Two outstanding explosives based on 1,2-dinitroguanidine: ammonium-dinitroguanidine and 1,7-Diamino-1,7-dinitrimino-2,4,6-trinitro-2,4,6- triazaheptane www.zaac.wiley-vch.de

Article abstract of DOI:10.1002/zaac.200900560

Ammonium-dinitroguanidine (ADNQ) and 1,7-diamino-1,7-dinitrimino-2,4,6- trinitro-2,4,6-triazaheptane (APX) have been synthesized in high yield and purity. Both compounds were characterized by multinuclear NMR (¹H, ¹³C, ¹⁴N) and vibrational spectroscopy. The molecular structures were elucidated by single-crystal X-ray diffraction. ADNQ crystallizes in the monoclinic space group P2₁/c with a crystal density of ρ = 1.735 g ·cm^-3, APX in the orthorhombic space group Pbnc with a crystal density of ρ = 1.911 g ·cm ^-3 ADNQ decomposes at 197°C, APX at 174°C. Impact (IS), friction (FS) and electrostatic discharge (ESD) sensitivities were determined experimentally for both compounds. (ADNQ: IS ≥ 10 J, FS ≥ 252 N and ESD ≥ 0.4 J, APX: IS ≥ 3 J, FS ≥ 80 N and ESD ≥ 0.1 J). Polymer bonded mixtures of APX with 5 % PVAA resin proved, to be less sensitive towards mechanical stimuli (IS ≥ 5J, FS = 160 N). The detonation parameters (EXPLO5 code) were calculated using combined quantum chemical (CBS-4M) methods and a chemical equilibrium calculation based on the steady-state model of detonation: ADNQ ( V_det = 9066 m·s^-1, p_C-J = 332 kbar, Q_v = -5193 kJ·kg^-1), APX (V_det = 9540 m·s^-1, p_C-J = 395 kbar, Q_v = -5935 kJ·kg^-1). The experimentally determined detonation velocity (fibre optic technique) agrees well with the theoretical values, indicating that APX shows better detonation performance than HMX (1,3,5,7-Tetranitro-1,3,5,7- tetraazoctane).

Full text of DOI:10.1002/zaac.200900560

ARTICLE
DOI: 10.1002/zaac.200900560
Two Outstanding Explosives Based on 1,2-Dinitroguanidine: Ammonium-
dinitroguanidine and 1,7-Diamino-1,7-dinitrimino-2,4,6-trinitro-2,4,6-
triazaheptane
Thomas Altenburg,[a] Thomas M. Klapötke,*[a] Alexander Penger,[a] and
Jörg Stierstorfer[a]
Keywords: Dinitroguanidine; High Explosives; X-ray diffraction; Energetic Properties; Nitrogen
Abstract. Ammonium-dinitroguanidine (ADNQ) and 1,7-diamino- APX: IS ≥ 3 J, FS ≥ 80 N and ESD ≥ 0.1 J). Polymer bonded mixtures
1,7-dinitrimino-2,4,6-trinitro-2,4,6-triazaheptane (APX) have been of APX with 5 % PVAA resin proved to be less sensitive towards
synthesized in high yield and purity. Both compounds were character- mechanical stimuli (IS ≥ 5J, FS = 160 N). The detonation parameters
ized by multinuclear NMR (1H, 13C, 14N) and vibrational spectroscopy. (EXPLO5 code) were calculated using combined quantum chemical
The molecular structures were elucidated by single-crystal X-ray dif- (CBS-4M) methods and a chemical equilibrium calculation based on
fraction. ADNQ crystallizes in the monoclinic space group P21/c with the steady-state model of detonation: ADNQ (Vdet = 9066 m·s–1, pC–J
=
a crystal density of ρ = 1.735 g·cm–3, APX in the orthorhombic space 332 kbar, Qv = –5193 kJ·kg–1), APX (Vdet = 9540 m·s–1, pC–J = 395
group Pbnc with a crystal density of ρ = 1.911 g·cm–3. ADNQ decom- kbar, Qv = –5935 kJ·kg–1). The experimentally determined detonation
poses at 197 °C, APX at 174 °C. Impact (IS), friction (FS) and electro- velocity (fibre optic technique) agrees well with the theoretical values,
static discharge (ESD) sensitivities were determined experimentally for indicating that APX shows better detonation performance than HMX
both compounds. (ADNQ: IS ≥ 10 J, FS ≥ 252 N and ESD ≥ 0.4 J, (1,3,5,7-Tetranitro-1,3,5,7-tetraazoctane).
[2a] in DNQ makes it possible to produce monoanionic dini-
Introduction
Exceeding the detonation performance of known explosives
like RDX (1,3,5-trinitro-1,3,5-hexahydrotriazine) is a long
term goal in the research of new energetic compounds. The
troguanidine salts. Furthermore nucleophilic substitution reac-
tions with the dinitroguanidine anion are reported in literature.
development of strained cages like CL-20 (HNIW:
2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaiso-wurzitane)
[1a] or ONC (octanitrocubane) [1b] has attracted lots of inter-
est, however both materials bear several drawbacks. The pres-
ence of polymorphs as well as a costly preparation makes both
compounds unlikely to find contemporary application. These
caged, highly nitrated compounds like HNB (hexanitroben-
zene) showed most promising properties, but often the chemi-
cal stability towards acids or bases is insufficient. As the mate-
rial density is the key for good performing high explosives a
different approach was started with the concept of zwitterionic
structures. A model capable for these requirements is 1,2-dini-
troguanidine (DNQ), which was previously reported in litera-
ture and well described [2a–f]. The crystallographic characteri-
zation of DNQ illustrates different nitro group surroundings,
contrary to dissolved DNQ which shows rapid prototropic tau-
tomerism. The presence of an acidic nitramine (pKa = 1.11)
Results and Discussion
Synthesis
1,2-Dinitroguanidine (1) was synthesized as reported by As-
´
tratyev [2a]. As it is known that strong nucleophiles like hydra-
zine or ammonia can substitute nitramine groups at elevated
temperatures, ADNQ was produced from a stoichiometric
amount of ammonium carbonate to avoid free base. 1,7-Diam-
ino-1,7-dinitrimino-2,4,6-trinitro-2,4,6-triaza-heptane (APX)
´
was synthesized according to the method of Astratyev [2a],
starting from 1,3-bis(chloromethyl)nitramine (2) and potas-
sium dinitroguanidine (3). The former compound is readily
available starting from the nitrolysis of hexamine with subse-
quent chlorination [3] (Scheme 1).
X-ray Diffraction Structures
To obtain suitable crystals for X-ray diffraction, APX was
recrystallized from an acetone chloroform mixture by slow
evaporation of the solvent at room temperature. In the case of
ADNQ recrystallization from an ethanol water mixture yielded
crystalline material. Data sets were collected with an Oxford
Diffraction Xcalibur 3 diffractometer equipped with a CCD
detector using the Crys-Alis CCD software [4]. The data re-
* Prof. Dr. T. M. Klapötke
Fax: +49-89-2180-77492
E-Mail: tmk@cup.uni-muenchen.de
[a] Department of Chemistry and Biochemistry
Energetic Materials Research
Ludwig-Maximilian University
Butenandtstr. 5–13 (D)
81377 Munich, Germany
Z. Anorg. Allg. Chem. 2010, 636, 463–471
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
463

T. Altenburg, T. M. Klapötke, A. Penger, J. Stierstorfer
Table 2. Bond lengths and bond angles of APX.
ARTICLE
atoms
bond length atoms
bond length
O3–N3
O5–N7
N6–C1
N7–O5
N4–N3
N1–N2
N1–C1
N5–H5B
C1–H1A
1.234(2) Å
1.229(2) Å
1.447(2) Å
1.229(2) Å
1.362(2) Å
1.396(3) Å
1.470(3) Å
0.85(3) Å
0.95(3) Å
O4–N3
N6–N7
O1–N2
N4–C2
O2–N2
N1–C2
N5–C2
N5–H5A
C1–H1B
1.242(2) Å
1.375(4) Å
1.220(2) Å
1.335(3) Å
1.220(2) Å
1.419(3) Å
1.297(3) Å
0.93(3) Å
0.95(3) Å
atoms
bond angle
atoms
bond angle
N7–N6–C1
O5–N7–O5
C2–N4–N3
N2–N1–C1
C2–N5–H5B
H5B–N5–H5A
O1–N2–N1
N6–C1–N1
N1–C1–H1A
N1–C1–H1B
N5–C2–N4
N4–C2–N1
O3–N3–N4
118.0(1)°
126.4(3)°
117.4(2)°
115.0 (2)°
118.0 (2)°
128.0 (3)°
115.9(2)°
111.5(2)°
106.2(1)°
109.1(1)°
129.9(2)°
110.7(2)°
115.0 (2)°
C1–N6–C1
O5–N7–N6
N2–N1–C2
C2–N1–C1
C2–N5–H5A
O1–N2–O2
O2–N2–N1
N6–C1–H1A
N6–C1–H1B
H1A–C1–H1B
N5–C2–N1
O3–N3–O4
O4–N3–N4
124.0(3)°
116.8(1)°
121.4(2)°
121.3(2)°
113.5(2)°
125.5 (2)°
118.5 (2)°
109.2(1)°
108.9(1)°
112.0 (2)°
119.4 (2)°
121.9(2)°
123.1 (2)°
Scheme 1. Synthesis of ADNQ and APX.
duction was performed with Crys-Alis RED software [5].
Structures were solved using the software packages implanted
in WinGX [6–9] and finally checked by using PLATON [10].
All non-hydrogen atoms were refined anisotropically, whereas
the hydrogen atoms were located from difference Fourier elec-
Table 3. Bond lengths and bond angles of ADNQ.
atoms
bond length atoms
1.247(2) Å O4–N5
bond length
O1–N4
O2–N4
1.253(2) Å
1.253(2) Å
0.99(2) Å
0.88(3) Å
1.360(2) Å
1.377(2) Å
1.306(2) Å
1.246 (2) Å O3–N5
N2–H2B
N2–H2C
N4–N6
0.94(2) Å
0.90(2) Å
N2–H2A
N2–H2D
1.348 (2) Å N6–C1
Table 1. Crystallographic data and parameters.
N3–N5
1.325(2) Å
0.82(2) Å
0.87(2) Å
N3–C1
N1–C1
N1–H1A
N1–H1B
ADNQ
APX
Formula
CH6N6O4
C4H8N12O10
384.18
atoms
bond angle
atoms
bond angle
Formula Mass /g·mol–1 166.09
H2B–N2–H2A
H2A–N2–H2D
H2A–N2–H2C
O2–N4–O1
114.0(2)°
109.2(2)°
109.1(2)°
120.2(1)°
115.1(1)°
118.9(1)°
125.0(1)°
115.3(1)°
125.3(2)°
125.85(2)°
H2B–N2–H2D
H2B–N2–H2C
H2D–N2–H2C
O2–N4–N6
N4–N6–C1
112.0 (2)°
106.8(2)°
105(2)°
124.70(1)°
118.20(1)°
118.96(2)°
115.98(1)°
119.2(1)°
127.52(2)°
106.61(2)°
Crystal system
Space Group
Color / Habit
Size /mm
a /Å
Monoclinic
Orthorhombic
Pbcn (No. 60)
colorless platelet
0.11 × 0.08 × 0.02
8.9909(18)
6.3392(13)
23.4311(47)
90
P21/c (No. 14)
colorless cubic
0.4 × 0.3 × 0.28
10.7925
6.2994
O1–N4–N6
N5–N3–C1
O3–N5–N3
C1–N1–H1A
H1A–N1–H1b
N1–C1–N3
O3–N5–O4
O4–N5–N3
C1–N1–H1B
N1–C1–N6
b /Å
c /Å
10.6651
118.679
636.13(8)
4
β /°
V /Å3
1335.5(5)
4
N6–C1–N3
Z
ρ
/g·cm–3
1.735
1.911
calcd.
μ /mm–1
0.17
0.183
F(000)
344
784
λ Mo-Kα /Å
T /K
0.71073
173
0.71073
tron density maps and refined isotropically. The structure solu-
tion and refinement are tabulated in Table 1. Bond lengths and
angles are given in Table 2 and Table 3, whereas the hydrogen
bonding system is shown in Table 4 and Table 5. Further infor-
mation concerning the crystal structure determinations in CIF
formal are deposited at the Cambridge Crystallographic Data
Centre [11] and are available free of charge (ADNQ: CCDC-
757221, APX: CCDC-757222).
200
qmin–max /°
4.30–26.00
3.48–25.34
Dataset h; k; l
Reflect. coll.
Independ. refl.
Reflection obs.
No. parameters
R1 / R1 (I > 2 σ)
wR2 / wR2 (I > 2 σ)
S
–13:11; –5:7; –10:13 –10:10; –7:7; –28:28
3026
7353
1240
1221
839
1038
124
135
0.0331 / 0.0589
0.0676 / 0.0724
0.891
0.0389/ 0.0472
0.1024/ 0.1077
1.157
APX crystallizes in the orthorhombic space group Pnma
with four molecules in the unit cell and a density of
1.911 g·cm–3. The molecular structure is shown in Figure 1,
Resd. Dens /e·Å–3
CCCD
0.19 / –019
757221
0.214/ –0.266
757222
464
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 463–471

Two Outstanding Explosives Based on 1,2-Dinitroguanidine
Table 4. Hydrogen bonds present in APX.
1.3956(2) Å. The hyperconjugative effect, which is well
known for nitramines is most significant for the N3–N4 bond.
The shortening of the bond is a consequence of the favored
zwitterionic form in the crystalline state. The description of
the crystal structure is strongly connected to the presence of
hydrogen bonds, which are shown in Figure 2 and listed in
Table 4. Besides the intramolecular hydrogen bonds in a dini-
troguanidine unit, there are three different kinds of hydrogen
bonding present. The intermolecular hydrogen bonds N5–
H5B···O4 and N5–H5A···O3 are highly directional and due to
the zwitterionic character. This results in dimer formation of
two APX units as basic building block (see Figure 2), which
is elongated in the crystal to wavelike strings. In between this
layers the N5–H5B···O2 hydrogen bond works like a cross
linker, see Figure 3. A consequence of this interaction is the
twisting of one nitro group out of the dinitroguanidine unit by
a torsion angle of 13.5°.
D–H···A
d(H–A)
d(H···A)
<DHA
d(D···A)
N5–H5B···O2
N5–H5A···O4
N5–H5B···O4
N5–H5A···O3
N5–H5B···O2
0.853 Å
0.934 Å
0.853 Å
0.934 Å
0.853 Å
2.076 Å
1.827 Å
2.350 Å
2.564 Å
2.367 Å
119.03° 2.599 Å
130.97° 2.540 Å
118.83° 2.861 Å
125.26° 3.196 Å
134.01° 3.023 Å
a)
b)
c)
Symmetry code: a) [x–1/2, –y+3/2, –z]; b) [x–1/2, –y+3/2, –z]; c)
[x+3/2, y+1/2, z].
Table 5. Hydrogen bonds present in ADNQ.
D–H···A
d(H–A)
d(H···A)
<DHA
d(D···A)
a)
a)
b)
b)
c)
d)
d)
N1–H1A···N6
N1–H1B···O1
N2–H2B···O1
N2–H2B···O2
N2–H2A···O4
N2–H2D···O3
N2–H2D···O4
N1–H1A···O3
N1–H1B···O2
N2–H2C···N6
N2–H2C···N3
0.816 Å
0.866 Å
0.936 Å
0.936 Å
0.986 Å
0.883 Å
0.883 Å
0.816 Å
0.866 Å
0.902 Å
0.902 Å
2.567 Å
2.315 Å
1.974 Å
2.466 Å
1.897 Å
2.132 Å
2.436 Å
1.942 Å
1.951 Å
2.486 Å
2.095 Å
127.60° 3.132 Å
122.76° 2.877 Å
171.71° 2.903 Å
129.11° 3.141 Å
174.68° 2.881 Å
151.22° 2.937 Å
135.07° 3.125 Å
133.49° 2.572 Å
126.58° 2.563 Å
132.72° 3.168 Å
164.84° 2.975 Å
Symmetry codes: a) [x, –y+1/2, z–1/2]; b) [–x+1, y+1/2, –z+1/2]; c)
[–x, –y+1, –z]; d) [–x, y+1/2, –z–1/2].
Figure 2. Selected hydrogen bonds of APX: Dimer formation.
bond lengths and angles are given in Table 2. The zwitterionic
bonding situation agrees well with the crystallographic observed
bond lengths. The typical bond length for conjugated guanidine
systems (1.328 Å) [12] agree perfectly with the C2–N4
bond length (1.335(3) Å), valuating this bond in between a sin-
gle and a double bond. The C2–N5 bond length is shortened to
1.297(3) Å, which is in accordance with the reported value for
2
Csp = N-double bonded systems (1.279 Å) [12]. The C2–N1
bond length (1.419(3) Å) can be evaluated as a typical single
bond, as the reported value for Csp2–N systems is 1.416 Å in
literature [12]. The bond lengths for C1–N1 (1.470(3) Å) and
C1–N6 (1.447(2) Å) fit for Csp3–N systems quite well [12].
Figure 3. Wavelike arrangement of APX with all hydrogen bonds
present (view along a axis).
Besides the described hydrogen bond interactions, additional
ionic interactions can be discussed. As the inner nitramine
(N6–N7) is not capable to hydrogen bonding it arranges in a
way to be surrounded by electropositive charged parts of the
molecule.
ADNQ crystallizes in the monoclinic space group P21/c with
four molecules in the unit cell and a crystal density of
1.735 g·cm–3 (Figure 4). The C–N bond length for C1–N1
(1.306(2) Å) is significantly shorter as for C1–N3 (1.377(2) Å)
and C1–N6 (1.360(2) Å). This evidences that a zwitterionic
description with charge separation is probably the best way to
describe the bonding situation inside the dinitroguanidine an-
ion. The N–N bond lengths for the deprotonated nitramines
are 1.3484(19) Å and 1.3250(19) Å, which stands for a slight
Figure 1. Molecular Structure of APX, ellipsoids of non-hydrogen at-
oms are displaced with 50 % probability level.
N–N bond lengths are in the known magnitude for nitram- hyperconjugative effect. Interestingly, the dinitroguanidine an-
ines as reported [13] ranging from 1.3624(2) Å to ion loses its planarity, as one nitro group is twisted out of the
Z. Anorg. Allg. Chem. 2010, 463–471
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
465

T. Altenburg, T. M. Klapötke, A. Penger, J. Stierstorfer
ARTICLE
plane by 11.8°. Reasonable for this phenomenon is a competi- zinc at a heating rate of 5 °C·min–1. The DSC plot shown in
tion of hydrogen bonds: Intramolecular vs. intermolecular to Figure 7 indicates that decomposition of APX is starting at an
the ammonium cation.
onset temperature of 174 °C. In contrast to this behavior the
decomposition temperature of the ionic compound ADNQ is
raised to 197 °C. Both compounds were tested according to
UN3c standard in a Systag, FlexyTSC Radex Oven at 75 °C
for 48 hours with the result, that no weight loss or decomposi-
tion products were detected.
Figure 4. Molecular Structure of ADNQ, ellipsoids of non-hydrogen
atoms are displaced with 50 % probability level.
The crystal structure of ADNQ can be described best as wa-
velike formation of layers (see Figure 5). In between these lay-
ers the N2–H2C–N6 and N2–H2C–N3 hydrogen bonds are
crosslinking (Figure 6).
Figure 7. DSC thermogram for APX and ADNQ with a heating rate
of β = 5 °C·min–1.
Figure 5. Wavelike arrangement of ADNQ with N–H···N interaction
between the layers.
Theoretical Calculations
All calculations were carried out using the Gaussian G03W
(revision B.03) program package [15]. The enthalpies (H) and
free energies (G) were calculated using the complete basis set
(CBS) method of Petersson and co-workers in order to obtain
very accurate energies. The CBS models use the known asymp-
totic convergence of pair natural orbital expressions to extrapo-
late from calculations using a finite basis set to the estimated
complete basis set limit. CBS-4 begins with a HF/3-21G(d) ge-
ometry optimization; the zero point energy is computed at the
same level. It then uses a large basis set SCF calculation as a
base energy, and a MP2/6-31+G calculation with a CBS extrap-
olation to correct the energy through second order. A
MP4(SDQ)/6-31+(d,p) calculation is used to approximate higher
order contributions. In this study we applied the modified CBS-
4M method (M referring to the use of minimal population locali-
zation) which is a reparametrized version of the original CBS-4
method and also includes some additional empirical corrections
[16a,b]. The enthalpies of the gas-phase species M were com-
puted according to the atomization energy method [Equa-
tion (1)] (Table 6, Table 7, and Table 8) [17a–c].
Figure 6. Hydrogen bonds present in ADNQ, light dashes are inside
the wave layer, thick ones in between the layers.
Thermal and Energetic Properties
Differential scanning calorimetry (DSC) measurements to
determine the decomposition temperatures of APX and ADNQ
were performed in covered aluminum containers containing a
ΔfH°(g, M, 298) = H(Molecule, 298) – ∑H°(Atoms, 298) + ∑ΔfH°(Atoms, 298) (1)
hole in the lid with a nitrogen flow of 20 mL·min–1 on a Lin- The solid state energy of formation (Table 9) of APX was cal-
seis PT10 DSC [14] calibrated by standard pure indium and culated by subtracting the gas-phase enthalpy with the heat of
466
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 463–471

Two Outstanding Explosives Based on 1,2-Dinitroguanidine
sublimation (19.2 kcal·mol–1) obtained by the Troutman rule and Cowan-Fickett’s equation of state for solid carbon [22].
(ΔHsub = 188·Tm) [19a,b]. In the case of ADNQ, the lattice The calculation of the equilibrium composition of the detona-
energy (UL) and lattice enthalpy (ΔHL) were calculated from tion products is done by applying modified White, Johnson and
the corresponding molecular volumes (Table 10) according to Dantzig’s free energy minimization technique. The program is
the equations provided by Jenkins [20a,b]. With the calculated designed to enable the calculation of detonation parameters at
lattice enthalpy (Table 11) the gas-phase enthalpy of formation the CJ point. The BKW equation in the following form was
(Table 8) was converted into the solid state (standard condi- used with the BKWN set of parameters (α, β, κ, θ) as stated
tions) enthalpy of formation (Table 6). These molar standard below the equations and Xi being the mol fraction of i-th gase-
enthalpies of formation (ΔHm) were used to calculate the molar ous product, ki is the molar covolume of the i-th gaseous prod-
solid state energies of formation (ΔUm) according to Equa- uct [22]:
tion (2) (Table 9).
pV / RT = 1 + xeβx x = (κ Σ Xiki) . [V (T + θ)]α
Table 6. CBS-4M results.
α = 0.5, ꢀ = 0.176, κ = 14.71, θ = 6620.
point group
el. state
–H298 /a.u.
NIMAG
The detonation parameters calculated with the EXPLO5 pro-
gram using the experimentally determined densities (X-ray)
are summarized in Table 12.
APX
Cs
1564.066859
56.796608
613,123370
0.500991
37.786156
54.522462
74.991202
0
0
0
0
0
0
0
+
NH4
Td
1A1
1A
DNQ– Cs
H
C
N
O
2A1g
Table 10. Molecular volumes.
4A1g
VM .Å3
VM .nm3
+
NH4
21.0 [20]
0.021
0.138
0.159
+
DNQ–
ADNQ
138.0
a)
159.0
Table 7. Literature values for atomic ΔH°f298 /kcal·mol–1.
a) From X-ray data (ADNQ) V = 636.1, Z = 4; NH4 from literature
[20].
NIST [18]
H
C
N
O
52.1
171.3
113.0
59.6
Table 11. Lattice energies and lattice enthalpies.
VM .nm3 UL .kJ·mol–1 ΔHL .kJ·mol–1 ΔHL .kcal·mol–1
ADNQ 0.159
536.8
540.3
129.0
Table 8. Enthalpies of the gas-phase species M.
M
M
ΔfH°(g, M) /kcal·mol–1
APX
C4H8N12O10
+392.6
+151.8
–24.3
Table 12. Detonation parameters.
+
+
NH4
NH4
DNQ–
CH2N5O4
–
APX
APX + 5 % PVAA
ADNQ
NH4 DNQ–
CH6N6O4
+127.5
+
r .g·cm–3
Ω .%
1.911
–8.33
–5935
4489
398
1.875
–16.28
–5878
4377
373
1.735
–9.63
–5193
3828
327
9066
934
Qv .kJ·kg–1
Tex .K
ΔUm = ΔHm – Δn RT
(2)
pC–J .kbar
Vdet .m·s–1
V0 .L·kg–1
9540
816
9211
784
(Δn being the change of moles of gaseous components)
Detonation Parameters
The calculation of the detonation parameters was performed
with the program package EXPLO5 (version 5.03) [21]. The
program is based on the chemical equilibrium, steady-state
Electrostatic Potential
The electrostatic potential of APX is illustrated using Gauss-
model of detonation. It uses the Becker-Kistiakowsky-Wilson’s View 4.1 [23]. Figure 8 (grayscale) as well as the cover picture
equation of state (BKW EOS) for gaseous detonation products of this issue (color) show the 0.001 electron bohr–3 3D isosur-
Table 9. Solid state energies of formation (ΔfU°).
ΔfH°(s) .kcal·mol–1
ΔfH°(s) .kJ·mol–1
Δn ΔfU°(s) .kJ·mol–1
M .g·mol–1
ΔfU°(s) .kJ·kg–1
APX
ADNQ
65.0
–1.5
272.1
–6.4
–15 309.3
–8 13.5
384.24
166.13
805.0
81.0
Z. Anorg. Allg. Chem. 2010, 463–471
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
467

T. Altenburg, T. M. Klapötke, A. Penger, J. Stierstorfer
ARTICLE
wards discharge (ESD) was determined to be 0.4 J. APX
should be handled like primary explosive, as the compound is
very sensitive towards impact (3 J) or friction (80 N) and a
ESD of 0.1 J. Desensitizing of high explosives by coating or
mixing with binder systems is common. Therefore we tested a
mixture containing 95 % of APX and 5 weight% of PVAA
(polyvinyl alcohol acetate) resin towards mechanical stimuli.
Impact sensitivity was reduced to 5 J (sensitive) and friction
to 160 N (sensitive). Optimization of the plastic bonded explo-
sives with curing agents and for example HTPB (hydroxyl ter-
minated polybutadien binder) should be an effective way for
desensitizing the material.
Detonation Parameters
Especially the detonation parameters of APX show to be
very promising exceeding those of TNT and RDX and in part
even those of HMX. The most important criteria of high explo-
sives are detonation velocity (Vdet. = APX: 9540, ADNQ:
9066, TNT: ~7178, RDX: 8906, HMX: 9324 m·s–1), detona-
tion pressure (pC–J. = APX: 398, ADNQ: 327, TNT: 205,
RDX: 346, HMX: 393 kbar) and energy of explosion (ΔEU° =
APX: –5943, ADNQ: –5193, TNT: 5112, RDX: –6043,
HMX: –6049 kJ·kg–1) [21]. Due to these great values, we tried
to determine the detonation velocity of APX experimentally.
Figure 8. Calculated (CBS-4M) electrostatic potential of APX show-
ing two different orientations. The dark grey regions represent electron
rich regions, the black regions extremely electron-deficient regions.
Detonation Velocity Measurement of APX
The measurement of the detonation velocity of APX was
performed using the OZM detonating velocity measuring sys-
tem EXPLOMET-FO-2000. The use of the fiber optic tech-
nique insures excellent electrical noise immunity (Figure 9).
The system used had two independent timers measuring the
time intervals (in μs) between the illumination of two adjacent
optical probes and calculated the velocity of detonation
(m·s–1). The WinExplomet software package was used to trans-
fer the results to a PC via a serial interface. For the detonation
velocity measurement a 14 mm PE tube was equipped with
two optical fibers in a distance of 2.0 cm. The amount of APX
used for the test was 8.5 g. APX was loaded into the PE tube
and manually compressed with 80 N. As a booster charge 0.5 g
of nitropenta (PETN) were added on top and carefully com-
pressed manually. Initiation was achieved with an electrically
ignited (40 V, 5 A) PETN-Pb(N3)2 detonator (0.8 g PETN,
0.2 g lead azide). The experimentally determined detonation
velocity of 4853 m·s–1 with an explosive density of
0.63 g·cm–3 deviates less than 1 % to the theoretical value
(4900 m·s–1).
face of electron density for APX with an electrostatic potential
contour value of 0.05 hartree. The red regions represent ex-
tremely electron-rich regions (V(r) < 0.05 hartree) and the blue
regions extremely electron-deficient regions (V(r) > 0.05 har-
tree). In general, the patterns of the calculated electrostatic po-
tentials of the surface of molecules can be related to the impact
sensitivities [24, 25a,b]. In contrary to non energetic organic
molecules, where the positive potential is larger but weaker in
strength, in nitro and azo compounds usually more extensive
regions with larger and stronger positive potentials are ob-
served which can be related to the increased impact sensitivi-
ties (see below).
Sensitivities
For initial safety testing, the impact and friction sensitivities
as well as the electrostatic sensitivity were determined [26].
The impact sensitivity tests were carried out according to
STANAG 4489 [27] modified according to instruction [28]
using a BAM (Bundesanstalt für Materialforschung) [29] drop-
hammer [30]. The friction sensitivity tests were carried out
according to STANAG 4487 [31] modified according to in-
struction [32] using the BAM friction tester. The electrostatic
Koenen Steel Sleeve Test
APX was investigated according to its explosion perform-
sensitivity tests were carried out using an electric spark tester ance under confinement using a “Koenen test” steel sleeve ap-
ESD 2010EN (OZM Research) operating with the “Winspark paratus [35, 36a,b]. Also the shipping classification of the sub-
1.15 software package” [33]. According to the UN recommen- stance can be determined and the degree of venting required
dations [34] ADNQ is classified as sensitive towards impact to avoid an explosion during processing operations can be
and friction (IS: 10 J, FS: 252 N). Electrostatic sensitivity to- evaluated. The explosion is initiated via thermal ignition using
468
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 463–471

Two Outstanding Explosives Based on 1,2-Dinitroguanidine
was also computed to the higher detonation parameters than
RDX and HMX.
Figure 10. Main picture: Collected fragments of the Koenen test. Left:
Steel Sleeve with closing plate; right: Koenen test setup showing the
four Bunsen burner.
Conclusions
From this combined theoretical and experimental study the
following conclusions can be drawn:
(i) 1,7-Diamino-1,7-dinitrimino-2,4,6-trinitro-2,4,6-triaza-
heptane (APX) and ammonium dinitroguanidine (ADNQ)
were prepared in high yield and purity. Both compounds were
fully characterized spectroscopically and structurally.
(ii) The theoretical calculations indicate that both materials,
especially APX, have excellent properties as energetic fillers
in high explosive formulations.
(iii) An experimental detonation test revealed that the deto-
nation performance of APX is in agreement with the theoreti-
cal determined values.
(iv) Sensitivities for both compounds were investigated ex-
perimentally. A calculation of the electrostatic potential of
APX fits well to the experimental determined values for the
impact sensitivities. A plastic bonded mixture with PVAA
resin was tested and found to be less sensitive to impact and
friction.
Figure 9. Picture series showing the detonation velocity test: A) mo-
ment of initiation; B) start of detonation; C) shockwave expansion
(time gap: 0.25 s).
(v) The crystal structures of APX and ADNQ were deter-
mined by X-ray diffraction and analysis of the structure param-
eters clearly proved the presence of a zwitterionic structure.
four Bunsen burners, which are started simultaneously. The
test is completed when either rupture of the tube or no reaction
is observed, after heating the tube for a minimal time period
of at least 5 min. In case of the tube’s rupture the fragments
are collected and weighed. The reaction is evaluated as an ex-
plosion if the tube is destroyed into three or more pieces. The
Koenen test was performed with 19.0 g APX using a closing
plate with an orifice of 10 mm. The first trial was successful
indicated by the rupture of the steel tube into part powder
(<100 μm) like pieces, which are depicted in Figure 10. TNT
destroys the steel sleeve up to an orifice width of 6 mm, RDX
and HMX even up to 8 mm [37]. Compared to these applied
Experimental Section
General Procedure: All reagents and solvents were used as received
(Sigma–Aldrich, Fluka, Acros Organics). Melting points were meas-
ured with a Perkin–Elmer Pyris6 DSC, using heating rates of
5 °C·min–1 1H, 13C and 14N spectra were recorded with a JEOL
.
Eclipse 270, JEOL EX 400 or a JEOL Eclipse 400 instrument. All
chemical shifts are quoted in ppm relative to TMS (1H, 13C). Infrared
(IR) spectra were recorded using a Perkin–Elmer Spektrum One FT-
IR instrument. Raman spectra were measured using a Bruker MULTI-
explosives the performance of APX is obviously better, which RAM with a Nd:YAG laser (1064 nm). Elemental analyses were per-
Z. Anorg. Allg. Chem. 2010, 463–471
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de 469

T. Altenburg, T. M. Klapötke, A. Penger, J. Stierstorfer
formed with a Netsch STA 429 simultaneous thermal analyzer. Mass C 12.64, H 2.28, N 43.66. Bomb Calorimetry: ΔUc = 1783 cal·g–1.
ARTICLE
spectra were measured on a JEOL Mstation TM MS-700 with a high-
performance double focusing magnetic sector.
DSC: Tdec = 174 °C (onset). Sensitivities: IS = 3 J (< 100μm), FS =
80 N (< 100 μm), ESD = 0.1 J (< 100 μm).
CAUTION! The prepared compounds ADNQ and APX are highly
explosive compounds. Although we had no problems during synthesis
and investigation, the materials should be treated with proper safety
measures such as safety glasses, face shield, leather coat, earthened
equipment and shoes, Kevlar® gloves and ear plugs.
1,3-Dichloro-2-nitrazapropane (2): A two liter 3-necked flask was
charged with acetic anhydride (384 mL, 4.07 mol) and cooled to 0–
10 °C, while 99 % nitric acid (144 mL, 3.43 mol) was added. To this
nitrating mixture a solution of hexamine (94.9 g, 0.66 mol) in acetic
acid (176 mL) was added within one hour. The reaction mixture was
left standing for 12 h at room temperature. The solid 1,7-diacetoxy-
2,4,6-trinitrazaheprane was filtered off and the acid filtrate was diluted
with dichloromethane (150 mL). The organic layer was washed with
water, 16 % sodium hydroxide solution and water. After evaporation,
the crude reaction product 1,3-diacetoxy-2-nitrazapropane remained
and was distilled yielding 34.7 g of sufficient purity for chlorination.
After dissolving this material in dioxane (60 mL), gaseous hydrogen
chloride was bubbled at a temperature range of 5–15 °C through the
solution for 1.5 hours. The solution was stored for 80 hours in the
refrigerator and concentrated with a rotary evaporator. After distilla-
tion (b.p. 51 °C at 4 %10–2 mbar), 20.4 g of 1,3-dichloro-2-nitrazapro-
pane remained as a colorless liquid, which corresponds a total yield of
28 % with respect to the hexamine and 76 % with respect to the 1,3-
diacetoxy-2-nitrazapropane.
Ammonium dinitroguanidine (ADNQ): 1,2-Dinitroguandine (5.0 g,
33.6 mmol) was dissolved in warm ethanol (50 mL). To this solution,
ammonium carbonate (1.61 g, 16.8 mmol) was added in small por-
tions. Afterwards, water (10 mL) was added and the mixture was
stirred until gas evolution stopped. The reaction mixture was allowed
to cool to room temperature and the product precipitated as colorless
crystals. ADNQ was filtered off and washed with diethyl ether (5.02 g,
1
90 %). H NMR (d6-DMSO): δ = 7.46 (br., 2 H, C=NH2). 13C NMR
(d6-DMSO): δ = 161.4 (C=NH2). 14N NMR (d6-DMSO): δ = –9
(NO2), –130 (NNO2), –284 (NH2), –359 (NH4). IR: ν = 3602 (w),
3503 (w), 3450 (s), 3415 (vs), 3392 (vs), 3316 (s), 3283 (vs), 3241
(vs), 3198 (vs), 3073 (s), 2806 (s), 1717 (w), 1659 (m), 1605 (vs),
1529 (m), 1514 (m), 1501 (m), 1409 (s), 1344 (vw), 1417 (vs), 1129
(s), 1103 (s), 1103 (s), 1070 (m), 1040 (s), 945 (m), 783 (m), 771 (w),
750 (vw), 729 (w), 668 (w), 639 (w) cm–1. Raman (300 mW): ν =
3133 (2), 1596 (24), 1346 (7), 1267 (6), 1207 (24), 1131 (100), 1052
(10), 966 (61), 792 (11), 684 (4), 549 (9), 426 (5), 361 (14), 240 (3),
199 (3), 136 (2), 113 (74), 94 (18), 80 (10) cm–1. MS (FAB+): m.z =
18 (100). MS (FAB-): m.z = 148 (100). EA: C4H8N12O10. Calculated
(%): C 7.23; H 3.64; N 50.60; Found (%): C 7.18, H 3.68, N 50.15.
DSC: Tdec = 197 °C (onset). Sensitivities: IS = 10 J (100–500μm),
FS = 252 N (100–500μm), ESD = 0.4 J (100–500μm).
Potassium dinitroguanidine (3): Dinitroguanidine (1) (5.00 g,
33.5 mmol) was dissolved in warm ethanol (30 mL). To this solution
potassium hydrogen carbonate (3.36 g, 33.5 mmol) dissolved in water
was added dropwise whilst stirring. After the addition was completed,
the solution was cooled to room temperature and stirred for additional
20 minutes, until no gas evolution appeared. The colorless solid was
filtered, washed with cold ethanol (10 mL) and dried in air yielding
6.6 g of potassium dinitroguanidine, which corresponds a yield of
95 %. IR: ν = 3334 (vs), 3242 (vs), 1585 (m), 1486 (m), 1455 (m),
1359 (s), 1314 (m), 1220 (s), 1130 (s), 1036 (m), 944 (w), 787 (m),
724 (vs), 677 (w), 635 (w) cm–1. Raman (300 mW): ν = 3249 (3),
1575 (10), 1460 (30), 1386 (31), 1270 (4), 1210 (35), 1132 (100), 1042
(12), 962 (56), 795 (26), 680 (4), 544 (22), 442 (7), 367 (35), 258 (8),
221 (17), 108 (57), 87 (83), 74 (92) cm–1. EA: KCH2N5O4. Calculated
(%): C 6.42; H 1.08; N 37.42; Found (%): C 6.37; H 1.10; N 36.65.
DSC: Tdec = 174 °C (onset). Sensitivities: IS = 9 J (100–500μm), FS =
160 N (100–500μm).
1,7-Diamino-1,7-dinitrimino-2,4,6-trinitro-2,4,6-triazaheptane
(APX): Potassium 1,2-dinitroguanidine (4.22 g, 23 mmol) was sus-
pended in acetone (30 mL) and 1,3-bis(choromethyl)nitramine (1.79 g,
11 mmol) dissolved in acetone (5 mL) was added. Afterwards, sodium
iodide (150 mg) and 18-crown-6 (100 mg) was added and the colorless
solution turned slightly yellow. The reaction mixture was heated under
reflux for 2 hours and cooled to room temperature. The inorganic salts
were filtered off and the filter cake was washed with additional acetone
till colorless. The acetone solutions were evaporated to dryness and a
brownish oily solid remained. This solid was treated with hot 70 %
ethanol for approximately 20 minutes and the colorless fine precipitate
was filtered and washed with additional ethanol (50 mL) to yield
3.69 g of 1,7-diamino-1,7-dinitrimino-2,4,6-trinitro-2,4,6-triazahep-
tane (APX), which corresponds to a yield of 85 %. The finely pow-
dered material can be crystallized from an acetone chloroform solution,
Acknowledgement
Financial support of this work by the Ludwig-Maximilian University
of Munich (LMU) and the Fonds der Chemischen Industrie (FCI) is
gratefully acknowledged. The authors are indebted to and thank Mr.
Stefan Huber for performing the sensitivity tests as well as Dipl.-
Chem. Susanne Scheutzow for the experimental determination of the
detonation velocity.
1
when slow evaporation of acetone is ensured. H NMR (d6-DMSO):
δ = 9.93 (br., 4 H, NH2), 6.68 (s, 4 H, CH2). 13C NMR (d6-DMSO):
δ = 156.9 (C=NH2), 64.5 (CH2). 14N NMR (d6-DMSO): δ = –17, –
35, –41 (NO2), –272 (NH2). IR: ν = 3427 (s), 3294 (s), 3053 (w),
3002(w), 2978 (w), 2899 (w), 1656 (m), 1631 (s), 1604 (s), 1564 (m),
1518 (m), 1465 (m), 1448 (m), 1399 (m), 1358 (m), 1328 (m), 1266
(s), 1243 (s), 1220 (vs), 1150 (m), 1105(m), 1028 (m), 952 (w), 920
(s), 909 (s), 869 (w), 796 (w), 776 (w), 764 (w), 748 (w), 724 (w),
676 (w), 623 (w) cm–1. Raman (300 mW): ν = 3283 (3), 3055(5),
3007(14), 2924 (3), 1653 (11), 1588 (10), 1510 (11), 1450 (9), 1408
(21), 1377 (22), 1329 (15), 1271 (24), 1242 (23), 1200 (18), 1151 (7),
1105 (10), 1042 (14), 953 (24), 915 (7), 870 (45), 797 (16), 751 (5),
670 (8), 653 (8), 636 (12), 533 (18), 468 (8), 430 (13), 415 (11), 306
(38), 270 (9), 245 (10), 120 (100) cm–1. MS (DCI+): m.z = 385.3
(0.4), 265 (33), 177(6), 168 (6), 150 (40), 105 (31), 75 (42). EA:
C4H8N12O10. Calculated (%): C 12.51; H 2.10; N 43.75; Found (%):
References
[1] a) S. V. Sysolyatin, A. A. Lobanova, Y. T. Chernikova, G. V.
Sakovich, Russ. Chem. Rev. 2005, 74, 757; b) P. E. Eaton, R. L.
Gilardi, M. X. Zhang, Adv. Mater. 2000, 12, 1143.
[2] a) A. A. Astratýev, D. V. Dashko, L. L. Kuznetsov, Russ. J. Org.
Chem. 2003, 39, 501; b) A. D. Vasiliev, A. M. Astachov, M. S.
Molokeev, L. A. Kruglyakova, R. S. Stepanov, Acta Crystallogr.,
Sect. C 2003, 59, o550; c) A. M. Astachov, V. A. Sokolenko,
P. V. Brovchenko, A. L. Rubailo, Kyimiya Khimicheskaya Tekh-
nologiya 2005, 48, 36; d) N. V. Latypov, M. Johansson, L. N.
Yudina-Wahlstroem, S. Ek, C. Eldsaeter, P. Goede, New Trends
470
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 463–471

Two Outstanding Explosives Based on 1,2-Dinitroguanidine
in Research of Energetic Materials, Proceedings of Seminar, 9th, [18] NIST Chemistry WebBook (Eds.: P. J. Linstrom, W. G. Mallard),
Pardubice, 2006, (Pt. 1), 160; e) A. M. Astachov, V. A. Revenko,
A. D. Vasiliev, A. A. Nefedov, L. A. Kruglyakova, K. P. Kon-
stantin, R. S. Stepanov, Internation Annual Conference of ICT
2006, 173.1; f) N. V. Latypov, M. Johannson, L. N. Yu-
dina Wahlstroem, S. Ek, C. Eldsaeter, P. Goede, Cent. Eur. J.
Energetic Mater. 2007, 4, 3.
NIST Standard Reference Database Number 69, June 2005, Na-
tional Institute of Standards and Technology, Gaithersburg MD,
20899 (http:..webbook.nist.gov).
[19] a) M. S. Westwell, M. S. Searle, D. J. Wales, D. H. Williams, J.
Am. Chem. Soc. 1995, 117, 5013; b) F. Trouton, Philos. Mag.
1884, 18, 54.
[20] a) H. D. B. Jenkins, H. K. Roobottom, J. Passmore, L. Glasser,
Inorg. Chem. 1999, 38, 3609; b) H. D. B. Jenkins, D. Tudela, L.
Glasser, Inorg. Chem. 2002, 41, 2364.
[3] J. E. Flanagan, M. B. Frankel, US 4085123.
[4] CrysAlis CCD, Version 1.171.27p5 beta; Oxford Diffraction Ltd.
[5] CrysAlis RED, Version 1.171.27p5 beta; Oxford Diffraction Ltd.
[6] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J. [21] M. Sućeska, EXPLO5.3, Zagreb, Croatia, 2009.
Appl. Crystallogr. 1993, 26, 343.
[22] a) M. Sućeska, Materials Science Forum, 2004, 465–466, 325;
b) M. Sućeska, Propellants Explos. Pyrotech. 1991, 16, 197;
c) M. Sućeska, Propellants Explos. Pyrotech. 1999, 24, 280;
d) M. L. Hobbs, M. R. Baer, Proc. of the 10th Symp. (Interna-
tional) on Detonation, ONR 33395–12, Boston, MA, July 12–16,
1993, p. 409.
[23] Gaussview 4.1.2, Gaussian, Inc.: Wallingford, CT, 2006.
[24] B. M. Rice, J. J. Hare, J. Phys. Chem. A 2002, 106, 1770.
[25] a) P. Politzer, J. S. Murray, J. M. Seminario, P. Lane, M. E.
Grice, M. C. Concha, J. Mol. Struct. 2001, 573, 1; b) J. S. Mur-
ray, P. Lane, P. Politzer, Mol. Phys. 1995, 85, 1.
[26] M. Suceska, Test Methods for Explosives, Springer, New York
1995, p. 21 (impact), p. 27 (friction).
[27] NATO Standardization Agreement (STANAG) on explosives, im-
pact sensitivity tests, no. 4489, Ed. 1, Sept. 17, 1999.
[28] WIWEB-Standardarbeitsanweisung 4–5.1.02, Ermittlung der Ex-
plosionsgefährlichkeit, hier der Schlagempfindlichkeit mit dem
Fallhammer, Nov. 8, 2002.
[29] http:..www.bam.de.
[30] http:..www.reichel-partner.de.
[31] NATO Standardization Agreement (STANAG) on explosive, fric-
tion sensitivity tests, no. 4487, Ed. 1, Aug. 22, 2002.
[32] WIWEB-Standardarbeitsanweisung 4–5.1.03, Ermittlung der Ex-
plosionsgefährlichkeit or der Reibeempfindlichkeit mit dem Reib-
eapparat, Nov. 8, 2002.
[33] a) S. Zeman, V. Pelikán, J. Majzlík, Centr. Eur. J. Energy Mater.
2006, 3, 45; b) D. Skinner, D. Olson, A. Block-Bolten, Propel-
lants Explos. Pyrotechn. 1997, 23, 34; c) OZM research, Czech
Republic, http:..www.ozm.cz.testing-instruments.pdf.TI-
SmallSpark.pdf.
[34] impact: insensitive > 40 J, less sensitive ≥ 35 J, sensitive ≥ 4 J,
very sensitive ≤ 3 J; friction insensitive > 360 N, less sensitive =
360 N, sensitive < 360 N;. > 80 N, very sensitive ≤ 80 n, extreme
sensitive ≤ 10 N; According to the UN recommendations on the
transport of dangerous goods (+) indicates: not safe for transport.
[35] J. Köhler, R. Meyer, A. Homburg, Explosives, 6th Ed., Wiley-
VCH, Weinheim, 2007, pp. 162.
[36] a) T. M. Klapötke, J. Stierstorfer, Phys. Chem. Chem. Phys. 2008,
10, 4340; b) T. M. Klapötke, J. Stierstorfer, Dalton Trans. 2008,
4, 643.
[7] SHELXS-97, Program for Crystal Structure Solution, G. M. Shel-
drick, Institut für Anorganische Chemie der Universität, Tamman-
strasse 4, 3400 Göttingen, Germany, 1994.
[8] SHELXS-97, Program for Crystal Structure Solution, G. M. Shel-
drick, Institut für Anorganische Chemie der Universität, Tamman-
strasse 4, 3400 Göttingen, Germany, 1997.
[9] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837.
[10] PLATON, A Multipurpose Crystallographic Tool. A. L. Spek,
Utrecht, The Netherlands, 1999.
[11] A copy of the cif files for compound APX and ADNQ can be
obtained free of charge on application to The Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336-
033. E-mail for inquiry: fileserv@ccdc.cam.ac.uk. E-mail for dep-
osition: deposit-@ccdc.cam.ac.uk).
[12] F. H. Allen, O. Kennard, D. G. Watson, J. Chem. Soc., Perkin
Trans. 1, 1987, S1.
[13] Y. Kohno, U. A. Imamura, J. Phys. Chem. 1996, 100, 4701.
[14] http:..www.linseis.com.
[15] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M.
A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K.
N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi,
V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fuk-
uda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B.
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador,
J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels,
M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Ragha-
vachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S.
Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P.
Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A.
Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M.
W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and
J. A. Pople, Gaussian 03, Revision B04, Gaussian Inc., Walling-
ford, CT, 2004.
[16] a) J. W. Ochterski, G. A. Petersson, J. A. Montgomery Jr., J.
Chem. Phys. 1996, 104, 2598; b) J. A. Montgomery Jr., M. J.
Frisch, J. W. Ochterski, G. A. Petersson, J. Chem. Phys. 2000,
112, 6532.
[17] a) L. A. Curtiss, K. Raghavachari, P. C. Redfern, J. A. Pople, J.
Chem. Phys. 1997, 106, 1063; b) E. F. C. Byrd, B. M. Rice, J.
Phys. Chem. A 2006, 110, 1005; c) B. M. Rice, S. V. Pai, J. Hare,
Comb. Flame 1999, 118, 445.
[37] J. Köhler, R. Meyer, A. Homburg, Explosives, 6th Ed., Wiley-
VCH, Weinheim, 2007, pp. 174.
Received: December 11, 2009
Published Online: February 11, 2010
Z. Anorg. Allg. Chem. 2010, 463–471
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
471