Synthesis, crystal structure, and thermal properties of Ni(NH3)4(AFT)2

Article abstract of DOI:10.1177/1747519820939475

Ni(NH₃)₄(AFT)₂ [NiC₆H₁₆N₁₈O₂, AFT = 4-amino-3-(5-tetrazolate)furazan] is synthesized and characterized by elemental analysis and Fourier-transform infrared spectroscopy for the first time. X-ray diffraction measurements are used to determine the crystal structure of compound 1. The results demonstrate that compound 1 crystallized in the orthorhombic crystal system. The nickel(II) ion is six-coordinated by N atoms from two AFT-ligands and four NH₃ molecules. Its thermal properties are investigated by differential scanning calorimetry and thermogravimetry-derivative thermogravimetry methods, with the results demonstrating that the differential scanning calorimetry curve exhibits two endothermic and one exothermic processes. The endothermic processes are in the range of 130–510 °C with a peak temperature of 188 °C. The temperature from 230 to 400 °C is the exothermic process in which the peak temperature is 314.58 °C. In addition, Kissinger’s and Ozawa-Doyle’s methods are used for calculating the non-isothermal kinetics parameters. Moreover, the apparent activation energy (E), safety, and thermal stability parameters (T_SADT, T_TIT, T_b) for Ni(NH₃)₄(AFT)₂ are calculated. In addition, the calculated thermodynamic functions (?S^≠, ?H^≠, and ?G^≠) for the exothermic decomposition process of Ni(NH₃)₄(AFT)₂ are 55.07 J mol^?1 K^?1, 196.18 kJ mol^?1, and 164.90 kJ mol^?1, respectively.

Full text of DOI:10.1177/1747519820939475

9
research-arti
3cle2020 9475CHL0010.1177/1747519820939475Journal of Chemical ResearchWei et al.
Research Paper
Journal of Chemical Research
–8
1
Synthesis, crystal structure, and thermal
properties of Ni(NH ) (AFT)
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3
4
2
1
,2
1
1
1
Shu-han Wei , Xiao Ma , Zi-mei Ding , Kang-zhen Xu ,
2
1
2
Hong-xu Gao , Jie Huang
and Feng-qi Zhao
Abstract
Ni(NH ) (AFT) [NiC H N O , AFT=4-amino-3-(5-tetrazolate)furazan] is synthesized and characterized by elemental
3
4
2
6
16 18
2
analysis and Fourier-transform infrared spectroscopy for the first time. X-ray diffraction measurements are used
to determine the crystal structure of compound 1. The results demonstrate that compound 1 crystallized in the
orthorhombic crystal system. The nickel(II) ion is six-coordinated by N atoms from two AFT-ligands and four NH3
molecules. Its thermal properties are investigated by differential scanning calorimetry and thermogravimetry-derivative
thermogravimetry methods, with the results demonstrating that the differential scanning calorimetry curve exhibits two
endothermic and one exothermic processes. The endothermic processes are in the range of 130–510°C with a peak
temperature of 188°C. The temperature from 230 to 400°C is the exothermic process in which the peak temperature
is 314.58°C. In addition, Kissinger’s and Ozawa-Doyle’s methods are used for calculating the non-isothermal kinetics
parameters. Moreover, the apparent activation energy (E), safety, and thermal stability parameters (T
, T , T )
SADT
TIT
b
≠
≠
≠
for Ni(NH ) (AFT) are calculated. In addition, the calculated thermodynamic functions (∆S , ∆H , and ∆G ) for
3
4
2
−1
−1
−1
−1
the exothermic decomposition process of Ni(NH ) (AFT) are 55.07Jmol K , 196.18kJmol , and 164.90kJmol ,
3
4
2
respectively.
Keywords
crystal structure, 4-amino-3-(5-tetrazolate)furazan, nitrogen-rich heterocycles, synthesis, thermal behavior
Date received: 7 April 2020; accepted: 13 June 2020
N
N
N
NH
NH2
Ni(NO3)2 3H O
2
N
N
O
1School of Chemical Engineering, Northwest University, Xi’an, P.R. of
China
Science and Technology on Combustion and Explosion Laboratory,
Jie Huang, School of Chemical Engineering, Northwest University, Taibai
North Road, Xi’an 710069, Shaanxi Province, P.R. of China.
Email: huangjie@nwu.edu.cn
2
Xi’an Modern Chemistry Research Institute, Xi’an, P.R. of China
Corresponding authors:
Hong-xu Gao, Science and Technology on Combustion and Explosion
Laboratory, Xi’an Modern Chemistry Research Institute, Xi’an 710065,
P.R. of China.
Email: gaohx204@163.com

2
Journal of Chemical Research 00(0)
furazan rings can eliminate the acidic proton and optimize
28,29
the detonation properties.
A furazan derivative, 4-amino-
3
-(5-tetrazolate)furazan (HAFT), first synthesized by
30
Shreeve and colleagues, is made up of amino, tetrazole, and
furazan rings. This compound can be used to construct new
multi-dimensional (one-, two-, three-dimensional (1D, 2D,
3D)) energetic metal-organic frameworks (MOFs) with sev-
eral metal ions. Hence, a series of complexes of HAFT have
been reported such as [Cd(NH NH )(AFT) ·0.7H O] , [Cd(NH
2
2
2
2
n
Figure 1. Molecular structure of complex 1.
31
32
NHCOCONHNH ) (AFT) ·5H O] , [Cd(H O) (AFT) ],
2
2 1.5
2
2
n
2
2
2
33
[Cu(C H N H ) (AFT) ],[Cu(NH ) (AFT) ] and[Zn(NH )
3 6 2 4 2 2 3 4 2 3 4
34
Introduction
(AFT)2], which meet the needs of insensitive impact and
thermal stability.
The preparation and design of high-density and low-sensi-
tivity energetic materials, including pyrotechnics, propel-
lants and explosives, are the focus of intense research
interest in the chemical and materials industries. Energetic
materials have found significant use in military and civilian
applications during the past century.1–10 Although the early
energetic materials demonstrate considerable performance,
Herein, we have synthesized the new energetic complex
Ni(NH ) (AFT) . This complex will allow us to study the
coordination chemistry of the metal ion. In addition, we
have studied its crystal structure, thermal decomposition
mechanism, and sensitivity properties.
3
4
2
they often generate exhaust gases that are harmful to the Results and discussion
environment. Further research is directed toward finding a
Structure description
balance between excellent performance and the environ-
11
mental friendliness of energetic materials.
Single-crystal X-ray diffraction (XRD) indicated that com-
Efficient methods to promote the performance of ener- pound 1 belongs to the orthorhombic crystal system of the
getic materials involve the utilization of nitrogen-rich hetero- space group Cmce. It was observed that the structural unit
cycles such as furazan, triazole, pyrazole, imidazole, tetrazole of Ni(NH ) (AFT) (Figure 1) includes one nickel cation,
3
4
2
and their derivatives, which satisfy the pursuit of high-den- four neutral ammonia molecules, and two AFT anions. The
sity, high-oxygen content and pollution-free generated coordination environment of the Ni(NH ) (AFT) complex
3
4
2
1
2–16
33
gases.
They all possess high positive heats of formation is similar to that of Cu(NH ) (AFT) . In contrast, this
due to the presence of a large number of energetic bonds structure is different from that of Zn(NH ) (AFT) . Four
3 4 2
3
4
3
4
2
17,18
such as N–N, N=N, and N–C.
What is more, nitrogen- neutral ammonia molecules and two AFT anions form a
rich heterocycles such as furazan rings can ameliorate the centrosymmetric structure with respect to the central Ni
performance of energetic materials, especially in terms of atom. A octahedral configuration is adopted by the Ni and
19–22
oxygen balance.
Simple nitrogen-rich heterocycles N atoms, which are, respectively, from the central atom of
materials are not a current focus in energetic material the Ni(NH ) (AFT) complex, the AFT anion tetrazole ring
3
4
2
research, due to the requirements of higher energy and safer [N(2), N(2A)] and the four ammonia molecules [N(8),
properties. Scientists have studied the combination of two or N(8A), N(8B), N(8C)], which can form a six-coordinate
more nitrogen-rich heterocycles that can sharply promote environment. According to Table 1, the bond angles of the
23–27
2
energetic properties.
The combination of tetrazole and central Ni + and three contrapositioned N atoms are 180°
Table 1. Selected bond lengths (Å) and bond angles (°) for compound 1.
Bond
Distance (Å)
Angle
(°)
Ni(1)–N(2)
Ni(1)–N(2A)
Ni(1)–N(8)
Ni(1)–N(8A)
Ni(1)–N(8B)
Ni(1)–N(8C)
O(1)–N(5)
O(1)–N(6)
N(1)–N(3)
N(1)–C(4)
N(2)–N(3)
N(2)–N(4)
N(4)–C(4)
N(5)–C(5)
N(6)–C(9)
2.1088(15)
2.1088(15)
2.1176(14)
2.1176(14)
2.1176(14)
2.1176(14)
1.393(3)
1.376(3)
1.338(2)
1.337(3)
1.318(2)
N(2)–Ni(1)–N(2A)
N(8)–Ni(1)–N(8C)
N(8A)–Ni(1)–N(8B)
N(2A)–Ni(1)–N(8)
N(2A)–Ni(1)–N(8A)
N(2A)–Ni(1)–N(8A)
N(2A)–Ni(1)–N(8C)
N(2)–Ni(1)–N(8B)
N(2)–Ni(1)–N(8A)
N(2)–Ni(1)–N(8C)
N(2)–Ni(1)–N(8)
180.0
180.0
180.0
89.07(5)
89.07(5)
89.07(5)
89.07(5)
91.63(5)
91.63(5)
91.63(5)
91.63(5)
88.36(6)
88.36(6)
91.63(6)
91.63(6)
1.335(2)
1.326(2)
1.294(3)
1.285(3)
N(8)–Ni(1)–N(8A)
N(8)–Ni(1)–N(8B)
N(8C)–Ni(1)–N(8A)
N(8C)–Ni(1)–N(8B)

Wei et al.
3
Table 2. Hydrogen bond lengths (Å) and bond angles (°) for compound 1.
D–H···A
D–H (Å)
H···A (Å)
D–H···A (°)
N(8)–H(8C)···N(5)#1
N(7)–H(7A)···O(1)#2
N(8)–H(8A)···N(1)#3
N(7)–H(7A)···N(4)#3
0.84(3)
0.87(3)
0.87(3)
0.87(3)
2.47(3)
2.25(2)
2.61(2)
2.28(3)
168(3)
123(2)
159(2)
129(2)
Symmetry codes: #1 1 – x, −0.5 + y, 0.5 – z; #2 1 – x, 0.5 + y, −0.5 + z; #3 1.5 – x, −y, −0.5 + z.
Figure 3. Packing structure of complex 1.
Figure 2. The 2D chain of complex 1.
form a two-dimensional structure. As illustrated in Figure
[
<N(2)–Ni(1)–N(2A), <N(8)–Ni(1)–N(8C), <N(8A)– 3, compound 1 is described as a 1D chain structure.
Ni(1)–N(8B)]. In addition, we surprisingly find that the Intermolecular hydrogen bonds between the AFT ligands
bond angles of the N atoms and the Ni(II) ion are very close and NH molecules form the 2D supramolecular layer of
3
to 90° [<N(2A)–Ni(1)–N(8)=89.07(5)°, <N(2A)–Ni(1)– complex 1 and can improve the thermal stability.
N(8A)=89.07(5)°, <N(2A)–Ni(1)–N(8B)=89.07(5)°,
<
N(2A)–Ni(1)–N(8C)=89.07(5)°, <N(2)–Ni(1)–N(8)=
Thermal decomposition behavior
9
1.63(5)°, <N(2)–Ni(1)–N(8A)=91.63(5)°, <N(2)–Ni(1)–
N(8B)=91.63(5)°,<N(2)–Ni(1)–N(8C)=91.63(5)°,<N(8)– The thermal behavior of compound 1 was analyzed by dif-
Ni(1)–N(8B)=88.37(10)°,<N(8)–Ni(1)–N(8A)=88.37(6)°, ferential scanning calorimetry (DSC) and thermogravime-
<
N(8C)–Ni(1)–N(8A)=91.63(6)°, <N(8C)–Ni(1)–N(8B)= try-derivative thermogravimetry (TG-DTG), with a linear
8.37(6)°, <N(8C)–Ni(1)–N(8B)=88.37(6)°]. Hence, these heating rate of 10°Cmin− under a nitrogen atmosphere.
1
8
almost vertical bonds form a twisted octahedral geometry, The thermal behavior curves are shown in Figures 4 and 5.
where the equatorial plane is determined by four N atoms The DSC curve of compound 1 exhibits two exothermic
[
N(8), N(8A), N(8B), N(8C)], and the axial plane is com- and one endothermic processes. The exothermic process
posed of two N atoms [N(2), N(2A)]. The data in Table 1 occurs from 230 to 400°C, with a peak temperature of
include the Ni bond lengths and the bond angles of the six 314.58°C. The endothermic process is in the range of 130–
N atoms surrounding Ni [Ni(1)–N(2) = 2.1088(15) Å, 510°C, with a peak temperature of 188°C. As shown in the
Ni(1)–N(2A) = 2.1088(15) Å, Ni(1)–N8(A/B/C) = TG curve in Figure 6, the first mass loss stage occurs
2
.1176(14) Å]. Thus, we can easily determine the axial between 120 and 230°C and reveals a weight loss of
plane, which includes two equivalent bonds, and is equally 17.11% during this period, which may be due to the loss of
divided by the equatorial plane composed of four equidis- molecules of H O and the NH . The main mass loss of 48%
2
3
tant bonds.
of compound 1 occurs from 230 to 400°C, where the DSC
Since there are many N and O atoms present in this com- curve illustrates a sharply exothermic peak at 314.58°C,
pound, a significant number of hydrogen bonds are also and is probably due to decomposition of HAFT. The final
present. As can be seen in Table 2, three intermolecular mass loss stage of 29.03% can be ascribed to the decompo-
hydrogen bonds exist in the Ni complex. There is no inter- sition of the residues and we observe a small exothermic
molecular hydrogen bond between two Ni(NH ) (AFT)
peak at 462.37°C as evidence of this in the DSC curves. It
3
4
2
molecules, which are connected by van der Waals forces. is very interesting that the major mass loss in compound 1,
3
3
34
As shown in Figure 2, the hydrogen bonds N(8)– Cu(NH ) (AFT) and Zn(NH ) (AFT) all occur from
3
4
2
3 4
2
H(8C)···N(5), N(7)–H(7A)···O(1), N(8)–H(8A)···N(1) and the 200 to 400°C. The main loss of mass from compound 1
N(7)–H(7A)···N(4) and the molecule of Ni(NH ) (AFT)
occurs during the middle period of the TG process.
3
4
2

4
Journal of Chemical Research 00(0)
in which the linear heating rate is β, the peak temperature
−
1
(
K) is T , A is the pre-exponential constant (s ), the gas
p
−1
−1
constant (8.314JK mol ) is represented by R, and the
apparent activation energy (kJmol ) is referred to as E.
−1
Based on the above data, the kinetic parameters, includ-
ing the extrapolated onset temperature (T ) and peak tem-
e
perature (T ), have been calculated. The values of T and
p
e0
Tp0 (extrapolated temperature and peak temperature when
the heating rates approach to 0) can be obtained through
equation (3)
2
3
T
= T
+ aβ + bβ + cβ
i
i = 1, 2, 3, 4
3)
(
e or p
)
i
(
e0 or p0
)
i
i
(
in which the coefficients are a, b and c.
The acquired E (the average of E and E ) and A values
−
1
Figure 4. DSC curve of compound 1 at 10°C·min .
a
k
o
k
can be used for expressing the Arrhenius equation of com-
pound 1, as follows
3
lnk = 36.73− 200.63 × 10 /
(
RT
)
Thermal stability, safety parameters,
and thermodynamic functions
As is already known, the self-accelerating decomposition
temperature (TSADT or T ), thermal ignition temperature
e0
(
(
TTIT or Tbe0) and critical temperature of thermal explosion
Tb or Tbp0) are important parameters, which can ensure safe
storage and process operations for evaluating the thermal
stability of energetic materials. The TSADT, TTIT and T val-
b
ues of compound 1 are calculated from equations (4) and
Figure 5. TG-DTG curves of compound 1 at 10°C·min−1
(5), respectively (see Table 4), and are 265.69, 278.31 and
3
08.94°C, respectively. We find that compound 1 shows
3
3
preferable thermal stability in the exothermic decomposi-
tion stage
However, the main mass losses for Cu(NH ) (AFT) and
3
4
2
3
4
Zn(NH ) (AFT) occur during the final period of the TG
3
4
2
process. Although the peak temperature of compound 1 is
3
4
TSADT = Te0
lower than that of Zn(NH ) (AFT) (320.58°C), it is
(4)
3
4
2
higher than those of Cu(NH ) (AFT) (310.92°C),
3
4
2
3
3
Cu(C H N H ) (AFT) (219.08°C), RDX (219°C) and
HMX (275°C). These data indicate that compound 1 pos-
3
6
2
4 2
2
3
5
2
O
Tbe0
bp0
= E − E − 4E RT
e0
p0
) / 2R
(5)
sesses high thermal stability.
(
)
(
O
O
(
)
The Ozawa method can be employed for obtaining the
Non-isothermal kinetic analysis
apparent activation energy (E ). In line with A and E , the
0
a
The apparent activation energy (E /E ), pre-exponential
k
o
thermodynamic parameters of the decomposition process
of compound 1 were obtained. The entropy of activation
ΔS≠), enthalpy of activation (ΔH≠), and free energy of
factor (A ), and linear correlation coefficients (r /r ) have
k
k
o
3
6
37
been calculated by Kissinger’s and Ozawa-Doyle’s
(
methods. These data are given in Table 3. The equations for
Kissinger’s and Ozawa-Doyle’s methods are as follows
activation (ΔG≠) of the main thermal decomposition reac-
tion of complex 1 corresponding to A=A , T=T and
k
p0
E =E can be computed from equations (6)–(8). The data
are shown in Table 4
a
k
β
 RA Ea
1
ln
= ln
−
.
(1)




2
TP
Ea
R T
P
≠
e∆
S
/R
A =
(
kBT h
)
(6)
(7)
0
.4567E
logβ +
= C
(2)
≠
RTP
∆H = E − RT
a

Wei et al.
5
The standard molar enthalpy of combustion (Δ Hθ) can
c
be verified by using equation (10). The parameter Δn is the
change of the total molar amount of gases in the reaction
−1
−1
process, and R and T are 8.314Jmol K and 298.15K,
respectively. The enthalpy of combustion of compound 1
−1
is −4952.20kJmol , which is lower than those of
−1
Cu(NH ) (AFT) (−4857.18kJmol ) and Zn(NH ) (AFT)
3
4
2
3 4
2
−1
(−4888.54kJmol ).
Hess’ law and the combustion reactions were employed
for obtaining the standard enthalpy of formation (Δ Hθ) of
f
compound 1. The enthalpies of formation of CO
2
−1
−1
(
(
g, −393.51kJmol ), H O (l, −285.83kJmol ), and NiO
2
−1
s, −244.3kJmol ) are known, while the enthalpy of com-
−1
bustion of compound 1 is 60.20kJmol .
−
1
Figure 6. TG-DSC curves of compound 1 at 10°C·min .
Detonation property
The detonation parameters, including the detonation veloc-
ity (D), the detonation pressure (P), and the heat of detona-
tion (Q), are significant for energetic performance
evaluation in energetic materials. Currently, the largest
≠
≠
≠
∆
G = ∆H −T∆S
(8)
where kB and h represent the Boltzmann constant
1.381×10 JK ) and the Planck constant (6.626×
Js), respectively.
Compared with Cd(pztza) and Cd(pzpha)(CH OH) ,
the critical temperatures of which are 275.85°C and
64.75°C, compound 1 has a higher critical temperature.
39
exothermic principle proposed by Kamlet and Jacobs is a
–
23
−1
(
1
40
valuable reference for research. Pang and colleagues
–
34
0
adopted a new empirical strategy to calculate these param-
eters that can be used as a basis to make predictions about
metal-based energetic materials. It is easy to estimate the
detonation reaction by using this strategy, which includes
the arbitrary theory of Kamlet and Jacobs (K-J) and the
hypothesis of the Becker–Kistiakowsky–Wilson (BKW)
equation. The detonation reaction of compound 1 is
described by equation (11). Furthermore, the K-J equations
are given in equations (12)–(15)
3
8
2
3
2
2
Energy of combustion and enthalpy of
formation
The energy of combustion (Δ Hθ), the enthalpy of forma-
tion (Δ Hθ), and the constant-volume energy of combustion
c
f
(
ΔcU) of complex 1 were measured using an IKA C5000
oxygen bomb calorimeter. The value of ΔcU is
C H N O Ni → Ni + 2H O + 4NH + 6C + 7N
2
(11)
(12)
(13)
(14)
6
16 18
2
2
3
−
1
−4933.61kJmol . The bomb combustion reaction equa-
tions are displayed as follows
1/2
D =1.01Φ
(
1+1.30ρ0
)
C H N O Ni
(
s
)
+19/2O2
(
g
)
=NiO
(
s
)
l
+6CO2
+9N2
( )
(
g
6
16 18
2
(9)
2
+
8H O
(
)
g
)
P =1.558Φρ0
2
1
)
/2
θ
m
∆c H = ∆ U + ∆nRT
(10)
Φ = 31.68N
(
MQ
c
m
Table 3. Parameters determined from the DSC curves at different heating rates (β) for compound 1.
−
1
Te0 (°C) Tp0 (°C) E (kJmol ) logA (s−1) rk
−1
−1
Ē (kJ·mol−1)
0.9871 200.63
β (°Cmin ) Te (°C)
Tp (°C)
E (kJmol ) ro
k
o
5
1
1
2
.0
276.23
286.77
294.69
297.20
304.73
314.58
317.36
324.19
265.69
294.88 200.97
15.95
0.9858 200.29
0.0
5.0
0.0
Subscript k, data obtained by the Kissinger method; subscript o, data obtained by the Ozawa method.
≠
≠
≠
Table 4. Values of TSADT, Tbe0, Tbp0, ΔS , ΔH , and ΔG for compound 1.
≠
−1
≠
−1
≠
−1
Sample
TSADT (°C)
Tbe0 (°C)
Tbp0 (°C)
ΔS (JmolK )
ΔH (kJmol )
ΔG (kJmol )
1
265.69
278.31
308.94
55.07
196.18
164.90

6
Journal of Chemical Research 00(0)
Table 5. Detonation properties of compound 1 and some similar compound.
−
1
Q (kJg−1)
Sample
D (kms )
P (GPa)
Ni(NH ) (AFT) (1)
5.54
5.41
6.02
5.62
13.15
12.80
14.95
18.36
1.894
2.673
2.887
1.146
3
4
2
Zn(NH ) (AFT)
3
3
2
Cu(pn) (AFT)
2
2
Pb(HCONHNH ) (AFT)
2
2
2
N
N
N
NH
2
H N
Ni(NO
3
)
2
2
3H O
+
aqueous ammonia
3 4 2
Ni(NH ) (AFT)
N
N
O
HAFT
Scheme 2. Synthesis of compound 1.
Scheme 1. Preparation of HAFT.
Impact sensitivity
θ
m
θ
m
∆ f H (denotationproducts) − ∆ H (explosive)
f
Q =
The impact sensitivity (IS) is considered to be a significant
property of energetic materials from the view point of per-
sonal safety. Energetic materials are required to be insensi-
tive, which can reduce the risk of unnecessary accidents.
The data on the IS were obtained using a drop hammer IS
device with a 2.5kg hammer weight at a height of 1.2m.
The experiment revealed that compound 1 had a lower IS
(
15)
Formula weight of explosive
−1
where D and P represent the detonation velocity (kms )
and the detonation pressure (GPa), respectively; the density
of explosive (gcm ) is ρ; N can express the moles of deto-
nation gases per gram of explosive; M is the average
molecular weight of these gases; and the heat of detonation
kcalg ) is referred to as Q.
We can easily obtain many details from the above equa-
tions. The detonation velocity (D), the detonation pressure
P), and the heat of detonation (Q) were 5.54kms ,
−
3
3
4
(
(
15.9J), being less sensitive than Zn(NH ) (AFT)
3 4 2
3
3
42
15.0J), Cu(NH ) (AFT)
2
(12.0J), and HMX (7.4J).
−
1
3 4
(
The advantage of this IS makes compound 1 an interesting
candidate as a new, safe energetic material.
−1
(
1
−
1
−1
Conclusion
3.15GPa, and 0.452kcalg (1.894kJg ) for compound
1
. The detonation properties of some similar compounds In conclusion, Ni(NH ) (AFT) has been synthesized for the
3 4 2
4
1
are given in Table 5.
first time and structurally characterized. Ni(NH ) (AFT)
3 4 2
From Table 5, it can be seen that. Zn(NH ) (AFT) has the crystallized in the orthorhombic space group Cmce. Moreover,
34
3
3
2
lowest detonation velocity (D). The highest detonation pres- the DSC and TG-DTG curves show that Ni(NH ) (AFT)
3
4
2
sure (P) of 18.36 GPa is exhibited by Pb(HCONHNH2)2 possesses one endothermic decomposition peak and two exo-
AFT) .As for the heat of detonation (Q), Cu(pn) (AFT)
thermic decomposition peaks, the former is sharp and the lat-
has the highest value of the compounds presented in ter is smooth, and the thermal decomposition processes can
(
2
2
2
Table 5.
be divided into three stages. The endothermic process is in the
range of 130–510°C with a peak temperature of 188°C. The
exothermic process occurs from 230 to 400°C, with a peak
temperature of 314.58°C. The self-accelerating decomposi-
tion temperature (TSADT), thermal ignition temperature (TTIT),
Specific heat capacity
The continuous specific heat capacity of compound 1 was
measured by using a Micro-DSC III instrument. Equation
and critical temperature of thermal explosion (T ) for
b
Ni(NH ) (AFT) are 265.69, 278.31, and 308.94°C, respec-
(
16) accurately expresses the specific heat capacity equa-
3 4
2
tively, which indicate good thermal safety. The non-isother-
mal kinetic analysis data indicate the Arrhenius equation can
tion of compound 1. The specific heat capacity at
−
1
−1
2
98.15 K is 1079.27 J g K . Thus, the temperature is an
3
be expressed as lnk=36.73–200.63×10 /(RT). At the same
essential factor that influences the specific heat capacity
of compound 1
−3
time, complex 1 shows higher density (1.700gcm ) and a
relatively low IS (15.9J), being much lower than RDX and
HMX. Therefore, Ni(NH ) (AFT) should be investigated
3
4
2
−
1
−1
−2
−4
2
Cp J•g K =1.0102 +1.2294×10 T −5.9527×10 T
(
)
further as a competitive energetic material.
−
5
3
−7
4
+
+
1.7228×10 T − 2.2246×10 T
Experimental
−
9
5
1.0309×10 T
Most energetic materials are flammable and explosive sub-
(16) stances. In some experiments, many harmful substances

Wei et al.
7
Table 6. Crystal data and structure refinement details of
compound 1.
Preparation of HAFT
A three-step literature procedure was used to synthesized
Compound 1
43
HAFT in Scheme 1.
Chemical formula
NiC H N O
6 16 18 2
−
1
Formula weight (gmol ) 431.08
Synthesis of [Ni(NH ) ](AFT) (1)
3
4
2
Temperature (K)
Wavelength (Å)
Crystal system
Space group
296(2)
0.71073
orthorhombic
Cmce
HAFT (0.3828g, 2.5mmol) was dissolved in deionized
water (5mL) and charged into a glass reactor with a water
bath. The reaction solution was stirred with a mechanical
agitator and heated at ambient temperature. Ni(NO3)2
(0.1914g, 1.25mmol) dissolved in 5mL of deionized water
was added to HAFT solution during 15min. Then, aqueous
ammonia solution (1mL) was added to the above-men-
tioned reacting mixture under constant stirring. The solu-
tion was stirred for an additional 60min. Finally, filter
Size (mm)
Volume (Å )
0.21×0.16×0.18
1684.3(5)
4
1.700
888
3
Z
−
3
Dcalc (gcm )
F(000)
θ range (°)
Index ranges
Reflections collected
Reflections unique
Refinement method
R(int)
2.070–26.109
−7⩽h⩽8, −24⩽k ⩽20, −15⩽l⩽14 residue was filtered out. The mother liquor was sealed and
4411
left at room temperature (Scheme 2). Appropriate crystals
for X-ray measurements were obtained after 2months.
m.p.: 155–155.8°C. Anal. calcd. for NiC H N O : C,
917
Full-matrix least-squares on F2
6
16 18
2
0.0236
1
5
–
9
6.72; H, 3.74; N, 58.50; found: C, 16.74; H, 3.72; N,
a (Å)
b (Å)
c (Å)
α (°)
6.9055(11)
19.676(3)
12.3964(19)
90.00
8.46. IR (KBr): 3491 (w, –NH ), 3365 (m, –NH), 1639 (m,
2
C=O), 1594 (m, N=N), 1200 (m, –C–N), 1171 (s, –C–N),
87 (m, –NH ), 865 (w, –NH ), 667 (s, –NH ).
3
2
3
β (°)
90.00
γ (°)
90.00
1.048
0.0219
Crystal structure determination
and refinement
2
Goodness-of-fit on F
R1 [I>2r(I)]
wR [I>2r(I)]
R1 (all data)
0.0611
0.0246
0.0628
1903740
The single-crystal X-ray determination was carried out
with a Bruker SMART APEX CCD X-ray diffractometer
using graphite-monochromated Mo-Ka radiation (λ=
2
wR (all data)
2
CCDC
0
.71073nm) and an ϕ–ω scan mode at 296(2) K. The struc-
tures were resolved by direct methods (SHELXTL-97) and
optimized by the full-matrix least-squares method on F
CCDC: Cambridge Crystallographic Data Centre.
2
with anisotropic thermal parameters for all non-hydrogen
are produced, such as strong acids and bases. Therefore, atoms.44,45 The hydrogen atoms were determined with theo-
extreme care should be taken when conducting these retical models. CheckCIF was used for checking the final-
experiments. Appropriate protective equipment must be ized Crystallographic Information File (CIF) file. The
used.
refinement parameters and crystallographic data for
Ni(NH ) (AFT) are collected in Table 6.
3
4
2
Materials and methods
Declaration of conflicting interests
All chemicals were commercially available reagents of
analytical grade and used directly. A VarioEL III elemental
analyzer (Elementar Co., Germany) was used to record the
elemental analysis. An EQUINX55 infrared spectrometer
was used to acquire the Fourier-transform infrared spec-
troscopy (FTIR) spectrum as a KBr pellet in the range of
The author(s) declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
article.
Funding
−
1
The author(s) disclosed receipt of the following financial support
for the research, authorship, and/or publication of this article: The
authors are very grateful for the financial support from the
National Natural Science Foundation of China (No. 21673168)
and the Natural Science Basic Research Foundation of Shaanxi
Province (No. 2018JM2061).
4
000–500cm . DSC was performed using a DSC-Q2000
apparatus (TA, USA) under a nitrogen atmosphere at a flow
−
1
rate of 50mLmin , with heating rates (β) of 5, 10, 15, and
−
1
2
0°Cmin from 70 to 470°C. The TG-DTG experiment
was implemented with an SDT-Q600 apparatus (TA, USA)
under the conditions of a flow of nitrogen gas with a flow
−
1
−1
rate of 100mLmin and a heating rate of 10.0°Cmin . A
ZBL-B IS instrument (Nachen Co., China) was used for
determining the IS.
ORCID iD
Jie Huang
https://orcid.org/0000-0003-3561-2819

8
Journal of Chemical Research 00(0)
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