Synthesis and characterization of a novel energetic complex [Cd(DAT) 6](NO3)2 (DAT = 1,5-diamino-tetrazole) with high nitrogen content

Article abstract of DOI:10.1002/zaac.200900502

The novel high nitrogen-containing energetic complex [Cd(DAT) ₆](NO₃)₂was synthesized by reaction of Cd(NO₃)₂·6H₂O with 1,5-diamino-tetrazole (DAT). It was characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction, analysis. The central Cd²⁺ ion is coordinated by six nitrogen atoms from six DAT ligand molecules to form a hexacoordinate distorted octahedral compound. The [Cd(DAT)₆](NO ₃)₂ molecules are linked together through two types of hydrogen bonds thus forming a stable three-dimensional net structure. The thermal decomposition mechanism of [Cd(DAT)₆](NO₃) ₂ was investigated by DSC and TG/DTG analyses and FT-IR spectroscopy. The kinetic parameters of the exothermic process were studied by using Kissinger's and Ozawa-Doyle's methods.

Full text of DOI:10.1002/zaac.200900502

ARTICLE
DOI: 10.1002/zaac.200900502
Synthesis and Characterization of a Novel Energetic Complex
[Cd(DAT)6](NO3)2 (DAT = 1,5-diamino-tetrazole) with High Nitrogen
Content
Jian-Guo Zhang,*[a] Jing-Yu Li,[a] Yan Zang,[b] Yuan-Jie Shu,[c] Tong-Lai Zhang,[a]
Li Yang,[a] and Philip P. Power[d]
Keywords: Nitrogen; Cadmium; 1,5-Diamino-tetrazole (DAT); Thermochemistry; Structure elucidation
Abstract. The novel high nitrogen-containing energetic complex through two types of hydrogen bonds thus forming a stable three-di-
[Cd(DAT)6](NO3)2 was synthesized by reaction of Cd(NO3)2·6H2O mensional net structure. The thermal decomposition mechanism of
with 1,5-diamino-tetrazole (DAT). It was characterized by elemental [Cd(DAT)6](NO3)2 was investigated by DSC and TG/DTG analyses
analysis, FT-IR spectroscopy and single-crystal X-ray diffraction anal- and FT-IR spectroscopy. The kinetic parameters of the exothermic
ysis. The central Cd2+ ion is coordinated by six nitrogen atoms from six process were studied by using Kissinger’s and Ozawa–Doyle’s meth-
DAT ligand molecules to form a hexacoordinate distorted octahedral ods.
compound. The [Cd(DAT)6](NO3)2 molecules are linked together
getic salts have aroused great interest [25–28], and some new
Introduction
complexes using DAT as ligand were also reported [23, 29–
In recent years, increased attention has been paid to multi-
32]. In order to study a new series of DAT-based azole ener-
nitrogen heterocyclic compounds [1–3], which have been
getic coordination compounds, the novel energetic complex
recognized as a class of useful and promising structures for the
[Cd(DAT)6](NO3)2 with high nitrogen content has been synthe-
design and synthesis of high-energy density materials
sized and characterized by elemental analysis, FT-IR spectro-
(HEDMs) [4–6]. A large number of heterocycle-based ener-
scopy and X-ray single crystal diffraction analysis. Addition-
getic compounds were reported and used as high explosives
ally, the thermal decomposition mechanism and non-
and ingredients of propellants. Azole heterocycle compounds
isothermal kinetics of [Cd(DAT)6](NO3)2 were investigated by
have aroused great interests because of their advantages, such
using DSC and TG/DTG analyses and FT-IR spectroscopy.
as high nitrogen content, high positive heat of formation, high
density and easier to reach oxygen balance [7–9]. Because of
their unique structures and properties, they might be useful as
Results and Discussion
Synthesis of DAT and [Cd(DAT)6](NO3)2
ligands in the preparation of energetic complexes [10–18].
1,5-Diamino-tetrazole (DAT) has a high nitrogen content,
positive enthalpy of formation, and good thermal stability [19–
22]. It has six nitrogen atoms in its molecular structure; five
of them are able to bind to metal ions. It is a promising ligand
that can combine with transition metals to form energetic coor-
dination compounds [23, 24]. In recent years, DAT-based ener-
1,5-diamino-tetrazole (DAT) has been synthesized by reac-
tion of diamino-guanidinium chloride and sodium nitrite with
the concentrated hydrochloric acid as catalyst according to the
reference method [33]. DAT is precipitated by adjustment of
the pH value with Na2CO3. The reaction route is shown in
Scheme 1. We optimized the reaction conditions and obtained
pure DAT in 72 % yield.
* Dr. J.-G. Zhang
Fax: +86-10-68913818
E-Mail: zhangjianguobit@yahoo.com.cn
[a] State Key Laboratory of Explosion Science and Technology
Beijing Institute of Technology
Beijing 100081, P. R. China
[b] Department of Arming Remanufacture Engineering
Academy of Armored Forces Engineering
Beijing 100072, P. R. China
[c] Institute of Chemical Materials
Chinese Academy of Engineering Physics
Mianyang, Sichuan 621900, P. R. China
[d] Department of Chemistry
Scheme 1. Synthesis of 1,5-Diamino-tetrazole (DAT).
The reaction of stoichiometric amounts of Cd(NO3)2·6H2O
and DAT in aqueous solution afforded the title compound
[Cd(DAT)6](NO3)2 in 85 % yield. It is well soluble in water,
University of California, Davis
One Shields Avenue
Davis, CA 95616, USA
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J.-G. Zhang, J.-Y. Li, Y. Zang, Y.-J. Shu, T.-L. Zhang, L. Yang, P. P. Power
ARTICLE
and slightly soluble in common organic solvents such as di-
chloromethane, tetrahydrofurane and toluene. After 20 days,
colorless prism single crystals of the title compound suitable
for X-ray analysis were obtained by slowly evaporating the
saturated [Cd(DAT)6](NO3)2 solution.
Crystal Structure Description of [Cd(DAT)6](NO3)2
The molecular structure of [Cd(DAT)6](NO3)2 is shown in
Figure 1, and its packing diagrams viewed along the a and c
axes are shown in Figure 2 and Figure 3, respectively. Single
crystal X-ray analysis reveals that the central Cd2+ ion is coor-
dinated to six nitrogen atoms from six DAT molecules, corre-
sponding to N3, N3A, N3B, N3C, N3D, N3E (Figure 1). Nota-
bly, the Cd2+ ion has a hexacoordinate distorted octahedral
structure, since it has peripheral d10 electron configuration and
adopts sp3d2 hybridization in theory. Because of its peripheral
d10 electron configuration, it exhibits no d–d electronic transi-
tion and is a colorless.
Figure 3. Packing diagram of [Cd(DAT)6](NO3)2, view along the c axis.
and N3E, the bond angles N3B–Cd1–N3E and N3–Cd1–N3E
also amount 90.81(13)°. However, the atoms Cd1, N3, N3A,
N3C and N3E are not coplanar, and the bond angle of N3B–
Cd1–N3D amounts 168.56 (18)°. Thus, the α and β plane are
not coplanar, and the angle between the two planes amounts
11.5°. It is obvious that the central Cd2+ ion can not be co-
planar with the nitrogen atoms of its four surrounding DTA
molecules, so the hexacoordinate configuration forms a distor-
tion octahedral structure. The bond angles N3–Cd1–N3C,
N3B–Cd1–N3D, and N3A–Cd1–N3E formed by the central
Cd2+ ion connected to the opposite nitrogen atoms amount to
168.56(18)°. Because of the repulsive interaction among the
six tetrazole rings, they are able to reach the most stable struc-
ture. The [Cd(DAT)6](NO3)2 molecule is formed when DAT
and Cd2+ form a coordinated cation, which combines with ni-
tric acid through the force of electrovalence.
Figure 1. Molecular structure of [Cd(DAT)6](NO3)2.
Table 1. Selected bond lengths for [Cd(DAT)6](NO3)2.
Chemical bond Bond length /Å Chemical bond Bond length /Å
Cd1–N3#1
Cd1–N3
2.368(4)
2.368(4)
2.368(4)
2.368(4)
2.368(4)
2.368(4)
1.330(6)
0.891(10)
0.895(10)
1.331(6)
N2–N3
1.335(6)
1.375(5)
1.285(6)
1.353(6)
1.389(6)
0.898(10)
0.898(10)
1.233(6)
1.233(6)
1.233(6)
N3–N4
Cd1–N3#2
Cd1–N3#3
Cd1–N3#4
Cd1–N3#5
N1–N2
N4–N5
N5–C1
N6–C1
N6–H6A
N6–H6B
O1–N7
N1–H1B
N1–H(1A)
N2–C1
N7–O1#6
N7–O1#7
Symmetry operations: #1: –x + 2, –x+y+1, –z + 1/2; #2: –x+y+2, –x
+ 1, z; #3: y + 1, x – 1, –z + 1/2; #4: x–y, –y, –z + 1/2; #5: –y + 1,
x–y–1, z; #6: –x+y, –x + 1, z; #7: –y + 1, x–y+1, z.
Figure 2. Packing diagram of [Cd(DAT)6](NO3)2, view along the a axis.
Selected bond lengths and angles are summarized in Table 1
Each DAT ligand in the [Cd(DAT)6](NO3)2 molecule has
and Table 2, respectively. All N–Cd bond lengths (Cd1–N3, well co-planarity. The DAT molecule is a five-membered ring
Cd1–N3A, Cd1–N3B, Cd1–N3C, Cd1–N3D and Cd1–N3E) formed by C1, N2, N3, N4, N5, the torsion angles amount:
amount 2.368(4) Å. The atom N3D is perpendicular to the C1–N2–N3–N4, 0.8(5)°; N2–N3–N4–N5, –0.2(5)°; N3–N4–
α plane formed by Cd1, N3A and N3C, the bond angles N5–C1, –0.4 (5)°; N3–N2–C1–N5, 1.0(5)°; N4–N5–C1–N2,
N3–Cd1–N3B and N3C–Cd1–N3D amount 90.81(13)°; The 0.8 (5)°. The analysis shows that the five atoms of the tetrazole
atom N3B is perpendicular to the β plane formed by Cd1, N3 molecule are coplanar, with the plane equation –2.424x
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The Complex [Cd(DAT)6](NO3)2 (DAT = 1,5-diamino-tetrazole)
Table 2. Selected bond angles for [Cd(DAT)6](NO3)2.
Table 3. Selected hydrogen bonds for [Cd(DAT)6](NO3)2.
Chemical bond
N3#1–Cd1–N3
Bond angle /° Chemical bond Bond angle /°
D–H···A
D–H /Å H···A /Å D···A /Å D–H···A /°
97.86(18)
N1–N2–C1
N1–N2–N3
C1–N2–N3
N2–N3–N4
N2–N3–Cd1
N4–N3–Cd1
N5–N4–N3
N4–N5–C1
C1–N6–H6A
C1–N6–H6B
H6A–N6–H6B
N2–C1–N5
N5–C1–N6
O1#6–N7–O1
124.50(4)
127.80(4)
107.70(4)
105.80(4)
128.70(3)
119.10(3)
110.50(4)
106.60(4)
110.00(5)
100.00(5)
113.10(18)
109.40(4)
125.80(4)
119.91(8)
N1–H1B···O1 #1
N1–H1B···O1 #2
N1–H1A···N4
0.891
0.891
0.895
0.898
2.137
2.607
2.125
2.367
2.989
3.147
2.993
3.248
159.67
119.86
163.05
166.92
N3#1–Cd1–N3#2 81.66(18)
N3–Cd1–N3#2
90.81(13)
N3#1–Cd1–N3#3 90.81(13)
N6–H6A···O1 #3
N3–Cd1–N3#3
168.56(18)
Symmetry operations: #1: x, y – 1, z; #2: –x+y, –x, z; #3: –y + 1, x–y–1, z.
N3#2–Cd1–N3#3 97.86(18)
N3#1–Cd1–N3#4 90.81(13)
N3–Cd1–N3#4
81.66(18)
Thermal Decomposition Mechanism of [Cd(DAT)6](NO3)2
N3#2–Cd1–N3#4 168.57(18)
N3#3–Cd1–N3#4 90.81(13)
N3#1–Cd1–N3#5 168.56(18)
In order to investigate the thermal decomposition of
[Cd(DAT)6](NO3)2, the DSC and TG/DTG experiments were
carried out with a linear heating rate of 10 °C·min–1 under ni-
trogen. The DSC curve of [Cd(DAT)6](NO3)2 shown in Fig-
ure 4 exhibits two sharp peaks, the first is a sharp endothermic
peak, caused by melting. The melting peak starts at 203.2 °C
with a peak temperature of 215.9 °C; afterwards the melting
product immediately decomposes to form an exothermic proc-
ess, with a peak temperature of 242.4 °C, and ends at
266.0 °C.
N3–Cd1–N3#5
90.81(13)
N3#2–Cd1–N3#5 90.81(13)
N3#3–Cd1–N3#5 81.66(18)
N3#4–Cd1–N3#5 97.85(19)
O1#6–N7–O1#7 119.90(8)
O1–N7–O1#7 119.91(8)
N2–N1–H1B
120.00(3)
Symmetry operations: #1: –x + 2, –x+y+1, –z + 1/2; #2: –x+y+2, –x
+ 1, z; #3: y + 1, x – 1, –z + 1/2; #4: x–y, –y, –z + 1/2; #5: –y + 1,
x–y–1, z; #6: –x+y, –x + 1, z; #7: –y + 1, x–y+1, z.
+2.094y +12.427z = –0.1957 and a deviation of 0.0033. From
the torsion angle data: N1–N2–N3–N4, –177.2(4)°; N1–N2–
C1–N5, 177.1(4)°, it is obvious that the amino nitrogen atom
N1 is coplanar to the tetrazole ring with the plane equation –
2.384x +2.213y +12.419z = –0.1445 and a deviation of 0.0134.
The torsion angle data N3–N2–C1–N6, –176.7(5)°; N4–N5–
C1–N6, 176.5(5)° shows that the tetrazole ring and amino ni-
trogen atom N6 are coplanar, with the plane equation –2.238x
+2.024y +12.465z = –0.0410 and a deviation of 0.0127. In
addition, it was found that the [Cd(DAT)6]2+ ion is almost cen-
trosymmetric, so the rest of plane equations are not listed.
Six DAT ligand molecules forming tetrazole ring planes are
shown: plane I [C1, N2, N3, N4, N5], plane II [C1A, N2A,
N3A, N4A, N5A], plane III[C1B, N2B, N3B, N4B, N5 B],
plane IV[C1C, N2C, N3C, N4C, N5C], plane V[C1D, N2D,
N3D, N4D, N5D], plane VI[C1E, N2E, N3E, N4E, N5E].
From the six planes it is obvious that in the opposite angle
position the DAT tetrazole ring planes (plane I and IV, plane
II and VI, plane III and V) are almost parallel to each other
with an angle of 3.2°; the angle between adjacent planes (plane
I and V, plane II and IV, plane III and VI) amounts 23.7°; and
the angle between the other adjacent planes (plane I and VI,
plane II and V, plane III and IV) amounts 20.4° and the angle
of the interval planes amounts 22.2°.
In the crystal structure of [Cd(DAT)6](NO3)2, two types of
hydrogen bonds were observed. One occurs between the nitro-
gen atom of the tetrazole ring and a hydrogen atom of the
amino group of an adjacent tetrazole ring, N1–H1A···N4. This
type of hydrogen bonding combines the DAT molecules to-
gether to stabilze the inner [Cd(DAT)6](NO3)2 structure. An-
other type of hydrogen bonding occurs between the hydrogen
atoms of the amino groups of the tetrazole rings and the oxy-
gen atoms of the nitrate ions, N6–H6A···O1 and N1–H1B···O1,
which bridge [Cd(DAT)6](NO3)2 molecules together to form a
Figure 4. DSC curve of [Cd(DAT)6](NO3)2 with a heating rate of
10 °C·min–1.
As we can see from the TG/DTG diagram (Figure 5), three
main thermal decomposition processes can be observed for
[Cd(DAT)6](NO3)2. The first mass loss happens in the range
178.3–265.7 °C and amounts to 58.9 %, the maximum mass
loss rate shows up at 231.1 °C, with a rate of 18.1 %·min–1; the
second mass loss happens in the range 265.7–401.1 °C with a
value of 17.7 %; the third mass loss happens in the range 401.1–
531.6 °C, the final residual quantity is 13.9 %. FT-IR spectro-
scopy shows that no obvious characteristic peaks exist in the
range 400–4000 cm–1. Combined with the element analysis, the
residue is CdO. However, there is a certain deviation of 15.4 %
of the theoretical residua amount. It may occur because
[Cd(DAT)6](NO3)2 decomposes and exothermic so rapidly.
Non-isothermal Kinetic Analysis of the Main Exothermic
Peak of [Cd(DAT)6](NO3)2
From the DSC and TG/DTG analyses of [Cd(DAT)6](NO3)2,
stable three-dimensional net structure. Selected hydrogen we can infer that the exothermic process has a dominant effect
bonds of [Cd(DAT)6](NO3)2 are listed in Table 3.
on the decomposition of the title compound. Kissinger’s and
Z. Anorg. Allg. Chem. 2010, 1147–1151
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J.-G. Zhang, J.-Y. Li, Y. Zang, Y.-J. Shu, T.-L. Zhang, L. Yang, P. P. Power
ARTICLE
Conclusions
The
novel
energetic
coordination
compound
[Cd(DAT)6](NO3)2 with high nitrogen content was synthesized
by reaction of 1,5-diamino-tetrazole(DAT) and Cd(NO3)2·
6H2O. It displays a hexacoordinate, distorted octahedral con-
figuration; the central Cd2+ ion coordinates with six nitrogen
atoms of six DAT molecules. The [Cd(DAT)6](NO3)2 molecu-
les are connected by hydrogen bonds forming a stable three-
dimensional net structure. Additionally, it has an exothermic
activation energy of 121.7 kJ·mol–1.
Figure 5. TG/DTG curves of [Cd(DAT)6](NO3)2 with a heating rate
of 10 °C·min–1.
Experimental Section
Caution
1,5-Diamino-tetrazole and [Cd(DAT)6](NO3)2 are both energetic mate-
rials and tend to explode under certain stimuli. Although we had no
problems in synthesis, proper protective measures (safety glasses, face
shield, leather coat, shoes, gloves and ear plugs) should be taken, espe-
cially when the compound is prepared on a larger scale.
Ozawa–Doyle’s methods were applied to study the kinetic pa-
rameters of the exothermic process of the title compound,
based on the DSC curve obtained under the condition of static
air at heating rates of 2, 5, 10, 15 and 20 °C· min–1. The Kiss-
inger and Ozawa–Doyle equations are shown in Scheme 2.
Materials and General Methods
Diamino-guanidinium chloride (industrial grade) and all chemical rea-
gents and solvents used to prepare DAT and [Cd(DAT)6](NO3)2 were
of analytical grade and purchased commercially.
Elemental analysis was performed with a Flash EA 1112 fully-auto-
mated trace element analyzer. The FT-IR spectrum was recorded on a
Bruker Equinox 55 infrared spectrometer (KBr pellets) in the range of
4000–400 cm–1 with a resolution of 4 cm–1. DSC measurement was
carried out with a Pyris-1 differential scanning calorimeter in static
air. Thermogravimetric (TG) analysis was carried out with a Pyris-1
thermogravimetric analyzer under dry oxygen-free nitrogen with a
flowing rate of 20 mL· min–1. A sample of about 0.5 mg was sealed
in aluminum pans for DSC and held in platinum pans for TG in the
temperature range 30–600 °C.
Scheme 2. The Kissinger and Ozawa–Doyle equations. Tp: peak tem-
perature /K; R: gas constant, 8.314 J·mol–1·K–1; β: linear heating rate /
K·min–1; C: constant.
The peak temperatures Tp /°C of the exothermic process at
different heating rates, the apparent activation energy Ek and
Eo /kJ·mol–1, the pre-exponential factor Ak /s–1 and the linear
coefficient Rk and Ro were determined and are listed in Ta-
ble 4. The calculated results using both methods are similar
and they are all in the normal range of kinetic parameters for
the thermal decomposition reaction of solid materials [34].
Synthesis of the Title Compound
Cd(NO3)2·6H2O (1.7 g, 5 mmol) was dissolved in distilled water
(20 mL) afterwards it was added dropwise to a solution of DAT (1.2 g,
12mmol) in distilled water (30 mL) at 70 °C. The mixture was stirred
at the same temperature for another hour. Afterwards it was slowly
cooled to room temperature. The precipitate was collected by filtration,
washed with ethanol, and dried in a vacuum drier. The title compound
[Cd(DAT)6](NO3)2 was obtained in 65 % yield. Elemental analysis:
Anal. Calcd.(%) for [Cd(DAT)6](NO3)2 :C, 8.61; H, 2.87; N, 63.60.
Table 4. Peak temperatures of the first main exothermic stage at differ-
ent heating rates and kinetic parameters for [Cd(DAT)6](NO3)2.
Heating rates /°C·min–1
2
5
10
15
20
Found: C, 8.58; H, 2.92; N, 63.64. IR (KBr): ν = 3365cm–1 (s),
˜
Pack temperatures /°C
Kissinger’s method:
215.8 234.1 242.4 250.1 253.8
121.7 / 10.28 / –0.9937
123.7 / –0.9944
3162(s), 1675(s), 1626(s), 1358(s), 1118(s), 994 (w), 834(w), 695(s),
572(m) cm–1.
Ek /kJ·mol–1 / ln(Ak /s–1) / Rk
Ozawa–Doyle’s method:
Eo(kJ·mol–1) / Ro
X-ray Crystallography
The crystal data of [Cd(DAT)6](NO3)2 were collected with a Bruker
Smart CCD diffractometer with graphite monochromatic Mo-Kα radia-
tion (λ = 0.71073 Å) at 294 (2) K using φ and ω scan modes. The
structure was determined and refined by using direct methods
SHELXS-97 [35] and SHELXL-97 [36] program. All hydrogen atoms
were located from difference Fourier electron-density maps and refined
isotropically, while all non-hydrogen atoms were obtained from the
difference Fourier map and refined anisotropically. Detailed informa-
The Arrhenius equations can be expressed by using the cal-
culated Ea (the average of Ek and Eo) and lnAk (Table 4) val-
ues, as follows: lnk = 10.28–121.7 × 103/RT for the exothermic
decomposition. The Arrhenius equation can be used to esti-
mate the rate constants of the initial thermal decomposition
process of [Cd(DAT)6](NO3)2.
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The Complex [Cd(DAT)6](NO3)2 (DAT = 1,5-diamino-tetrazole)
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tary crystallographic data for this paper, these data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif (or from the Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; Fax: +44-1223-336033; E-Mail: deposit@ccdc.cam.ac.uk or
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Empirical formula
C6H24CdN38O6
Formula weight
837.03
Crystal dimension /mm
0.24 × 0.18 ×0.16
Trigonal
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Crystal system
¯
Space group
P3c1
a /Å
11.8249(8)
11.8249(8)
12.7457(16)
90
b /Å
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c /Å
β /°
V /Å3
1543.4(2)
2
Z
ρ /g·cm–3
1.801
F(000)
844
λ /Å
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θ /°
0.175
1.99–24.99
7389
Reflections collected
Independent reflections (Rint)
912(0.0317)
0.0433, 0.1285
0.0466, 0.1321
–14–13/–11–14/–15–12
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Acknowledgement
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We gratefully acknowledge the financial support from the National
Natural Science Foundation of China (No. 10776002, 20911120033),
the project of State Key Laboratory of Science and Technology (No.
ZDKT08-01), the 111 project (B07012) and the Program for New Cen-
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Received: October 24, 2009
Published Online: February 11, 2010
Z. Anorg. Allg. Chem. 2010, 1147–1151
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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