Preparation, crystal structure, and thermal decomposition of the energetic compound [Co(IMI)4(PA)](PA) (IMI = imidazole and PA = picrate)

Article abstract of DOI:10.1002/zaac.201200295

The novel multi-ligand coordination compound [Co(IMI)₄(PA)](PA) (1) was synthesized by using imidazole (IMI) and picrate (PA) and characterized by elemental analysis and FT-IR spectroscopy. The crystal structure was determined by X-ray single crystal diffraction and the crystallographic data showed that the compound crystallizes in the triclinic space group P1 (α = 8.839(2) A, b = 13.550(3) A, c = 13.840(3) A, α = 68.386(6)°, β = 88.349(9)°, and γ = 87.494(9)°). Furthermore, the Co^II ion is six-coordinated by four nitrogen atoms from four imidazole ligands and two oxygen atoms from a PA group. Its thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG) analysis. The kinetic parameters of the first exothermic process were studied by using Kissinger's and Ozawa's method, respectively. The energy of combustion and the enthalpy of formation were measured and calculated. They showed good combustion performance of the compound. Additionally, the sensitivity properties were determined with standard methods. The results of all these studies showed that [Co(IMI)₄(PA)](PA) has potential application as ignition composition. Copyright

Full text of DOI:10.1002/zaac.201200295

Job/Unit: Z12295
/KAP1
Date: 05-09-12 17:34:23
Pages: 7
ARTICLE
DOI: 10.1002/zaac.201200295
Preparation, Crystal Structure, and Thermal Decomposition of the Energetic
Compound [Co(IMI)4(PA)](PA) (IMI = Imidazole and PA = Picrate)
Bi-Dong Wu,[a] Tong-Lai Zhang,*[a] Li Yang,[a] Jian-Guo Zhang,[a] and Zun-Ning Zhou[a]
Keywords: Cobalt; Imidazole; Crystal structure; Thermal decomposition; Sensitivity
Abstract. The novel multi-ligand coordination compound
[Co(IMI)4(PA)](PA) (1) was synthesized by using imidazole (IMI) and
picrate (PA) and characterized by elemental analysis and FT-IR spec-
mined based on differential scanning calorimetry (DSC) and thermo-
gravimetry-derivative thermogravimetry (TG-DTG) analysis. The ki-
netic parameters of the first exothermic process were studied by using
troscopy. The crystal structure was determined by X-ray single crystal Kissinger’s and Ozawa’s method, respectively. The energy of combus-
diffraction and the crystallographic data showed that the compound tion and the enthalpy of formation were measured and calculated. They
¯
crystallizes in the triclinic space group P1 (α = 8.839(2) Å, b =
showed good combustion performance of the compound. Additionally,
the sensitivity properties were determined with standard methods. The
results of all these studies showed that [Co(IMI)4(PA)](PA) has poten-
13.550(3) Å, c = 13.840(3) Å, α = 68.386(6)°, β = 88.349(9)°, and γ
= 87.494(9)°). Furthermore, the CoII ion is six-coordinated by four
nitrogen atoms from four imidazole ligands and two oxygen atoms tial application as ignition composition.
from a PA group. Its thermal decomposition mechanism was deter-
and, therefore, studies of the coordination properties of this
molecule and its derivatives are of interest.
In previous studies,[45,46] the nitrogen-rich materials
Introduction
Nitrogen-rich energetic compounds are among the most re-
cent and exiting area in the development of modern high en- Cu(IMI)4(N3)2, Ni(IMI)4(N3)2, [Ni(IMI)6](ClO4)2, [Ni(IMI)6]-
ergy density materials (HEDMs) with higher performance and (NO3)2, and [Cu(IMI)4](PA)2 with nitrogen contents of
environmental compatibility.[1,2] This is mostly derived from 46.70%, 47.27%, 25.23%, 33.17%, and 24.74% were re-
their high positive heats of formation from the large number ported. They have potential application as energetic materials
of inherently energetic N–N (160 kJ·mol–1), N=N (418 kJ·mol–1), in the near future. Especially, Ni(IMI)4(N3)2 has a combustion
and C–N bonds. Klapötke and other chemists have done lots heat, which is higher than that of TNT (2,4,6-trinitrotoluene),
of studies about nitrogen-rich energetic compounds on the ba- RDX (1,3,5-trinitro-1,3,5-triaza-cyclohexane), and HMX
sis of imidazoles, triazoles, tetrazoles, tetrazines, and their de- (1,3,5,7-tetranitro-1,3,5,7-tetraazocane), and it is regarded as
rivatives.[3–31]
an energy additive, which can improve the explosion perform-
Imidazoles (IMI) are nitrogen-rich compounds, covering a ance of the traditional explosives and propellant formulations.
wide range of their derivatives, 2-azidoimidazole,[32] imid- In order to deepen the studies on the imidazole compounds,
azole-4-acetic acid,[33,34] nitroimidazole,[35–41] trinitroimida- [Co(IMI)4(PA)](PA) was synthesized and its crystal structure,
zole,[42–44] and so on. Imidazoles are pentacyclic heterocyclic the thermal decomposition mechanism, and sensitivity proper-
compounds containing two nitrogen atoms and three carbon ties were studied in the presented work.
atoms with relatively small volume, which may reduce steric
hindrance. The advantages of imidazoles include high-nitrogen
content, ready availability, high positive heat of formation, and
Results and Discussion
good thermal stability. What is particularly important, the de-
composition of imidazole results in the generation of large vol-
umes of environmentally friendly nitrogen, which makes them
promising candidates for applications requiring environmen-
tally friendly highly energetic materials. The role of the imid-
azole ring as metal-binding site in compounds is well-known,
Crystal Structure Description
The highest occupied molecular orbitals (HOMOs) and low-
est unoccupied molecular orbitals (LUMOs) of the IMI group
were exploited in our previous study[45] and they again are
shown in Figure 1, the electronic density of the HOMO at N(1)
atom of the imidazole group is relatively higher. This enables
a better understanding of the coordination bond formation be-
tween the nitrogen atom and the CoII ion because of the unoc-
cupied 3d orbitals of the metal ion.
* Prof. Dr. T.-L. Zhang
Fax: +86-10-68911202
E-Mail: ztlbit@bit.edu.cn
[a] State Key Laboratory of Explosion Science and Technology
Beijing Institute of Technology
Beijing 100081, P. R. China
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

Job/Unit: Z12295
/KAP1
Date: 05-09-12 17:34:23
Pages: 7
T.-L. Zhang et al.
ARTICLE
Figure 1. HOMO (left) and LUMO (right) of the imidazole group.[44]
¯
Compound 1 crystallizes in the triclinic space group P1 with
a cell volume of 1539.4(7) Å3 and only two molecular moieties
Figure 2. Molecular structures of [Co(IMI)4(PA)](PA) (1), thermal el-
lipsoids drawn at 30% probability level.
in the unit cell (Table 1). In 1 (Figure 2), there are one co-
Table 1. Crystal data and structure refinement for [Co(IMI)4(PA)](PA)
(1).
[Co(IMI)4(PA)](PA) (1)
Empirical formula
Formula mass
CoC24H20N14O14
787.47
Temperature /K
153(2)
Crystal shape
prismatic
Crystal dimensions /mm
Crystal system
Space group
Z
0.56ϫ0.18ϫ0.07
triclinic
P1
¯
2
a /Å
b /Å
c /Å
α /°
β /°
γ /°
8.839(2)
13.550(3)
13.840(3)
68.386(6)
88.349(9)
87.494(9)
–11 to 11, –17 to 18, –18 to
18
1539.4(7)
1.699
0.653
Figure 3. Octahedral coordination structure of cobalt and its coplanar
structure.
h, k, l
balt(II) cation, four imidazole molecules, and two PA groups.
The six basically equivalent Co–N and Co–O bonds are ap-
proximately equal (2.1 nm) (see Table 2). The bond angle of
the two nitrogen atoms from two contra-positioned imidazole
ligands and the CoII cation, N1–Co1–N5, is 172.54(7)°. The
bond angles of the nitrogen atoms of imidazole group and the
contra-positioned oxygen atoms of the PA group and the CoII
Unit cell dimensions V /Å3
Dc /g·cm–3
μ (Mo-Kα) /mm–1
F(000)
802
θ Range /°
2.77–29.13
0.9557, 0.7103
17089
8059 (Rint = 0.0332)
0.0483, 0.1020
0.0775, 0.1118
1.002
Max. and min. transmission
Measured reflections
Unique data
cation are 172.41(7)° and 169.87(6)° (N3–Co1–O2
=
R1, wR2 [I Ͼ 2σ(I)]a)b)
R1, wR2 (all data)a)b)
Goodness of fit
172.41(7)° and O1–Co1–N7 = 169.87(6)°). In addition, the
bond angles of the nitrogen (or oxygen) atom from two border
ligands and the CoII cation are all close to 90°. Therefore, all
of the above data demonstrates that the CoII cation exhibits a
distorted octahedral configuration (Figure 3).
δpmax, δpmin /e·Å–3
0.570, –0.536
a) wR2 = [∑w(Fo –Fc ) /∑w(Fo )]1/2, P = (Fo + 2Fc )/3. b) w =
2
2 2
2
2
2
2
1/[σ2(Fo )+(0.0510P)2+0.1600P].
Table 2. Selected bond lengths /Å and bond angles /° for [Co(IMI)4(PA)](PA) (1).
Bond
Bond
Bond
Co1–N1
Co1–N3
2.111(2)
2.0931(18)
Co1–N5
Co1–N7
2.1321(19)
2.125(2)
Co1–O1
Co1–O2
2.1068(16)
2.1896(16)
Angle
Angle
Angle
N1–Co1–N5
N3–Co1–O2
O1–Co1–N7
N1–Co1–O(2)
N1–Co1–N(7)
172.54(7)
172.41(7)
169.87(6)
84.32(7)
90.17(8)
N(3)–Co1–O1
N(3)–Co1–N1
N(3)–Co1–N(7)
N(3)–Co1–N(5)
O1–Co1–N1
93.93(7)
93.59(7)
95.19(7)
93.81(7)
93.65(7)
O1–Co1–N(5)
N(5)–Co1–O(2)
N(7)–Co1–O(2)
N(7)–Co1–N(5)
O1–Co1–O(2)
86.73(7)
88.45(7)
92.12(7)
88.27(8)
78.95(6)
2
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z12295
/KAP1
Date: 05-09-12 17:34:23
Pages: 7
The Energetic Compound [Co(IMI)4(PA)](PA)
In compound 1, the plane A (Co1–N1–N2–N5–N6) is
formed by two contra-positioned imidazole rings and the co-
balt(II) cation with a plane equation of –3.059x + 7.417y +
12.380z = 4.2935 (R = 0.0274). Furthermore, a second plane
B with the benzene ring is made up; the plane equation is
7.071x–7.198y–0.025z = 1.7719 (R = 0.0300). The angle be-
tween plane A and B is 116.6° (see Figure 3)
From the packing diagram it can be seen that all of these
intermolecular hydrogen bonds extend the structure into a 3D
supermolecular structure, which makes an important contri-
bution to enhance the thermal stability of the compound (Fig-
ure 4).
Figure 6. TG-DTG curve in a nitrogen atmosphere with a heating rate
of 5 K·min–1.
In compound 1, the melting point with an endothermic pro-
cess was observed in the temperature range of 450–510 K and
the peak temperature in the DSC curve was at 480 K. The TG-
DTG curves showed that in the first stage a mass loss of
14.6% occurred in this temperature range, which reached the
largest rate at 462 K with a mass loss percentage of 2.8%·min–1.
Afterwards, two successive exothermic processes appeared in
the temperature range from 580 K to 850 K with peak tempera-
tures of 627 K and 727 K, respectively. Corresponding to the
exothermic processes, the TG-DTG curves showed two con-
secutive mass losses stages in a tardigrade process and the
mass loss is 74.7%, where the largest mass loss percentage
was 7.2%·min–1 at 603 K. The mass of the final residue was
10.7%, which is coincident with the calculated value of Co3O4
(10.19%). The absorption band in the FT-IR spectrum of the
residue at 850 K proved that the final residue is Co3O4.
Figure 4. Packing of the unit cells view along the a axis.
Non-Isothermal Kinetics Analysis
Thermal Decomposition Mechanism
[47]
In the presented work, Kissinger’s method
method
and Ozawa’s
In order to investigate the thermal behavior of 1, the DSC
and TG curves with the linear heating rate of 5 K·min–1 in a
nitrogen gas flow at the rate of 20 mL·min–1 are shown in
Figure 5 and Figure 6, respectively.
[48]
are widely used to determine the apparent acti-
vation energy (Ea) and the pre-exponential factor (A). The
Kissinger Equation (1) and Ozawa equation (Equation 2) are
as follows, respectively:
2
ln β / Tp = ln [RA / Ea ] – Ea / RTp
(1)
lg β = lg [AEa / RG(α)] – 2.315 – 0.4567Ea / RTp
(2)
Tp is the peak temperature (in K), A is the pre-exponential
factor (s–1), Ea is the apparent activation energy (kJ·mol–1) R
is the gas constant (8.314 J·K–1·mol–1), β is the linear heating
rate (K·min–1), and G(α) is reaction mechanism function.
Based on the first exothermic peak temperatures measured
with four different heating rates of 5, 10, 15, and 20 K·min–1,
Kissinger’s method and Ozawa’s method were applied to study
the kinetic parameters of the title compound. From the original
data, the apparent activation energy Ek and Eo, pre-exponential
factor Ak, and linear coefficients Rk and Ro were determined and
showed in Table 3. Accordingly, the Arrhenius Equation of 1 can
be expressed as follows (E is the average of Ek and Eo):
Figure 5. DSC curve in a nitrogen atmosphere with a heating rate of
5 K·min–1.
lnk = 3.759–76.27ϫ103/(RT)
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
3

Job/Unit: Z12295
/KAP1
Date: 05-09-12 17:34:23
Pages: 7
T.-L. Zhang et al.
ARTICLE
Table 3. Peak temperatures of the first exotherm at different heating poles and was hit by a 5.0 kg drop hammer at 25 cm height.
rates and chemical kinetics parameters.
The test result showed that the firing rate was 0%.
Friction sensitivity was determined on a MGY-1 pendular
friction sensitivity apparatus by a standard procedure using
20 mg of the sample. Compound 1 was compressed between
two steel poles with mirror surfaces at the pressure of
1.96 MPa, and was hit horizontally with a 1.5 kg hammer from
90° angle, the firing rate was 0%.
[Co(IMI)4(PA)](PA) (1)
Peak temperatures Tp /K
Heating rates β /K·min–1
5
594.45
618.85
631.05
649.05
10
15
20
Flame sensitivity was determined by a standard method, in
which the sample was ignited by standard black powder pellet.
Compound 1 (20 mg) was pressed into a copper cap under a
pressure of 58.8 Mpa and was ignited by a standard black pow-
der pellet. The test result showed that the 50% firing height
(h50) was 13 cm.
Kissinger’s method
Ek /kJ·mol–1
73.16
3.759
ln(Ak/s–1)
Linear correlation coefficient (Rk) –0.992
Standard deviation
Ozawa’s method
Eo /kJ·mol–1
0.0815
Therefore, the compound had higher flame sensitivity.
79.38
Linear correlation coefficient (Ro) –0.994
Standard deviation 0.03499
Conclusions
The novel environmental friendly cobalt(II) imidazole ener-
getic compound, [Co(IMI)4(PA)](PA) (1), was synthesized and
characterized. The crystal structure analysis showed that the
CoII ion is six-coordinated in a slightly distorted octahedral
arrangement with four imidazole molecules and the PA group.
Surprisingly, the PA group is able to coordinate with the metal
ion through the oxygen atoms. In 1, thermal analysis indicated
that one endothermic process occurred between 450 K and
510 K and two main exothermic processes occurred in the tem-
perature range from 580 K to 850 K as shown in the DSC
curve corresponding to TG-DTG curves. The results of the
non-isothermal kinetic analysis indicated that the Arrhenius
Equation of 1 can be expressed as follows: lnk = 3.759–
76.27ϫ103/(RT). The experiment found the energy of
combustion and the enthalpy of formation of 1 were
–14.39 MJ·kg–1 and +12896 kJ·mol–1 (+16.38 MJ·kg–1),
respectively. More importantly, compound 1 was regarded as
the less toxic energy additive that can be applied to improve
the explosion performance of the traditional explosives and
propellant formulations. The results of the studies showed that
[Co(IMI)4(PA)](PA) has potential application as ignition com-
position in the near future.
Energy of Combustion and Enthalpy of Formation
In order to study the energy of combustion and the enthalpy
of formation of 1, the constant volume energy of combustion
(Qv) was measured by oxygen bomb calorimetry and was de-
termined to have a value of –14.36 MJ·kg–1.
The bomb equation is as follows:
32
3
1
CoC24H20N14O14
+
O2 Ǟ Co3O4 + 10H2O + 12CO2 + 7N2
(3)
3
And the energy of combustion is as follows (T = 298.15 K):
ΔH = Qp = Qv + ΔnRT = –11329 kJ·mol–1 = –14.39 MJ·kg–1
(4)
It was reported in the literature[49] that the energies of com-
bustion of RDX, HMX, and TNT were –9.60 MJ·kg–1, –9.44
to –9.88 MJ·kg–1, and –15.22 MJ·kg–1, respectively. Conse-
quently, the energy of combustion of 1 was equal to that of
TNT.
The metal coordination compound should have relatively
thermodynamically stable structures. The standard enthalpies
of formation was back calculated from the energy of combus-
tion on the basis of Equation (3), and Hess’s Law as applied
in thermochemical Equation (5). With the known enthalpies of
formation of cobalt(II,III) oxide [ΔfH°298(Co3O4,s)
=
=
–891.0 kJ·mol–1], carbon dioxide [ΔfH°298(CO2,g)
Experimental Section
+393.5 kJ·mol–1] and water [ΔfH°298(H2O,l) = –285.8 kJ·mol–1],
the enthalpy of formation of 1 can now be calculated as:
General Caution: The title compound is energetic material and tends
to explode under certain conditions. Appropriate safety precautions
(safety glasses, face shields, leather coat and ear plugs) should be
taken, especially when the compound is prepared on a large scale and
in dry state.
ΔfH°(1,s) =1/3ΔfH°(Co3O4,s)+10ΔfH°(H2O,l)+12ΔfH°(CO2, g)–ΔcH°(s)
(5)
ΔfH°298(1,s) = +12896 kJ·mol–1 = +16.38 MJ·kg–1.
Materials and Physical Techniques: All the reagents and solvents
were of analytical grade and used without further purification as com-
mercially obtained.
Sensitivity Tests
On the basis of the China National Military Standard, the
impact and friction sensitivities as well as the flame sensitivity
were determined.[50]
Elemental analyse was performed on a Flash EA 1112 full automatic
trace element analyzer. The FT-IR spectra was recorded with a Bruker
Equinox 55 infrared spectrometer (KBr pellets) in the range of 4000–
400 cm–1 with a resolution of 4 cm–1. DSC and TG measurements were
Impact sensitivity was determined using a Fall Hammer Ap-
paratus. Compound 1 (50 mg) was placed between two steel carried out with a Pyris-1 differential scanning calorimeter and Pyris-
4
www.zaac.wiley-vch.de © 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z12295
/KAP1
Date: 05-09-12 17:34:23
Pages: 7
The Energetic Compound [Co(IMI)4(PA)](PA)
[12] T. M. Klapötke, B. Krumm, R. Moll, Z. Anorg. Allg. Chem. 2011,
637, 507.
[13] N. Fischer, T. M. Klapötke, J. Stierstorfer, Eur. J. Inorg. Chem.
Eur. J. Inorg. Chem 2011, 4471.
1 thermogravimetric analyzer (Perkin-Elmer, USA) in a dry nitrogen
atmosphere with flowing rate of 20 mL·min–1. The combustion heat
was measured by oxygen bomb calorimetry (Parr 6200, USA).
[14] N. Fischer, T. M. Klapötke, J. Stierstorfer, Z. Anorg. Allg. Chem.
2011, 637, 1273.
[15] N. Fischer, T. M. Klapötke, K. Peters, M. Rusan, J. Stierstorfer,
Z. Anorg. Allg. Chem. 2011, 637, 1693.
[16] T. Fendt, N. Fischer, T. M. Klapötke, J. Stierstorfer, Inorg. Chem.
2011, 50, 1447.
[17] J. Evers, M. Goebel, B. Krumm, F. Martin, S. Medvedyev, G.
Oehlinger, F. X. Steemann, I. Troyan, T. M. Klapötke, M. I. Ere-
mets, J. Am. Chem. Soc. 2011, 133, 12100.
[18] A. A. Dippold, T. M. Klapötke, Z. Anorg. Allg. Chem. 2011, 637,
1453.
Synthesis of [Co(IMI)4(PA)](PA) (1): The synthesis of 1 was as fol-
lows: Co(NO3)2·6H2O (10 mmol) was dissolved in distilled water
(30 mL), and charged into a glass reactor with a water bath. It was
kept under mechanical stirring and heated to the temperature of 60–
70 °C. Imidazole (40 mmol) and picric acid (20 mmol) were dissolved
in distilled water (20 mL), respectively, and subsequently they were
added to the CoII aqueous solution during 25–30 min with continuous
stirring. In the end, the solution was cooled to room temperature natu-
rally. FT-IR (KBr): ν˜ = 3315, 1613, 1361, 1067, 787, 656, 611 cm–1.
CoC24H20N14O14 (molar mass: 787.47 g·mol–1): calcd. C 36.61 N
24.90 H 2.56%; found C 36.60 N 24.91 H 2.54%.
[19] A. Dippold, T. M. Klapötke, F. A. Martin, Z. Anorg. Allg. Chem.
2011, 637, 1181.
[20] Y. C. Li, C. Qi, S. H. Li, H. J. Zhang, C. H. Sun, Y. Z. Yu, S. P.
Pang, J. Am. Chem. Soc. 2010, 132, 12172.
[21] N. Fischer, K. Karaghiosoff, T. M. Klapötke, J. Stierstorfer, Z.
Anorg. Allg. Chem. 2010, 636, 735.
[22] T. M. Klapötke, J. Stierstorfer, B. Weber, Inorg. Chim. Acta 2009,
362, 2311.
[23] T. M. Klapötke, C. Miró Sabaté, J. M. Welch, Heteroat. Chem
2009, 20, 35.
[24] T. M. Klapötke, C. Miró Sabaté, Z. Anorg. Allg. Chem. 2009, 635,
X-ray Data Collection and Structures Refinement: The prism crys-
tal was chosen for X-ray determination. The X-ray diffraction data
collection were performed with a Rigaku AFC-10/Saturn 724+ CCD
detector diffractometer with graphite monochromated Mo-Kα radiation
(λ = 0.71073 Å) with multi-scan mode at the 153(2) K. The structures
were solved by direct methods using SHELXS–97[51] (Sheldrick,
1990) and refined by full-matrix least-squares methods on F2 with
SHELXL-97[52] (Sheldrick, 1997). And all non-hydrogen atoms were
obtained from the difference Fourier map and subjected to anisotropic
refinement by full-matrix least-squares on F2. Detailed information
concerning crystallographic data collection and structures refinement
are summarized in Table 1.
1812.
[25] K. Karaghiosoff, T. M. Klapötke, C. M. Sabaté, Eur. J. Inorg.
Chem. 2009, 238.
[26] Y. Zhang, D. A. Parrish, J. n. M. Shreeve, Chem. Eur. J. 2012, 18,
987.
[27] G. H. Tao, D. A. Parrish, J. n. M. Shreeve, Inorg. Chem. 2012,
51, 5305.
[28] K. Wang, D. A. Parrish, J. n. M. Shreeve, Chem. Eur. J. 2011, 17,
Crystallographic data (excluding structure factors) for the structure in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the de-
pository number CCDC-880778 (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
14485.
[29] V. Thottempudi, J. n. M. Shreeve, J. Am. Chem. Soc. 2011, 133,
19982.
[30] V. Thottempudi, H. Gao, J. n. M. Shreeve, J. Am. Chem. Soc.
2011, 133, 6464.
[31] H. Gao, J. n. M. Shreeve, Chem. Rev. 2011, 111, 7377.
[32] Z. Tang, L. Yang, X. J. Qiao, B. D. Wu, T. L. Zhang, Z. N. Zhou,
K. B. Yu, Chem. Res. Chin. U. 2012, 28, 4.
[33] Y. Amao, K. Aoki, J. Biobased Mater. Bio. 2008, 2, 51.
[34] S. Materazzi, E. Vasca, Thermochim. Acta 2001, 373, 7.
[35] D. Olender, J. Zwawiak, L. Zaprutko, J. Heterocycl. Chem. 2010,
47, 1049.
[36] G. F. Zhang, Y. Wang, M. Y. Cai, D. M. Dai, K. Yan, A. S. Ma,
P. Chen, R. Wang, P. Li, J. H. Yi, F. Q. Zhao, J. Z. Li, X. Z. Fan,
J. Coord. Chem. 2010, 63, 1480.
Acknowledgements
The project were supported by Science and Technology on Applied
Physical Chemistry Laboratory (9140C3703051105); the State Key
Laboratory of Explosion Science and Technology (No. YBKT10–05
and ZDKT10–01b) and Program for New Century Excellent Talents
in University (NCET–10–0051) (CNET–09–0051).
[37] W. Zhang, X. Fan, Z. Liu, J. Li, X. Ren, Acta Chim. Sin. 2009,
67, 420.
References
[38] D. L. Cao, F. D. Ren, J. L. Wang, W. L. Wang, J. Mol. Struct.
2007, 825-846, 53.
[1] J. Giles, Nature 2004, 427, 580.
[2] T. M. Klapötke, G. Holl, Green Chem. 2001, 3, G75.
[3] T. M. Klapötke, F. A. Martin, J. Stierstorfer, Chem. Eur. J. 2012,
18, 1487.
[39] S. G. Cho, Y. G. Cheun, B. S. Park, J. Mol. Struct. 1998, 440-
473, 41.
[40] A. J. Bracuti, J. Chem. Crystallogr. 1998, 28, 367.
[4] N. Fischer, T. M. Klapötke, D. G. Piercey, J. Stierstorfer, Z. [41] A. J. Bracuti, J. Chem. Crystallogr. 1995, 25, 625.
Anorg. Allg. Chem. 2012, 638, 302.
[5] N. Fischer, D. Izsak, T. M. Klapötke, S. Rappenglueck, J. Stier-
storfer, Chem. Eur. J. 2012, 18, 4051.
[42] X. Su, X. Cheng, S. Ge, J. Mol. Struct. 2009, 917-938, 44.
[43] H. Gao, C. Ye, O. D. Gupta, J.-C. Xiao, M. A. Hiskey, B. Twam-
ley, J. n. M. Shreeve, Chem. Eur. J. 2007, 13, 3853.
[6] N. Fischer, E. D. Goddard-Borger, R. Greiner, T. M. Klapötke, [44] J. R. Cho, K. J. Kim, S. G. Cho, J. K. Kim, J. Heterocycl. Chem.
B. W. Skelton, J. Stierstorfer, J. Org. Chem. 2012, 77, 1760. 2002, 39, 141.
[7] M. Schmeisser, P. Keil, J. Stierstorfer, A. Koenig, T. M. Klapötke, [45] B. D. Wu, S. W. Wang, L. Yang, T. L. Zhang, J. G. Zhang, Z. N.
R. van Eldik, Eur. J. Inorg. Chem. 2011, 4862.
[8] T. M. Klapötke, D. G. Piercey, Inorg. Chem. 2011, 50, 2732.
[9] T. M. Klapötke, F. A. Martin, J. Stierstorfer, Angew. Chem. Int.
Ed. 2011, 50, 4227.
Zhou, K. B. Yu, Eur. J. Inorg. Chem. 2011, 2616.
[46] B. D. Wu, S. W. Wang, L. Yang, T. L. Zhang, J. G. Zhang, Z. N.
Zhou, Z. Anorg. Allg. Chem. 2011, 637, 2252.
[47] H. E. Kissinger, Anal. Chem. 1957, 29, 1702.
[10] T. M. Klapötke, D. G. Piercey, J. Stierstorfer, Chem. Eur. J. 2011,
[48] T. Ozawa, Bull. Chem. Soc. Jpn. 1965, 38, 1881.
[49] Z. T. Liu, Y. L. Lao, Initiating Explosive Experimental, Beijing
Institute of Technology, China, 1995, p.238.
17, 13068.
[11] T. M. Klapötke, D. G. Piercey, Inorg. Chem. 2011, 50, 2732.
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
5

Job/Unit: Z12295
/KAP1
Date: 05-09-12 17:34:23
Pages: 7
T.-L. Zhang et al.
ARTICLE
[50] Y. X. Ou, Explosives, Beijing Institute of Technology Press,
China, 2006, p.143.
finement from Diffraction Data, University of Göttingen, Ger-
many, 1997.
[51] G. M. Sheldrick, SHELXS 97, Program for the Solution of Crystal
Structures, University of Göttingen, Germany, 1990.
[52] G. M. Sheldrick, SHELXL 97, Program for Crystal Structure Re-
Received: June 25, 2012
Published Online: ᭿
6
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z12295
/KAP1
Date: 05-09-12 17:34:23
Pages: 7
The Energetic Compound [Co(IMI)4(PA)](PA)
B.-D. Wu, T.-L. Zhang,* L. Yang, J.-G. Zhang, Z.-
N. Zhou .............................................................................. 1–7
Preparation, Crystal Structure, and Thermal Decomposition of
the Energetic Compound [Co(IMI)4(PA)](PA) (IMI = Imid-
azole and PA = Picrate)
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
7