ZTO·2H2O and - KCS Publications

2086 Bull. Korean Chem. Soc. 2013, Vol. 34, No. 7
http://dx.doi.org/10.5012/bkcs.2013.34.7.2086
Cong Ma et al.
Preparation, Structural Investigation and Thermal Decomposition Behavior of Two
High-Nitrogen Energetic Materials: ZTO·2H2O and ZTO(phen)·H2O
Cong Ma, Jie Huang,* Yi Tang Zhong, Kang Zhen Xu, Ji Rong Song,† and Zhao Zhang
Department of Chemical Engineering, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University,
Xian, Shaanxi 710069, China. *E-mail: [email protected]
†
Conservation Technology Department, the Palace Museum, Beijing 100009, China
Received April 1, 2013, Accepted April 16, 2013
Two new high-nitrogen energetic compounds ZTO·2H2O and ZTO(phen)·H2O have been synthesized (where
ZTO = 4,4-azo-1,2,4-triazol-5-one and phen = 1,10-phenanthroline). The crystal structure, elemental analysis
and IR spectroscopy are presented. Compound 1 ZTO·2H2O crystallizes in the orthorhombic crystal system
with space group Pnna and compound 2 ZTO(phen)·H2O in the triclinic crystal system with space group P-1.
In ZTO(phen)·H2O, there is intermolecular hydrogen bonds between the -NH group of ZTO molecule (as
donor) and N atom of phen molecule (as acceptor). Thermal decomposition process is studied by applying the
differential scanning calorimetry (DSC) and thermo thermogravimetric differential analysis (TG-DTG). The
DSC curve shows that there is one exothermic peak in ZTO·2H2O and ZTO(phen)·H2O, respectively. The
critical temperature of thermal explosion (Tb) for ZTO·2H2O and ZTO(phen)·H2O is 282.21 oC and 195.94 oC,
respectively.
Key Words : Preparation, 1,10-Phenanthroline, Crystal structure, Thermal decomposition
Introduction
High energy density materials (HEDM's) form an important class of explosive compounds. High nitrogen content
materials have a large number of N–N and C–N bonds,
while possess large positive heats of formation on them. The
low percentage of hydrogen and carbon in these compounds
allows a good oxygen balance to achieve easily and produces more number of moles of gaseous products per
gram.1,2 When explosive materials undergo decomposition,
they produce energy by a process called oxidation. During
the oxidation reaction, an explosive is detonated with sudden
release of energy or a fule is burnt. The oxidation reaction
produces heat because the internal energy of reactant molecule is higher than that of the end product. The difference
between the internal energies of reactant and product of a
reaction is called heat of reaction.3-5 So, the significant
advantages such as high heats of combustion, high specific
impulse, high propulsive power, as well as smokeless combustion make them very useful as explosives, propellants,
and pyrotechnics.6-9 Notable among the most promising
recent developments in the chemistry of HEDM's are compounds that combine a high nitrogen content (molecular
nitrogen forms the major component of the decomposition
products) with a high heat of formation and insensitivity to
shock, friction, and electrostatic discharge.10
4-Amino-1,2,4-triazol-5-one (ATO) is high nitrogen content (56%), making it of interest for the synthesis of highly
enegetic materials. ATO was first prepared using carbohydrazide by Kroeger et al. in 1964.11 The triazolone compound can easily coordinate with metals due to the presence
of lone electron pairs on the oxygen atom of the cabony
group, the nitrogen atom of the amino group and the nitrogen atom of the five-member ring. Therefore, ATO has been
used to prepare energetic complexes besides its potential
useage in energetic explosives as an intermediate.12 Zhang
and Zhang13,14 have synthesized a series of ATO deratives,
such as {[Ag(ATO)2]ClO4}n and [Mn(ATO)2(H2O)4](PA)2.
We have synthesized the single crystal of ATO and
[K(ZTO)·H2O]∞ (Scheme 2), reported their molecular structure, and studied their thermal decomposition mechanism.
Ma15 describes that the thermal decomposition process of
[K(ZTO)·H2O]∞ is composed of one endothermic and one
exothermic peak.
In this paper, in order to explore new energetic compounds,
we describe the preparation of ZTO·2H2O (Scheme 1) and
ZTO(phen)2·2H2O (Scheme 3), respectively. The crystal structure, fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetry-derivative thermogravimetry (TG-DTG), thermal decomposition
behaviours and the decomposition kinetic analysis are presented.
Experimental
Synthesis. ATO,11 ZTO·2H2O16 and [K(ZTO)·H2O]∞15 were
prepared by ourselfves. The compound ZTO(phen)·H2O was
synthesized as follows (Scheme 3): Phen (2.00 g) was
dissolved in 20 ml ethanol, and the solution was added to a
suspending solution of [K(ZTO)·H2O]∞ (1.00 g) in 30 mL
distilled water at 40 oC with vigorous stirring. The mixture
was stirred for 6 h and the white precipitate was collected by
filtration, washed with ethanol and dried in vacuum, with a
yield of 70%. Element analysis: Anal. Calcd. (%) for ZTO
Bull. Korean Chem. Soc. 2013, Vol. 34, No. 7
Preparation, Structural and Thermal Decomposition
2087
Scheme 1. Synthetic route of ZTO·2H2O.
Scheme 3. Synthetic route of ZTO(phen)·H2O.
Scheme 2. Synthetic route of [K(ZTO)·H2O].
(phen)·H2O: C 57.14, H 3.43, N 28.56; Found (%): C 57.12,
H 3.45, N 28.51. ZTO·2H2O Anal. Calcd. (%): C 24.50, H
2.06, N 57.13; Found (%): C 24.48, H 2.58, N 57.15.
Instruments and Conditions. Infrared spectra were recorded on a Bruker Equinox 55 infrared spectrometer as
KBr microdiscs in the wavenumber range 4000-400 cm−1
with a resolution of 4 cm−1. The DSC experiments for
ZTO·2H2O and ZTO(phen)·H2O were performed using a
DSC-Q2000 apparatus (TA, USA) under a nitrogen atmosphere at a flow rate of 50 mL·min−1. The heating rates used
were 5.0, 10.0, 15.0 and 20.0 oC·min−1 from ambient temper-
ature to 500.0 oC. Kinetic analysis of the compounds was
done by the method of Kissinger and Ozawa, using differential heating rate method, while energy of activation was
calculated from the peak values of exothermic decomposition peaks from the ZTO·2H2O and ZTO(phen)·H2O thermogram.
The TG-DTG analyses for ZTO·2H2O and ZTO(phen)·H2O
were conducted using a SDT Q600 under a nitrogen gas with
flowing rate of 100 mL·min−1 and heating rate of 10 oC·min−1
and the amount of used sample was about 0.40 and 0.12 mg,
respectively.
Crystal Structure Determination. Single crystals suitable
for X-ray measurement were obtined by slow evaparation of
the above filtrate at room temperature. A white crystal with
dimensions of 0.36 × 0.27 × 0.16 mm and 0.37 × 0.31 × 0.25
mm were chosen for X-ray determination, respectively. The
Table 1. Crystal data and structure refinement details for ZTO·2H2O and ZTO(phen)·H2O
Parameter
ZTO·2H2O
ZTO(phen)·H2O
Chemical formula
Formula weight
Temperature/K
Crystal system
Space group
a/nm
b/nm
c/nm
β/(°)
Volume/nm3
Z
Dc/(g·cm−3)
Absorption coefficient/mm−1
F(000)
θ range/(°)
Index ranges
Reflections collected
Reflections unique (Rint)
Final R indices [I > 2σ(I)]
C4H8N8O4
232.18
293(2)
Orthorhombic
Pnna
6.7027(10)
13.262(2)
10.2789(3)
90
913.7(2)
4
1.688
0.148
480
2.51-25.04
−7 ≤ h ≤ 7, −15 ≤ k ≤ 15, −9 ≤ l ≤ 12
4131
1287 (0.0300)
R1 = 0.0484, wR2 = 0.1098
C28H20N12O4
588.56
296(2) K
Triclinic
P-1
8.8293(16)
9.5453(17)
9.5581(17)
102.847(3)
675.9(2)
1
1.446
0.104
304
2.46-25.10
−10 < h < 10, −11 < k < 6, −11 < l < 11
3398
2816(0.0179)
R1 = 0.0565, wR2 = 0.1759
2088
Bull. Korean Chem. Soc. 2013, Vol. 34, No. 7
Cong Ma et al.
datas were collected on a Bruker SMART APEX II CCD Xray diffractometer using graphite-monochromated MoKα
radiation (λ = 0.071073 nm). The structure was solved by
the direct methods (SHELXTL-97 17) and refined by the fullmatrix-block least-squares method on F2 with anisotropic
thermal parameters for all non-hydrogen atoms. The hydrogen atoms were added according to the theoretical models.
The crystal data, experimental details and refinement results
for ZTO·2H2O and ZTO(phen)·H2O were summarized in
Table 1.
Results and Discussion
IR Spectra Analysis. The IR spectra of ZTO(phen)·H2O
is shown in Figure 1. The N-H stretching vibration is found
in this case at 2904 cm−1. The N-H in-plane and out-plane
bending vibrations are established at 1612 and 718 cm−1. All
the observed N-H vibrations are within the expected
range.18,19 This view shows the dominant character of N-H.
Sundaraganesan et al.20 assigned C-N stretching absorption
in the range 1382-1266 cm−1 for aromatic amines. Hence,
the bands are observed at 1334, 1189 cm−1 for C-N stretching
vibrations. The N=N stretching vibration normally occurs at
1410-1440 cm−1.21 The same has been found at 1491 cm−1.
The bands observed at 2843 and 1732 cm−1 are assigned to
Figure 1. The IR spectra of ZTO(phen)·H2O.
C-H and C=N stretching vibrations, respectively.
Crystal Structures. The selected bond lengths, bond
angles and torsion angles of ZTO(phen)·H2O and ZTO·2H2O
are summarized in Tables 2 and 3, respectively. The hydrogen
bond distances and angles of ZTO(phen)·H2O are summarized in Table 4. The crystal structure, the intermolecular
Table 2. Selected bond lengths (Å), bond angles ( o ) and torsion angles ( o ) of ZTO(phen)·H2O
Bond length (Å)
N(5A)-C(26A)
N(5A)-N(6A)
N(6A)-C(25A)
N(7A)-C(26A)
N(7A)-C(25A)
N(7A)-N(8A)
N(8A)-N(9A)
N(9A)-N(10A)
N(10A)-C(27A)
N(10A)-C(28A)
N(11A)-C(28A)
N(11A)-N(12A)
N(12A)-C(27A)
O(1A)-C(25A)
O(2A)-C(27A)
1.284(10)
1.368(10)
1.341(10)
1.371(10)
1.420(10)
1.385(8)
1.243(4)
1.348(9)
1.385(10)
1.381(10)
1.297(11)
1.393(10)
1.322(10)
1.195(9)
1.282(10)
N(3A)-C(13A)
N(3A)-C(24A)
N(4A)-C(22A)
N(4A)-C(23A)
C(13A)-C(14A)
C(14A)-C(15A)
C(15A)-C(16A)
C(16A)-C(24A)
C(16A)-C(17A)
C(17A)-C(18A)
C(18A)-C(19A)
C(19A)-C(23A)
C(19A)-C(20A)
C(20A)-C(21A)
C(21A)-C(22A)
1.343(10)
1.367(10)
1.291(11)
1.358(9)
1.388(13)
1.319(15)
1.379(13)
1.383(11)
1.420(14)
1.398(15)
1.396(13)
1.384(10)
1.388(13)
1.357(14)
1.368(13)
Bond angles ( o )
N(5A)-C(26A)-N(7A)
N(6A)-C(25A)-N(7A)
C(26A)-N(7A)-N(8A)
C(26A)-N(7A)-C(25A)
N(9A)-N(8A)-N(7A)
N(8A)-N(9A)-N(10A)
N(9A)-N(10A)-C(27A)
111.1(7)
100.1(6)
131.3(7)
108.7(6)
110.7(5)
111.3(5)
122.4(7)
N(9A)-N(10A)-C(28A)
C(27A)-N(10A)-C(28A)
C(28A)-N(11A)-N(12A)
C(27A)-N(12A)-N(11A)
O(2A)-C(27A)-N(12A)
O(2A)-C(27A)-N(10A)
129.7(7)
107.8(6)
105.3(7)
112.2(7)
129.6(8)
125.8(7)
Torsion angles ( o )
C(25A)-N(7A)-N(8A)-N(9A)
N(8A)-N(9A)-N(10)-C(27A)
N(7A)-N(8A)-N(9A)-N(10A)
N(8A)-N(7A)-C(25A)-N(6A)
-177.8(6)
178.5(6)
179.5(9)
178.9(7)
N(8A)-N(7A)-C(26A)-N(5A)
N(11A)-N(12A)-C(27A)-O(2A)
N(9A)-N(10A)-C(27A)-N(12A)
-177.7(9)
-178.2(9)
-177.5(7)
Preparation, Structural and Thermal Decomposition
Bull. Korean Chem. Soc. 2013, Vol. 34, No. 7
2089
Table 3. Selected bond lengths (Å), bond angles ( o ) and torsion angles ( o ) of ZTO·2H2O
Bond length (Å)
N(1A)-N(1)
N(1)-N(2)
N(2)-C(2)
N(2)-C(1)
N(3)-C(1)
1.238(3)
1.377(2)
1.382(3)
1.395(2)
1.329(3)
N(3)-N(4)
N(3)-H(3)
N(4)-C(2)
O(1)-C(1)
1.392(2)
0.8600
1.292(3)
1.243(2)
Bond angles ( o )
N(1A)-N(1)-N(2)
N(1)-N(2)-C(2)
N(1)-N(2)-C(1)
N(4)-C(2)-N(2)
C(2)-N(2)-C(1)
110.6(2)
132.44(16)
119.45(16)
109.78(18)
107.67(16)
C(1)-N(3)-N(4)
C(2)-N(4)-N(3)
O(1)-C(1)-N(3)
O(1)-C(1)-N(2)
N(3)-C(1)-N(2)
111.20(16)
106.61(17)
130.21(18)
125.05(18)
104.73(17)
Torsion angles ( o )
N(1A)-N(1)-N(2)-C(2)
N(1A)-N(1)-N(2)-C(1)
C(1)-N(3)-N(4)-C(2)
N(4)-N(3)-C(1)-O(1)
N(4)-N(3)-C(1)-N(2)
N(1)-N(2)-C(1)-O(1)
20.4(2)
-168.16(13)
-1.2(2)
179.7(2)
1.2(2)
7.2(3)
C(2)-N(2)-C(1)-O(1)
N(1)-N(2)-C(1)-N(3)
C(2)-N(2)-C(1)-N(3)
N(3)-N(4)-C(2)-N(2)
N(1)-N(2)-C(2)-N(4)
C(1)-N(2)-C(2)-N(4)
-179.4(2)
-174.09(16)
-0.7(2)
0.7(2)
172.19(19)
0.0(2)
hydrogen bond and packing arrangement viewed along caxis of ZTO(phen)·H2O are shown in Figures 2-4, respectively. The crystal structure and packing arrangement of
ZTO·2H2O are shown in Figures 5, 6, respectively.
ZTO(phen)·H2O crystallizes with a triclinic unit cell in the
space group P-1. The crystallographic studies reveal that
ZTO(phen)·H2O consists of one ZTO molecule, one phen
molecule and one lattice water molecule. ZTO·2H2O crystallizes with a orthorhombic unit cell in the space group Pnna
and is made up of one ZTO molecule and two lattice water
molecules.
From Tables 2 and 3, we can see that the corresponding
bond lengths, bond angles and torsion angles of ZTO
(phen)·H2O differ slightly in comparison with ZTO·2H2O. In
ZTO(phen)·H2O, N(5A)-C(26A), N(6A)-C(25A), N(12A)C(27A), N(11A)-C(28A), N(7A)-C(26A), N(7A)-C(25A),
N(10A)-C(27A), N(10A)-C(28A) bond distances are 1.284
(10) Å, 1.341(10) Å, 1.322(10) Å, 1.297(11) Å, 1.371(10) Å,
1.420(10) Å, 1.385(10) Å, 1.381(10) Å between the isolated
C-N (1.471 Å) and C=N (1.273 Å). N(5A)-N(6A), N(11A)N(12A) bond distances are 1.368(10) Å, 1.393(10) Å
between the isolated N-N (1.449 Å) and isolated N=N (1.273
Å). Therefore, C(25A), C(26A), N(5A), N(6A), N(7A) (plane
equation: 3.550 x + 1.224 y + 5.464 Z = 5.5799) and
C(27A), C(28A), N(10A), N(11A), N(12A) (plane equation:
3.596 x + 1.293 y + 5.375 Z = 5.4480) of ZTO molecule
form a conjugated ring, respectively. The bond angles all
derivate from 105o, which are 111.1(7)o for N(5A)-C(26A)N(7A), 108.7(6)o for C(26A)-N(7A)-C(25A), 100.1(6)o for
N(6A)-C(25A)-N(7A), 112.2(7)o for C(27A)-N(12A)-N(11A),
107.8(6)o for C(27A)-N(10A)-C(28A), and 105.3(7)o for
C(28A)-N(11A)-N(12A).
As shown in Figure 2, the intermolecular hydrogen bonds
in ZTO(phen)·H2O link the molecules into a two-dimen-
Table 4. Selected hydrogen bonds (Å) and angles ( o ) of ZTO
(phen)·H2O
D−H…A
N(6A)−H(6A)…N(4A)
N(6A)−H(6A)…N(3A)
N(12)−H(12A)…N(1A)
N(12)−H(12A)…N(2A)
d(D−H) d(H…A)
0.860
0.860
0.860
0.860
∠DHA
d(D…A)
163.61
125.14
164.43
123.88
3.034
3.029
2.964
3.043
2.199
2.451
2.127
2.478
sional network structure. The intermolecular hydrogen bonds
are formed between the -NH group belong to ZTO molecule
and N atom belong to phen molecule. The N(6A) and N(12)
atoms act as donors in the hydrogen bonds, while N(1),
N(2), N(3A) and N(4A) atoms as acceptors with hydrogen
distances of 2.127-2.478 Å and angles of 123.88-164.43o.
Therefore, we can conclude that these extensive intermolecular hydrogen bonds make an important role to the stability
of ZTO(phen)·H2O.
Figure 2. Crystal structure of ZTO(phen)·H2O.
2090
Bull. Korean Chem. Soc. 2013, Vol. 34, No. 7
Figure 3. The intermolecular hydrogen bonds of ZTO(phen)·H2O.
Cong Ma et al.
Figure 6. Packing diagram of ZTO·2H2O.
Figure 4. Packing diagram of ZTO(phen)·H2O.
Figure 7. The TG-DTG curve of [K(ZTO)·H2O]∞, ZTO·2H2O and
ZTO(phen)·H2O.
Figure 5. Crystal structure of ZTO·2H2O.
Thermal Analysis. The typical TG-DTG curve of ZTO·2H2O
and ZTO(phen)·H2O are carried out under the linear heating
rate of 10 oC·min−1 in Figure 7. The DSC curve of ZTO·2H2O
is carried out under the linear heating rate of 10 oC·min−1 in
Figure 8. The detailed datas of the exothermic process for
ZTO·2H2O and ZTO(phen)·H2O are shown in Table 5, while
the detailed calculated kinetic parameters of the exothermic
process are listed in Table 6.
The DSC curve shows that there is one exothermic peak in
ZTO(phen)·H2O and ZTO(phen)·H2O, respectively. The exothermic process of ZTO(phen)·H2O under the linear heating
Table 5. Parameters of ZTO·2H2O and ZTO(phen)·H2O determined by DSC curves at different heating rates (β) in exothermic stage
Compound
β/oC·min−1
T0/oC
Te/oC
Tp/oC
ΔH/kJ·mol−1
T00/oC
Te0/oC
Tp0/oC
ZTO·2H2O
5
10
15
20
264.97
275.41
278.85
279.34
278.63
287.76
291.08
295.85
281.28
290.82
294.77
299.27
316.15
250.57
269.14
270.76
ZTO(phen)·H2O
5
10
15
20
183.81
184.59
185.75
183.81
189.39
196.02
197.41
199.14
211.51
222.08
226.32
232.99
349.84
180.80
181.71
201.18
Bull. Korean Chem. Soc. 2013, Vol. 34, No. 7
Preparation, Structural and Thermal Decomposition
2091
Table 6. Kinetic parameters of ZTO·2H2O and ZTO(phen)·H2O obtained by the data in Table 5
Compound
Ek/kJ·mol−1
lgA/s−1
rk
E0/kJ·mol−1
r0
Ea /kJ·mol−1
ZTO·2H2O
ZTO(phen)·H2O
197.00
126.9
16.36
11.41
-0.9974
-0.9936
196.20
128.5
-0.9976
-0.9943
196.6
127.7
Te: onset temperature in the DSC curve; Tp: maximum peak temperature. r: linear coefficient; A: pre-exponential factor; E: the apparent activation
energy. Subscript K: Kissinger’s method; O: Ozawa’s method. ΔH: enthalpy of the exothermic decomposition reaction
o
C·min−1, the values of the extrapolated onset temperature
(Te) and the peak temperature (Tp) are obtained by DSC
curves of the exothermic process. The values of the apparent
activation energy (EK and E0) (where, subscript K: Kissinger’s
method; subscript O: Ozawa-Doyle’s method), the preexponential factor (AK) and linear correlation coefficient (rK
and r0) of the exothermic process are determined by Kissinger’s
method22 and Ozawa-Doyle’s method,23 respectively.
One can see that the apparent activation energeies (E) and
linear coefficient (r) obtained by Kissing method agree well
with that obtained by Ozawa method, and they are in the
normal range of kinetic parameters for the thermal decomposition reaction of the solid materials.24
2
Tei = Te0 + nβi + mβ i
Figure 8. The DSC curve of [K(ZTO)·H2O]∞ and ZTO·2H2O.
i = 1-4
(3)
Where n and m are coefficients.
2
o
−1
o
rate of 5 C·min is in the range of 183.81-252.80 C with
peak temperature of 211.51 oC, and its exothermic enthalpy
change is 229.24 kJ·mol−1. The exothermic process of
ZTO·2H2O is from 275.41 to 292.72 with peak temperature
of 290.82, and its exothermic enthalpy change is 391.69
kJ·mol−1.
In the TG-DTG curve of ZTO(phen)·H2O, there are two
main mass loss stages. The first mass loss with 25.61% starts
at 143.50 oC, and ends at 247.68 oC, while reaching its
highest rate at 217.78 oC. The second stage with 37.40%
starts at 251.29 oC and ends at 385.89 oC, while reaching its
highest rate at 318.05 oC.
In the TG-DTG curve of ZTO·2H2O, there is one mass
loss tage. The mass loss with 85.98% starts at 255.09 oC to
342.31 oC, while reaching its highest rate at 287.57 oC. The
mass loss coincides with the calculated value (84.49%)
which is the value of the ZTO molecule from ZTO·2H2O.
Therefore, it is inferred that the mass loss stage is assigned to
be the ZTO molecule from ZTO·2H2O.
The Kissinger and Ozawa equations are as follows:
β- = ln AR
1ln ---------- − E
--- ⋅ ---2
E
R
T
P
TP
(1)
0.4567E- = C
ln β + ------------------RTP
(2)
where β is the linear heating rate, TP is the peak temperature,
A is the pre-exponential constant, R is the gas constant, E is
the apparent activation energy and C is a constant.
Based on the multiple non-isothermal DSC curves
obtained at four different heating rates of 5, 10, 15 and 20
E0 – E0 – 4E0RTe0
Tb = ------------------------------------------2R
(4)
where E0 is the value of the apparent activation energy
obtained by Ozawa’s method.
The value of Te0 in the exothermic decomposition stage
corresponding to β → 0 obtained by Eq. (3) for ZTO·2H2O
and ZTO(phen)·H2O is 269.14 and 181.71 oC, respectively.
The critical temperature of thermal explosion (Tb) of
ZTO·2H2O and ZTO(phen)·H2O obtained by Eq. (4) is
282.21 and 195.94 oC,25,26 which is 299.64 oC, 275.08 oC and
237.74 oC for ATO, [K(ZTO)·H2O]15 and GZTO·H2O,16 respectively. Therefore, it is a good way to gain thermal stability
and low sensitivity through leading into carbon conjugated
system.
The Arrhenius equation can be expressed with Ea (the
average of Ek and Eo) and lnAk as follows:
3
196.6 × 10
For ZTO·2H2O: ln K = 37.67− -------------------------RT
3
127.7 × 10
For ZTO(phen)·H2O: ln K = 26.27− -------------------------RT
Above equations can be used to estimate the rate constants
of the initial thermal decomposition process of ZTO·2H2O
and ZTO(phen)·H2O.
Conclusion
ZTO(phen)·H2O and ZTO·2H2O were synthesized and their
structures were characterized by single crystal X-ray diffraction, elemental analyses, IR spectra analysis and thermal
investigation. The compound ZTO(phen)·H2O is made up of
2092
Bull. Korean Chem. Soc. 2013, Vol. 34, No. 7
one ZTO molecule, one phen molecule and one lattice water
molecule. The corresponding bond lengths, bond angles and
torsion angles of ZTO(phen)·H2O change slightly in comparison with ZTO·2H2O. In ZTO(phen)·H2O, the atom
N(6A) and N(12) atoms from ZTO molecule act as donors in
the hydrogen bonds, while N(1), N(2), N(3A) and N(4A)
atoms from phen molecule as acceptors with hydrogen
distances of 0.2127-0.2478 nm and angles of 123.88164.43o. The critical temperature of thermal explosion (Tb)
of ZTO(phen)·H2O and ZTO·2H2O is 195.94, 282.21 oC,
respectively.
Acknowledgments. The crystallographic information file
has been deposited by us in the Cambridge structure database (ZTO(phen)·H2O CCDC: 921610; ZTO·2H2O CCDC:
875646). These data can be obtained free of charge via
www.ccdc.cam.ac.uk., by e-mailing [email protected].
This investigation received financial assistance from the Key
Science and Technology Program of Shaanxi Province (No.
2013K02-25). And the publication cost of this paper was
supported by the Korean Chemical Society.
References
1. Badgujar, D. M.; Talawar, M. B.; Asthana, S. N.; Mahulikar, P. P.
J. Hazard. Mater. 2008, 15, 289.
2. Pagoria, P. F.; Lee, G. S.; Mitchell, A. R.; Schmidt, R. D.
Thermochim. Acta 2002, 384, 187.
3. Chavez, D. E.; Hiskey, M. A. J. Energy Mater. 1999, 17, 357.
4. Petrie, M. A.; Sheehy, J. A.; Boatz, J. A.; Rasul, G. J. Am. Chem.
Soc. 1997, 119, 8802.
5. Talawar, M. B.; Sivabalan, R.; Mukundan, T.; Muthurajan, H.;
Sikder, A. K.; Gandhe, B. R.; Rao, A. S. J. Hazard. Mater. 2009,
Cong Ma et al.
161, 589.
6. Nair, U. R.; Asthana, S. N.; Rao, A. S.; Gandhe, B. R. Def. Sci. J.
2010, 60, 137.
7. Hiskey M. A.; Goldman N.; Stine J. R. J. Energet. Mater. 1998,
16, 119.
8. Rice, B. M.; Byrd, E. F. C.; Mattson, W. D. Struct. Bond. 2007,
125, 153 (High Density Materials).
9. Oestmark, H.; Walin, S.; Goede, P. Cent. Eur. J. Energetic Mater.
2007, 4, 83.
10. Deblitz, R.; Hrib, C. G.; Plenikowski, G.; Edelmann, F. T. Inorg.
Chem. Comm. 2012, 18, 57.
11. Kroeger, C. F.; Hummel, L.; Mutscher, M.; Beyer, H. Berichte der
Deutschen Chemische Gcsellschaft. 1965, 98, 3025.
12. Ma, H. X.; Song, J. R.; Hu, R. Z. J. Anal. Appl. Pyrolysis. 2008,
83, 145.
13. Zhang, J. G.; Zhang, T. L. Acta Chim. Sin. 2000, 58, 1563.
14. Zhang, J. G.; Zhang, T. L. Chin. J. Phys. Chem. 2000, 16, 1110.
15. Ma, C.; Huang, J.; Ma, H. X. J. Mol. Struct. 2013, 1036, 521.
16. Zhong, Y. T.; Huang, J.; Song, J. R. Chin. J. Chem. 2011, 29,
1672.
17. Sheldrick, G. M. SHELXL-97, Program for X-ray Crystal Structure Refinement, University of Gottingen: Germany, 1997.
18. Roeges, N. P. G. A Guide to the Complete Interpretatin of Infraed
Spectra of Organic Structures, Wiley: New York, 1994.
19. EI-Shahawy, A. S.; Ahmed, S. M.; Sayed, N. K. Spectrochim.
Acta A 2007, 66, 143.
20. Sundaraganesan, N.; Karpagam, J.; Sebastian, S.; Cornard, J. P.
Spectrochim. Acta A 2009, 73, 11.
21. Socrates, G. Infrared and Raman Characteristic Group Frequencies,
3rd ed.; Wiley: New York, 2001.
22. Kissinger, H. E. Anal. Chem. 1957, 29, 1702.
23. Ozawa, T. Bull. Chem. Soc. Jpn. 1965, 38, 1881.
24. Hu, R. Z.; Yang, A. Q.; Ling, Y. J. Thermochim. Acta 1988, 123,
135.
25. Hu, R. Z.; Gao, S. L.; Zhao, F. Q. Thermal Analysis Kinetics, 2nd
ed.; Beijing: Science Press, 2008.
26. Zhang, T. L.; Hu, R. Z.; Xie, Y. Thermochim. Acta 1994, 244, 17.