Transition metal complexes of 3-Amino-1-nitroguanidine as laser ignitible primary explosives: Structures and properties

Article abstract of DOI:10.1021/ic402038x

3-Amino-1-nitroguanidine (ANQ, 2) was synthesized via hydrazinolysis of nitroguanidine. By dissolving 2 in solutions containing transition metal salts, several complexes M²⁺(ANQ)₂X₂(H ₂O)_y with M²⁺ = Co, Ni, Cu, Zn as well as M(ANQ)₂X(H₂O)_y with M = Ag could be isolated. In these cases, nitrate as well as perchlorate and chloride served as the respective anions X. Additionally, the ANQ complexes of Co, Ni, and Ag with dinitramide as the anion were synthesized from ANQ and silver dinitramide and by reacting the cobalt and nickel ANQ perchlorate complexes with ammonium dinitramide. The crystal structures of all described complexes were determined by low temperature single-crystal X-ray diffraction. Additionally, they were characterized using IR spectroscopy and elemental analysis. The decomposition temperatures were determined by differential scanning calorimetry and the sensitivities toward impact and friction were assessed using a BAM drophammer and a BAM friction tester (BAM = Bundesanstalt fuer Materialforschung und -pruefung). Additionally, the sensitivity toward electrostatic discharge was determined on a small-scale ESD device. The potential use of the nitrate, dinitramide and perchlorate containing species as primary explosives was investigated in a laser ignition test.

Full text of DOI:10.1021/ic402038x

Article
pubs.acs.org/IC
Transition Metal Complexes of 3‑Amino-1-nitroguanidine as Laser
Ignitible Primary Explosives: Structures and Properties
Niko Fischer, Manuel Joas, Thomas M. Klapotke,* and Jorg Stierstorfer
̈
̈
Energetic Materials Research, Department of Chemistry, University of Munich (LMU), Butenandtstrasse 5−13, D-81377, Germany
S
* Supporting Information
ABSTRACT: 3-Amino-1-nitroguanidine (ANQ, 2) was synthesized
via hydrazinolysis of nitroguanidine. By dissolving 2 in solutions
containing transition metal salts, several complexes
M2+(ANQ)2X2(H2O)y with M2+ = Co, Ni, Cu, Zn as well as
M(ANQ)2X(H2O)y with M = Ag could be isolated. In these cases,
nitrate as well as perchlorate and chloride served as the respective
anions X. Additionally, the ANQ complexes of Co, Ni, and Ag with
dinitramide as the anion were synthesized from ANQ and silver
dinitramide and by reacting the cobalt and nickel ANQ perchlorate
complexes with ammonium dinitramide. The crystal structures of all
described complexes were determined by low temperature single-
crystal X-ray diffraction. Additionally, they were characterized using
IR spectroscopy and elemental analysis. The decomposition temperatures were determined by differential scanning calorimetry
and the sensitivities toward impact and friction were assessed using a BAM drophammer and a BAM friction tester (BAM =
Bundesanstalt fur Materialforschung und -prufung). Additionally, the sensitivity toward electrostatic discharge was determined on
̈
̈
a small-scale ESD device. The potential use of the nitrate, dinitramide and perchlorate containing species as primary explosives
was investigated in a laser ignition test.
of nitroguanyl azide,11 or as a cationic species in ionic energetic
1. INTRODUCTION
materials.12
In the continuous research toward new energetic materials,
Because of the considerable amount of electron density at its
high-energy capacity transition metal complexes have become
amine and nitramine substituent, it expectedly shows fairly
more and more popular.1−3 These materials mostly combine
good characteristics as a ligand in transition metals complexes,
facile syntheses and good thermal stabilities with energetic
which have not been described in the literature before.
properties similar to that of the prominent primary explosive
Furthermore, although amine substituted guanidine derivatives
lead azide, which should be replaced because of its high toxicity.
are subject to oxidative decomposition in air, ANQ is stable
For the synthesis of energetic complexes, especially nitrogen-
under ambient conditions.
rich heterocycles4 or guanidine-based ligands can be used.
The guanidine building block is one of the first structural
moieties that has been known to the chemical and biological
Ilyushin et al. report on the synthesis of a cobalt(III)
complex bearing tetrazole as a ligand and perchlorate as the
counterion and its use as nontoxic initiating explosive.13
community and was discovered as early as 1866, when the first
Bearing this in mind, the choice of counterions was directed
to anions such as the nitrate, dinitramide, or perchlorate anion,
guanidine derivative was prepared by Hofmann.5 Since then,
guanidine chemistry has evolved into an extremely wide ranging
field of applications starting from bioorganic chemistry and
biochemistry6 to inorganic chemistry, which most importantly
can be traced back to a vast variability of derivatization of the
guanidine moiety itself. Whereas a lot of correspondence can be
found dealing with either aminated or nitrated guanidines such
as aminoguanidine7 or nitroguanidine,8 only very few sources
report on the synthesis9 and use of the mixed 3-amino-1-
nitroguanidine (ANQ, 2), which is the only today known
guanidine derivative containing both, an amine and a nitro
substituent. Nevertheless, it has found application as a useful
intermediate for cylization reactions yielding bis-nitramino-
triazoles,10 for the synthesis of 5-nitriminotetrazole, which
proceeds via a diazotization reaction and following cyclization
which frequently have been reported as counterions in ionic
energetic materials.14,15 The first reported synthesis of a
dinitramide compound was that of its ammonium salt.16 To
overcome the problems, which nowadays are discussed
regarding the safe handling of commonly used primary
explosives such as lead azide, which aside from being toxic
has a high impact and friction sensitivity, a new class of
initiating charges, which are laser-igitable primary explosives,
are investigated.17 If insensitive toward impact and friction,
these materials can easily be ignited by a short but highly
energetic laser pulse with a specific wavelength. This
Received: October 29, 2013
© XXXX American Chemical Society
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considerably reduces the probability of being accidentally
ignited, which oftentimes happened while handling the
commonly used impact and friction sensitive primary
explosives. Here, the use of transition metal complexes has
already been discussed, whereas the exact mechanism, by which
transition metal containing complexes are ignited upon laser
irradiation, is still under investigation.
19 proceeds after dissolving the respective Co2+, Ni2+, Cu2+,
Zn2+, and Ag+ perchlorates, nitrates, or chlorides, as indicated in
Scheme 2, in a boiling solution of ANQ. The stoichiometry of
the reaction of ANQ: metal salt was chosen to be 1:1 instead of
2:1 (which is the stoichiometry found in the crystalline
products), because poorly water-soluble ANQ tends to
precipitate from the mixture upon cooling down. In some
cases, precipitated ANQ indeed had to be filtered off from the
mixture, before crystals of the complex began to grow, which
especially was observed for the zinc(II) complexes. The yields
of the described reactions were determined only of the first
isolated fraction of crystals and lie between <10% and 49%,
which presumably can be optimized by further evaporation of
the mother liquors.
As possible candidates for laser ignitable primary explosives,
the ANQ complexes of Co2+, Ni2+, Cu2+, Zn2+, and Ag+ with a
−
−
−
choice of counterions (NO3 , N(NO2)2 , ClO4 , Cl−) were
investigated including their synthesis and structure determi-
nation.
2. RESULTS AND DISCUSSION
2.1. Synthesis. 3-Amino-1-nitroguanidine (ANQ, 2) was
synthesized in aqueous solution employing a hydrazinolysis
reaction of commercially available nitroguanidine (1, see
Scheme 1), whereas it is important to control the temperature
accurately.18 The product itself shows fairly poor solubility in
water and therefore can be recrystallized from hot water.
The ANQ complexes bearing a dinitramide counterion in the
cases of the cobalt and nickel complexes 13 and 14 were
synthesized from the respective metal perchlorate-containing
solutions after addition of ammonium dinitramide in a
stoichiometric ratio of metal perchlorate:ADN = 1:2 (see
Scheme 3). The advantage of the perchlorate containing
solutions as starting material over the nitrate or chloride
containing solutions is the better solubility of the metal−ANQ
perchlorates as compared to the nitrates or chlorides, so that
they do not precipitate before the dinitramides were isolated
from the mother liquors. Using potassium dinitramide instead
is disadvantageous because of the simultaneous precipitation of
both potassium perchlorate and the metal-ANQ dinitramides.
The silver complex was formed after combining solutions of 3-
amino-1-nitroguanidinium chloride19 and acetonitrile-stabilized
silver dinitramide20 in a 1:1 stoichiometric ratio. After filtering
off AgCl, the silver−ANQ dinitramide monohydrate crystallizes
from the mother liquor in colorless needles.
a
Scheme 1. Hydrazinolysis of Nitroguanidine
a
Reaction conditions: stirring, 55 °C, 15 min.
The formation of the perchlorate, nitrate, and chloride-based
3-amino-1-nitroguanidinium complexes 3−7, 8−12, and 16−
Scheme 2. Formation of Perchlorate, Nitrate, and Chloride-Based 3-Amino-1-nitroguanidinium Complexes 3−7, 8−12, and
16−19
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Scheme 3. Formation of Dinitramide-Based 3-Amino-1-Nitroguanidinium Complexes 13−15
2.2. Single-Crystal X-ray Structure Analysis. The low-
temperature determination of the crystal structures of 3−19
was performed on a Oxford Xcalibur3 diffractometer with a
Spellman generator (voltage 50 kV, current 40 mA) and a
KappaCCD detector. The data collection and reduction were
carried out using the CrysAlisPro software.21 The structures
were solved either with SIR-9222 or SHELXS-97,23 refined with
SHELXL-9724, and finally checked using the PLATON25
software integrated in the WinGX26 software suite. The
absorptions were corrected by a Scale3 Abspack multiscan
method.27 Selected data and parameter of the X-ray
determinations are given in the Supporting Information in
Tables S1−S3. Cif files have been deposited within the
Cambridge Crystallographic Data Centre using the CCDC
Nos. 900148 (3), 900144 (4), 900147 (5), 900149 (6), 900143
(7), 900142 (8), 900139 (9), 900141 (10), 900146 (11),
900140 (12), 900155 (13), 900154 (14), 900138 (15), 900152
Figure 1. Molecular moiety of 3. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Perchlorate anions are strongly
disordered. Only selected split positions are depicted. Selected
coordination distances (Å): Co−O7 2.088(3), Co−N4 2.108(3),
Co−N1 2.130(3); angles (deg): O7−Co−N4 89.24(11), O7−Co−N1
90.69(13), N4−Co−N1 75.76(11). Symmetry codes: (i) 1 − x, −y,
−z; (ii) 1 − x, 0.5 + y, 0.5 − z.
(16), 900153 (17), 900151 (18) and 900156 (19)
The ANQ ligand shows a similar structure in all investigated
complexes in this work. Recently we published the structure of
neutral ANQ as well as some inorganic salts.12,19 The ligand is
almost planar. The C−N bonds are significantly shorter than
C−N single bonds, with lengths between 1.28 and 1.38 Å.
Coordination to the metal centers take place by the outer
hydrazine nitrogen atom N4 and nitrogen atom N1. The
coordination angles N1−M−N4 approximately increase with
the following order. Ag (ca. 68°) < Zn = Co < Ni < Cu (ca.
80°).
[Co(ANQ)2(H2O)2](ClO4)2 (3) crystallizes in the mono-
clinic space group P21/c with two formula units in the unit cell.
The molecular moiety is depicted in Figure 1. A similar
coordination sphere has been described for diaqua-tetrakis-
picoline cobalt(II) diperchlorate.28
The molecular structure of [Zn(ANQ)2(H2O)2](ClO4)2 (6)
is shown in Figure 4. The zinc(II) cations in 6, which
crystallizes in the monoclinic space group P21/c, have a
centrosymmetric 6-fold coordination sphere.
The molecular moiety of [Ag(ANQ)2]ClO4 (7), which
crystallizes in the triclinic space group P1, is depicted in Figure
̅
5. The silver cations are coordinated by four nitrogen atoms in
square planar arrangement.
The corresponding nickel complex [Ni(ANQ)2(H2O)2]-
(ClO4)2 (4) crystallizes in the orthorhombic space group
Pca21 with four formula units in the unit cell. The molecular
moiety is depicted in Figure 2. With the exception of the
copper salt the densities of the perchlorates increase with rising
atomic numbers (ρ [g cm−3]: 3 (2.068) < 5 (2.128) < 4
(2.159) < 6 (2.193) < 7 (2.316)).
In agreement to all copper complexes investigated in this
work, [Cu(ANQ)2(ClO4)2](H2O)2 (5) also shows a Jahn−
Teller29 distorted octahedral coordination sphere due to the d9
electron configuration (see Figure 3). The elongation of the
octahedron is due to longer Cu−OClO3 coordination bonds in
comparison to the Cu−N coordination bonds which is similar
described for dimethylethylendiamine bis-perchlorate.30 The
water molecules do not participate in metal coordination. The
One formula unit of [Co(ANQ)2(H2O)2](NO3)2 (8) shown
in Figure 6 is incorporated in the centrosymmetric triclinic unit
cell. The nirate anions do not participate in the coordination of
the Co2+ centers.
Figure 7 is used exemplarily for the molecular structures of
[Ni(ANQ)2(H2O)2](NO3)2 (9) and [Zn(ANQ)2(H2O)2]-
(NO3)2 (11). The complexes are crystallizing isotypically in
the triclinic space group P−1 showing almost the same unit cell
dimensions (see Table S2 in the Supporting Information) and
densities (ρ [g cm−3]: 9 (2.011), 11 (1.992).
The copper complex [Cu(ANQ)2(NO3)2] (10) is shown in
Figure 8. It crystallizes in the monoclinic space group C2/c with
a density of 2.171 g cm−3. The Cu2+ cations reveal a distorted
octahedral coordination sphere. This is indicated by the Cu−O
bond lengths, which significantly differ from each other and the
O5−Cu−O8 angle of ∼160°.
triclinic unit cell (P1) contains one molecular moiety.
̅
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Figure 4. Molecular moiety of 6. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Zn−N4 2.106(2), Zn−N1 2.148(2), Zn−O7 2.164(2); angles
(deg): N4−Zn−N1 74.70(8), N4−Zn−O7 88.51(8), N1−Zn−O7
84.43(10). Symmetry codes: (i) −x, 1 − y, −z.
Figure 2. Molecular moiety of 4. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Ni−N4 2.0692, Ni−O14 2.0764, Ni−N6 2.0821, Ni−N9 2.0877,
Ni−N1 2.0891, Ni−O13 2.125; angles (deg): N4−Ni−O14 94.8,
N4−Ni−N6 101.9, O14−Ni−N6 86.6, O14−Ni−N9 87.0, N6−Ni−
N9 77.5, N4−Ni−N1 76.7, O14−Ni−N1 95.0, N4−Ni−O13 88.4,
N6−Ni−O13 93.9, N9−Ni−O13 89.8, N1−Ni−O13 84.5.
Figure 5. Molecular moiety of 7. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Ag1−N4 2.346(3), Ag1−N9 2.359(3), Ag1−N1 2.374(3), Ag1−
N6 2.396(3); angles (deg): N4−Ag1−N9 175.12(8), N4−Ag1−N1
68.55(10), N9−Ag1−N1 116.31(10), N4−Ag1−N6 107.47(10), N9−
Ag1−N6 67.88(10), N1−Ag1−N6 167.67(15).
Figure 3. Molecular moiety of 5. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Cu−N1 1.982(2), Cu−N4 2.032(2), Cu−O3 2.4364(19), angles
(deg): N1−Cu−N4 79.58(9), N1−Cu−O3 85.41(10), N4−Cu−O3
83.44(8). Symmetry codes: (i) −x, 1 − y, −z.
The density of complex [Ag(ANQ)2NO3] (11) is consid-
erably smaller (2.235 g cm−3) than that observed for silver(I)
nitrate (4.35 g cm−3).31 The silver cations in the structure of
11, which crystallizes in the orthorhombic space group Pbca,
are distorted tetrahedrally coordinated by only nitrogen atoms.
The dinitramide complexes 13 and 14 crystallize isotypically
as tetrahydrates in the monoclinic crystal system within the
space group P21/c. Two water molecules participate in the
coordination sphere, while the others are connected to the
dinitramide anions by formation of hydrogen bonds (see Figure
10). The density of the cobalt complex 13 is slightly lower
(1.964 g cm−3) than that of nickel complex 14 (1.982 g cm−3).
Figure 6. Molecular moiety of 8. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Co−O11 2.0623(11), Co−N1 2.1307(14), Co−N4 2.1543(13);
angles (deg): O11−Co−N1 90.93(5), O11−Co−N4 88.74(5), N1−
Co−N4 74.77(5). Symmetry codes: (i) 1 − x, 1 − y, −z; (ii) 1 − x, 1
− y, −z.
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Figure 9. Molecular moiety of 12. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Ag−N6 2.344(4), Ag−N1 2.328(3), Ag−N9 2.301(3), Ag−N4
2.318(2); angles (deg): N9−Ag−N4 145.28(10), N9−Ag−N1
130.40(12), N4−Ag−N1 69.55(11), N9−Ag−N6 69.33(11), N4−
Ag−N6 122.72(11), N1−Ag−N6 131.09(16).
Figure 7. Molecular moiety of 9 (M1 = Ni) and 11 (M1 = Zn).
Thermal displacements of non-hydrogen atoms were set at 50%
probability. Hydrogen atoms are shown as spheres of arbitrary radius.
Selected coordination distances (Å): 9: Ni−N1 2.0587(19), Ni−O3
2.0805(18), Ni−N4 2.1023(19); 11: Zn−N1 2.1144(17), Zn−O3
2.1315(15), Zn−N4 2.1650(15); angles (deg) 9: N1−Ni−O3
86.99(8), N1−Ni−N4 77.27(7), O3−Ni−N4 92.03(8); 11: N1−
Zn−O6 91.33(7), N1−Zn−N4 75.66(6), O6−Zn−N4 87.98(7).
Symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) 1 − x, 1 − y, 1 − z.
investigated in this work crystallize isotypically in the
monoclinic space group P21/n. Also, 18 shows very similar
unit-cell dimensions; however, for the space group P21/c. The
molecular unit for 16, 17, and 19 is depicted in Figure 12. In
contrast to the crystal water molecules the chlorido anions are
enclosed in coordination. The densities of 16 (1.927 g cm−3),
17 (1.950 g cm−3), 18 (1.945 g cm−3), and 19 (1.944 g cm−3)
are similar and in total the lowest observed in this work.
As already observed for the coordination sphere of the
cations in 16, 17, and 19, the copper cations in 18 possess an
elongated octahedral coordination sphere due to the Jahn−
Teller effect (see Figure 13). The copper chlorine coordination
bonds are much longer (∼2.71 Å) than the Cu−O bonds in the
previously described complexes 5 and 10. This is in agreement
to the recently published structure of dichlorido-tetrakis-1,2,4-
triazole copper(II), where the Cu−Cl bonds are even longer
(2.83 Å).34
2.3. IR Spectroscopy. The assignments of absorptions
were undertaken referring to values reported in literature.14,35
Strong absorptions are observed in all spectra in the region
above 3000 cm−1, indicating N−H and O−H valence
vibrations. Here, the N−H valence vibration of the hydrazine
moiety of the ligand is visible as a relatively sharp absorption
band at 3430−3378 cm−1. This is in contrast to the absorptions
of O−H valence vibrations at around 3300−3200 cm−1 of the
crystal water containing complexes, which are broadened
because of hydrogen bond formation. In comparison to the
IR absorptions of neutral, uncomplexed ANQ, the N−H
valence vibrations are observed at somewhat lower energies if
complexed (3551 cm−1 in ANQ). Other important absorptions
are the antisymmetric and the symmetric N−O valence
vibration of the nitramine moiety both of which are present
as strong absorptions in all spectra at 1687−1651 cm−1 (asym)
and 1297−1275 cm−1 (sym). For both absorptions, again lower
wave numbers are observed as compared to uncomplexed
ANQ, which reveals values of 1692 and 1329 cm−1 for the
absorptions of the aforementioned vibrations. A relatively
strong absorption at 1245−1203 cm−1 can be assigned to the
N−N valence vibration of the nitramine moiety, whereas a
second absorption at slightly lower energy (1139−1097 cm−1)
Figure 8. Molecular moiety of 10. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Cu−N6 1.982(2), Cu−N1 1.989(2), Cu−N4 2.0326(19), Cu−
N9 2.0370(19), Cu−O5 2.3382(19); Cu−O8 2.586(2); angles (deg):
N6−Cu−N1 178.8(1), N6−Cu−N4 99.67(8), N1−Cu−N4 79.69(8),
N6−Cu−N9 79.02(9), N1−Cu−N9 101.65(9), N4−Cu−N9
178.13(8), N6−Cu−O5 84.27(9), N1−Cu−O5 94.70(9), N4−Cu−
O5 94.28(7), N9−Cu−O5 86.93(8), O5−Cu−O8 160.18(7).
The dinitramide anions are not planar and follow the twisted
structure observed for, for example, lithium and potassium
dinitramide.32
The silver complex 15 could only be obtained crystalline
(monoclinic, P21/c) as a monohydrate. The molecular motif is
shown in Figure 11. The density of 2.456 g cm−3 is the highest
observed in this work and is similar to that (2.488 g cm−3) of
silver dinitramide as its acetonitrile adduct.33
Remarkably, the chlorido complexes [M(ANQ)Cl2](H2O)2
(16 (M = Co2+), 17 (M = Ni2+) and 19 (M = Zn2+)
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Figure 10. Molecular moiety of 13 (M2 = Co) and 14 (M2 = Ni). Thermal displacements of non-hydrogen atoms were set at 50% probability.
Hydrogen atoms are shown as spheres of arbitrary radius. Selected coordination distances (Å): 13: Co−O7 2.0998(12), Co−N1 2.1128(14), Co−
N4 2.1413(13); 14: Ni−N1 2.0652(13), Ni−O7 2.0877(11), Ni−N4 2.1024(12); angles (deg) 13: O7−Co−N1 89.87(6), O7−Co−N4 90.67(5),
N1−Co−N4 76.44(5); 14: N1−Ni−O7 90.76(5), N1−Ni−N4 78.19(5), O7−Ni−N4 89.47(5). Symmetry codes: (i) 1 − x, 1 − y, 1 − z.
Figure 11. Molecular moiety of 15. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Ag−N7 2.147(9), Ag−N3 2.260(9), Ag−N2 2.340(10); angles
(deg): N7−Ag−N3 147.4(4), N7−Ag−N2 142.3(3), N3−Ag−N2
70.1(3).
Figure 12. Molecular moiety of 16 (M3 = Co), 17 (M3 = Ni), and 19
(M3 = Zn). Thermal displacements of non-hydrogen atoms were set
at 50% probability. Hydrogen atoms are shown as spheres of arbitrary
can be attributed to the N−N valence vibration of the
hydrazine moiety of the ligand. Furthermore, the characteristic
radius. Selected coordination distances (Å): 16: Co−N1 2.1212(14),
absorptions of the nitrate and the perchlorate anion at 1385−
Co−N4 2.1305(13), Co−Cl 2.4810(4); 17: Ni−N1 2.0651(13), Ni−
1382 and 1097−1083 cm−1 are observed in the respective IR
N4 2.0949(12), Ni−Cl 2.4600(4); 18: Cu−N1 1.997(2), Cu−N4
spectra. The dinitramide anion can be detected by strong
2.053(2), Cu−Cl 2.7155(7); 19: Zn−N1 2.1071(15), Zn−N4
absorptions at 1539−1529 cm−1 (asymmetric in phase N−O
2.1439(14), Zn−Cl 2.5473(4); angles (deg) 16: N1−Co−N4
valence vibration) and 1434−1431 cm−1 (asymmetric out of
75.69(5), N1−Co−Cl 90.66(4), N4−Co−Cl 90.61(4); 17: N1−Ni−
phase N−O valence vibration).
N4 77.66(5), N1−Ni−Cl 89.71(4), N4−Ni−Cl 89.46(3); 18: N1−
Cu−N4 79.14(8), N1−Cu−Cl 89.11(7), N4−Cu−Cl 89.90(6); 19:
N1−Zn−N4 76.18(6), N1−Zn−Cl 89.24(5), N4−Zn−Cl 89.41(4).
Symmetry codes: (i) 1 − x, −y, 1 − z.
2.4. Sensitivities and Thermal Stability. The impact
sensitivity tests were carried out according to STANAG 448936
modified instruction37 using a BAM (Bundesanstalt fur
̈
Materialforschung) drophammer.38 The friction sensitivity
tests were carried out according to STANAG 448739 modified
instruction40 using the BAM friction tester. The classification of
the tested compounds results from the “UN Recommendations
on the Transport of Dangerous Goods”.41 Additionally, all
compounds were tested upon the sensitivity toward electrical
discharge using the Electric Spark Tester ESD 2010 EN.42
Because the described complexes are transition metal
complexes with an energetic ligand together with energetic
counterions such as nitrate, perchlorate, and dinitramide, we
expect enhanced sensitivities toward outer stimuli. The
perchlorates 3−7 are very sensitive toward impact, some of
them (5, 7) even bearing values of less than 1 J, which in the
case of the silver complex is not least due to fact, that it
crystallizes water free. Also the friction sensitivities are in a
range between very sensitive (3−6) and extremely sensitive
(7). The complexes bearing a nitrate counterion (8−12) at an
average are less sensitive toward impact and friction than the
perchlorate containing compounds, however they are still
sensitive toward impact with two exceptions, the copper (10)
and the silver (12) complex, which crystallize water free, again
are very sensitive toward impact, a trend that has already been
observed for the perchlorate containing compounds 5 and 7.
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complex (19: 172 °C). The dinitramides expectedly decompose
at relatively low temperatures (13: 118 °C, 14: 142 °C),
whereas the trend of higher decomposition temperatures of the
nickel complexes is again confirmed. A detailed list of all
decomposition and dehydration temperatures as well as the
sensitivities toward impact, friction, and electrostatic discharge
can be found in Table 1.
Table 1. Sensitivities and thermal Behavior of 3−19
#
IS (J)
FS (N)
ESD (J)
Tdehydr (°C)
Tdec (°C)
a
3
4
3
3
10
10
0.03
0.04
0.50
0.30
0.01
0.70
0.08
0.50
0.50
0.01
0.70
0.60
0.10
0.70
0.70
0.70
170
176
230
134
198
148
139
186
77
162
a
5
<1
3
16
120
6
28
108, 154
b
7
<1
9
<5
80
c
8
a
9
4
120
<5
120
<5
80
160
b
10
11
12
13
14
15
16
17
19
<1
5
119
b
181
142
118
142
108
186
250
172
Figure 13. Molecular moiety of 18. Thermal displacements of non-
hydrogen atoms were set at 50% probability. Hydrogen atoms are
shown as spheres of arbitrary radius. Selected coordination distances
(Å): Cu−N1 1.997(2), Cu−N4 2.053(2), Cu−Cl 2.7155(7); angles
(deg): N1−Cu−N4 79.14(8), N1−Cu−Cl 89.11(7), N4−Cu−Cl
89.90(6); Symmetry codes: (i) −x, −y, 2 − z; (ii) −x, −0.5 + y, 0.5 −
z.
<1
5
85
a
3
80
138
2
7
71
144
150
104
10
10
10
360
360
360
a
Decomposition (exothermic) occurs immediately after dehydration
Almost the same argumentation can be applied to the friction
sensitivities of the nitrates. Interestingly, the dinitramides 13−
15, while still being comparatively sensitive, do not reach the
high sensitivity levels of, for example, 7, 10, and 12 in terms of
impact as well as friction sensitivity, presumably because of the
inclusion of four (13, 14) and one (15) molecule of crystal
water per formula unit, respectively. Holding no energetic
anion, the four chloride complexes 16, 17, and 19 show
moderate impact sensitivity and are less sensitive toward
friction. Unfortunately, the yields of 18 allowed no determi-
nation of sensitivities.
Differential scanning calorimetry (DSC) measurements to
determine the dehydration- and decomposition temperatures of
3−17 and 19 (about 1.5 mg of each energetic material) were
performed in covered Al-containers containing a hole in the lid
and a nitrogen flow of 20 mL min−1 on a Linseis PT 10 DSC43
calibrated by standard pure indium and zinc at a heating rate of
5 °C min−1. All decomposition temperatures are given as
absolute onset temperatures, whereas dehydration temperatures
are set at the minimum of the endothermic peak in the DSC
curve.
Several interesting trends can be observed while comparing
the decomposition temperatures of the complexes 3−17 and
19. The nickel complexes reveal the highest decomposition
temperatures if compounds bearing the same anion are
compared to each other (e.g., 4: 230 °C). For the perchlorates
and nitrates, the zinc complexes follow the nickel complexes
(e.g., 6: 198 °C) having the second highest decomposition
temperatures again followed by the cobalt complexes (e.g., 3:
176 °C). The silver and especially the copper complexes
decompose at relatively low temperatures oftentimes even
below 100 °C (e.g., 5: 134 °C, 10: 77 °C). Comparing
complexes with the same metal ion, the perchlorates have
higher decomposition temperatures as the nitrates (e.g., 7: 148
°C, 12: 142 °C). Most of the chlorides show decomposition at
even higher temperatures as the perchlorates except for the zinc
b
c
(endothermic). No crystal water contained. No dehydration
(endothermic event) observed before decomposition (exothermic
event). Exothermic decomposition of the water free or dehydrated
compounds.
#
Most of the crystal water containing complexes can be
dehydrated after heating (4, 6, 11, 13, 14−16, 19), indicated by
an endothermic peak in the DSC curve, which is well-separated
from the exothermic decomposition event. Some of the
complexes decompose immediately after they start to lose
their crystal water (3, 5, 9, 14), whereas for 8, no endothermic
event before decomposition can be observed, although it
crystallizes as a dihydrate.
2.5. UV−Vis−NIR Spectroscopy and Laser Ignition
Tests. Further, the synthesized metal complexes 3−5, 7−10, as
well as 13 and 14 were investigated upon their behavior toward
single pulsed laser irradiation at a wavelength of 940 nm and a
pulse length of 100 μs. The cobalt(II) complex 3, copper(II)
complex 5, and also the silver(I) complex 7 could be initiated
by a single pulse laser beam and led to detonation of samples,
which previously to the experiment were pressed into pellets of
approximately 8 mm diameter and 2 mm thickness. The
nickel(II) complex 4 and all corresponding nitrate complexes
8−10 as well as even the complexes holding the highly
energetic dinitramide anion 13−14 did not show any response
to laser irradiation. The laser initiation mechanism (electroni-
cally, thermally, etc.) of transition metal complexes is still
unknown. Related to that, the UV−vis−NIR reflectance of the
solid samples 3 ([Co(ANQ)2(H2O)2](ClO4)2), 4 ([Ni-
(ANQ)2(H2O)2](ClO4)2), 5 ([Cu(ANQ)2(ClO4)2](H2O)2),
and 7 ([Ag(ANQ)2]ClO4) were measured on a Varian Cary
500 spectrometer in a wavelength range of 350−1300 nm. The
measured diffuse reflectance R [%] was transformed after
applying the Kubelka−Munk eq 1 to give the absorption
function F(R) (no unit).44
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Inorganic Chemistry
Article
Figure 14. UV−vis−NIR spectra of complexes 3−5 and 7. The absorption function F(R) is obtained after applying the Kubelka−Munk equation.
(1 − R∞)2
decomposition temperatures of the samples with their laser
ignitability. For example, [Cu(ANQ)2(NO3)2] (10) could not
be initiated by the laser beam but shows the lowest thermal
stability (Tdec. = 77 °C) of the investigated compounds.
The role of the nature of the ligand in the laser initiation
process is not yet fully understood and therefore under current
investigation.
K
S
=
2R∞
(1)
Where K is the absorption component, S the scattering
component, and R∞ the reflectance of an infinite thick sample.
The step in the absorption intensity F(R) at 800 nm in
Figure 14 is caused by a detector change. The spectra have only
qualitative character. Due to technical limits no quantitative
information about the absorption intensity can be obtained
from the spectra. Commonly, R∞ is technically approximated
by a sample layer thick enough that the measuring instrument
cannot detect differences in the thickness-dependent diffuse
reflectance. However, not all samples could be coated on the
object plate thick enough that there were no differences
detectable anymore.
The information obtained from the UV−vis−NIR spectra
essentially is, that the four samples considerably differ in their
absorption only at wavelengths in the visible and near UV
region of the electromagnetic spectrum, what we would expect
of four obviously differently colored samples. However in the
NIR region, the samples 3−5 equally absorb radiation,
especially at 940 nm, which is the wavelength of the laser
beam used for laser initiation experiments. However, the silver
complex shows no absorption at this wavelength.
Considering, that all metal perchlorates 3−5 except the
silver(I) complex 7 were light absorbing at 940 nm together
with the initiation results it seems that there is no relation
between optical absorption properties and the photosensitivity
toward pulsed laser irradiation, which is in agreement with the
laser initiation experiments made by Ilyushin et al.13,45 The fact
that only perchlorate compounds and no nitrates could be
initiated fits to the literature claimed initiation mechanism
where an active perchlorate radical is formed by a one-electron
transfer from the perchlorate anion to the metal cation induced
by the laser beam.45
3. CONCLUSION
From the experimental study of energetic complexes based on
3-amino-1-nitroguanidine the following conclusions can be
drawn:
• Combining boiling solutions of 3-amino-1-nitroguani-
dine (ANQ) and a transition metal (M = Co, Ni, Cu, Zn,
Ag) perchlorate (X = ClO4) or nitrate (X = NO3) affords
complexes M2+(ANQ)2(X−)2(H2O)n (n = 0, 2) in the
case of Co, Ni, Cu, and Zn or M+(ANQ)2(X−) in the
case of Ag, which readily crystallize from their aqueous
mother liquors, but in minor yields. For Co, Ni, Cu, and
Zn, the respective chlorides M2+(ANQ)2(X−)2(H2O)2
were also isolated following the same procedure.
• Complexes M2+(ANQ)2(X−)2(H2O)4 with X = N(NO2)2
were isolated in the case of M = Co and Ni starting from
the rescpective perchlorate containing complexes upon
addition of ammonium dinitramide to the solutions.
Ag(ANQ)(N(NO2)2)(H2O) crystallized after combining
solutions of silver dinitramide and 3-amino-1-nitro-
guanidinium chloride (ANQ+Cl−).
• The complexes crystallize in the space groups P1 (5, 7−
̅
9, 11), P21/c (3, 6, 13−15, 18), P21/n (16, 17, 19), C2/c
(10), Pca21 (4) and Pbca (12) with densities between
1.927 (16) and 2.456 (15), whereas perchlorates, if
hydrated, reveal higher densities than nitrates and
chlorides. The highest densities are observed for the
silver complexes.
Consequently, it seems, that the initiation of energetic
materials by a short pulsed laser beam rather is an electronic
process than a thermal one, especially when comparing the
• All perchlorate, nitrate, and chloride containing com-
plexes crystallize as dihydrates, except for the silver
complexes 7 and 12 and the copper complex 10, which
H
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Inorganic Chemistry
crystallize water free. The dinitramides crystallize as
Article
(5), 961 (100), 770 (27), 483 (30), 419 (33), 378 (10), 248 (13). 1H
NMR (DMSO-d6, 25 °C, ppm) δ: 9.29 (s, 1H, NH), 8.23 (s, 1H, C−
NHAHB), 7.52 (s, 1H, C−NHAHB), 4.64 (s, 2H, N−NH2). 13C NMR
(DMSO-d6, 25 °C, ppm) δ: 161.5 (C(NNO2)(N2H4)(NH2)). 15N
NMR (DMSO-d6, 25 °C, ppm) δ: −13.3 (NO2), −146.3 (NNO2),
−276.4 (NH/NH2), −301.8 (NH/NH2), −327.9 (NH/NH2). MS
(FAB−): m/z = 117.99 [M−H] −. EA (CH5N5O2, 119.08) calcd: C
10.09, H 4.23, N 58.81%; found: C 10.51, H 4.32, N 58.90%. BAM
drophammer: 20 J; friction tester: 144 N; ESD: 0.15 J (at grain size
100−500 μm).
tetrahydrates (13, 14) and monohydrate (15), respec-
tively. Most of the crystal water containing complexes
can be dehydrated (4, 6, 11, 13, 15−19) without
decomposition.
• Nickel complexes generally show the highest decom-
position temperatures (17: 250 °C), whereas copper and
silver complexes decompose at relatively low temper-
atures (10: 77 °C). Also a trend of higher decomposition
temperatures for chlorides and perchlorates as compared
to nitrates and dinitramides is observed.
• All complexes bearing energetic counterions show
enhanced sensitivities toward impact and friction,
which especially applies to the solvate water free silver
and copper complexes 7, 10, and 12 with values of <1 J
(IS) and <5 N (FS).
• Selected perchlorate, nitrate and dinitramide containing
complexes were tested upon their laser ignitability with a
100 μs laser pulse at 940 nm. Only the perchlorate
containing complexes 3, 5, and 7 could successfully be
initiated.
• UV−vis−NIR spectra of the perchlorate containing
complexes 3−5 and 7 were recorded and show, that
there is no relationship between their absorption
behavior at the designated wavelength of the laser
beam (940 nm) and their initiation properties.
Bis(3-amino-1-nitroguanidine)diaquacobalt(II) Perchlorate
(3). 3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) was dissolved in
20 mL of boiling water. Cobalt(II) perchlorate hexahydrate (1.548 g,
4.23 mmol) was added and the mixture was boiled until a clear
solution resulted. The clear solution was filtered and slowly cooled to
room temperature. After a few days, the product started to crystallize
as red blocks. Yield: 35% (788 mg, 1.48 mmol). The crystal density
was 2.068 g cm−3.
DSC (5 °C min−1, °C): 176 °C (dec.). IR (KBr, cm−1): v = 3548
̃
(m), 3407 (s), 3321 (s), 3303 (s), 2964 (w), 2615 (w), 2231 (w),
2135 (w), 2059 (w), 1660 (s), 1579 (w), 1508 (m), 1480 (m), 1424
(m), 1385 (m), 1278 (s), 1211 (s), 1097 (vs), 938 (m), 820 (w), 808
(w), 779 (m), 717 (w), 671 (w), 663 (w), 627 (m), 599 (m), 520 (m).
EA (C2H14Cl2N10O14Co, 532.03) calcd: C 4.52, H 2.65, N 26.33%;
found: C 3.96, H 2.60, N 23.03%. BAM drophammer: 3 J; friction
tester: 10 N; ESD: 0.03 J (at grain size 500−1000 μm).
Bis(3-amino-1-nitroguanidine)diaquanickel(II) Perchlorate
(4). 3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) was dissolved in
20 mL of boiling water. Nickel(II) perchlorate hexahydrate (1.547 g,
4.23 mmol) was added and the mixture was boiled until a clear
solution resulted. The clear solution was filtered and slowly cooled to
room temperature. After a few days, the product started to crystallize
as light purple blocks. Yield: 21% (467 mg, 0.88 mmol).
4. EXPERIMENTAL SECTION
Caution! The herein described metal complexes of ANQ are energetic
materials with increased sensitivities toward shock and friction.
Therefore, proper safety precautions (safety glass, face shield, earthed
equipment and shoes, Kevlar gloves, and ear plugs) have to be applied
while synthesizing and handling the described compounds. All
chemicals and solvents were employed as received (Sigma-Aldrich,
Fluka, Acros). 1H and 13C and 15N NMR spectra were recorded using
a JEOL Eclipse 270, JEOL EX 400 or a JEOL Eclipse 400 instrument.
The chemical shifts quoted in ppm in the text refer to typical standards
such as tetramethylsilane (1H, 13C) or nitromethane (15N). To
determine the melting and decomposition temperatures of the
described compounds a Linseis PT 10 DSC (heating rate 5 °C
min−1) was used. Infrared spectra were measured using a Perkin-Elmer
Spectrum One FT-IR spectrometer as KBr pellets. Raman spectra
were recorded on a Bruker MultiRAM Raman Sample Compartment
D418 equipped with a Nd:YAG-Laser (1064 nm) and a LN-Ge diode
as detector. Mass spectra of the described compounds were measured
at a JEOL MStation JMS 700 using FAB technique. To measure
elemental analyses, we employed a Netsch STA 429 simultaneous
thermal analyzer.
DSC (5 °C min−1, °C): 230 °C (dec.). IR (KBr, cm−1): v = 3527
̃
(m), 3439 (s), 3401 (s), 3307 (s), 3247 (s), 2774 (w), 2626 (w), 2510
(w), 2219 (w), 2219 (w), 2054 (w), 2021 (w), 1657 (s), 1613 (s),
1569 (m), 1511 (s), 1492 (m), 1459 (m), 1412 (m), 1390 (m), 1283
(s), 1207 (s), 1108 (vs), 1083 (s), 938 (m), 814 (w), 776 (m), 716
(m), 672 (m), 625 (m), 600 (m), 515 (m). EA (C2H14Cl2N10O14Ni,
531.79) calcd: C 4.52, H 2.65, N 26.34%; found: C 4.72, H 2.50, N
25.98%. BAM drophammer: 3 J; friction tester: 10 N; ESD: 0.04 J (at
grain size 500−1000 μm).
Bis(3-amino-1-nitroguanidine)diperchloratocopper(II) Dihy-
drate (5). 3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved
in 20 mL of boiling water. Copper(II) perchlorate hexahydrate (1.567
g, 4.23 mmol) is added and the mixture is boiled until a clear solution
results. The clear solution is filtered and slowly cooled down to room
temperature. After 1 h, the product starts to crystallize in blue blocks.
Yield: 6.5% (137 mg, 0.27 mmol).
DSC (5 °C min−1, °C): 134 °C (dec.). IR (KBr, cm−1): v = 3500
̃
(m), 3406 (s), 3285 (m), 3203 (m), 3076 (m), 1651 (s), 1610 (m),
1558 (w), 1511 (m), 1495 (s), 1432 (w), 1385 (m), 1322 (m), 1281
(s), 1212 (s), 1135 (s), 1108 (vs), 1083 (vs), 935 (m), 820 (w), 773
(w), 735 (w), 707 (w), 653 (w), 622 (m), 606 (m), 521 (m). EA
(C2H14Cl2N10O14Cu, 536.64) calcd: C 4.48, H 2.63, N 26.10%; found:
C 4.73, H 2.50, N 25.85%. BAM drophammer: 1 J; friction tester: 16
N; ESD: 0.50 J (at grain size 100−500 μm).
3-Amino-1-nitroguanidine (2). Commercially available nitro-
guanidine (20% H2O, 25 g, 192 mmol) was dispended in 250 mL of
water and the mixture was heated to 55 °C. Hydrazine hydrate (10.5
mL, 216 mmol) was added dropwise over a period of 15 min and the
temperature was kept at 55 °C for a further 15 min under constant
stirring. After the mixture turned to a clear, orange solution, it was
cooled to room temperature in an ice bath and the reaction was
quenched with conc. hydrochloric acid (pH 7). 3-Amino-1-nitro-
guanidine starts to precipitate after the solution was cooled to 4 °C
overnight. The product was separated by filtration and recrystallized
from hot water. Yield: 10.3 g (86 mmol, 45%).
Bis(3-amino-1-nitroguanidine)diaquazinc(II) Perchlorate (6).
3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in 20 mL
of boiling water. Zinc(II) perchlorate hexahydrate (1.575 g, 4.23
mmol) is added and the mixture is boiled until a clear solution results.
The clear solution is filtered and slowly cooled to room temperature.
Slow evaporation of the solvent affords 5 as colorless crystals. Yield:
21% (441 mg, 0.82 mmol).
DSC (5 °C min−1, °C): 184 °C (dec 1), 200 °C (dec.2); IR (KBr,
DSC (5 °C min−1, °C): 198 °C (dec.). IR (KBr, cm−1): v = 3531
cm−1): ν
̃
= 3551 (s), 3411 (s), 3234 (s), 2025 (w), 1692 (m), 1637
̃
(m), 3487 (m), 3430 (s), 3338 (s), 3312 (s), 1655 (s), 1630 (m),
1576 (m), 1519 (m), 1495 (m), 1413 (m), 1384 (m), 1288 (s), 1217
(m), 1139 (s), 1090 (vs), 936 (m), 815 (w), 778 (m), 720 (w), 636
(m), 626 (m), 592 (w), 544 (w), 468 (w). EA (C2H14Cl2N10O14Zn,
538.49) calcd: C 4.46, H 2.62, N 26.01%; found: C 4.48, H 2.67, N
(s), 1616 (vs), 1545 (m), 1502 (m), 1443 (m), 1384 (m), 1329 (m),
1134 (m), 1108 (m), 1088 (m), 1031 (m), 1005 (w), 963 (w), 870
(w), 772 (w), 745 (w), 696 (w), 622 (m), 571 (w), 482 (m). Raman
(1064 nm, 200 mW, 25 °C, cm−1): ν
̃
= 3319 (4), 3255 (13), 1659 (5),
1616 (4), 1580 (32), 1381 (13), 1287 (32), 1190 (5), 1111 (39), 1019
I
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24.33%. BAM drophammer: 3 J; friction tester: 28 N; ESD: 0.30 J (at
grain size 100−500 μm).
DSC (5 °C min−1, °C): 181 °C (dec.). IR (KBr, cm−1): v = 3414
̃
(s), 3272 (s), 3240 (s), 3176 (s), 2763 (w), 2643 (w), 2426 (w), 2295
(w), 2223 (w), 2147 (w), 2064 (w), 1766 (w), 1663 (s), 1590 (m),
1526 (m), 1487 (s), 1384 (vs), 1280 (s), 1221 (s), 1114 (s), 1044
(m), 1030 (m), 935 (m), 827 (w), 813 (w), 780 (m), 745 (w), 696
(m), 638 (w), 584 (w), 527 (m). EA (C2H14N12O12Zn, 463.60) calcd:
C 5.18, H 3.04, N 36.26%; found: C 5.48, H 2.83, N 36.09%. BAM
drophammer: 5 J; friction tester: 120 N; ESD: 0.50 J (at grain size
100−500 μm).
Bis(3-amino-1-nitroguanidine)silver(I) Perchlorate (7). 3-
Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in 20 mL
of boiling water. Silver(I) perchlorate (0.877 g, 4.23 mmol) is added
and the mixture is boiled until a clear solution results. The clear
solution is filtered and slowly cooled to room temperature. A fine gray
precipitate, which forms upon standing of the solution after several
hours, is removed by filtration, whereafter light yellow fascicular
crystals began to grow. Slow evaporation of the solvent affords 6 in
22% yield (407 mg, 0.91 mmol).
Bis(3-amino-1-nitroguanidine) Silver(I) Nitrate (12). 3-Amino-
1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in 20 mL of boiling
water. Silver(I) nitrate (0.719 g, 4.23 mmol) is added and the mixture
is boiled until a clear solution results. The clear solution is filtered and
slowly cooled to room temperature. After 15 min, the product starts to
crystallize as colorless blocks, which turn gray after several hours if not
isolated and dried. Yield: 26% (448 mg, 1.10 mmol).
DSC (5 °C min−1, °C): 148 °C (dec.). IR (KBr, cm−1): v = 3400
̃
(s), 3305 (s), 3228 (s), 1656 (s), 1623 (s), 1583 (m), 1504 (m), 1460
(m), 1401 (m), 1291 (s), 1203 (m), 1095 (vs), 1023 (m), 1001 (m),
923 (m), 801 (w), 774 (w), 704 (w), 624 (m), 584 (m), 485 (w). EA
(C2H10ClN10O8Ag, 445.48) calcd: C 5.39, H 2.26, N 31.44%; found: C
5.68, H 2.94, N 31.31%. BAM drophammer: <1 J; friction tester: <5
N; ESD: 0.01 J (at grain size 100−500 μm).
DSC (5 °C min−1, °C): 142 °C (dec.). IR (KBr, cm−1): v = 3432
̃
(s), 3401 (s), 3313 (s), 3219 (s), 3104 (m), 3010 (m), 2923 (m),
1665 (s), 1618 (s), 1580 (m), 1522 (m), 1473 (s), 1382 (s), 1355
(vs), 1292 (vs), 1245 (s), 1179 (s), 1108 (m), 1028 (m), 960 (m), 919
(m), 831 (w), 820 (w), 795 (w), 776 (w), 735 (w), 696 (m), 600 (m),
578 (m), 540 (m), 482 (w); EA (C2H10N11O7Ag, 408.04) calcd: C
5.89, H 2.47, N 37.76%; found: C 6.25, H 2.28, N 37.30%. BAM
drophammer: 1 J; friction tester: <5 N; ESD: 0.01 J (at grain size <100
μm).
Bis(3-amino-1-nitroguanidine)diaquacobalt(II) Nitrate (8). 3-
Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in 20 mL of
boiling water. Cobalt(II) perchlorate hexahydrate (1.231 g, 4.23
mmol) is added and the mixture is boiled until a clear solution results.
The clear solution is filtered and slowly cooled down to room
temperature. 7 starts to crystallize in red blocklike crystals after 30 min.
Yield: 47% (910 mg, 1.99 mmol).
DSC (5 °C min−1, °C): 139 °C (dec.). IR (KBr, cm−1): v = 3409
Bis(3-amino-1-nitroguanidine)diaquacobalt(II) Dinitramide
Dihydrate (13). 3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is
dissolved in 15 mL of boiling water. Cobalt(II) perchlorate
hexahydrate (1.55 g, 4.23 mmol) is added and the mixture is boiled
until a clear solution results. Ammonium dinitramide (1.05 g, 8.46
mmol) is added to the solution and dissolved. The resulting solution is
allowed to slowly cool to room temperature. The product crystallizes
in flat orange prisms in 46% yield (1.13 g, 1.94 mmol).
̃
(s), 3329 (m), 3273 (s), 3237 (m), 3196 (m), 1666 (s), 1638 (m),
1588 (m), 1524 (s), 1486 (s), 1384 (vs), 1340 (s), 1315 (m), 1275
(s), 1219 (s), 1111 (s), 1044 (m), 1028 (m), 937 (m), 825 (w), 814
(w), 780 (m), 694 (m), 647 (w), 616 (w), 597 (w), 523 (m). EA
(C2H14N12O12Co, 457.14) calcd: C 5.25, H 3.09, N 36.77%; found: C
5.59, H 2.94, N 36.51%. BAM drophammer: 7 J; friction tester: 240 N;
ESD: 0.50 J (at grain size 500−1000 μm).
DSC (5 °C min−1, °C): 118 °C (dec.); IR (KBr, cm−1): v = 3597
̃
Bis(3-amino-1-nitroguanidine)diaquanickel(II) Nitrate (9). 3-
Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in 20 mL of
boiling water. Nickel(II) nitrate hexahydrate (1.230 g, 4.23 mmol) is
added and the mixture is boiled until a clear solution results. The clear
solution is filtered and slowly cooled to room temperature. After a few
minutes, the product starts to crystallize as light purple plates. Yield:
49% (950 mg, 2.08 mmol).
(m), 3406 (s), 3302 (s), 3244 (s), 1658 (s), 1630 (m), 1612 (m),
1529 (s), 1512 (s), 1454 (s), 1434 (s), 1390 (m), 1344 (m), 1281 (s),
1204 (vs), 1178 (s), 1123 (m), 1099 (s), 1031 (s), 952 (m), 936 (m),
827 (w), 808 (w), 778 (w), 761 (w), 732 (m), 688 (w), 640 (w), 594
(w), 507 (m); EA (C2H18N16O16Co, 581.20) calcd: C 4.13, H 3.12, N
38.56%; found: C 4.65, H 2.78, N 38.68%. BAM drophammer: 5 J;
friction tester: 80 N; ESD: 0.70 J (at grain size 100−500 μm).
Bis(3-amino-1-nitroguanidine)diaquanickel(II) Dinitramide
Dihydrate (14). 3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is
dissolved in 15 mL of boiling water. Nickel(II) perchlorate
hexahydrate (1.55 g, 4.23 mmol) is added and the mixture is boiled
until a clear solution results. Ammonium dinitramide (1.05 g, 8.46
mmol) is added to the solution and dissolved. The resulting solution is
allowed to slowly cool to room temperature. The product crystallizes
in light purple plates in 36% yield (0.888 g, 1.53 mmol).
DSC (5 °C min−1, °C): 186 °C (dec.); IR (KBr, cm−1): v = 3412
̃
(s), 3274 (s), 2637 (w), 2417 (w), 2296 (w), 2225 (w), 2142 (w),
2060 (w), 1972 (w), 1766 (m), 1662 (s), 1635 (s), 1522 (m), 1489
(s), 1385 (vs), 1278 (s), 1220 (s), 1111 (s), 1031 (m), 938 (m), 825
(w), 817 (w), 776 (m), 688 (m), 647 (w), 598 (w), 532 (m). EA
(C2H14N12O12Ni, 456.90) calcd: C 5.26, H 3.09, N 36.79%; found: C
5.57, H 2.94, N 36.07%. BAM drophammer: 4 J; friction tester: 120 N;
ESD: 0.08 J (at grain size 500−1000 μm).
DSC (5 °C min−1, °C): 142 °C (dec.). IR (KBr, cm−1): v = 3405
Bis(3-amino-1-nitroguanidine)dinitratocopper(II) (10). 3-
Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in 20 mL
of boiling water. Copper(II) nitrate trihydrate (1.022 g, 4.23 mmol) is
added and the mixture is boiled until a clear solution results. The clear
solution is filtered and slowly cooled to room temperature. After 1 h,
the product starts to crystallize as deep blue, blocklike crystals. Yield:
15% (274 mg, 0.64 mmol).
̃
(s), 3302 (s), 3243 (s), 1658 (s), 1612 (m), 1539 (s), 1512 (s), 1454
(s), 1434 (s), 1388 (m), 1344 (m), 1283 (s), 1205 (vs), 1178 (s),
1122 (m), 1099 (s), 1022 (s), 952 (w), 936 (m), 827 (w), 808 (w),
778 (w), 761 (m), 749 (w), 732 (m), 688 (m), 640 (w), 593 (w), 509
(m); EA (C2H18N16O16Ni, 580.96): calcd C 4.13, H 3.12, N 38.58%;
found: C 4.57, H 2.99, N 38.09%. BAM drophammer: 3 J; friction
tester: 80 N; ESD: 0.60 J (at grain size 100−500 μm).
DSC (5 °C min−1, °C): 77 °C (dec.). IR (KBr, cm−1):∼;v = 3439
(m), 3412 (m), 3280 (m), 3126 (m), 1665 (s), 1629 (m), 1500 (m),
1382 (vs), 1281 (s), 1212 (s), 1141 (m), 1111 (m), 1045 (w), 943
(w), 820 (w), 773 (w), 724 (w), 705 (w), 653 (w), 603 (w), 565 (w),
480 (w). EA (C2H10N12O10Cu, 425.72) calcd: C 5.64, H 2.37, N
39.48%; found: C 6.00, H 2.24, N 37.98%. BAM drophammer: <1 J;
friction tester: <5 N; ESD: 0.50 J (at grain size 100−500 μm).
Bis(3-amino-1-nitroguanidine)diaquazinc(II) Nitrate (11). 3-
Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in 20 mL of
boiling water. Zinc(II) nitrate hexahydrate (1.258 g, 4.23 mmol) is
added and the mixture is boiled until a clear solution results. The clear
solution is filtered and slowly cooled to room temperature. Slow
evaporation of the solvent affords 10 as colorless crystals. Yield: 25%
(492 mg, 1.06 mmol).
3-Amino-1-nitroguanidinedinitramidosilver(I) Hydrate (15).
Ten milli,oles of silver dinitramide acetonitrile adduct was prepared
according to the literature.20 1-Amino-3-nitroguanidinium chloride19
(1.00 g, 6.4 mmol) was dissolved in 10 mL of boiling water. After the
solution was cooled to about 60 °C, the silver dinitramide acetonitrile
adduct, dissolved in 5 mL of acetonitrile, was added to the solution.
After which the mixture was stirred under the exclusion of light at 35
°C for a further 2 h. The mixture was filtrated and 15 crystallizes from
the clear filtrate in colorless needles. Yield: 0.61 g (2.50 mmol, 39%).
DSC (5 °C min−1, °C): 71 °C (dehydr.), 108 °C (dec.). IR (KBr,
cm−1): ν
̃
= 3398 (m), 3304 (m), 3218 (m), 1671 (m), 1622 (m), 1580
(m), 1539 (s), 1431 (s), 1344 (m), 1297 (s), 1205 (vs), 1176 (vs),
1108 (w), 1031 (s), 951 (w), 827 (w), 761 (w), 732 (w), 706 (w), 594
J
dx.doi.org/10.1021/ic402038x | Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(w), 484 (w), 470 (w). 1H NMR (DMSO-d6, 25 °C, ppm) δ: 9.31 (s,
1H, NH), 8.19 (s, 1H, C−NHAHB), 7.69 (s, 1H, C−NHAHB), 4.76 (s,
2H, N−NH2), 3.36 (s, 2H, H2O). 13C NMR (DMSO-d6, 25 °C, ppm)
δ: 160.9 (C(NNO2)(N2H4)(NH2)). 14N NMR (DMSO-d6, 25 °C,
ppm) δ: −11.0 (NO2), −14.5 (NNO2). m/z (FAB+): 120.1
[C(NNO2)(N2H3)(NH2)+H+], 107.0 [Ag+]; m/z (FAB−): 106.0
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: tmk@cup.uni-muenchen.de. Fax: + 49 89 2180 77492.
Notes
−
The authors declare no competing financial interest.
[N(NO2)2 ]; EA (AgCH7N8O7, 244.12) calcd: C 3.42, H 2.01, N
31.93%; found: C 3.31, H 1.80, N 31.61%; BAM drophammer: 2 J;
friction tester: 7 N; ESD: 0.10 J.
ACKNOWLEDGMENTS
■
Bis(3-amino-1-nitroguanidine)dichlorocobalt(II) Dihydrate
(16). 3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in
15 mL of boiling water. Cobalt(II) chloride hexahydrate (1.006 g, 4.23
mmol) is added and the mixture is boiled until a clear solution results.
The solution is allowed to slowly cool to room temperature. The
product starts to crystallize in red blocklike crystals in 32% yield (0.555
g, 1.37 mmol).
Financial support of this work by the Ludwig-Maximilian
University of Munich (LMU), the European Research Office
(ERO) of the U.S. Army Research Laboratory (ARL), the
Armament Research, Development and Engineering Center
(ARDEC) and the Strategic Environmental Research and
Development Program (SERDP) under Contract W911NF-09-
2-0018 (ARL), W911NF-09-1-0120 (ARDEC), W011NF-09-1-
0056 (ARDEC), and 10 WPSEED01-002/WP-1765 (SERDP)
is gratefully acknowledged. The authors acknowledge collabo-
rations with Dr. Mila Krupka (OZM Research, Czech
Republic) in the development of new testing and evaluation
methods for energetic materials and with Dr. Muhamed
Sucesca (Brodarski Institute, Croatia) in the development of
new computational codes to predict the detonation and
propulsion parameters of novel explosives. We are indebted
to and thank Drs. Betsy M. Rice and Brad Forch (ARL,
Aberdeen, Proving Ground, MD) and Mr. Gary Chen
(ARDEC, Picatinny Arsenal, NJ) for many helpful and inspired
discussions and support of our work. The authors thank Mr.
Stefan Huber for the sensitivity measurements.
DSC (5 °C min−1, °C): 186 °C (dec.). IR (KBr, cm−1): v ≅ 3457
̃
(s), 3393 (vs), 3295 (s), 3245 (s), 3029 (m), 2963 (m), 1667 (s),
1626 (s), 1577 (m), 1521 (m), 1491 (s), 1430 (m), 1384 (m), 1277
(vs), 1217 (s), 1106 (s), 1015 (w), 931 (m), 777 (w), 748 (w), 705
(m), 594 (m). EA (C2H14Cl2N10O6Co, 404.04) calcd: C 5.95, H 3.49,
N 34.67%; found: C 5.93, H 3.47, N 34.42%. BAM drophammer: 10 J;
friction tester: 360 N; ESD: 0.70 J (at grain size 100−500 μm).
Bis(3-amino-1-nitroguanidine)dichloronickel(II) Dihydrate
(17). 3-Amino-1-nitroguanidine (0.50 g, 4.23 mmol) is dissolved in
15 mL of boiling water. Nickel(II) chloride hexahydrate (1.005 g, 4.23
mmol) is added and the mixture is boiled until a clear solution results.
The solution is allowed to slowly cool to room temperature. The
product starts to crystallize in light blue blocklike crystals in 42% yield
(0.722 g, 1.79 mmol).
DSC (5 °C min−1, °C): 250 °C (dec.). IR (KBr, cm−1): v = 3378
̃
(s), 3303 (s), 3245 (s), 2963 (m), 2923 (m), 2549 (m), 2457 (m),
1687 (vs), 1626 (m), 1519 (w), 1494 (m), 1432 (w), 1379 (m), 1277
(m), 1217 (m), 1196 (m), 1120 (m), 1094 (m), 1037 (m), 975 (m),
935 (m), 775 (w), 746 (w), 728 (w), 705 (w), 562 (m), 537 (m). EA
(C2H14Cl2N10O6Ni, 403.80) calcd: C 5.95, H 3.49, N 34.69%; found:
C 6.04, H 3.28, N 34.91%. BAM drophammer: 10 J; friction tester:
360 N; ESD: 0.70 J (at grain size <100 μm).
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available free of charge via the Internet at http://pubs.acs.org.
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