymorph 4 b. Analysis of the hydrogen-bond graph sets[44]
shows that isolated chains are formed owing to C11(5) and
R22(8). Between the chains, only weak interactions can be
observed, because of the low density of 1.50 g cm3. A fur-
ther description of 4 a and 4 b is given in the Supporting In-
formation.
1-(2-Hydroxyethyl)-5-nitriminotetrazole (5) crystallizes in
the triclinic space group P1̄ with two molecules in the unit
cell and a density of 1.733 g cm3. The molecular geometry,
depicted in Figure 8, is in agreement with that observed for

5780 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2009, 15, 5775 – 5792
Energetic Materials
FULL PAPER
Table 4. Bond lengths () and angles (8) of polymorphs 4 a and 4 b. the orthorhombic space group
Bond lengths 4a 4b P212121 with four molecules in
N1C1 1.347(2) 1.349(2) the unit cell and a density of
N1N2 1.366(2) 1.363(2) 1.724 g cm3. The molecular
N2N3 1.287(2) 1.280(2) moiety is shown in Figure 9.
N3N4 1.363(2) 1.357(2)
Figure 10 shows the molecu-
N4C1 1.335(2) 1.335(2)
N5C1 1.331(2) 1.330(2) lar structure of 1-(2-nitratoeth-
N1C2 1.463(2) 1.460(2) yl)-5-nitriminotetrazole mono-
C2C3 1.512(2) 1.509(3) hydrate (7), which crystallizes Figure 9. Molecular structure
N6C3 1.483(2) 1.479(3) in the triclinic space group P1̄. of 6. Thermal ellipsoids repre-
N6N7 1.222(2) 1.222(2)
N7N8 1.131(2) 1.130(2)
The density of 1.781 g cm3 is sent the 50 % probability level.

Angles 4a 4b
C1-N1-N2 108.4(1) 108.6(1)
N3-N2-N1 106.0(1) 105.8(1)
N2-N3-N4 112.0(1) 112.4(1)
C1-N4-N3 105.4(1) 105.4(1)
N4-C1-N1 108.3(1) 107.9(1)
N5-C1-N1 126.0(1) 126.2(2)
N5-C1-N4 125.8(1) 126.0(2)
C1-N1-C2 131.1(1) 130.2(1)
N2-N1-C2 120.5(1) 121.2(1)
N1-C2-C3 112.1(1) 111.7(2)
N6-C3-C2 111.5(1) 111.4(2) Figure 10. Molecular structure of 7. Thermal ellipsoids represent the
N7-N6-C3 115.2(1) 115.8(2) 50 % probability level.
N8-N7-N6 173.5(2) 173.3(2)

higher than those observed for 5 and 6, although 7 includes

Figure 7. Hydrogen bonding in 4 a. Three graph sets are marked. Selected
hydrogen bonds (, , ,8): N5H5B···N3i = 0.89(2), 2.12(2), 3.006(2),
172(2); N5H5 A···N4ii = 0.88(2), 2.15(2), 3.015(2), 172(2); i) 1 + x, y, z;
ii) 1x, 1y, 1z.
one water molecule of crystallization. This may be a reason
for the intensive hydrogen-bond network described in the
Supporting Information.
The lowest density (1.665 g cm3) of nitriminotetrazoles 5–
8 is calculated for 1-(2-azidoethyl)-5-nitriminotetrazole (8),
which crystallizes in the monoclinic space group P21/c. The
molecular structure is depicted in Figure 11. Interestingly,
next to the classical hydrogen bonds, dimer pairs are formed
by an uncommon linear azide–nitro interaction (shorter
than the sum of van der Waals radii), which is shown in
Figure 12. A possible explanation of this phenomenon is the
concept of “s-hole bonding”. The noncovalent interaction
based on positive holes in the electrostatic surface is best ex-
plained by Murray, Politzer and co-workers.[46] In our case,
the s hole is likely to be located on the oxygen atom along
the extension of the NO bond of the nitro group, which
can interact linearly with a negative region of the outer
azide nitrogen atom. This electrostatic interaction elongates
the NO bond. The best Lewis structure is also shown in
Figure 12.

Figure 8. Molecular structure
of 5. Thermal ellipsoids repre-
sent the 50 % probability level.
1-methyl-5-nitriminotetrazole
but also neutral 5-nitriminote-
trazole.[19a] The C1N5 bond
length is 1.343(2) , which is
closer to a C=N double bond
(1.28 ) than a CN single
bond (1.46 ).[45] The nitramine
bond N5N6 shows a distance
of 1.362(2) .
1-(2-Chloroethyl)-5-nitrimi- Figure 11. Molecular structure of 8. Thermal ellipsoids represent the
notetrazole (6) crystallizes in 50 % probability level.

Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 5781

Figure 12. Azide–nitro s-hole bonding interaction in 8 and the corre-
sponding Lewis structure.
Potassium 1-(2-azidoethyl)-5-nitriminotetrazolate (9) crys-
tallizes in a triclinic space group with 2  3 independent mo-
lecular moieties in the unit cell. For clarity, only one is
shown in Figure 13.
Figure 13. One molecular moiety of the crystal structure of 9. Thermal el-
lipsoids represent the 50 % probability level. The disorder of the outer
azide nitrogen atoms can be seen in the large ellipsoids.
Sodium (10 a) and ammonium (10 b) 1-(2-chloroethyl)-5-
nitriminotetrazolate crystallize in the monoclinic space
group P21/c with four molecules in the unit cell and densities
of 1.862 and 1.637 g cm3, respectively. The densities and
also the bond lengths and angles of the molecular structures
(shown in Figures 14 and 15) are in agreement with those of
Figure 14. Molecular structure of 10 a. Thermal ellipsoids represent the
50 % probability level.
5782 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. M. Klapçtke et al.
Figure 15. Molecular structure of 10 b. Thermal ellipsoids represent the
50 % probability level.
ammonium 5-nitriminotetrazolate[47] and other 1-substituted
5-nitriminotetrazolates, for example, ammonium 1-methyl-5-
nitriminotetrazolate[48] and sodium 1-methyl-5-nitriminote-
trazolate.[49] The sodium atoms in 10 a are coordinated by six
atoms to show multiple coordination of symmetry-related
atoms (O1  2, O2  2, N4, and N3) forming no regular coor-
dination polyhedron. Dimers are formed from the coordina-
tion of oxygen atom O1 to two different sodium atoms (see
the Supporting Information). An extensive hydrogen-bond
network is formed in the packing of 10 b. The hydrogen
atoms of one ammonium cation participate in several strong
hydrogen bonds to different atoms (O1, O2, N3, N4, and
N5) of five different nitriminotetrazolate anions. A detailed
description can also be found in the Supporting Informa-
tion.
Protonation of 2 takes place at the expected nitrogen
atom N4, due to the similarity to protonation of 1-methyl-5-
aminotetrazole, which has been investigated in detail.[50] 1-
(2-Hydroxyethyl)-5-aminotetrazolium nitrate (11) crystalli-
zes in the monoclinic space group P21/c with four molecules
in the unit cell. The molecular unit is shown in Figure 16.
Figure 16. Molecular structure of 11. Thermal ellipsoids represent the
50 % probability level.
The density of 1.602 g cm3 is lower than that of 1-methyl-5-
aminotetrazolium nitrate (1.653 g cm3).[46]
1-(2-Azidoethyl)-5-aminotetrazolium nitrate (12) and 1-
(2-azidoethyl)-5-aminotetrazolium perchlorate monohydrate
(13) also crystallize in the monoclinic space group P21/c with
four molecules in the unit cell. In both molecular structures,
which are shown in Figures 17 and 18, protonation takes
place at the nitrogen atom N4. The densities of 1.663 and
1.655 g cm3, respectively, are in the range of 1-methyl-5-
aminotetrazolium nitrate and perchlorate,[49] but significant-
ly lower than that of 1,5-diaminotetrazolium nitrate
Chem. Eur. J. 2009, 15, 5775 – 5792
Energetic Materials
Figure 17. Molecular structure of 12. Thermal ellipsoids represent the
50 % probability level.
Figure 18. Molecular structure of 13. Thermal ellipsoids represent the
50 % probability level.
(1.72 g cm3) and perchlorate (1.90 g cm3).[51] The packings
of 11–13 are shown in the Supporting Information.
trans-[Diaquabis{1-(2-hydroxyethyl)-5-nitriminotetrazola-
to-k2N4,O5}copper(II)] (14) crystallizes in the triclinic space
group P1̄ with one molecule in the unit cell (Figure 19). The
Figure 19. Molecular structure of 14. Thermal ellipsoids represent the
50 % probability level. Selected coordination bond lengths (): CuN4
1.977(2), CuO1 2.405(2), CuO4 1.983(2); angles (8): N4-Cu-O1
74.84(6), N4-Cu-O4 89.00(7), O4-Cu-O1 91.99(6).
copper atoms are located on the center of inversion, where-
by the 5-nitriminotetrazolate acts as bidentate ligand with a
bite angle of 74.84(6)8. The N4Cu bond length is
1.997(4) , which is a typical CuN coordination length,
also found in recently described copper nitriminotetrazo-
lates,[52] but also found in copper nitrogen complexes such as
[CuACHTUNGRE(NH3)4ACHTUNGRE(NO3)2].[53] The distances observed between the
copper and oxygen atoms are 2.405(2) (CuO1) and
1.983(2)  (CuO3), resulting in a Jahn–Teller-distorted oc-
tahedral coordination sphere. This coordination geometry of
the elongated octahedron is typical for this kind of chromo-
phore distorted by the Jahn–Teller[54] effect and is similar to
those found for other complexes of both 2-substituted and
1-substituted tetrazoles.[55]
The molecular structure of 15 is shown in Figure 20. Al-
though no comparable neutral complex can be found in lit-
erature, 15 is a further example of 1-(2-chloroethyl)-substi-
tuted tetrazole complexes. In 2001, 2002, and 2003 Stassen
Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
Figure 20. Molecular structure of 15. Thermal ellipsoids represent the
50 % probability level. Selected coordination bond lengths (): CuN4
1.982(1), CuO1 2.367(1), CuO3 1.9849(14); angles (8): N4-Cu-O1
77.30(5), N4-Cu-O3 91.24(6), O4-Cu-O1 86.26(6).
et al. reported the synthesis and X-ray crystal structure of
bis{1-(2-chloroethyl)-tetrazole}bisACHTUNGRE(nitrato)copper(II) ni-
trate,[56] chloride,[57] and perchlorate.[58] Several 1-(2-chlor-
oethyl)-tetrazole iron complexes have also been reported.[59]
The copper cations are coordinated by the atoms N4 and
O1 with a bite angle of 77.29(5)8. Again the Jahn–Teller-dis-
torted octahedral coordination sphere is observed. The axial
positions are occupied by the oxygen atoms O1 with a dis-
tance of 2.367(1) .
Interestingly, there is one known copper complex of 1-azi-
doethyl-5H-tetrazole.[60] Ivashkevic et al. describe polyACHTUNGRE[bis{1-
(2-azidoethyl)-tetrazole-kN4}dichlorocopper(II)] as an exam-
ple of a layered polymeric crystal structure with a formula
[CuCl2L2]. Diaquabis{1-(2-azidoethyl)-5-nitriminotetrazola-
to-k2N4,O5}copper(II) (16), shown in Figure 21, crystallizes
in the monoclinic space group P21/c with four molecules in
the unit cell and has the lowest density (1.764 g cm3) of the
investigated copper complexes. In contrast to the structures
of 14 and 15, the copper atoms are not located on the center
of inversion.
Figure 21. Molecular structure of 16. Thermal ellipsoids represent the
50 % probability level. The outer azide nitrogen atoms are strongly disor-
dered. Selected coordination bond lengths (): CuN4 1.950(5), CuN13
1.961(5), CuO5 2.013(5), CuO1 2.066(4), CuO6 2.181(5), CuO3
2.343(5); angles (8): N4-Cu-N13 169.2(2), N4-Cu-O5 92.6(2), N13-Cu-O5
95.9(2), N4-Cu-O1 83.4(2), N13-Cu-O1 87.2(2), O5-Cu-O1 170.5(2), N4-
Cu-O6 88.5(2), N13-Cu-O6 98.3(2), O5-Cu-O6 89.2(2), O1-Cu-O6
99.2(2), N4-Cu-O3 97.2(2), N13-Cu-O3 76.7(2), O5-Cu-O3 86.5(2), O1-
Cu-O3 85.5(2), O6-Cu-O3 173.1(2).
www.chemeurj.org 5783
 T. M. Klapçtke et al.

Spectroscopy: NMR spectrosco-

py, particularly 13C and 15N
NMR spectroscopy, is a valua-
ble method to identify 5-amino-
tetrazoles as well as 5-nitrimi-
notetrazoles. The tetrazole
carbon atom shifts are about
the same for the different deriv-
atives of the 5-aminotetrazoles
(d = 156.5 (2), 155.9 (3), and
156.3 ppm (4)), 5-nitriminote-
trazoles (d = 150.9 (5, 6) and
151.1 ppm (8)), or salts (d =
157.2 (10 a) and 158.8 ppm
(10 b)). The signals of the 5-
aminotetrazole derivatives cor-
respond to the one of unsubsti-
tuted 5-aminotetrazole (d =
156.6 ppm).[61] The shifts of the
signals for the tetrazolates (9,
10) to lower fields can be ex-
plained with orbital effects.[62]
The signals of the CH2 groups
are all in the same range,
whereas those of 2 and 5 are
shifted to higher ppm values by
the hydroxy moiety. 15N NMR
spectra of 2–6 as well as 8 mea-
sured in [D6]DMSO can be
seen in Figure 22. The signal
were assigned by evaluating the
JACHTUNGRE( H,15N) and 3JACHTUNGRE(1H,15N) cou-
2 1

pling constants and comparing

these with literature values.[63]
Also, vibrational spectrosco-
py such as IR and Raman spec-
troscopy can be used for specif-
ic characterization of substitut-
ed tetrazole derivatives. The
characteristic vibrations of the
tetrazole ring framework at
1000–1030, 1045–1085, and
1095–1120 cm1[64] and the
stretching motion of the N
N=N fragment at 1265–
1320 cm1[65] appear in the IR
spectra of all investigated com-
pounds. The signal caused by
the stretching motion of the
cyclic (C=N) bond at 1580–
1600 cm1 is in the same range
15
as the exocyclic one of the nitri- Figure 22. N NMR spectra of 2–6 and 8 measured in [D6]DMSO. Chemical shifts are given in ppm with re-
[66] spect to MeNO2 as external standard.
minotetrazoles (5–10). The
NH and CH valence vibra-
tions generate broad signals in
the same range at 2800–3200 cm1. In the case of the 5-nitri- NNO2 fragment appears at 1330 cm1. The OH valence
minotetrazoles, the symmetric valence vibration of the motion is found at 3330–3380 cm1 in the spectra of 2 a, 5,

5784 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2009, 15, 5775 – 5792
Energetic Materials
and 11. The nas vibration of the azide group in 4, 8, 9, 12, 13,
and 16 appears between 2110 and 2150 cm1.
Physicochemical properties: Since 2–16 are high-energy-
density compounds with exceedingly high nitrogen contents,
their energetic behavior was investigated and a detailed de-
scription is given in the following sections. The energetic
properties are summarized in Tables 5 and 6.
Thermal behavior: The thermal behavior of 2–16 (ca.
1.5 mg) was investigated on a Linseis PT10 DSC (differen-
tial scanning calorimeter)[67] as well as on a Perkin–Elmer
Pyris 6 DSC,[68] calibrated by standard pure indium and zinc
at heating rates of 5 K min1. The thermograms of the 50–
300 8C temperature range are shown in Figure 23. The 5-
aminotetrazoles 2–4 show melting points between 130 and
158 8C, followed by a broad decomposition range of the
FULL PAPER
melt. Compounds 5–8 have decomposition temperatures be-
tween 112 and 142 8C. Except for 6, no prior melting could
be observed. Salts 9, 10 a, and 10 b show significantly higher
decomposition temperatures than neutral compounds 6 and
8, which is as expected for a comparison of tetrazoles with
their corresponding tetrazolates.[19b] In contrast, protonation
of tetrazoles mostly decreases the decomposition tempera-
ture, which is in agreement with the thermograms of 11–13.
In addition, 11–13 show melting points at 85 (13), 95 (12),
and 135 8C (11).
The copper complexes 14–16 show the highest as well as
the sharpest decomposition temperatures of 217 (16), 233
(15), and 245 8C (14). In none of the thermograms in
Figure 24 melting points or loss of crystal water could be ob-
served.

Table 5. Physicochemical properties of 2–8.

2 3 4 5 6 7 8
formula C3H7N5O C3H6ClN5 C 3 H 6 N8 C3H6N6O3 C3H5ClN6O2 C3H7N7O6 C3H5N9O2
form. weight [g mol1] 129.14 147.58 154.16 174.14 192.58 237.16 199.16
impact sensitivity[a] [J] > 100 > 100 10 6 28 25 2
friction sensitivity[b] [N] > 360 > 360 360 55 > 360 360 80
N[c] [%] 54.24 47.46 72.70 48.27 43.64 44.75 63.31
W[d] [%] 105.32 64.88 93.42 55.13 49.85 23.61 52.2
Tdecomp[e] [8C] 160 (mp) 150 (mp) 130 (mp) 138 130 128 140
density[f] [g cm3] 1.50 1.55 1.50 1.73 1.72 1.781 1.67
DcH[g] [kJ mol1] 3852 3460 3652 3080 2655 2570 –
DfHm8[h] [kJ mol1] 105 143 413/550[n] 201 278 165 629[n]
DfU8[i] [kJ kg1] 689 1976 2824/3679[n] 1261 1534 800 3256[n]
values calculated by EXPLO5:
DEUm8[j] [kJ kg1] 1842 – 3455/4321[n] 5353 – 6160 5719[n]
TE[k] [K] 1643 – 2581/3010[n] 3710 – 4352 4184[n]
p[l] [kbar] 133 – 191/218[n] 280 – 341 275[n]
D[m] [m s1] 6645 – 7619/8043[n] 8254 – 8943 8320[n]
[a] BAM drop hammer; [b] BAM methods; [c] nitrogen content; [d] oxygen balance; [e] decomposition temperature from DSC (b = 5 8C); [f] determined
by X-ray crystallography; [g] enthalpy of combustion; [h] molar enthalpy of formation; [i] energy of formation; [j] total energy of detonation,
EXPLO5 V5.02; [k] explosion temperature; [l] detonation pressure; [m] detonation velocity; [n] calculated DfHm8.

Table 6. Physicochemical properties of 9–13 compared with those of RDX.

9 10 a 10 b 11 12 13 RDX
formula C3H4KN9O2 C3H4ClN6NaO2 C3H8ClN7O2 C3H8N6O4 C3H7N9O3 C3H9ClN8O5 C3H6N6O6
form. weight [g mol1] 237.25 214.56 209.61 192.15 217.15 272.61 222.11
impact sensitivity[a] [J] 25 > 50 > 50 > 50 7 5 7
friction sensitivity[b] [N] 300 > 360 > 360 > 360 160 120 120
N[c] [%] 53.14 39.17 46.78 43.74 58.05 41.10 37.8
W[d] [%] 53.95 48.47 57.24 49.96 47.89 29.35 21.6
Tdecomp[e] [8C] 205 184 196 160 148 172 ca. 213
density[f] [g cm3] 1.78 1.86 1.64 1.60 1.66 1.66 1.82
DcH[g] [kJ mol1] – – – 2912 2910 – –
DfHm8[h] [kJ mol1] – – – 11 457 – 2105
DfU8[i] [kJ kg1] – – – 173 2674 – 66.5
values calculated by EXPLO5:
DEUm8[j] [kJ kg1] – – – 5107 6010 – 6043
TE[k] [K] – – – 3512 4176 – 4321
p[l] [kbar] – – – 233 271 – 346
D[m] [m s1] – – – 7784 8329 – 8750
[a] BAM drop hammer; [b] BAM methods; [c] nitrogen content; [d] oxygen balance; [e] decomposition temperature from DSC (b = 5 8C); [f] determined
by X-ray crystallography; [g] enthalpy of combustion; [h] molar enthalpy of formation; [i] energy of formation; [j] total energy of detonation,
EXPLO5 V5.02; [k] explosion temperature; [l] detonation pressure; [m] detonation velocity.

Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 5785

Figure 23. Thermograms of 2–13 in the temperature range 50–300 8C.
Temperatures are given as Tonset.
Figure 24. Thermograms of 14–16 in the temperature range 50–300 8C.
Heats of formation: The heats of formation of 2–7 as well as
11 and 12 were calculated by using experimentally obtained
heats of combustion. In bomb-calorimetric measurements
nitrogen-rich highly energetic compounds, such as 4 and 8
carrying the covalent azide group, tend to burn incompletely
because of their tendency to explode. Often, wrong heats of
combustion (DcH) and thus wrong heats of formation
(DfH8) are obtained. Therefore, the heats of formation of 4
5786 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. M. Klapçtke et al.
and 8 were computed on the CBS level and using the atomi-
zation method. Details can be found in the Supporting In-
formation. For all calorimetric measurements, a Parr 1356
bomb calorimeter (static jacket) equipped with a Parr
1108CL oxygen bomb for the combustion of highly energetic
materials were used.[69] The samples (ca. 200 mg) were press-
ed with a well-defined amount of benzoic acid (ca. 800 mg)
to form a tablet, and a Parr 45C10 alloy fuse wire was used
for ignition. In all measurements, a correction of 2.3 cal cm1
wire burned was applied, and the bomb was examined for
evidence of noncombusted carbon after each run. A Parr
1755 printer was furnished with the Parr 1356 calorimeter to
produce a permanent record of all activities within the calo-
rimeter. The reported values are the average of three single
measurements. The calorimeter was calibrated by combus-
tion of certified benzoic acid (SRM, 39i, NIST) in an oxygen
atmosphere at a pressure of 3.05 MPa. Typical experimental
results of the constant volume combustion energy (DcU) of
the salts are summarized in Table 5. The standard molar en-
thalpy of combustion (DcH8) was derived from DcH8 = DcU
+ DnRT (Dn = Dni (products, g)  Dni (reactants, g); Dni is
the total molar amount of gases in the products or reac-
tants). The enthalpy of formation, DfH8, for each of com-
pounds 2–7 as well as 11 and 12 was calculated at 298.15 K
by using the Hess thermochemical cycle and the following
combustion reactions (Scheme 3).
The heats of formation of the combustion products H2O(l)
(286 kJ mol1), CO2 (g) (394 kJ mol1), and HCl(g)
(92 kJ mol1) were obtained from the literature.[70, 71]
Except for 2, all compounds were calculated to be formed
endothermically. The detailed values are summarized in
Table 5. Of the covalent derivatives, compound 8 was cal-
culated to have the largest positive heat of formation
(+ 629 kJ mol1). Of the salts, 12 has the highest value
(+ 457 kJ mol1).
Detonation parameter: The detonation parameters were cal-
culated with the program package EXPLO5 (version
5.02).[72] Unfortunately, only compounds containing C, H, N,
O, Al, or F can be calculated. Therefore, it was not possible
to calculate compounds 3, 6, 9, 10 a, 10 b, and 13, which con-
tain chlorine. The program is based on the chemical-equilib-
rium, steady-state model of detonation. It uses the Becker–
Kistiakowsky–Wilson equation of state (BKW EOS) for gas-
eous detonation products and the Cowan–Fickett equation
of state for solid carbon.[73, 74] The equilibrium composition
of the detonation products is calculated by applying a modi-
fied White, Johnson, and Dantzig free-energy minimization
technique. The program is designed to enable the calcula-
tion of detonation parameters at the Chapman–Jouguet (CJ)
point. The BKW equation [Eq. (1)] was used with the
BKWN set of parameters (a, b, k, q) as stated in Equa-
tion (2); Xi is the molar fraction of ith gaseous product and
ki is the molar covolume of the ith gaseous product.
X
pV=RT ¼ 1 þ xebx x ¼ ðk X i ki Þ=V ðT þ qÞa ð1Þ
Chem. Eur. J. 2009, 15, 5775 – 5792
Energetic Materials
Scheme 3. Combustion equations of 2–7, 11, and 12.
a ¼ 0:5, b ¼ 0:176, k ¼ 14:71, q ¼ 6620 ð2Þ
The detonation parameters, calculated with the EXPLO5
program using the experimentally determined densities (X-
ray), are summarized in Tables 5 and 6.
Among the investigated compounds, 7 shows the best det-
onation parameters. The calculated detonation velocity of
8943 m s1 even exceeds that of RDX. Similar values were
calculated for the detonation pressure (7: 341 kbar, RDX:
346 kbar). The detonation velocities of compounds 8, 12,
and 5 reveal values significantly higher than 8000 m s1. Al-
though showing detonation pressures of pCJ = 280 (5), 275
(8), and 271 kbar (12) and explosion temperatures of more
than 3500 K, the performance data are lower than those of
RDX. The influence of the density can clearly be seen on
the values of 4, which, although it is formed very endo-
thermically, shows low calculated detonation parameters.
The remaining products stay below Ddet. = 8050 m s1. How-
ever, they also exceed the detonation parameter of TNT
(Ddet.  7000 m s1).
Sensitivities: For initial safety testing, the impact, friction,
and electrostatic sensitivity were determined.[75] The impact
sensitivity (IS) tests were carried out according to the stan-
dard STANAG 4489[76] and were modified[77] by using a
BAM (Bundesanstalt fr Materialforschung[78]) drop
hammer.[79] The friction sensitivity (FS) tests were carried
out according to STANAG 4487[80] and were modified[81] by
using the BAM friction tester. The sensitivity data strongly
depend on the particle size, shape, and texture. Although we
tried to use fine crystalline materials (1–100 mm), we cannot
guarantee exact values for these new energetic materials.
Appropriate tests should be re-run before the compounds
are synthesized in larger scales. Compounds 5 (IS: 6 J, FS:
55 N) and 8 (IS: 2 J, FS: 80 N) are the most sensitive com-
pounds investigated in this work, whereas 2, 3, 10 a, and 10 b
are completely insensitive towards impact and friction.
Under the “UN recommendations on the transport of dan-
gerous goods”,[82] 8 is classified as “very sensitive” regarding
the impact sensitivity, and 5 is classified as “very sensitive”
towards friction. Also, 13 is classified as “sensitive” in both
categories. In general, the nitrated 5-aminotetrazoles (5–9)
or compounds carrying a covalent azide group (4, 8, 9, 12,
Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
and 13) are higher in sensitivi-
ties. The inclusion of water mol-
ecules of crystallization de-
creases the sensitivity, which
can be seen in the values of 7
(IS: 25 J, FS: 360 N). We could
not observe any differences in
the sensitivities of polymorphs
4 a and 4 b. Their impact sensi-
tivities of complexes 14–16
were also tested. Only 16 (10 J)
was found to be moderately
sensitive towards impact.
Conclusion
Functionalized 1-ethyl-5-amino- and 1-ethyl-5-nitriminote-
trazoles were synthesized and characterized in the effort to
develop new energetic materials (explosives, propellants,
and pyrotechnics). From this combined experimental and
theoretical work, the following conclusions can be drawn:
1) Functionalized 1-ethyl-5-aminotetrazoles can be synthe-
sized starting by the reaction of sodium 5-aminotetrazo-
late with 2-chloroethanol. The substituent is stable to-
wards hydrolysis and can be modified under typical SN2
reaction conditions. Several 5-nitriminotetrazoles were
obtained by nitration of the 5-aminotetrazole derivatives.
2) The crystal structures of 1-(2-hydroxyethyl)-5-aminote-
trazole (2), 1-(2-chloroethyl)-5-aminotetrazole (3), 1-(2-
azidoethyl)-5-aminotetrazole (4), 1-(2-hydroxyethyl)-5-
nitriminotetrazole (5), 1-(2-chloroethyl)-5-nitriminotetra-
zole (6), 1-(2-nitratoethyl)-5-nitriminotetrazole monohy-
drate (7), 1-(2-azidoethyl)-5-nitriminotetrazole (8), po-
tassium 1-(2-azidoethyl)-5-nitriminotetrazolate (9),
sodium 1-(2-chloroethyl)-5-nitriminotetrazolate (10 a),
ammonium 1-(2-chloroethyl)-5-nitriminotetrazolate
(10 b), 1-(2-hydroxyethyl)-5-aminotetrazolium nitrate
(11), 1-(2-azidoethyl)-5-aminotetrazolium nitrate (12),
and 1-(2-azidoethyl)-5-aminotetrazolium perchlorate
monohydrate (13) were determined by low-temperature
single-crystal X-ray diffraction.
3) 5-Nitriminotetrazoles can be used as bidentate ligands.
Therefore, the coordination abilities of 5, 6, and 8 were
tested by reaction with copper nitrate trihydrate, yielding
the copper complexes trans-[diaquabis{1-(2-hydroxyeth-
yl)-5-nitriminotetrazolato-k2N4,O5}copper(II)] (14), trans-
[diaquabis{1-(2-chloroethyl)-5-nitriminotetrazolato-
k2N4,O5}copper(II)] dihydrate (15), and [diaquabis{1-(2-
azidoethyl)-5-nitriminotetrazolato-k2N4,O5}copper(II)]
(16).
4) The energetic properties and sensitivities of all com-
pounds were determined. They range from “insensitive”
(2, 3, 10 a, 10 b) to “very sensitive” (8). The calculated
energetic performances, based on the crystallographically
calculated densities and the heats of formation, range
www.chemeurj.org 5787

from values assigned to the group of propellants (4) to
values of high explosives (5, 7, 8). Unfortunately, most of
the compounds show low decomposition temperatures in
the range 120–150 8C.
5) The color performance of the copper complexes 14–16
was tested for application as coloring agents in “green”
pyrotechnics. Complexes 14 and 16 show a brilliant
green flame, and complex 15 gives a bright blue flame.
The combustion of complexes is almost smokeless, which
makes them promising coloring agents in modern pyro-
technical compositions.
Experimental Section
All reagents and solvents were used as received (Sigma–Aldrich, Fluka,
Acros Organics), unless stated otherwise. Melting points were measured
with a Perkin–Elmer Pyris6 DSC at a heating rate of 5 K min1. Other-
wise melting points were determined with a Bchi Melting Point B-450
apparatus and are not corrected. 1H and 13C NMR spectra were recorded
with a JEOL Eclipse 270, JEOL EX 400, or a JEOL Eclipse 400 instru-
ment. All chemical shifts are quoted in ppm relative to tetramethylsilane
(TMS) and MeNO2, respectively. Infrared (IR) spectra were recorded on
a Perkin–Elmer Spektrum One FT-IR instrument. Raman spectra were
measured using a Perkin–Elmer Spektrum 2000R NIR FT-Raman instru-
ment equipped with a Nd:YAG laser (1064 nm). Elemental analyses
were performed with a Netsch STA 429 simultaneous thermal analyzer.
Bomb calorimetry was performed in a Parr 1356 bomb calorimeter with
a Parr 1108CL oxygen bomb. The sensitivity data were performed using
a BAM drop hammer and a BAM friction tester. The electrostatic sensi-
tivity tests were carried out using an electric spark tester ESD 2010EN
(OZM Research) operating with the “Winspark 1.15 software package”.
1-(2-Hydroxyethyl)-5-aminotetrazole (2): A solution of 5-aminotetrazole
(85.1 g, 1.0 mol) and NaOH (40.0 g, 1.0 mol) in 200 mL H2O was heated
to reflux at 120 8C for 1 h. 2-Chloroethanol (74 mL, 1.1 mol) was added
dropwise and the literature procedure was followed further.[27] 41.3 g,
32 % yield; DSC (5 K min1): 160–161 8C; IR (KBr, cm1): ñ = 3331 (s,
br), 3153 (s, br), 2965 (m), 2946 (s), 2881 (m), 2749 (m), 2684 (m), 2577
(w), 2478 (w), 2437 (w), 2265 (w), 2217 (w), 2132 (w), 2067 (vw), 2019
(vw), 1925 (vw), 1869 (vw), 1662 (s), 1598 (s), 1484 (m), 1450 (s), 1422
(w), 1396 (w), 1355 (w), 1335 (w), 1289 (m), 1279 (m), 1245 (w), 1200
(vw), 1142 (w), 1123 (m), 1100 (s), 1071 (s), 1040 (s), 983 (m), 952 (w),
860 (m), 779 (m), 744 (m), 698 (w), 664 (m), 502 (m), 464 (w); Raman
(200 mW, 25 8C, cm1): ñ = 3335 (6), 3151 (11), 3007 (15), 2967 (19), 2948
(41), 2881 (5), 2756 (3), 1662 (13), 1595 (18), 1481 (15), 1454 (20), 1427
(7), 1357 (16), 1333 (20), 1293 (40), 1248 (10), 1125 (19), 1098 (14), 1073
(17), 986 (22), 951 (12), 861 (37), 778 (100), 667 (18), 498 (7), 467 (17),
363 (10), 324 (14), 269 (18), 215 (9), 181 (22); 1H NMR ([D6]DMSO,
25 8C, TMS): d = 6.63 (br s, 2 H, NH2), 4.73 (br s, 1 H, OH), 4.18 (t, 3J =
6 Hz, 2 H, CH2), 3.71 (t, 3J = 6 Hz, 2 H, CH2); 13C NMR ([D6]DMSO,
25 8C, TMS): d = 156.5 (C), 59.6 (CH2), 47.8 (CH2); m/ z (DEI): 129 [M] +
(100), 98 (78), 86 (43), 70 (14), 57 (14), 45 (48), 43 (78), 31 (15), 28 (31),
27 (13); elemental analysis calcd (%) for C3H7N5O (129.12): C 27.91, H
5.46, N 54.24; found: C 27.85, H 5.45, N 54.07; IS: > 100 J; FS: > 100 N.
1-(2-Chloroethyl)-5-aminotetrazole (3): Compound 3 was prepared ac-
cording to a literature procedure using 25.8 g (0.2 mol) 1-(2-hydroxyeth-
yl)-5-aminotetrazole.[27] Recrystallization from water yielded colorless 3
(22.1 g, 75 % yield). DSC (5 K min1): 150–151 8C; IR (KBr, cm1): ñ =
3312 (s, br), 3241 (s, br), 3102 (s, br), 2829 (m), 2741 (m), 2658 (m, br),
1773 (w), 1694 (s), 1651 (m), 1645 (m), 1557 (w), 1552 (w), 1505 (w),
1488 (w), 1439 (m), 1384 (w), 1364 (w), 1311 (m), 1283 (w), 1249 (m),
1209 (w), 1112 (w), 1056 (w), 1029 (m), 994 (w), 944 (w), 904 (w), 814
(w), 771 (w), 711 (w), 670 (m), 601 (m), 504 (w); Raman (200 mW, 25 8C,
cm1): ñ = 3235 (3), 3082 (9), 3021 (23), 2989 (32), 2970 (61), 2954 (58),
5788 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. M. Klapçtke et al.
2863 (7), 1692 (11), 1496 (13), 1441 (40), 1366 (33), 1282 (11), 1250 (34),
1207 (14), 1109 (5), 1070 (12), 1033 (34), 996 (15), 946 (8),l 908 (9), 770
(100), 712 (8), 671 (67), 647 (36), 506 (12), 427 (14), 339 (24), 307 (21),
231 (41), 188 (28); 1H NMR ([D6]DMSO, 25 8C, TMS): d = 7.08 (br s, 2 H,
NH2), 4.50 (t, 3J = 6 Hz, 2 H, CH2), 3.95 (t, 3J = 6 Hz, 2 H, CH2); 13C NMR
([D6]DMSO, 25 8C, TMS): d = 155.9 (C), 46.8 (CH2), 42.5 (CH2); elemen-
tal analysis calcd (%) for C3H6N5Cl (147.57): C 24.42, H 4.10, N 47.46;
found: C 24.44, H 3.77, N 47.44; IS: > 100 J; FS: > 100 N.
1-(2-Azidoethyl)-5-aminotetrazole (4): A solution of 3 (2.0 g, 13.6 mmol)
in 30 mL DMF was combined with NaN3 (1.0 g, 15 mmol) in 30 mL DMF
and heated to reflux at 100 8C for 4 h. The warm solvent was evaporated,
and the crude product was recrystallized from H2O to yield colorless nee-
dles (1.57 g, 76 % yield). DSC (5 K min1): 129–130 8C; IR (KBr, cm1):
ñ = 3342 (s), 3262 (m), 3160 (s), 2955 (w), 2741 (w), 2438 (vw), 2231 (vw),
2133 (s), 2096 (s), 2039 (m), 1652 (s), 1593 (s), 1479 (m), 1445 (m), 1434
(m), 1375 (vw), 1349 (w), 1333 (w), 1303 (m), 1287 (m), 1221 (w), 1134
(w), 1105 (m), 1055 (w), 1009 (w), 970 (vw), 954 (vw), 910 (vw), 821 (w),
781 (vw), 744 (w), 694 (vw), 664 (m), 647 (w), 631 (w), 521 (m); Raman
(200 mW, 25 8C, cm1): ñ = 3150 (19), 3000 (24), 2988 (26), 2962 (71), 2868
(10), 2127 (11), 2097 (13), 1668 (14), 1594 (22), 1474 (16), 1445 (37), 1374
(25), 1351 (30), 1334 (26), 1291 (41), 1258 (15), 1221 (15), 1138 (28), 1100
(15), 1058 (17), 1011 (20), 972 (14), 956 (17), 822 (22), 780 (100), 667
(16), 630 (21), 450 (17), 356 (28), 317 (31), 270 (36), 232 (54), 162 (33);
1
H NMR ([D6]DMSO, 25 8C, TMS): d = 6.80 (s, 2 H, NH2), 4.31 (t, 3J =
6 Hz, 2 H, CH2), 3.71 (t, 3J = 6 Hz, 2 H, CH2); 13C NMR ([D6]DMSO,
25 8C, TMS): d = 156.3 (C), 49.4 (CH2), 44.6 (CH2); m/ z (ESI): 309
[2 M+H] + (100), 155 [M+H] + (34); elemental analysis calcd (%) for
C3H6N8 (154.13): C 23.38, H 3.92, N 72.70; found: C 23.38; H 3.91; N
72.36; IS: 10 J; FS: 360 N.
General procedure for preparation of 5, 6, and 7: To a cooled solution of
nitric acid (20 mL, 100 %) was added portionwise the respective 1-ethyl-
5-aminotetrazoles (2, 3, and 4) (25 mmol). The solution was stirred for
12 h at room temperature and then poured onto ice. The solvent was re-
moved under high vacuum to obtain the crude product, which was
washed until it became free of acid. Recrystallization resulted from an
appropriate solvent (see below).
1-(2-Hydroxyethyl)-5-nitriminotetrazole (5): Recrystallization from dilute
HNO3 yielded colorless rods (4.13 g, 95 % yield). DSC (5 K min1): 137–
139 8C; IR (KBr, cm1): ñ = 3359 (m, br), 3153 (w), 2966 (m), 2881 (w),
2637 (w), 1786 (vw), 1586 (s), 1506 (s), 1448 (m), 1427 (w), 1379 (m),
1352 (w), 1337 (m), 1293 (m), 1257 (s), 1234 (s), 1215 (s), 1140 (w), 1076
(m), 1058 (m), 1041 (m), 979 (m), 956 (w), 875 (vw), 861 (w), 779 (w),
755 (vw), 720 (m), 680 (vw), 649 (w), 522 (vw); Raman (200 mW, 25 8C,
cm1): ñ = 3023 (13), 3001 (19), 2973 (44), 1571 (100), 1505 (14), 1454
(19), 1445 (27), 1414 (64), 1348 (24), 1290 (34), 1258 (26), 1224 (64), 1138
(14), 1073 (23), 1030 (41), 985 (23), 883 (23), 859 (12), 758 (39), 652 (27),
484 (38), 440 (20), 369 (19), 308 (50), 277 (28), 205 (21); 1H NMR
([D6]DMSO, 25 8C, TMS): d = 4.85 (br s, 1 H, OH), 4.22 (t, 3J = 5 Hz, 2 H,
CH2), 3.77 (t, 3J = 5 Hz, 2 H, CH2); 13C NMR ([D6]DMSO, 25 8C, TMS):
d = 150.9 (C), 58.1 (CH2), 50.4 CH2); m/ z (DEI): 174 [M] + (1), 147 (1),
131 (66), 129 (8), 98 (9), 85 (66), 55 (38), 45 (100), 28 (73), 27 (38); ele-
mental analysis calcd (%) for C3H6N6O3 (174.12): C 20.66, H 3.36, N
48.28; found: C 20.69, H 3.47, N 48.27; IS: 6 J; FS: 55 N.
1-(2-Chloroethyl)-5-nitriminotetrazole (6): Recrystallization from H2O
yielded colorless 6 (4.48 g, 93 % yield). DSC (5 K min1): 111–112 8C; IR
(KBr, cm1): ñ = 3170 (m), 3113 (m, br), 3025 (m), 2977 (m), 2885 (w),
2448 (vw), 2084 (vw), 1899 (vw), 1583 (s), 1574 (s), 1492 (s), 1450 (m),
1437 (s), 1418 (m), 1384 (w), 1328 (m), 1319 (m), 1285 (w), 1246 (m),
1209 (s), 1200 (s), 1125 (vw), 1058 (w), 1033 (m), 987 (m), 952 (vw), 905
(w), 866 (vw), 801 (vw), 777 (w), 723 (m), 682 (w), 648 (vw), 439 (w);
Raman (200 mW, 25 8C, cm1): ñ = 3028 (14), 3003 (18), 2977 (52), 2946
(32), 1582 (100), 1571 (71), 1490 (10), 1442 (23), 1406 (77), 1369 (15),
1328 (17), 1278 (19), 1241 (32), 1224 (24), 1205 (25), 1128 (6), 1055 (21),
1032 (23), 990 (60), 957 (22), 891 (8), 868 (22), 752 (40), 683 (21), 679
(16), 650 (79), 501 (41), 473 (15), 439 (14), 351 (9), 310 (32), 260 (29), 214
(15), 168 (22); 1H NMR ([D6]DMSO, 25 8C, TMS): d = 12.64 (br s, 1 H,
NH), 4.55 (t, 3J = 6 Hz, 2 H, CH2), 4.04 (t, 3J = 6 Hz, 2 H, CH2); 13C NMR
([D6]DMSO, 25 8C, TMS): d = 150.9 (C), 48.9 (CH2), 41.4 (CH2); m/ z
Chem. Eur. J. 2009, 15, 5775 – 5792
Energetic Materials
(DEI): 192 [M] + (22), 157 (24), 111 (24), 103 (77), 63 (96), 55 (73), 46
(23), 30 (46), 28 (64), 27 (100); elemental analysis calcd (%) for
C3H5N6ClO2 (192.56): C 18.71, H 2.62, N 43.64; found: C 18.71, H 2.74, N
43.34; ; IS: 28 J; FS: > 360 N.
1-(2-Nitratoethyl)-5-nitriminotetrazole monohydrate (7): Recrystalliza-
tion from very dilute HNO3 gave colorless 7 (2.46 g, 45 % yield). DSC
(5 K min1): 120 8C (decomp); IR (KBr, cm1): ñ = 3571 (m), 3374 (s, br),
3127 (s, br), 3016 (s), 2961 (s), 2648 (m), 2067 (w), 1690 (m), 1643 (s),
1583 (s), 1496 (s), 1448 (s), 1384 (s), 1312 (s), 1283 (s), 1250 (s), 1141 (m),
1031 (s), 978 (m), 892 (m), 846 (m), 779 (m), 755 (m), 720 (m), 678 (w),
649 (w), 579 (vw), 565 (vw), 543 (vw), 522 (vw), 504 (vw); Raman
(200 mW, 25 8C, cm1): ñ = 3020 (31), 2979 (69), 1621 (26), 1584 (100),
1508 (39), 1452 (43), 1422 (86), 1316 (38), 1279 (75), 1263 (78), 1247 (70),
1159 (21), 1084 (25), 1038 (56), 996 (40), 881 (37), 849 (31), 758 (92), 706
(25), 662 (38), 567 (33), 493 (48), 446 (26), 353 (32), 312 (55), 237 (41),
209 (37), 175 (42); 1H NMR ([D6]DMSO, 25 8C, TMS): d = 8.18 (s, 1 H,
NH), 4.88 (t, 3J = 5 Hz, 2 H, CH2), 3.76 (t, 3J = 5 Hz, 2 H, CH2); 13C NMR
([D6]DMSO, 25 8C, TMS): d = 151.1 (C), 48.7 (CH2), 41.6 (CH2); elemen-
tal analysis calcd (%) for C3H5N7O4 (219.12): C 16.44, H 2.30, N 44.75;
found: C 16.31, H 2.62, N 44.55; IS: 25 J; FS: 360 N.
1-(2-Azidoethyl)-5-nitriminotetrazole (8): An equimolar amount of dilute
(1 n) hydrochloric acid was added to potassium 1-(2-azidoethyl)-5-nitrimi-
notetrazolate. The solvent was evaporated and acetone was added to the
residue. KCl was removed by filtration and acetone was evaporated. The
crude product was recrystallized from a small amount of methanol to
yield colorless 8 (90 %). DSC (5 K min1): 140 8C (decomp); IR (KBr,
cm1): ñ = 3444 (w), 3019 (m), 2962 (m), 2115 (s), 1625 (m), 1581 (vs),
1495 (s), 1448 (m), 1308 (s), 1254 (s), 1152 (w), 1033 (m), 976 (w), 873
(w), 780 (w), 722 (w), 661 (w), 633 (w), 555 (w), 440 (w); Raman
(200 mW, 25 8C, cm1): ñ = 3024 (8), 3000 (7), 2977 (12), 2119 (16), 1583
(100), 1505 (55), 1416 (72), 1330 (15), 1308 (17), 1278 (39), 992 (40), 957
(22), 868 (22), 755 (51), 656 (79), 480 (15), 311 (30), 170 (22); 1H NMR
([D6]DMSO, 25 8C, TMS): d = 9.58 (s, 1 H, NH), 4.40 (t, 3J = 6 Hz, 2 H,
CH2), 3.81 (t, 3J = 6 Hz, 2 H, CH2); 13C NMR ([D6]DMSO, 25 8C, TMS):
d = 151.3 (C), 49.9 (CH2), 46.6 (CH2); elemental analysis calcd (%) for
C3H5N9O2 (199.13): C 18.10, H 2.53, 63.30; found: C 17.78, H 2.91, N
62.72; IS: 2 J; FS: 80 N.
Potassium 1-(2-azidoethyl)-5-nitriminotetrazolate (9): 1-(2-Azidoethyl)-5-
aminotetrazole (4) (0.39 g, 3 mmol) was dissolved in MeCN (10 mL) and
cooled in an ice bath. To this solution was added nitronium tetrafluoro-
borate (0.33 g, 3 mmol). The solution was stirred for 30 min at 0 8C and
for 1 h at 25 8C. The solvent was evaporated and a solution of KOH
(168 mg, 3 mmol) in 20 mL ethanol was added. Precipitated KBF4 was re-
moved by filtration and a further equivalent of KOH (168 mg, 3 mmol)
in 20 mL ethanol was added. The solvent was evaporated and 20 mL cold
water was added. The insoluble starting material was removed by filtra-
tion and the water was evaporated. The crude product was recrystallized
from hot ethanol to yield 9 (0.24 g, 33 % yield). DSC (5 K min1): 205 8C
(decomp); IR (KBr, cm1): ñ = 2944 (w), 2142 (m), 2108 (m), 1506 (s),
1456 (s), 1432 (m), 1384 (s), 1355 (vs), 1343 (vs), 1235 (m), 1143 (m),
1103 (m), 1032 (m), 950 (w), 881 (w), 786 (w), 776 (w), 727 (w), 659 (w),
628 (w), 514 (w), 441 (w); Raman (200 mW, 25 8C, cm1): ñ = 3012 (7),
2982 (15), 2968 (14), 2123 (3), 1513 (100), 1457 (12), 1430 (11), 1388 (13),
1349 (12), 1321 (32), 1225 (7), 1106 (15), 1050 (15), 1035 (50), 884 (9),
836 (6), 756 (13), 662 (8), 633 (7), 488 (9), 375 (10), 213 (13); 1H NMR
([D6]DMSO, 25 8C, TMS): d = 4.22 (t, 3J = 6 Hz, 2 H, CH2), 3.69 (t, 3J =
6 Hz, 2 H, CH2); 13C NMR ([D6]DMSO, 25 8C, TMS): d = 157.6 (C), 49.2
(CH2), 45.6 (CH2); elemental analysis calcd (%) for KC3H4N9O2 (237.25):
C 15.13, H 2.12, N 52.92; found: C 15.00, H 2.31, N 52.90; IS: 25 J; FS:
300 N.
Sodium 1-(2-chloroethyl)-5-nitriminotetrazolate (10 a): A solution of 1-
(2-chloroethyl)-5-nitriminotetrazole (339 mg, 1.8 mmol) and NaOH
(80 mg, 2.0 mmol) in 10 mL H2O was heated at 100 8C for 2 min. The sol-
vent was removed under high vacuum to obtain colorless crystals. Recrys-
tallization from EtOH yielded colorless crystals (378 mg, 98 % yield).
DSC (5 K min1): 183–184 8C (decomp); IR (KBr, cm1): ñ = 3425 (m, br),
3018 (m), 2972 (m), 2736 (w), 2373 (w), 1978 (w), 1580 (m), 1502 (s),
1462 (s), 1454 (s), 1440 (s), 1391 (s), 1363 (s, br), 1289 (s), 1256 (m), 1237
Chem. Eur. J. 2009, 15, 5775 – 5792  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
(s), 1131 (m), 1104 (m), 1042 (m), 993 (w), 951 (w), 910 (m), 872 (w), 775
(m), 757 (w), 739 (w), 676 (m), 655 (m), 518 (vw), 477 (vw); Raman
(200 mW, 25 8C, cm1): ñ = 3015 (5), 2977 (7), 2984 (5), 1550 (3), 1498
(100), 1462 (5), 1433 (7), 1377 (8), 1347 (15), 1323 (8), 1298 (8), 1264 (3),
1134 (2), 1108 (10), 1037 (38), 992 (2), 875 (4), 759 (9), 678 (4), 653 (9),
510 (3), 443 (2), 370 (4), 307 (6), 246 (8), 208 (6); 1H NMR ([D6]DMSO,
25 8C, TMS): d = 4.41 (t, 3J = 6 Hz, 2 H, CH2), 3.98 (t, 3J = 6 Hz, 2 H, CH2);
13
C NMR ([D6]DMSO, 25 8C, TMS): d = 157.2 (C), 47.8 (CH2), 42.1
(CH2); elemental analysis calcd (%) for C3H4ClN6NaO2 (214.55): C
16.79, H 1.88, N 39.17; found: C 16.81; H 1.77; N 38.99; IS: > 50 J; FS:
> 360 N.
Ammonium 1-(2-chloroethyl)-5-nitriminotetrazolate (10 b): 1-(2-Chlor-
oethyl)-5-nitriminotetrazole (385 mg, 2.0 mmol) in 10 mL NH3 (25 %)
was heated for 10 min. The solvent was removed under high vacuum. Re-
crystallization from H2O resulted in colorless crystals (402 mg, 96 %
yield). DSC (5 K min1): 233 8C (decomp); IR (KBr, cm1): ñ = 3571 (w),
3176 (s, br), 3065 (s), 2840 (m), 2340 (w), 2237 (w), 2159 (w), 1879 (w),
1675 (w), 1648 (w), 1547 (m), 1426 (s), 1393 (s), 1360 (s), 1292 (m), 1267
(m), 1225 (m), 1146 (m), 1124 (m), 1084 (m), 1059 (m), 1037 (m), 1014
(m), 866 (w), 777 (vw), 756 (w), 730 (vw), 622 (w), 480 (vw); Raman
(200 mW, 25 8C, cm1): ñ = 3077 (5), 1552 (10), 1473 (72), 1441 (100), 1371
(18), 1273 (8), 1210 (27), 1151 (23), 1126 (28), 1084 (18), 1016 (71), 976
(9), 867 (9), 761 (15), 732 (14), 478 (11), 383 (22), 205 (25); 1H NMR
([D6]DMSO, 25 8C, TMS): d = 4.35 (t, 3J = 6 Hz, 2 H, CH2), 3.94 (t, 3J =
6 Hz, 2 H, CH2); 13C NMR ([D6]DMSO, 25 8C, TMS): d = 158.8 (C), 48.0
(CH2), 42.3 (CH2); elemental analysis calcd (%) for C3H8ClN7O2
(209.59): C 17.19, H 3.85, N 46.78; found: C 17.16; H 3.98, N 46.35; IS:
> 50 J; FS: > 360 N.
1-(2-Hydroxyethyl)-5-aminotetrazolium nitrate (11): 1-(2-Hydroxyethyl)-
5-aminotetrazole (2) (645 mg, 5 mmol) was heated with HNO3 2 n
(10 mL) to 60 8C for 15 min. The solvent was evaporated to obtain the
crude product. Recrystallization from EtOH yielded colorless needles
(845 mg, 88 % yield). DSC (5 K min1): 135–136 8C, 160 8C (decomp); IR
(KBr, cm1): ñ = 3346 (s, br), 3154 (s, br), 2965 (m), 2945 (m), 2881 (m),
2792 (m), 2750 (m), 2661 (m), 2489 (m), 2396 (m), 2132 (w), 2069 (w),
1923 (w), 1762 (w), 1688 (s), 1666 (s), 1598 (s), 1484 (m), 1433(m), 1386
(s), 1339 (w), 1309 (m), 1280 (m), 1264 (m), 1234 (m), 1123 (m), 1100
(m), 1071 (s), 1039 (s), 983 (m), 945 (m), 860 (m), 825 (w), 779 (w), 769
(w), 744 (w), 721 (w), 697 (w), 663 (m), 502 (m), 465 (w); Raman
(300 mW, 25 8C, cm1): ñ = 3423 (8), 3305 (5), 3153 (5), 3001 (10), 2950
(24), 1689 (8), 1663 (8), 1581 (12), 1482 (16), 1460 (28), 1430 (23), 1386
(16), 1357 (19), 1335 (18), 1294 (25), 1247 (18), 1124 (12), 1074 (22), 1038
(98), 987 (16), 950 (14), 862 (24), 813 (12), 778 (58), 766 (83), 727 (17),
718 (22), 669 (14), 649 (19), 468 (14), 451 (14), 356 (16), 257 (25), 182
(28), 91 (23); 1H NMR ([D6]DMSO, 25 8C, TMS): d = 4.10 (t, 2 H, CH2),
3.67 (t, 2 H, CH2); 13C NMR ([D6]DMSO, 25 8C, TMS): d = 156.1 (C), 59.4
(CH2), 47.9 (CH2); elemental analysis calcd (%) for C3H8N6O4 (192.13):
C 18.75, H 4.20, N 43.74; found C 18.77, H 4.19, N 43.60; IS: > 50 J; FS:
360 N.
1-(2-Azidoethyl)-5-aminotetrazolium nitrate (12): 1-(2-Azidoethyl)-5-
aminotetrazole (4) (462 mg, 3.0 mmol) was combined with HNO3 2 n
(5 mL) and heated to 60 8C for 15 min. The solvent was evaporated and
the crude product was recrystallized from wet EtOH to yield colorless
rods (521 mg, 80 % yield). DSC (5 K min1): 95 8C, 148 8C (decomp); IR
(KBr, cm1): ñ = 3354 (m), 3244 (m), 3166 (m), 3012 (w), 2948 (w), 2450
(w, br), 2132 (s), 2100 (s), 2035 (w), 1764 (w), 1690 (s), 1497 (m), 1401
(s), 1382 (s), 1328 (s), 1301 (s), 1237 (m), 1126 (w), 1084 (w), 1042 (m),
996 (w), 966 (w), 913 (w), 818 (w), 768 (w), 724 (w), 603 (w), 550 (w), 508
(w); Raman (300 mW, 25 8C, cm1): ñ = 3347 (4), 3297 (5), 3263 (6), 3011
(8), 2971 (18), 2949 (17), 2872 (5), 2665 (4), 2527 (5), 2424 (4), 2212 (4),
2136 (10), 1934 (5), 1889 (6), 1821 (5), 1746 (5), 1598 (9), 1501 (12), 1441
(22), 1375 (12), 1303 (17), 1226 (13), 1082 (12), 1051 (80), 996 (12), 818
(16), 770 (44); 719 (13), 695 (5), 662 (14), 626 (17), 564 (6), 545 (6), 443
(12), 345 (15), 304 (16), 259 (26), 230 (29), 166 (17); 1H NMR
([D6]DMSO, 25 8C, TMS): d = 7.32 (br s, 2 H, NH2), 4.30 (t, 2 H, CH2),
3.70 (t, 2 H, CH2); 13C NMR ([D6]DMSO, 25 8C, TMS): d = 155.7 (C), 49.3
(CH2), 44.7 (CH2); 14N NMR ([D6]DMSO): d = 12.90 (NO3), 135
(Nb), 177 (Ng), 327 (Na); elemental analysis calcd (%) for C3H7N9O3
www.chemeurj.org 5789

(217.15): C 16.59, H 3.25, N 58.05; found: 16.55, H 3.27, N 57.55; IS: 7 J;
FS: 160 N.
1-(2-Azidoethyl)-5-aminotetrazolium perchlorate monohydrate (13):
Perchloric acid (9 mL, 1 m) was added dropwise to a solution of 4 (1.39 g,
9 mmol) in H2O (7 mL). The solution was heated to 80 8C for 15 min.
The solvent was evaporated, and the crude product was recrystallized
from EtOH to give colorless rods (2.33 g, 95 % yield). DSC (5 K min1):
85 8C, 172 8C (decomp); IR (KBr, cm1): ñ = 3363 (s, br), 3298 (s), 2934
(w), 2871 (w), 2651 (w, br), 2531 (w, br), 2264 (w), 2147 (s), 2134 (s);
2102 (w), 1682 (s), 1505 (w), 1436 (m), 1368 (m), 1345 (m), 1288 (s), 1262
(m), 1246 (m), 1141 (s, br), 1088 (s, br), 1043 (s, br), 1043 (s), 1011 (s),
932 (m), 834 (w), 718 (w), 626 (s), 554 (m); Raman (300 mW, 25 8C,
cm1): ñ = 3191 (4), 3015 (10), 2095 (8), 1706 (12), 1607 (12), 1505 (18),
1445 (26), 1431 (28), 1370 (25), 1345 (18), 1307 (19), 1283 (23), 1223 (15),
1131 (19), 1039 (14), 977 (14), 932 (100), 834 (26), 767 (65), 652 (14), 624
(32), 456 (35), 366 (16), 255 (31), 205 (26); 1H NMR ([D6]DMSO, 25 8C,
TMS): d = 6.75 (br s, 2 H, NH2), 4.30 (t, 2 H, CH2), 3.70 (t, 2 H, CH2);
13
C NMR ([D6]DMSO, 25 8C, TMS): d = 155.7 (C), 49.3 (CH2), 44.8
(CH2); elemental analysis calcd (%) for C3H9ClN8O5 (272.61): C 13.22, H
3.33, N 41.10; found: C 13.00, H 3.71, N 41.09; IS: 5 J; FS: 120 N.
General procedure for preparation of 14, 15, and 16: To a hot solution of
CuACHTUNGRE(NO3)2·3 H2O (242 mg, 1.0 mmol) in 5 mL water was added a warm
aqueous solution (10 mL) containing two equivalents of the correspond-
ing nitriminotetrazole (5, 6, 8), and the mixture was stirred for 10 min at
80 8C. The solution was filtered and left to crystallize. After 1 or 2 days,
single crystals of 14–16 were obtained and isolated by filtration.
trans-[Diaquabis{1-(2-hydroxyethyl)-5-nitriminotetrazolato-
k2N4,O5}copper(II)] (14): DSC (5 K min1): 245 8C; IR (KBr, cm1): ñ =
3376 (s), 2987 (m), 2959 (m), 2364 (w), 1649 (w), 1536 (vs), 1491 (s), 1483
(s), 1459 (m), 1434 (vs), 1396 (m), 1348 (m), 1325 (m), 1291 (s), 1274 (s),
1239 (s), 1221 (s), 1119 (w), 1075 (w), 1057 (m), 1019 (m), 882 (w), 732
(m), 659 (w), 579 (w), 485 (w); elemental analysis calcd (%) for
C6H14CuN12O8 (445.80): C 16.17, H 3.17, N 37.70; found: C 16.12, H 3.12,
N 37.55; ISS: > 50 J.
trans-[Diaquabis{1-(2-chloroethyl)-5-nitriminotetrazolato-
k2N4,O5}copper(II)] dihydrate (15): DSC (5 K min1): 233 8C (decomp);
IR (KBr, cm1): ñ = 3596 (m), 3501 (m), 3177 (s, br), 2960 (m), 2341 (w),
2307 (w), 1654 (w), 1593 (m), 1517 (s), 1465 (s), 1425 (s), 1390 (vs), 1351
(vs), 1314 (vs), 1297 (vs), 1267 (s), 1211 (s), 1138 (m), 1110 (s), 1036 (m),
1010 (m), 960 (m), 905 (m), 872 (m), 814 (m), 773 (m), 764 (m), 741 (m),
685 (s), 662 (m), 509 (w); elemental analysis calcd (%) for
C6H16Cl2CuN12O8 (518.72): C 13.89, H 3.11, N 32.40; found: C 13.89, H
3.13, N 32.34; IS: > 50 J.
[Diaquabis{1-(2-azidoethyl)-5-nitriminotetrazolato-k2N4,O5}copper (II)]
(16): DSC (5 K min1): 217 8C (decomp); IR (KBr, cm1): ñ = 3456 (m,
br), 2963 (w), 2118 (s), 1637 (m), 1582 (s), 1528 (m), 1481 (s), 1417 (s),
1343 (s), 1303 (vs), 1261 (s), 1112 (w), 1033 (w), 874 (w), 802 (w), 757
(w), 675 (w), 628 (w), 555 (w); elemental analysis calcd (%) for
C6H12CuN18O6 (495.92): C 14.53, H 2.44, N 50.85; found: C 14.07, H 2.97,
N 49.99; IS: 10 J.
Acknowledgements
Financial support of this work by the Ludwig-Maximilian University of
Munich (LMU), the Fonds der Chemischen Industrie (FCI), the Europe-
an Research Office (ERO) of the US Army Research Laboratory
(ARL), ARDEC (Armament Research, Development and Engineering
Centre) under contract nos. N 62558–05-C-0027, R&D 1284-CH-01, R&D
1285-CH-01, 9939-AN-01, W911NF-07–1–0569, W911NF-08–1–0372, and
W911NF-08–1–0380, and the Bundeswehr Research Institute for Materi-
als, Explosives, Fuels and Lubricants (WIWEB) under contract nos. E/
E210/4D004/X5143 and E/E210/7D002/4F088 is gratefully acknowledged.
We acknowledge collaborations with Dr. M. Krupka (OZM Research,
Czech Republic) in the development of new testing and evaluation meth-
ods for energetic materials and with Dr. M. Sucesca (Brodarski Institute,
Croatia) in the development of new computational codes to predict the
5790 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
T. M. Klapçtke et al.
detonation parameters of high-nitrogen explosives. We are indebted to
and thank Dr. Betsy M. Rice (ARL, Aberdeen, Proving Ground, MD)
and Dr. Gary Chen (ARDEC, Picatinny Arsenal, NJ) for many helpful
and inspired discussions and support of our work. Last but not least we
are indebted to and thank Ines Thoma for preparing several samples and
Stefan Huber for doing the sensitivity tests.
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 T. M. Klapçtke et al.

[81] WIWEB-Standardarbeitsanweisung 4-5.1.03, Ermittlung der Explo- 35 J, sensitive  4 J, very sensitive  3 J; friction: insensitive > 360 N,
sions-gef hrlichkeit oder der Reibeempfindlichkeit mit dem Rei- less sensitive = 360 N, sensitive < 360 N and > 80 N, very sensitive 
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[82] Classifications according to the UN Recommendations on the Trans- Received: October 24, 2008
port of Dangerous Goods: impact: Insensitive > 40 J, less sensitive  Published online: April 16, 2009

5792 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2009, 15, 5775 – 5792