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Preparation, Crystal Structure, and Thermal Analysis of Two Energetic
Salts Based on Nitro Phenolic Compounds with Diamino-glyoxine
Zhi-Bin Zhang,[a] Jian Qin,[a] Xin Yin,[a] and Jian-Guo Zhang*[a]
Keywords: Energetic salt; Picric acid; Styphnic acid; Crystal structure; Energetic properties; Sensitivity
Abstract. As a key research objective for environmentally friendly
energetic materials, energetic salts without heavy metal have received
wide attention. The energetic salts DAG·PA·H2O (1) and
DAG·TNR·H2O (2) were synthesized by using diamino-glyoxine
(DAG) and picric acid (PA) or 2,4,6-trinitro-resorcinol (TNR) as raw
materials, and their structures were characterized by elemental analy-
sis, FT-IR, 1H NMR, and 13C NMR spectroscopy. Single crystals of
the title salts were cultured and their structures were determined by X-
ray single-crystal diffraction. Both salts belong to the triclinic space
group P1 with density values of 1.764 and 1.751 g·cm–3, respectively.
Introduction
Along with increasing attention to environmental protection,
the research on energetic materials has already changed to the
development of “green” energetic materials, which have high
energetic properties and good stability.[1,2] It is highly in need
to study new high energy density materials (HEDMs) with di-
verse standards such as excellent performance, environmental
compatibility, as well as safety concerns like lower impact sen-
sitivity, to satisfy the necessary future needs.[3,4] One important
branch of HEDMs are energetic ionic salts, which have be-
come the focus of research in the field of energetic materials,
because of their good thermal stability, high densities, high
heats of formation and so on.[5,6] And because of a large
number of N–N and C–N bonds, as well as intra- and intermo-
lecular hydrogen bonds in the structure of these substances,
they have stable aromatic structure, which help to improve the
stability.[7]
Nitro phenolic compounds such as 2,4,6-trinitrophenol (pic-
ric acid, PA) and 2,4,6-trinitroresorcinol (styphnic acid, TNR)
have been widely used in the explosive industry as the materi-
als.[8–10] Their metallic salts are promising primary explosives,
such as KPA or LTNR.[11,12] The π system and nitro groups in
the compound can also benefit to form intermolecular
hydrogen bonds, which can increase the stability of com-
* Prof. Dr. J.-G. Zhang
Fax: +86-10-68918091
E-Mail: zjgbit@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, 䊏,(䊏), 0–0
DOI: 10.1002/zaac.201600189
The thermal decomposition behaviors of both salts were investigated
by differential scanning calorimetry (DSC), the non-isothermal kinetic
parameters and the critical temperature of thermal explosion were cal-
culated. The heats of formation for the salts were also determined
through the combustion heats date measured by using the oxygen
bomb calorimetry. In addition, the detonation pressure (P) and detona-
tion velocities (D) of the salts were predicted by using the K-J equa-
tions, and their sensitivities towards impact and friction were tested.
The results indicated that the title salts have potential applications in
the field of energetic materials.
pounds.[13] Unfortunately, the heavy metallic salts are always
too sensitive to use, for example, LTNR is extremely sensitiv-
ity to static electric spark. Also, the presence of heavy metals
can cause environmental problems. Thus, the synthesis of ener-
getic, insensitive, low-toxic materials is a great demand. Nitro
phenol organic salts, which decomposed mainly as N2, have
a promising future as eco-friendly and chemically compatible
primary explosive and gas generators in industrial applica-
tions.[14–16]
In this work, two energetic ionic salts DAG·PA·H2O (1) and
DAG·TNR·H2O (2) were synthesized by using diamino-glyox-
ine (DAG) reacting with PA or TNR aqueous solution. The
crystal structures of 1 and 2 were also determined by using X-
ray single-crystal diffraction. Both salts were fully charac-
terized by elemental analysis, FT-IR spectroscopy, 1H and 13C
NMR spectroscopy. Their thermal decomposition behaviors,
heat of combustions were also investigated through DSC and
oxygen bomb calorimetry. In addition, their detonation proper-
ties and sensitivities toward impact and friction were predi-
cated.
Results and Discussion
Synthesis
Diamino-glyoxine (DAG) was synthesized based on litera-
ture.[17] DAG·PA·H2O (1) and DAG·TNR·H2O (2) were pre-
pared by reacting a DAG aqueous solution with an aqueous
suspension of PA or TNR, respectively. The synthesis route for
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Scheme 1. Synthesis route for salts 1 and 2.

salt 1 and 2 is shown in Scheme 1. Both synthetic routes Table 1. Crystal data and structure refinement details for salts 1 and
shown are basically acid-base reactions. 2.
1 2

Crystal Structures Empirical formula C8H11N7O10 C8H11N7O11

Formula mass 365.24 381.24
The powders of the salts were recrystallized from water. Temperature /K 298(2) 296(2)
Crystals of DAG·PA·H2O (1) with suitable sizes of Crystal system triclinic triclinic
Space group P1 P1
0.49 ⫻ 0.40 ⫻ 0.21 mm and DAG·TNR·H2O (2) with suitable Z 2 2
sizes of 0.18 ⫻ 0.20 ⫻ 0.22 mm were selected for single-crystal a /Å 7.4800(7) 7.5082(8)
XRD determination. The crystal data collection of the ener- b /Å 7.9953(8) 8.2576(9)
getic salts 1 and 2 were carried out by using graphite-mono- c /Å 12.7046(11) 12.9169(15)
α /° 87.563(2) 85.661(2)
chromated Mo-Kα radiation (λ = 0.071073 nm). The structures β /° 76.260(10) 74.347(2)
were solved by direct methods using SHELXS-97[18] and re- γ /° 68.838(10) 69.659(2)
fined anisotropically on F2 by the full-matrix least-squares Cell volume /Å3 687.50(11) 722.91(14)
technique using the SHELXL-97 programs.[19] All non- Dc /g·cm–3 1.764 1.751
hydrogen atoms were located from the differential Fourier F(000) 376 392
θ /° 2.73~25.02 2.63~28.39
map, and all hydrogen atoms were generated geometrically. h –8 to 6 –10 to 9
The results concerning crystallographic data collection and k –9 to 9 –11 to 10
structure refinements are summarized in Table 1. The selected l –14 to 15 –17 to 12
bond lengths and angles are listed in Table 2, while the Reflections collected 3492 5894
Reflections unique 2382 3597
hydrogen bond lengths and bond angles of 1 and 2 are col- Rint 0.0262 0.0133
lected in Table 3, respectively. Data/restraint/parameter 2382/0/229 3597/6/250
The crystal structures of the salts are shown in Figure 1, Goodness-of-fit on F2 1.037 1.006
Figure 2, and Figure 3, respectively. One diamino-glyoxime R1,[I ⬎ 2σ(I)] 0.0454 0.0559
(DAG) cation, one PA or TNR anion, and one crystal water wR2, [I ⬎ 2σ(I)] 0.1245 a) 0.1498 b)
R1, (all data) 0.0551 0.0669
exist in the unit cells of salts 1 and 2 (see Figure 1). A proton wR2, (all data) 0.1325 a) 0.1583 b)
from the hydroxyl group (O3 or O8) of PA/TNR molecule is Δρmax /e·Å–3 0.290 0.674
lost, and transferred to the N atom (N1 or N6) of the DAG Δρmin /e·Å–3 –0.286 –0.370
molecule. The PA/TNR negative anion and the DAG mono- a) w = 1/[s2(Fo2) + (0.0921P)2 + 0.0000P], where P = (Fo2 + 2Fc2)/3.
valent cation are bonded together by electrostatic attraction, b) w = 1/[s2(Fo2) + (0.0753P)2 + 0.5793P], where P = (Fo2 + 2Fc2)/3.
and the crystal water is connected through hydrogen bonds.
Both salt 1 and 2 crystallize in a triclinic system, space group
P1, with the density of 1.764 g·cm–3 and 1.751 g·cm–3, respec- polygon, due to the presence of oxygen atoms and nitro
tively groups, according to the values of bond angles in Table 2.
Some multiple-bond character is present in the nitro phen- The influence of hydrogen bonds is one of the important
olic anions, as can be seen in Table 2. The average values of factors in stabilizing the crystal structures for the title salts.
C–C bond lengths are 1.398 Å for PA anion, and 1.402 Å for The hydrogen atoms in amino groups and hydroxyl groups,
TNR anions, which are located in the range of normal C=C combined with oxygen atoms in nitro groups of the benzene
bond length (1.32 Å) and C–C bond length (1.53 Å). The ring and the crystal water, contributed to a lot of intermolecular
average values of C–N bond lengths are 1.449 Å for PA anion, and intramolecular hydrogen bonds in these two salts. The de-
and 1.451 Å for TNR anion, which is shorter than the normal tailed information is listed in Table 3. The DAG cations and
C–N bong length (1.47 Å), and significantly longer than the crystal water molecules are interconnected with each other by
normal C=N bond length (1.22 Å).[20] The results indicated hydrogen bonds forming ladder-like ribbon motifs (see Fig-
that the ring exists as a large π conjugated system, an irregular ure 2). The single PA/TNR anions are linked to the main chain

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Table 2. Selected bond lengths /Å and bond angles /° for salts 1 and 2.
1
N1–C1 1.305(3) N2–C2 1.282(2) C1–N1–O1 117.27(16) C2–N2–O2 109.30(16)
N1–O1 1.379(2) N2–O2 1.406(2) O4–N5–O5 121.89(17) O4–N5–C4 119.70(15)
N3–C1 1.298(2) C1–C2 1.475(3) O5–N5–C4 118.31(16) O7–N6–O6 123.37(18)
N4–C2 1.341(3) N5–O4 1.213(2) O7–N6–C6 118.24(17) O6–N6–C6 118.37(18)
N5–O5 1.218(2) C3–C8 1.444(3) O9–N7–O8 123.80(16) O9–N7–C8 118.76(16)
N5–C4 1.456(2) C3–C4 1.444(3) O8–N7–C8 117.42(16) N3–C1–N1 121.65(19)
N6–O7 1.221(2) C4–C5 1.370(3) N3–C1–C2 121.24(18) N1–C1–C2 117.11(16)
N6–O6 1.225(2) C5–C6 1.381(3) N2–C2–N4 126.18(19) N2–C2–C1 114.80(17)
N6–C6 1.441(3) C6–C7 1.387(3) N4–C2–C1 118.99(16) O3–C3–C8 123.00(17)
N7–O9 1.211(2) C7–C8 1.357(3) O3–C3–C4 125.10(17) C7–C8–N7 116.38(17)
N7–O8 1.217(2) C3–O3 1.250(2) C7–C6–N6 119.33(18) C5–C4–N5 116.46(16)
N7–C8 1.452(2) C3–C4–N5 119.70(16) C5–C6–N6 119.54(17)
2
N6–C7 1.305(2) N7–C8 1.288(2) O6–N3–O5 123.80(2) C2–C1–N1 119.10(2)
N6–O9 1.384(2) N7–O10 1.411(2) O5–N3–C5 117.70(2) C6–C1–N1 120.50(2)
N4–C7 1.306(2) C7–C8 1.482(3) C8–N7–O10 109.66(15) C2–C3–N2 116.70(18)
N5–C8 1.344(2) N1–O2 1.214(3) O4–N2–C3 119.25(19) O3–N2–C3 118.80(2)
N1–O1 1.257(3) N3–O5 1.208(3) O8–C4–C3 125.79(17) C7–N6–O9 117.03(16)
N2–C3 1.450(2) N1–C1 1.435(3) O6–N3–C5 118.50(2) C6–C5–N3 117.65(18)
N2–O4 1.205(3) C4–O8 1.261(2) O1–N1–C1 117.10(2) O4–N2–O3 121.60(2)
N2–O3 1.218(3) C1–C2 1.387(3) O7–C6–C1 126.68(19) O7–C6–C1 117.41(18)
N3–C5 1.467(3) C1–C6 1.406(3) N6–C7–N4 122.51(19) N6–C7–C8 116.51(16)
N3–O6 1.191(3) C2–C3 1.371(3) N4–C7–C8 120.97(17) N7–C8–N5 126.63(19)
C5–C6 1.377(3) C3–C4 1.445(3) N7–C8–C7 114.70(16) N5–C8–C7 118.67(17)
C6–O7 1.348(3) C4–C5 1.426(2) O2–N1–O1 123.00(2) O2–N1–C1 119.90(2)

Table 3. Hydrogen bond lengths /Å and angles /° of salts 1 and 2.

D–H···A D–H H···A D···A ⬍(D–H···A) Symmetry code
1
N1–H1···O10 0.860 1.950 2.736 151.38 x, y, z–1
N3–H3A···O5 0.860 2.489 3.000 118.89 –x+1, –y + 1, –z + 1
O10–H10D···O9 0.850 2.292 3.133 170.41 –x+1, –y + 1, –z + 1
N3–H3A···O7 0.860 2.504 3.004 117.88 –x, –y + 2, –z + 1
N3–H3B···O3 0.860 2.010 2.857 168.01 x–1, y, z
N3–H3B···O4 0.860 2.607 3.108 118.22 x–1, y, z
N4–H4B···O4 0.860 2.317 3.179 171.50 x–1, y, z
O1–H1A···N2 0.820 2.016 2.831 172.64 –x+1, –y + 1, –z
O2–H2···O3 0.820 1.861 2.634 156.64 –x+1, –y + 1, –z
O1–H1A···N2 0.820 2.478 2.936 116.36 –x+1, –y + 1, –z
O10–H10C···O2 0.850 2.096 2.937 170.16 –x+1, –y, –z + 1
2
O9–H10···N7 0.860 2.000 2.842 167.00 –x+1, –y, –z + 1
O11–H1···O10 0.830 2.220 3.034 167.00 –x+1, –y + 1, –z + 1
O10–H2A···O8 0.840 1.810 2.635 168.00 –x+1, –y + 1, –z + 1
O11–H2B···O5 0.800 2.400 2.989 131.00 –x+1, –y + 1, –z + 1
O7–H3···O1 0.880 1.790 2.581 148.00
O7–H3···N1 0.880 2.420 2.944 118.00
N4–H4A···O9 0.860 2.330 2.641 102.00
N4–H4A···O1 0.860 2.510 2.972 114.00 –x+2, –y, –z
N4–H4A···O3 0.860 2.460 3.034 125.00 –x+1, –y + 1, –z
N4–H4B···O4 0.860 2.560 3.072 119.00 x+1, y–1, z
N4–H4B···O8 0.860 2.070 2.923 171.00 x+1, y–1, z
N5–H5B···O4 0.860 2.570 3.422 169.00 x+1, y–1, z
N5–H5A···O10 0.860 2.290 2.577 100.00
N6–H6···O11 0.860 1.990 2.739 144.00
C2–H2···O3 0.930 2.340 2.658 100.00

of the cations by N–H···O hydrogen bonds between amino and ure 3. The two kinds of strong hydrogen bonds help building
nitro groups, finally forming a structure like a tower and many the whole molecules into huge 3D networks in a larger scale,
sightseeing platforms in different floors. The more detailed de- and also may make an important contribution in increasing the
scription of how the structures are formed is shown in Fig- density and decreasing the sensitivity at the same time.

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Figure 1. Molecular units of salts 1 (a) and 2 (b). Figure 2. Ribbon motifs formed through hydrogen bonding between
the DAG cations and crystal waters in the crystal structure for salts 1
Thermal Analyses and Enthalpies of Formation (a) and 2 (b).

The differential scanning calorimetry (DSC) measurement

peak temperature of 145.1 °C, and the enthalpy of this process
for determining the thermal behaviors of salts 1 and 2 were
was 116.5 kJ·mol–1. This indicated that salt 1 was easier to
performed in covered Al containers. The DSC plots show the
decompose, and the first thermal decomposition process of salt
thermal behaviors of 0.3 mg of salt in the temperature range
1 was more vigorously.
of 0–500 °C at the heating rate of 5 K·min–1(see Figure 4 and
The energy of combustion and formation are always the sig-
Figure 5).
nificant characteristics to study the energetic properties for a
For salt 1, it was found in the DSC curve that a main endo-
new energetic compound. A Parr 6200 bomb calorimeter
thermic process and two exothermic stages appeared. The en-
equipped with a Parr 1104 oxygen bomb was used to perform
dothermic process occurred at 107 °C with the peak tempera-
the constant volume combustion energy (ΔcU) of 1 and 2, and
ture of 123.37 °C, which can be identified as the stage of lost
the results are –12.0272 MJ·kg–1and –11.5924 MJ·kg–1,
crystal water. Next, the salt was decomposed, which is a sharp
respectively.
exothermic process with a peak temperature of 138.4 °C. The
The bomb equations of the energetic salts 1 and 2 are as
enthalpy of this exothermic process was 181.8 kJ·mol–1. There
follows:
was also a small exothermic stage at 215 °C, with a peak tem-
perature of 229.2 °C. C8H11N7O10(s) + 23/4O2(g) 씮 8CO2(g) + 11/2H2O(l) + 7/2N2(g) (1)
For salt 2, the thermal behavior was similar to that of 1. C8H11N7O11(s) + 21/4O2(g) 씮 8CO2(g) + 11/2H2O(l) + 7/2N2(g) (2)
There were also two decomposition processes, one sharp ex-
otherm followed with a further broad exotherm. The crystal The standard molar enthalpy of combustion (ΔcH) can be
water was lost at the temperature of 124 °C with the peak tem- confirmed on the basis of the formula ΔcH = ΔcU +ΔnRT [Δn
perature of this endothermic stage of 136.6 °C. The first exo- = Δni(products, g) – Δnj(reactants, g), Δni and Δnj are the total
thermic process of 2 was a little smaller than that of 1, with a molar amount of gases in the products and reactants]. Based

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Figure 3. Packing diagram of salts 1 (a) and 2 (b).
Figure 4. DSC curve of salt 1 at 5 K·min–1.
on Equation (1) and Equation (2), ΔcH can be calculated as
–4379.75 kJ·mol–1 and –4405.28 kJ·mol–1, respectively.
The standard enthalpies of formation (ΔfHθ298) for these
salts were calculated by using the Hess’ law from the enthalpy
Z. Anorg. Allg. Chem. 0000, 0–0
ARTICLE
Figure 5. DSC curve of salt 2 at 5 K·min–1.
of combustion.[21] With the known enthalpies of formation of
carbon dioxide [CO2(g), –393.5 kJ·mol–1] and water [H2O(l),
–285.8 kJ·mol–1], the enthalpies of formation can be deter-
mined as follows:
ΔfHθ298(1) = 8ΔfHθ(CO2,g) + + 11/2ΔfHθ(H2O,l) – ΔcH(1,s) =
340.13 kJ·mol–1 (3)
ΔfHθ298(2) = 8ΔfHθ(CO2,g) + + 11/2ΔfHθ(H2O,l) – ΔcH(2,s) =
314.62 kJ·mol–1 (4)
Non-Isothermal Kinetics and Thermodynamic Parameters
To determine the kinetic parameters [including the apparent
activation energy (E), the pre-exponential factor (A), and the
linear coefficient (R)] of the first exothermic decomposition
process for title salts, the Kissinger’s method[22] and Ozawa-
Doyle’s method[23] are employed. The Kissinger Equation (5)
and the Ozawa-Doyle Equation (6) are as follows [Tp is the
peak temperature (°C), R is the gas constant (8.314 J·mol–1·
K–1), β is the linear heating rate (K·min–1), and C is a con-
stant]:
ln(β/Tp2) = ln(AkR/Ek) – Ek/RTp (5)
logβ + 0.4567Ea/RTp = C (6)
Values of the peak temperature Tp (°C) under different heat-
ing rates (5, 10, 15 and 20 K·min–1) are measured and listed
in Table 4. From the original data, the kinetic parameters are
determined and also listed in Table 4. The apparent activation
energy (E) calculated by Kissinger method was consistent with
that by Ozawa method. The apparent activation energy of 2
was about 9.7 kJ·mol–1 higher than that of 1, revealing that the
energy barrier encountered for decomposition of 1 is smaller
than 2, and lightly easy to decompose, which is accordance
with the DSC curve.
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Table 4. Peak temperatures of the first exothermic stage and the kinetic absorb energy from outside. The positive values of ΔG⬆ show
parameters for salts 1 and 2. that the exothermic decomposition reaction of the salts must
1 2 proceed under the heating condition, and also salt 1 was
slightly easy to decompose than salt 2.
β /K·min –1
Peak temperatures Tp /°C
5 138.4 145.1
10 143.6 149.6
15 148.2 154.7 Energetic Properties
20 154.6 160.3
The critical detonation parameters of energetic salts includ-
Kissinger’s method ing the detonation velocity (D) and pressure (P) are predicted
Ek /kJ·mol–1 117.4 127.4
ln[Ak (s1–)] 12.8 13.8 by Empirical Kamlet-Jacobs method.[25,26] With the value for
Rk –0.9694 –0.9689 the enthalpy of formation and density of the title energetic salt,
Ozawa’s method
the critical detonation parameters P and D were determined as
E0 /kJ·mol–1 118.3 127.8 26.8 GPa and 7825 m·s–1 for 1, and 27.8 GPa and 7979 m·s–1
R0 –0.9727 –0.9720 for 2.
The impact and friction sensitivities of the salts are deter-
mined by following BAM standard methods.[27,28] The impact
Above all, the Arrhenius equations of salt 1 and 2 can be
sensitivity was determined by the Fall Hammer Method using
expressed as follows:
BAM FALL HAMMER BFH-10, and the frication sensitivity
lnk = 12.8 – 117.9 ⫻ 103/(RT) for 1 was determined with a BAM FRICTION APPARATUS FSKM
lnk = 13.8 – 127.6 ⫻ 103/(RT) for 2. –10 by using BAM standard. According to the “UN Recom-
The thermal safety of energetic materials is always evalu- mendations on the Transport of Dangerous Goods”,[29] the
ated through characteristic temperatures of thermal decomposi- salts can be depicted as “sensitive” to both impact and friction
tion. The thermal explosion critical temperature (Tbp) using with the results of 16.8 J, 180 N for 1, and 18.4 J, 210 N for
DSC data are calculated as follows:[24] 2.

Tpi = Tp0 + aβ + bβ2 + cβ3 (7)

Tbp = (E – 冪E2 – 4ERTp0)/2R (8)
Conclusions
The energetic salts DAG·PA·H2O (1) and DAG·TNR·H2O
where a, b and c are coefficients, R is the gas constant, and E
(2) were synthesized and fully characterized. Single crystals
is the value of Ek by Kissinger’s method. The calculated results
were obtained and their structures were determined by X-ray
are listed in Table 5.
single-crystal diffraction. Both salts crystallize in a triclinic
Table 5. The calculated critical thermodynamic parameters for 1 and system, space group P1, with densities of 1.764 and
2. 1.751 g·cm–3, respectively. Thermal decomposition behaviors
1 2 of the salts were investigated by DSC technology, and the de-
composition behaviors are similar to each other. The non-iso-
Tp0 /°C 130.2 141.3
Tbp /°C 142.3 153.1 thermal kinetic parameters were calculated by Kissinger and
ΔS⬆ /J·K–1·mol–1 –141.0 –132.9 Ozawa-Doyle methods, and the Arrhenius equation can be ex-
ΔG⬆ /kJ·mol–1 170.9 179.1 pressed as lnk = 12.8–117.9 ⫻ 103/(RT) for DAG·PA·H2O (1),
ΔH⬆ /kJ·mol–1 114.1 123.9 and lnk = 13.8–127.6 ⫻ 103/(RT) for DAG·TNR·H2O (2). The
enthalpies of formation of the salts are –340.15 kJ·mol–1 for 1
The entropy of activation (ΔS⬆), free energies of activation and –314.62 kJ·mol–1 for 2. Moreover, the values of the critical
(ΔG⬆), and enthalpy of activation (ΔH⬆) of the decomposition temperature for thermal explosion were determined as
reaction were obtained by the following Equation (9), Equation 142.3 °C and 153.1 °C. In addition, the detonation pressure (P)
(10), and Equation (11), corresponding to T = Tp0, Ea = Ek, and detonation velocities (D) of the salts were determined as
and A = Ak (the Kissinger’s method), where kB is the Boltz- 26.8 GPa and 7825 m·s–1 for 1, and 27.8 GPa and 7979 m·s–1
mann constant (1.381 ⫻ 10–23 J·K–1) and h is the Planck con- for 2 by using the K-J equations. The salts are “sensitive” to
stant (6.626 ⫻ 10–34 J·s–1). The calculated thermodynamic pa- impact and friction, according to the “UN Recommendations
rameters are shown in Table 5:[24] on the Transport of Dangerous Goods”.
A = (kBT/h) eΔS⬆/R (9)
⬆
ΔH = E – RT (10) Experimental Section
ΔG⬆ = ΔH⬆ – TΔS⬆ (11) Materials and Physical Techniques: All chemicals used reagents and
solvents were analytically pure, and purchased commercially. Elemen-
The thermal explosion critical temperature of salt 1 is tal analyses were performed with a Flash EA 1112 fully automatic
10.8 °C lower than 2, which implied that salt 2 is slightly trace element analyzer. The FT-IR spectra were recorder with a Bruker
stable turning to thermal decomposition. The values of ΔH⬆ Equinox 55 infrared spectrometer using KBr pellets in the range of
are greater than zero, indicating the activation reaction should 4000–400 cm–1 with a resolution of 4 cm–1. The DSC measurements

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 Journal of Inorganic and General Chemistry
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Zeitschrift für anorganische und allgemeine Chemie
were carried out with a Pyris-1 differential scanning calorimeter at the
heating rate of 5 K·min–1 in a dry nitrogen atmosphere with flowing
rate of 20 mL·min–1. The experimentally determined constant-volume
energies of combustion were tested with a Parr-6200 bomb calorimeter.
The X-ray single crystal diffraction analysis was carried out with a
Bruker CCD area-detector diffractometer.
Synthesis of the Energetic Salts: The salts DAG·PA (1) and
DAG·TNR (2) were synthesized by the reactions between the diamino-
glyoxine (DAG) and trinitrophenol (picric acid, PA) or trinitroresorci-
nol (styphnic acid, TNR) in methanol with 1:1 molar quantities. DAG
(0.118 g, 1 mmol) was added to a solution of PA (0.229 g, 1 mmol) or
TNR (0.245 g, 1 mmol) in 20 mL of methanol. The mixtures were
continuously stirred at 45 °C for 60 min. Afterwards, the solutions
were cooled to room temperature. The salts 1 and 2 were obtained as
yellow crystals after one week with yield of 78 % and 82 %.
DAG·PA·H2O (1): Yellow crystal (78 %). DSC (5 K·min–1): Tm,
106.6 °C (–H2O); Tm, 125.7 °C. IR (KBr): ν̃ = 3599, 3488, 3378, 3152,
2850, 1866, 1703, 1660, 1611, 1541, 1487, 1427, 1362, 1273, 1086,
984, 913, 787, 746, 719, 639, 596, 522, 431 cm–1. 1H NMR
([D6]DMSO, 400MHz): δ = 10.80, 8.58, 7.54, 1.21. 13C NMR
([D6]DMSO, 400 MHz): δ = 161.57, 142.54, 125.91, 124.99.
C8H11N7O10 (365.24): calcd. C 26.31, H 3.04, N 26.85 %; found C
26.27, H 3.01, N 26.92 %.
DAG·TNR·H2O (2): Yellow crystal (82 %). DSC (5 °C·min–1): Tm,
124.8 °C (-H2O); Tm, 141.7 °C. IR (KBr): ν̃ = 3484, 3421, 3177, 3072,
2820, 1702, 1659, 1632, 1540, 1454, 1379, 1335, 1288, 1172, 1083,
983, 927, 821, 759, 719, 654, 606, 439 cm–1. 1H NMR ([D6]DMSO,
400MHz): δ = 10.79, 8.63, 7.43, 1.22. 13C NMR ([D6]DMSO,
400 MHz): δ = 161.38, 142.35, 125.78, 124.87. C8H11N7O11 (381.05):
calcd. C 25.21, H 2.91, N 27.72 %; found C 25.23, H 2.83, N 27.78 %.
Crystallographic data (excluding structure factors) for the structures 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 numbers CCDC-1436345 for 1 and CCDC-1433078
for 2 (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk,
http://www.ccdc.cam.ac.uk).
Acknowledgements
The authors gratefully acknowledge the support of the project of State
Key Laboratory of Science and Technology (No. ZDKT16–04 and
YBT16–15).
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Received: May 25, 2016
Published Online: 䊏
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 Journal of Inorganic and General Chemistry

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Z.-B. Zhang, J. Qin, X. Yin, J.-G. Zhang* ....................... 1–8

Preparation, Crystal Structure, and Thermal Analysis of Two
Energetic Salts Based on Nitro Phenolic Compounds with Di-
amino-glyoxine

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