5-Amino-1: H-1,2,4-triazole-3-carbohydrazide and its applications in the synthesis of energetic salts: A new strategy for constructing the nitrogen-rich cation based on the energetic moiety combination

Article abstract of DOI:10.1039/c8dt01760c

Nitrogen-rich cation 5-amino-1H-1,2,4-triazole-3-carbohydrazide and its derivatives were synthesized by a new molecular design strategy based on the energetic moiety combination. All derivatives were fully characterized by vibrational spectroscopy (IR), multinuclear (¹H, ¹³C) NMR spectroscopy, elemental analysis, differential scanning calorimetry (DSC), and impact and friction-sensitivity tests. The structures of compounds 1-4, 7 and 8 were further confirmed by single-crystal X-ray diffraction and six different types of crystal packing were surprisingly discovered. The results show that the extensive hydrogen bonding interactions between the cations and anions lead to a complex 3D network, which contribute greatly to the high density, insensitivity and thermal stability of the 5-amino-1H-1,2,4-triazole-3-carbohydrazide salts. It is also found that the cationic form of 5-amino-1H-1,2,4-triazole-3-carbohydrazide can decrease the sensitivity and elevate the nitrogen content of the target salts effectively. Some of these salts exhibit reasonable physical properties, such as good thermal stability (up to 407 °C) and reasonable impact sensitivities (IS = 5-80 J). In addition, theoretical detonation properties of the energetic salts obtained with EXPLO 5 (version 6.02) confirm them as competitively energetic compounds comparable to those of RDX or HMX.

Full text of DOI:10.1039/c8dt01760c

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: G. Zhang, Y.
Chen, L. Liao, H. Lu, Z. Zhang, Q. Ma, G. Fan and H. Yang, Dalton Trans., 2018, DOI:
1
0.1039/C8DT01760C.
Volume 45 Number
1
7
January 2016 Pages 1–398
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
An international journal of inorganic chemistry
www.rsc.org/dalton
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

Page 1 of 12
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
View Article Online
DOI: 10.1039/C8DT01760C
Journal Name
ARTICLE
5
-amino-4H-1,2,4-triazole-3-carbohydrazide and its applications in
synthesis of energetic salts: a new strategy for constructing
nitrogen-rich cation based on the energetic moieties combination
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
b
b
b
b
*b
Guojie Zhang, Ya Chen, Longyu Liao, Huanchang Lu, Zhenqi Zhang, Qing Ma, Hongwei
*a
*b
DOI: 10.1039/x0xx00000x
Yang and Guijuan Fan
www.rsc.org/
Nitrogen-rich cation 5-amino-4H-1,2,4-triazole-3-carbohydrazide and its derivatives were synthesized by a new molecular
design strategy based on the energetic moieties combination. All derivatives were fully characterized by vibrational
spectroscopy (IR), multinuclear ( H, 13C) NMR spectroscopy, elemental analysis, differential scanning calorimetry (DSC),
impact and friction-sensitivity test. The structures of compounds 1-4,7 and 8 were further confirmed by single-crystal X-ray
diffraction and six different types of crystal packing were surprisingly discovered. The results show that the extensive
hydrogen bonding interactions between the cations and anions assemble into a complex 3D network, which contribute
greatly to the high density, insensitivity and thermal stability of the 5-amino-4H-1,2,4-triazole-3-carbohydrazide salts. It is
also found that the cation form of 5-amino-4H-1,2,4-triazole-3-carbohydrazide can decrease the sensitivity and elevate
nitrogen content of the target salts effectively. Some of these salts exhibit reasonable physical properties, such as good
thermal stability (up to 407°C), reasonable impact sensitivities (IS = 5–80 J). In addition, theoretical detonation properties of
1
the energetic salts obtained with EXPLO
5
(version 6.02) confirm them as competitively
energetic compounds comparable to those of RDX or HMX.
3
[1,2,4]triazolo[5,1-c][1,2,4]triazol-2-ium(TATOT),
,4-diamino-1,2,4-triazolium,
3,6,7-triamino-7H-
4,4’,5,5’-
Introduction
tetraamino-3,3’-bi-1,2,4-triazolium and 1,1’-(ethane-5-yl)-
bis(3,4-diamino-1,2,4-triazolium). Comparing with these
heterocyclic anions consist of N-N and C-N bonds directly
resulting in high heat of formation and high density, many
commercial heterocyclic cations with monoring were used
commonly in the construction of energetic compounds such as
Energetic salt is one of the latest and exciting developments in high
energy density materials (HEDMs), and continues to attract a lot of
work, which have been proved to possess advantages over
conventional neutral molecules, such as lower vapor pressure
and more insensitive towards stimuli, as well as higher thermal
stabilities. 1 As an important cross branch of organic and inorganic
explosive chemistry, the design and assembly of high-energy salt has
drawn much attention due to its potential and multi-purpose
3-amino-1,2,4-triazolium,
4-amino-1,2,4-triazolium,
3,4-
diamino-1,2,4-triazolium and 3,5-diamino-1,2,4-triazolium
instead because of their relatively low cost and easy synthesis
2
applications. However, the development of high energy compounds
5
routes. Among them, 1,3-diaminourea and oxalyl dihydrazide
were often used as a cationic ligand to enhance the
with high performance and low sensitivity is still an important and
challenging research topic for designing and synthesizing high energy
density materials. One of the effective ways to achieve this objective
is to form high-energy salts with various combinations of adjustable
cations and anions. 3
6
thermodynamic stability of energetic salts, however, their heat
of formation were lower when comparing with those cations
with heterocyclic rings. On the other hand, because these
cations involve large amounts of amino groups, it is
advantageous to form intramolecular and intermolecular
hydrogen bond interactions with an anion containing nitro or
nitramine groups, which devotes to lowering the sensitivity of
the polynitrogen precursor and improving the density of
energetic compounds. In the past few years, a series of azole-
based cations were discovered. For triazolium cations with five-
membered ring, 1,2,4-triazolium, 3,4-diaminotriazolium and
Researches on nitrogen-rich cations have been always
4
appealing to worldwide researchers. Some new nitrogen-rich
cations were detected and applied in the development of
energetic materials, such as 1,5-diamino-4H-tetrazolium, 5-
hydrazinotetrazolium, 3-hydrazino-4-amino-1,2,4-triazolium,
a
School of Chemical Engineering, Nanjing University of Science and Technology,
Xiaolinwei 200, Nanjing, 210094, China
Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang
3
,4,5-triamino-1,2,4-triazolium cations were synthesized. More
b
critically, the diversity of cations can provide more choices and
interests for the preparation of high energy salts and the study
6
21900, China.
E-mail: maq@caep.cn; fanguijuan@caep.cn; hyang@njust.edu.cn;
Electronic Supplementary Information (ESI) available: CCDC. For ESI and
†
crystallographic data in CIF or other electronic format see DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Page 2 of 12
ARTICLE
Journal Name
triazole-3-carboxylate was dissolved in hydrazine hVyiedwrAarttiecle(8O5nl%ine)
and heated to 70
DOI: 10.1039/C8DT01760C
℃ for 2h. The mixture was cooled to room
temperature and acidified with concentrated acetic acid to
pH=5-6. The resulting precipitate was collected by filtration to
afford 5-amino-1H-1,2,4-triazole-3-carbohydrazide (
Subsequently, the energetic salts of were synthesized by
means of Brønsted acid-base reactions. When was treated
with two equivalents of acid, dianion energetic salts , and
were isolated with cation/anion ratio of 1:2. In contrast,
energetic salts 11 were obtained by adding one equivalent of
1).
1
1
2
,
3
4
5
-
Scheme 1 A new strategy of combing two cations with
acid. In the beginning, we tried to synthesize di-protonated salt
by using organic acid 2,2’-dinitroamino-5,5’-bi(1,3,4-oxadiazole)
different frameworks into a new cation in this work
of physical and chemical properties. Unfortunately, in the
recent decade, combing chareacteristics of these traditional
cations such as carbohydrazide, oxalic hydrazide and 1,2,4-
triazolium was less considered, even in some new developed
cations. Thus, the design, synthesis and applications of
nitrogen-rich cations will become more attractive and be
worthy of investigation.
(
DNABO),
trinitrophloroglucinol (TNPG). To our surprise, it was found that
the acid-base reaction of with DNABO, TNPy, TNPG can only
2,4,6-trinitrophenyl
(TNPy),
2,4,6-
1
give rise to mono-protonated salt 4, 6 and 7.
Crystal Structure
Crystals of
diffraction were re-crystallized from hot water solution,
whereas crystals of was obtained by slow evaporation
methanol at room temperature The structure of these salts is
1, 2, 3, 4 and 8 suitable for single-crystal X-ray
Herein, as shown in Scheme 1, we proposed a design strategy
and synthesized a new nitrogen-rich cation 5-amino-1H-1,2,4-
7
.
triazole-3-carbohydrazide (
on triazole heterocycles, and a series of energetic salts (
1
) by introducing hydrazide groups
11),
shown in Fig. 1-6, and the selected crystalline parameters are
illustrated in Table 1. (Their crystalline parameters can be found
2
-
based on the 5-amino-1H-1,2,4-triazole-3-carbohydrazide
cation, was synthesized. All the compounds are fully
characterized by IR, H and 13C NMR spectroscopy, elemental
analysis, differential scanning calorimetry-thermal gravity (DCS-
in the ESI† including crystal of compound
related information includes bond lengths, bond angles, etc).
2, as well as other
1
-
3
Compound
in the monoclinic space group P2
1
crystallizes with a density (1.607 g cm at 296 K)
/n and with four molecules
1
TG), and in the case of compounds
crystal X-ray diffraction analysis.
1
–4, 7 and 8 with single-
per unit cell (Fig.1a). The high stability maybe rationalized by
the strong inter- and intra- molecular hydrogen-bonding
interaction. As can be seen in Fig. 1a, it has a cation structure
with a protonated atom N1 and N5. The C-N bond lengths of C-
hydrazine groups (C3-N4, 1.3230(17) Ǻ) are shorter than the C-
N bonds of the triazole rings (C1-N1, 1.3360(15) Ǻ; C2-N1,
O
O
O
N
SOCl
2
N
NH
2
NH
2
N
NH
HO
NH
O
H
2
NHN
NH2
2
NH
2
EtOH
N
NH
N
N
NH
1
M
1
1
1
.3626(16) Ǻ) and the C-N bonds of C-amino groups (C1-N6,
.3429(18) Ǻ) .The N-N bond of the hydrazine group (N4-N5,
.4148(15) Ǻ) are longer than the N-N bond of the triazole rings
O
M
O
O
H
N
H
N
N
H
3
NHN
NH
H
3
NHN
NH2
or
H
3
NHN
M2
2
or
NH
2
N
NH
M
N
NH
N
(N2-N3, 1.3622(16) Ǻ). All carbon and nitrogen atoms in cation
lie in the same plane as supported by the torsion angles (C(1)-
M
NH
2
,3,4
5,6,7
8,9,10,11
o
o
N(1)-C(2)-N(3), -0.19(14) ; N(2)-N(3)-C(2)-(3), 178.73(11) ; C(2)-
o
O
O
o
O
2
N
NO
2
O
2
N
NO
2
N(1)-C(1)-N(6), -178.90(15) ; N(3)-N(2)-C(1)-N(6), 178.97(14) ;
o
O
2
NHN
NNO
2
O
N
5
O
N
NO
3
3
ClO
4
4
M
=
Cl
2
N(5)-N(4)-C(3)-C(2), 179.51(12) ). As shown in Fig. 1b., the
N
N
HO
O
OH
NO
6
2
NO
2
extensive hydrogen-bonding interactions in the crystal
structure form a sandwich-like 3D network that significantly
contributes to the stability of the 5-amino-1H-1,2,4-triazole-3-
7
O
O
2
N
NO
2
2
O
2
NN
N
N
NNO
2
O
2
NN
NNO
2
N
N
N
N
M2
2-
N
N
N
=
SO
4
HN
NH
N
N
N
N
carbohydrazide (
arrangement.
1) though each molecule presents irregular
N
2
N
NO
O
O
8
9
10
11
Scheme 2. Synthesis of compound
Brønsted acid-base reaction.
1 and its salts 2–11 based on
Result and discussions
Synthesis
First, the intermediate product ethyl 5-amino-1H-1,2,4-triazole-
-carboxylate was prepared by the one-step reaction from
commercial 5-amino-1H-1,2,4-triazole-3-carboxylic acid
according to literature method. Then ethyl 5-amino-1H-1,2,4-
3
7
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 12
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Journal Name
ARTICLE
Fig.1 (a) Thermal ellipsoid plot (50%) and labelling scheme of 1. (b)
View Article Online
Sandwich-like crystal packing diagram of 1 v iDe Ow I e: 1d 0 d. 1 o0 w3 9 n/ Ct h8 De Tc 0 a1 7x 6i s0. C
Dashed lines indicate strong hydrogen bonding.
1
Compound 2 crystallizes in the monoclinic space group P2 /c
-
3
with a calculated density of 1.717 g cm at 173(2) K (Fig.1a). Due
to the protonation of N1 and N5, the C-N bond length of triazole
rings (C1-N1, 1.3430(18) Ǻ) is obviously longer than compound
1
(1.3360(15) Ǻ). All the nitrogen and carbon atoms in the
framework of 5-amino-1H-1,2,4-triazole-3-carbohydrazide are
nearly coplanar before and after deprotonation, which have
been revealed by basically unchanged torsion angles. Fig.2b
represents a graphene-like crystal packing, which can be
interpreted by chlorine anion serving as the centre of network
and strong intramolecular hydrogen bonds (N–H···O) and
halogen bonds (N–H···Cl) stabilizing the stack density. By and
large, the distances of halogen bonds in compound 2 are in the
range of 3.0671–3.3348 Ǻ, while those of hydrogen bonds range
from 2.8613–3.0392 Ǻ.
Table 1 Crystal data and structure refinement details for 1, 3, 4, 7 and 8
1
3
4
7
8
Formula
C
3
H
6
N
6
O
C
12
H
38
N
32
O
31
C
3
H
14Cl
2
N
6
O
12
C
9
H
9
N
9
O
10
C
3
H
8
N
6
O
5
S
-
1
M
w
[g mol ]
T [K]
142.14
296(2)
0.18×0.15×0.10
Monoclinic
1126.74
296(2)
397.10
100(2)
403.25
293(2)
240.21
173(2)
3
Crystal size [mm ]
Crystal system
Space group
a [Å]
0.20x 0.16x 0.05
Triclinic
0.18×0.15×0.11
Monoclinic
0.28×0.15×0.12
Triclinic
P-1
0.10×0.07×0.04
Monoclinic
P2
1
/n
P-1
P2
1
/n
1
P2 /c
5.2108(2)
8.5731(3)
13.2997(4)
90
98.5020(10)
90
8.1276(2)
11.7571(3)
12.4802(3)
68.1870(10)
73.4280(10)
85.5050(10)
1060.68(5)
2
14.953(5)
4.8569(12)
19.280(7)
90
93.743(6)
90
7.251(2)
8.401(2)
12.141(4)
96.687(16)
98.3178(19)
93.39(3)
724.6(4)
2
5.6170(2)
18.6083(6)
8.1288(3)
90
91.1320(10)
90
b [Å]
c [Å]
α [˚]
β [˚]
γ [˚]
3
V [Å ]
587.60(4)
4
1397.2(6)
4
849.48(5)
4
Z
-
3
ρ
calc [g cm ]
μ [mm ]
F (000)
1.607
0.128
296
1.764
0.169
582
1.888
0.546
816
1.848
0.169
412
1.878
0.401
496
-1
2
θ range [˚]
6.194-51.986
9651 / 1144
-6≤h≤6
2.616-25.999
41268 / 4157
-10≤h≤9
-14≤k≤14
-15≤l≤15
0.0729
3.344-52.714
8218 / 2772
-18≤h≤15
-6≤k≤6
-24≤l≤24
0.0712
3.418-51
5609 / 2656
-8≤h≤8
-10≤k≤10
-14≤l≤14
0.0300
4.378-51.982
12166 / 1658
-6≤h≤6
-22≤k≤22
-10≤l≤10
0.0449
Reflections collected
Index ranges
-
10≤k≤10
-16≤l≤16
R
int
0.0461
Data / restraints /
parameters
1144 / 0 / 115
4157 / 3 / 412
2769 / 8 / 219
2656 / 2 / 263
1658 / 0 / 169
Final R index [I >
R
1
=0.0364,
wR =0.1055
=0.0381,
wR =0.1081
1.065
1831245
R
1
=0.0485,
wR =0.1331
=0.0568,
wR =0.1427
1.029
1831247
R
1
=0.0528,
wR =0.1320
=0.0744,
wR =0.1450
1.029
1831248
R
1
=0.0473,
wR =0.1305
=0.0615,
wR =0.1404
1.016
1831250
R
1
=0.0341,
wR =0.0822
=0.0398,
wR =0.0873
1.098
2
σ(I)]
2
2
2
2
2
Final R index [all
data]
R
1
R
1
R
1
R
1
R
1
2
2
2
2
2
2
GOF on F
CCDC
1831249
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Page 4 of 12
ARTICLE
Journal Name
View Article Online
DOI: 10.1039/C8DT01760C
Fig.2 (a) Thermal ellipsoid plot (50%) and labelling scheme of 2. (b)
Graphene-like crystal packing diagram of 2 viewed down the b axis.
Dashed lines indicate strong hydrogen bonding.
Compound
2
3•3H O crystallizes in the triclinic space group P-
Fig.3 (a) Thermal ellipsoid plot (50%) and labelling scheme of
·3H O. (b) Lamellar-like crystal packing diagram of 3•3H O viewed
down the c axis. Dashed lines indicate strong hydrogen bonding.
1
with a calculated density of 1.764 g cm-3 at 296(2) K (Fig.3).
3
2
2
Due to the protonation of N1 and N6, the C-N bond length of
triazole rings (C1-N1, 1.365(2) Ǻ; C2-N1, 1.346(2) Ǻ; C3-N5
Compound 4•3H O crystallizes in the monoclinic space group
2
(
1.336(2) Ǻ) are longer than compound
.3360(15) Ǻ; 1.3230(17) Ǻ); however, the C-N bond length of
the C-amino groups (C2-N4, 1.310(3) Ǻ) are shorter than
compound (1.3429(18) Ǻ). The torsion angle of the cation
reveals an almost coplanar ring (C(2)-N(1)-C(1)-C(3),
77.34(17)°; N(2)-N(3)-C(2)-N(4), 179.50(2)°; N(6)-N(5)-C(3)-
1 (1.3626(16) Ǻ;
P2
1
/n with a calculated density of 1.888 g cm-3 at 100 K (Fig.4a).
1
Due to the protonation of N4 and N6, the C–N bond length of
triazole rings (C2–N4, 1.364(5) Ǻ; C3–N4, 1.350(4) Ǻ) are longer
than those from C-amino groups (C3–N1, 1.317 Ǻ). The C-N
bond of carbonyl groups (N5-N6, 1.424(4) Ǻ) is similar those of
1
1
1
(1.4148(15) Ǻ) and
3 (1.416(2) Ǻ). The torsion angle of the
C(1),-179.42(17)°;N(1)-C(1)-C(3)-N(5), 179.76(17)°) with the C-
O bond of carbonyl groups slightly twisted out of the plane.
Fig.3b represents a lamellar-like crystal packing, which can be
interpreted by nitrate anion serving as the act of nitro group in
some extent and strong intramolecular hydrogen bonds
stabilizing the stack density.
cation reveals an almost coplanar ring (N1-C3–N2–N3, 178.46o;
o
o
N1–C3–N4–N2, 178.10 ; N3–C2–C1–N5, 1.010 ; N4–C2–C1–N5,
o
o
1
77.60 ; C2-C1-N5-N6, 179.96 ) with the C-N bond of carbonyl
groups slightly twisted out of the plane. Fig.4b represents an
interlock-like crystal packing, which can be interpreted by
perchlorate anion filling in the space formed by cations as well
as strong intramolecular hydrogen bonds of N–H···O stabilizing
the stack density.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 12
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Journal Name
ARTICLE
View Article Online
DOI: 10.1039/C8DT01760C
Fig.4 (a) Thermal ellipsoid plot (50%) and labelling scheme of 4•
O. (b) Interlock-like crystal packing diagram of 4•3H O viewed
down the a axis. Dashed lines indicate strong hydrogen bonding.
3H
2
2
Fig.5 (a) Thermal ellipsoid plot (50%) and labelling scheme of 7. (b)
Compound
but with a higher calculated density of 1.848 g cm-3 at 173 K
Fig.5a), which can attribute to the high oxygen content and
7
crystallizes in the monoclinic space group P-1 “Face-to-face” crystal packing diagram of 7 viewed down the a axis.
Dashed lines indicate strong hydrogen bonding.
(
Table 2 Hydrogen bonds present in 7.
stronger intermolecular interactions. In the cation, due to the
N3 do not participate in protonation, the C-N bond length of
D–H···A
D–H/Ǻ
H···A/Ǻ D···A/Ǻ
D–H···A/o
2.498(3) 144.8
2.886(3) 140.7
triazole rings (N3
–
C8, 1.381 Ǻ; N3-C14, 1.353 Ǻ) are longer than
O3-H3…O1
N6–H6A···O10
N6–H6B···O9
O6-H6…O7
0.82
1.78
2.17
2.06
1.70
those of 3 (1.364(2) Ǻ; 1.343(3) Ǻ) and 4 (1.367 Ǻ; 1.343 Ǻ) and
the C-N bond length of triazole rings (C8-N6, 1.323 Ǻ) is also
longer compound 3 (1.310(3) Ǻ) and compound 4 (1.317 Ǻ). The
other C–N bond lengths show the regular situation as the
above-mentioned salts (C8–N4, 1.299(3) Ǻ; C15–N5, 1.349(3) Ǻ).
The C13-C14 bond is extremely longer than compound 1, 4and
0.86
0.86
2.806(3) 144.1
2.478(3) 153(4)
0.842(19)
Compound
with a calculated density of 1.878 g cm-3 at 173 (2) K (Fig. 6a).
The C N bond lengths of C-amino groups (C3–N4, 1.319(3) Ǻ )
are shorter than the C N bonds of the triazole rings (C1–N1,
.348(3) Ǻ; C2–N1, 1.372(3) Ǻ ), the N–N bonds of the triazole
1
8 crystallizes in the monoclinic space group P2 /c
7
(lie in range of 1.475–1.481 Ǻ). Though the oxygen atoms in
hydroxyl and deprotonated oxygen atoms (O6–C4–C3–N9, -5.54
o; O6–C4–C5–C6, 174.08 ; O3–C2–C1–N8, 3.37 ; O3–C2–C1–C6,
o
o
–
o
–
-172.00 ) are nearly coplanar with benzene ring, the oxygen
atoms in nitro groups are slightly twisted out of this plane by
1
o
o
o
rings (N2–N3, 1.383(3) Ǻ ) and the N-N bonds of the C-hydrazine
groups (N4-N5, 1,413(3) Ǻ ). The sulphate anion has s slightly
distorted tetrahedral geometry with each O-S-O bond lengths
between 108.47(10) o and 110.15(9) o and average S-O bond
lengths between 1.4626(17) Ǻ and 1.4879(16) Ǻ. Fig.6b shows a
“wave” crystal-packing, which may be formed because of the
dense hydrogen-bonding drive force caused by oxygen atoms in
sulphate and centred sulphur atom as a heavy atom. Meanwhile,
it is well known that sulphate has the weakest capability of
coordination compared with perchlorate and nitrate.6
1
N8-C1-C2, 164.29 ; O2- N8-C1-C6, 20.16 ). The carbon and
5–20 (O1–N8–C1–C2, -15.23 ; O1-N8-C1-C6, -160.32 ; O2-
o
o
nitrogen atoms in triazole ring and amino groups are basically
o
coplanar (N4–N5–C8–N6, 179.6(2) ; N5–N4–C14–C7, -179.9(2)
o). However, carbonyl groups show a bit distorted angle from
o
the triazole rings (N3–C2–C3–N4, -2,87 ; N1–C2–C3–N4, 176.95
o; N3-C2-C3-O1, 177.38 ; N3-C2-C3-O1,-2.80 ), which are still
o
o
nearer this plane lower the twisted nitro groups in the anions.
Fig.5 gives a network crystal packing mainly consist of
intermolecular N–H···O hydrogen bonds. The representative
hydrogen bond interactions in
the intramolecular O–H···O interaction (bond length 2.478–
.498 Ǻ) is stronger than intermolecular N–H···O interaction
bond length: 2.806–2.886 Ǻ).
7 are listed in Table 2. Basically,
2
(
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Page 6 of 12
ARTICLE
Journal Name
5
-amino-1H-1,2,4-triazole-3-carbohydrazide salts (3–V1ie1w)Aratinclde Ofnrleinee
DOI: 10.1039/C8DT01760C
base (1) were fully characterized by multinuclear NMR, IR
spectroscopy and elemental analysis. In the IR spectra, strong
absorption bands at 1300–1650 cm-1 were found for most
compounds with nitro-substituted anions (3,5-7 and 9-11).
Characteristic absorption bands of amino groups were observed for
-1
all compounds at 3000–3500 cm .
In the NMR spectra, owing to its insolubility of 1 in all deuterated
solvents with exception of its weak solubility in D
increased the quantity of samples and enhanced the number of scans
to obtain its 13C NMR in D
-DMSO. However, the chemical shifts of 1
6
-DMSO, we
6
in the 13C NMR were eventually not obtained, while there was only
1H NMR detected. For its cationic form, the 13C NMR spectra were in
a similar range between 120 ppm to 170 ppm. On the other hand, we
also found that compound 2 decomposed in deuterated solvents
such as deuterated water or DMSO.
Physicochemical properties and energetic performance
Considering the potential application of these energetic
compounds, their thermal behaviour and detonation
performance as well as mechanical sensitivities must be
Fig.6 (a) Thermal ellipsoid plot (50%) and labelling scheme of 8. (b)
Wave-like crystal packing diagram of 8 viewed down the c axis.
Dashed lines indicate strong hydrogen bonding.
evaluated. In Fig.8, with the exception of compounds 5 and 11
which decompose around 160 oC (onset), the others exhibit
o
thermal stabilities beyond 200 C (onset). It is worthy noting
Based on the above analysis of crystal structures, it is interesting
that six types of crystal packing based on this new cation are
discovered. Zhang et al and Shreeve et al have reported four main
types of crystal packing in neutral energetic compounds and
energetic salts based on new anion: face-to-face, crossing, wave-
that compounds
1
and
3
show high thermal stability up to 400
C (409 C and 384 C) while compounds and all give their
decomposition peaks beyond 300 C. Compound presents two
o
o
o
1
,
3
4
o
4
o
o
onset decomposition temperature at 213 C and 343 C. The
o
oneset decomposition temperature of compound 9 (248 C) is
higher than those of bis[3,4,5-triamino-(1,2,4-triazolium)] bis-
9
like and sheet-like. As a matter of fact, Lu et al and Snyder et al
recently found more crystal packing types in energetic anions and
energetic co-crystals, such as assembly 3D cube-layer stacking and
o
[
3-(5-nitroimino-1,2,4-triazolate)] hydrate (198 C) and carbonic
dihydrazidinium bis[3-(5-nitroimino-1,2,4-triazolate)] (222
oC).11 Among them,
and behave melting characteristics
10
herring-bone packing. However, crystal packing via energetic
cation has not been fully referred. In this work, six crystal structures
were cultivated, and to our surprise, they are all different in the
stacking forms. As shown in Fig. 7, six different types of stacking (1:
sandwich type, 2: graphene type, 3: lamellar type, 4: interlock type,
1
,
3
o
,
4
8
o
o
o
at 284 C, 200 C, 174 C and 242 C (onset), respectively. The
density is an important parameter which plays a significant role
in the calculation and prediction of energetic performance.
Here, densities were measured by using a gas pycnometer at 25
7: face-to-face type, 8: wavelike type) are listed, which may be
oC. Compound
4 shows the highest density among these
-3
useful for the analysis and further understanding of chemical and
physical phenomenon in energetic salts.
compounds (1.85 g cm ), while the others exhibit moderate
3
-
densities (≥1.63 g cm )
Fig.7 Six types of crystal packing formed by using this new cation
(Blue color indicates cation and orange color represents anion. In
Sandwich type, different colors stand for different assembly forms)
Spectroscopic data
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 12
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Journal Name
ARTICLE
6
.02) via HOF and measured densities at 298 K. VIniewdAertticaleil,Ontlhinee
calculated detonation velocities are in the range from 7658 m s-
DOI: 10.1039/C8DT01760C
1
-1
to 9571 m s , of which 8-11 are equal to or exceed that of RDX,
and only those of overtake those of HMX. The calculated
detonation pressure lies in the range 20.6 38.3 GPa. Among
8
–
them, those of 8-11 are close to that of RDX, which are obviously
lower than that of HMX. The measured impact sensitivities (IS)
show that with the exception of
more insensitive (10 80 J) than those of RDX and HMX. And
friction sensitivities (FS) suggest that most of them are more
insensitive (144 360 N) than those of RDX and HMX except for
, 9 and 11 (120 N).
4, 6, 11 (5–7.5 J) others are
–
–
3
Conclusions
A thermally stable energetic cation 5-amino-1H-1,2,4-triazole-
-carbohydrazide has been firstly synthesized and used as a
building block in preparing a new family of energetic salts. The
six strucutres of derivatives and were further
3
1
,
2
,
3
,
4
,
7
8
characterized by using single-crystal X-ray diffraction. These
materials have high thermal stabilities and promising energetic
performance, and thus may be useful as ingredients in energetic
materials applications.
Experimental section
Safety cautions
Although we experienced no difficulties in handling these
nitrogen-rich energetic derivatives, small scale and safety
training should be required. Mechanical actions such as
scratching and scraping must be avoided. Manipulations must
be performed behind a safety shield. Eye protection and leather
gloves must be worn as usual. All the synthesized salts in this
work are very stable in long-term storage at the ambient
temperature.
General methods
Fig.8 DSC plots of the referenced compounds measured with a
-1
o
heating rate of 5 C min .
All the physicochemical and energetic properties are listed in
Table 3. With exception of 3, 4, 6 and 7 which exhibit negative
-
1
heat of formation (HOF) (-2.03 to -0.44 kJ g ), others possess
-
1
positive HOF varying between 0.77 and 4.58 kJ g . For
compounds 5, 8, 9 ,10 and 11, their HOF are all higher than
-
1
those of currently used explosives (RDX and HMX, 0.36 kJ g ).
The detonation performance was obtained by EXPLO5 (version
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Page 8 of 12
ARTICLE
Journal Name
All chemical used in this research were analytical grade anisotropic thermal parameters for all non-H atoms.ViTewheArtHicleaOtonmlines
materials purchased for TCI or Sigma Aldrich without further
1
DOI: 10.1039/C8DT01760C
were included using a riding model. The non-H atoms were refined
13
purification. H and C spectra were recorded on a 400 MHz
Bruker AVANCE 400) or 600 MHz (Bruker AVANCE 600) nuclear
anisotropically. The finalized CIF files were checked with checkCIF,
and deposited at the Cambridge Crystallographic Data Centre as
supplementary publications (1)–(4), (7) and (8). Intra- or
intermolecular hydrogen-bonding interactions were analyzed with
Diamond software (version 3.2K) as well as the illustrations of
molecular structures. These data can be obtained free of charge from
(
magnetic resonance spectrometer. Chemical shifts in the H and
1
1
3
4
C spectra are reported relative to Me Si as external standards.
Differential scanning calorimetry (DSC) was performed using a
differential scanning calorimeter-thermal gravity instrument
e
(TGA/DSC2, METTLER TOLEDO STAR system) at the heating
rate of 5 C min . Infrared (IR) spectra were measured on
o
-1
The
Cambridge
Crystallographic
Data
Centre
via
SHIMADZU IRTracer-100 FT-IR spectrometer in the range of www.ccdc.cam.ac.uk/ data_request/cif.
000-400 cm- as KBr pellets at 25 C. Transmittance values are
1
o
4
qualitatively described as “strong” (s), “medium” (m) and “weak” Computational methodology
(w). Elemental analyses (C,H,N or C,H,N,S) were carried out on
For neural compound 1, its cations and all the onions used in this
a elemental analyzer (Vario EL Cube, Germany).
X-ray crystallography
work, the geometric optimization, frequency analysis and single-
point energies were accomplished by using Gaussian 09 package13 at
the B3LYP/6-311++G** level.14 The atomization energies of cations
A colorless prismatic crystal (1) of dimensions 0.180 x 0.150 x 0.100
3
mm , a colorless block crystal (2) of dimensions 0.190 x 0.160 x 0.110
and anions were obtained by employing CBS-4M method and solid
phase heat of formation was computed via isodesmic reactions.15 For
3
mm , a colorless prismatic crystal (3) of dimensions 0.200 x 0.160 x
0
0
0
0
.050 mm3,
a
colorless prismatic crystal (4) of dimensions
all the ionic derivatives (3–11), the solid phase heat of formation was
calculated based on the Born-Haber energy cycle16 according to the
3
.18×0.15×0.11 mm , a colorless prismatic crystal (7) of dimensions
3
.28×0.15×0.12 mm , a colorless prismatic crystal (8) of dimensions
literature method.
3
.100 x 0.070 x 0.040 mm , were mounted on a MiTeGen MicroMesh
Detonation parameters were carried out in the EXPLO5 (V6.02)
code17 using experimental densities which were measured by gas
using a small amount of Cargille Immersion Oil. Data were collected
on a Bruker three-circle platform diffractiometer equipped with a
SMART APEX II CCD detector. A Kryo-Flex low-temperature device
was used to keep the crystals at a constant 296 K, 173 K and 100 K
during data collection. Data collection was performed and the unit
cell was initially refined using APEX2 (v2010.3-0). Data reduction was
carried out using SAINT (v7.68A) and XPREP (v2008/2). Corrections
were applied for Lorentz, polarization, and absorption effects using
SADABS (v2008/1). The structures were further solved and refined
with the aid of the programs using direct methods and least-squares
minimization by SHELXS-97 and SHELXL-97 code.12 The full-matrix
least-squares refinement on F2 involved atomic coordinates and
o
pycnometer at 25 C.
Syntheses
The energetic compounds providing the anions: N,N'-([2,2'-bi(1,3,4-
oxadiazole)]-5,5'-diyl)dinitramide (BODNA), N,N'-(1H,1'H-[3,3'-
bi(1,2,4-triazole)]-5,5'-diyl)dinitramide (BNT), 2,4,6-trinitrophenyl
(TNPy), 2,4,6-trinitrophloroglucinol (TNPG), 4,4′-bis(nitramino)-
azoxyfurazan (DNAF), tetranitro-bisimidazole (TNBI), were
synthesized according to the literatures.3c,3d,11,18
5
-amino-4H-1,2,4-triazole-3-carbohydrazide (1). Thionyl
chloride (10 mL, 258 mmol) was added dropwise to a
suspension of 5-amino-1H-1,2,4-triazole-3-carboxylic acid (12.8
Table 3 Physicochemical and energetic properties of the title compounds
[c]
[d]
IS(J)[e]
>80
FS (N) [f]
360
120
168
168
144
160
324
120
252
120
120
120
-3 [g]
∆
f
H [kJ mol-1 ][h] P (GPa)[i] D (m s-1)[j]
Comp.
N (%)[a] Ω (%)[b]
T
m
T
d
d (g cm )
1
3
4
5
6
7
8
9
1
1
63.03
33.10
43.73
48.27
32.94
30.11
46.83
44.58
52.27
47.01
37.84
37.84
–90.14
–17.91
–4.66
284
200
174
–
401
1.70
-9.4
-544.7
-397.1
286.5
20.6
25.3
27.7
24.0
22.3
24.9
34.6
33.5
33.7
38.3
34.7
39.2
8038
7902
8053
7943
7658
7902
9571
9193
8820
9323
8872
9254
216,375 >80
1.74
1.85
1.69
1.72
1.81
1.80
1.76
1.63
1.75
1.81
1.90
213,343
159
7
10
7.5
18
>80
11
25
5
-44.00
–62.53
–49.63
-33.31
–56.28
–45.61
–36.04
-21.61
-21.61
–
241
-163.4
-519.9
638.8
–
202
242
–
259
248
1506.0
1601.5
2032.7
80.0
0
–
204
1
–
161
RDX
205
275
210
7.5
7
HMX
279
104.8
o
-1
[
a] Nitrogen content. [b] Oxygen balance. [c] Onset melting point measured by DSC at the heating rate of 5 C min . [d] Onset decomposition
o
-1
temperature measured by DSC at the heating rate of 5 C min . [e] Impact sensitivity determined by BAM drophammer. [f] Friction sensitivity
o
recorded on a BAM friction tester. [g] Density measured by a gas pycnometer at 25 C. [h] Calculated solid heat of formation. [i] Detonation
pressure. [j] Detonation velocity.
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 12
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Journal Name
g, 100 mmol) in ethanol (130 mL) at 0°C. Subsequently, the
ARTICLE
5-amino-4H-1,2,4-triazole-3-carbohydrazide sulphate (8). A
View Article
DOI: 10.1039/C8DT01760C
．
Online
．．
．
mixture was refluxed for 2 h and the solvent evaporated in suspension of 1 (0.710 g, 5 mmol) in deionic water (20 mL), 1M
vacuum. A saturated solution of sodium acetate (100 mL) was sulfuric acid (5 ml, 5 mmol) was added with portions. Then the
added to the remaining highly viscous residue, and the resulting mixture was stirred for another 0.5 h and filtered. The filtrate was
precipitate was collected by filtration and washed with cold left for crystallization at room temperature as colorless crystalline
o
o
water. The obtained colorless solid was dissolved in 80% solid (8). Yield: 1.156 g, 68.4 %. T
1
m
(onset): 239 C, T
d
(onset): 259 C.
13
hydrazine hydrate (66 mL) and heated to 70°C for 2 h. The
H (DMSO-d
6
): δ=10.58 (br, s, 2H), 6.43 (s, 2H) ppm. ．．C (DMSO-d
6
):
．
．
．． ．． ． ．．． ． ．．．． ．． ． ．．． ．．． ． ．．． ． ．． ．．．． ．．
．．
mixture was cooled to room temperature and acidified with δ=159.30, 157.74, 151.66 ppm. IR (KBr pellet): 3343 (s), 3128 (m),
．． ．． ．．． ．． ．． ．．． ．． ．． ．．． ．．．．．
concentrated acetic acid to pH 5-6. The resulting precipitate was 2734 (w), 2658 (w), 2374 (w), 2333 (w), 2289 (w), 1697 (s), 1582 (m),
collected by filtration to yield 5-amino-4H-1,2,4-triazole-3- 1553 (w), 14943(w), 1418 (w), 1305 (m), 1231 (w), 1120 (w), 1074
carbohydrazide (9.787 g, 69 mmol, 76%) as a colorless solid (
has poor solubility in most of solvents and is hardly soluble in 517 (w) cm . Elemental analysis calcd (%) for C
dimethylformamide (DMF) and dimethylsulfoxide (DMSO). T (15.00), H (3.36), N (34.99), S (13.35); found: C (14.55), H (3.19), N
): δ=12.22 (br, s, 1H), (35.18), S (14.55). The structure of 8 is supported by single crystal X-
.25 (s, 1H), 6.05 (s, 2H), 4.43 (s, 2H) ppm; IR (KBr pellet): 3418 (m), ray analysis.
1). (m), 1035 (w), 985 (w), 851 (m), 759 (w), 677 (w), 622 (m0, 566 (w),
-1
1
3 6 5
H8N O S (240.19): C
m
o
o
1
(
d 6
onset): 285 C, T (onset): 407 C. H (DMSO-d
9
3
1
314 (m), 3196 (w), 1787 (w), 1683 (w), 1655 (w), 1624 (w), 1587 (w),
General procedure for salts 5-7 and 9–11. A suspension of 1
536 (w), 1500 (m), 1401 (w), 1350 (m), 1254 (m), 1132 (m), 1096 (0.710 g, 5 mmol) in 20 mL deionic water was stirred at ambient
(
m), 1048 (m), 1011 (m), 863 (m), 827 (w), 790 (w), 759 (w), 727 (m), temperature while energetic acid (for 5-7 and 9-11, 5 mmol) was
-1
o
6
60 (w), 583 (w), 535 (w), 434 (w) cm . Elemental analysis calcd (%) added. The reaction was stirred for another 1 h at 60–100 C. Then,
10 (222.21): C (25.35), H (4.26), N (59.13); found: C (24.56), the precipitate for 5-7, 9–11 was filtered and dried in air.
6 10
for C H N
H (4.20), N (59.22). The structure of 1 is supported by single crystal
5-amino-4H-1,2,4-triazole-3-carbohydrazide
N,N'-([2,2'-
X-ray analysis.
bi(1,3,4-oxadiazole)]-5,5'-diyl)dinitramide (101) (5). Yellow solid.
5
-amino-4H-1,2,4-triazole-3-carbohydrazide dihydrochloride (2) Yield: 1.547 g, 83.4 %. 7 is easily soluble in anhydrous methanol.
(onset): 160 C. 1H (DMSO-d
o
was unstable and decomposed in any deuterated solution. 2 is non- Light-yellow solid. T
d
6
): δ=10.57 (br, s,
energetic compound. The structure of 2 is supported by single crystal H), 6.44 (br, s, 4H) ppm; 13C (DMSO-d
6
): δ=166.41, 166.02, 159.30,
X-ray analysis.
157.69, 157.20, 151.69, 148.26 ppm; IR (KBr pellet): 3435 (m), 3188
(w), 1785 (m), 1692 (s), 1645 (m), 1596 (m), 1413 (m), 1324 (s), 1258
5-amino-4H-1,2,4-triazole-3-carbohydrazide dinitrate (3). A
suspension of
1 (0.710 g, 5 mmol) in deionic water (15 mL), 1M (m), 1081 (s), 1052 (s), 951 (w), 892 (s), 773 (w), 711 (w), 641 (w), 559
-1
nitric acid (10 ml, 10 mmol) was added with portions. Then the (w) cm . Elemental analysis calcd (%) for C
7 8
H N
14
O
7
(400.23): C
mixture was stirred with heating to 80 C until it becomes clear. (21.01), H (2.01), N (49.00); found: C (20.42), H (2.87), N (49.35).
The filtrate was left for crystallization at room temperature as 5-amino-4H-1,2,4-triazole-3-carbohydrazide dipicrate (6).
o
colorless crystalline solid (3). Yield: 1.09 g, 81.3 %.
oC, T
T
m
(onset): 200 Yellow solid. Yield: 1.547 g, 83.4 %. 6 is easily soluble in anhydrous
o
(onset): 241 C. 1H (DMSO-d
): δ=10.84 (br, s, 2H), 8.60 (s, 2H), 6.41 (br, s, 2H) ppm; 13C (DMSO-d
o
d
(onset): 398 C. 3 can be easily soluble in water, DMF and methanol. Light-yellow solid. T
): δ=9.74 (br, s, 4H) ppm; 13C (DMSO-d
d
6
):
):
DMSO. 1H (DMSO-d
6
6
6
δ=156.62, 154.58, 146.01 ppm; IR (KBr pellet): 3415 (m), 3320 (w), δ=161.30, 159.35, 157.72, 151.74, 142.33, 125.68, 124.69 ppm; IR
3
1
9
101 (w), 2983 (w), 2767 (w), 2375 (w), 1702 (s), 1608 (w), 1560 (w), (KBr pellet): 3362 (w), 3325 (m), 3261 (m), 3231 (w), 3139 (w), 3100
510 (w), 1425 (w), 1389 (s), 1323 (m), 1217 (w), 1174 (w), 1033 (m), (w), 2975 (w), 2690 (w), 1720 (m), 1687 (m), 1636 (m), 1616 (w), 1555
87 (w), 840 (m), 783 (w), 717 (w), 678 (w), 606 (w), 547 (m), 464 (w) (m), 1542 (m), 1508 (w), 1490 (w), 1476 (w), 1430 (m), 1371 (w), 1341
-1
cm . Elemental analysis calcd (%) for C
H (3.01), N (41.79); found: C (12.58), H (3.03), N (41,70). The structure (m), 993 (m), 922 (w), 915 (w), 860 (w), 794 (w), 766 (w), 747 (w), 707
of 3 is supported by single crystal X-ray analysis.
(m), 683 (w), 610 (w), 586 (w), 547 (w), 525 (w), 472 (w), 458 (w) cm-
-amino-4H-1,2,4-triazole-3-carbohydrazide diperchlorate 1. Elemental analysis calcd (%) for C
(371.23): C (29.12), H
4). A suspension of 1 (0.710 g, 5 mmol) in deionic water (15 mL), (2.44), N (33.96); found: C (29.09), H (1.88), N (34.75).
perchloric acid (70 wt%, 0.82 ml, 10mmol) was added with portions. 5-amino-4H-1,2,4-triazole-3-carbohydrazide
The mixture becomes clear immediately. Then the solution was phloroglucinolate) (7). Pale yellow solid. Yield: 1.805 g, 89.6 %.
stirred for another 0.5 h and filtered. The filtrate was left for is easily soluble in anhydrous methanol. Light-yellow solid.
crystallization at room temperature as colorless crystalline solid (4). (onset): 201 C. 7 is soluble in most of high-polar solvents such as
3 8 8
H N O7 (268.15): C (13.44), (w), 1328 (w), 1274 (m), 1210 (m), 1166 (w), 1107 (w), 1091 (m), 1030
5
9 9 9 8
H N O
(
di(trinitro-
8
T
d
o
o
(onset): 210, 342 C. H methanol, aceton, DMF, DMSO and hot water. 1H (DMSO-d
o
1
Yield: 1.619 g, 94.1 %. T
m
(onset): 175 C, T
d
6
):
(
DMSO-d
6
): δ=8.30 (br, s, 4H) ppm; 13C (DMSO-d
6
): δ=155.78, 153.47, δ=10.77 (br, s, 2H), 6.37 (br, s, 4H) ppm. 13C (DMSO-d
6
): δ=159.43,
1
3
1
1
44.10 ppm; IR (KBr pellet): 3383 (w), 3344(w), 3241 (w), 3117 (w), 157.83, 154.71, 152.12, 122.37 ppm. IR (KBr pellet): 3397 (m), 3351
018 (w), 2949 (w), 2799 (w), 2744(w), 1699 (s), 1638 (w), 1599 (w), (w), 3310 (w), 3265 (w), 3204 (w), 3066 (w), 2967 (w), 1715 (s), 1689
563 (m), 1521 (m), 1495 (w), 1446 (w), 1313 (m), 1281 (w), 1213 (w), (s), 1610 (s), 1560 (m), 1519 (w), 1498 (w), 1484 (w), 1457 (w), 1404
143 (w), 1110 (w), 1089 (w), 990 (m), 941 (w), 859 (w), 775 (w), 737 (m), 1339 (s), 1285 (w), 1259 (w), 1213 (w), 1170 (m), 1121 (w), 1082
-1
(
w), 680 (w), 627 (m), 581 (w), 535 (w), 483 (w) cm . Elemental (w), 1047 (w), 1018 (w), 994 (m), 918 (m), 888(w), 855 (w), 816 (m),
analysis calcd (%) for C Cl (343.03): C (10.50), H (2.35), N 792 (m), 764 (w), 737 (w), 716 (w), 704 (m), 669 (w), 652 (m), 617 (w),
24.50); found: C (9.78), H (2.51), N (22.94). The structure of 4 is 601 (m), 535 (m), 486 (w), 417 (w) cm . Elemental analysis calcd (%)
3
H
8
2 6 9
N O
-1
(
supported by single crystal X-ray analysis.
14
for C12H N
18
O
8
(403.22): C (26.81), H (2.25), N (31.26); found: C
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Page 10 of 12
ARTICLE
Journal Name
(
31.63), H (2.07), N (31.63). The structure of 7 is supported by single
crystal X-ray analysis.
-amino-4H-1,2,4-triazole-3-carbohydrazide
nitroimino-1,2,4-triazolate)] (9). Colorless solid. Yield: 1.670 g,
5.4 %. has poor solubility in most of solvents except DMSO.
(onset): 248 C. H (DMSO-d
ppm; 13C (DMSO-d
): δ=159.47, 157.91, 156.02, 152.43, 146.29 ppm;
IR (KBr pellet): 3557 (w), 3426 (w),3368 (m), 3255 (m), 3158 (w), 2899
Notes and references
View Article Online
DOI: 10.1039/C8DT01760C
(a) H. Gao and J. M. Shreeve, Chem. Rev., 2011, 111, 7377-
1
5
bis[3-(5-
7
436; (b) T. M. Klapötke, High Energy Density Materials,
Springer, Berlin, 2015; (c) P. Yin, Q. Zhang and J. M. Shreeve,
Acc. Chem. Res., 2016, 49, 4–16; (d) P. Pagoria, Propellants
Explos. Pyrotech., 2016, 41, 452–469.
8
9
o
1
T
d
6
): δ=9.08 (br, s, 2H), 6.31 (br, s, 4H)
2
3
W. Liu, W. L. Liu and S. P. Pang, RSC Adv., 2017, 7, 3617–3627.
6
(a) G.-H. Tao, Y. Guo, D. A. Parrish and J. M. Shreeve, J. Mater.
Chem. A, 2010, 20, 2999–3005; (b) Q.-H. Lin, Y.-C. Li, C. Qi, W.
Liu, Y. Wang and S.-P. Pang, J. Mater. Chem. A, 2013, 1, 6776–
(
(
(
(
(
w), 2716 (m), 1693 (m), 1606 (s), 1529 (w), 1510 (m), 1443 (m), 1396
w), 1327 (m), 1264 (m), 1225 (s), 1154 (w), 1091 (m), 1048 (w), 1014
w), 950 (w), 854 (w), 768 (w), 727 (w), 628 (w), 596 (w), 504 (w), 459
6785; (c) J.-T. Wu, J.-G. Zhang, X. Yin, Z.-Y. Cheng and C.-X. Xu,
New J. Chem., 2015, 39, 5265–5271; (d) J.-T. Wu, J.-G. Zhang,
X. Yin and L. Wu, New J. Chem., 2016, 40, 5414–5419; (e) T. M.
Klapötke, P. C. Schmid, S. Schnell and J. Stierstorfer, J. Mater.
-1
w) cm . Elemental analysis calcd (%) for C12
21.11), H (2.53), N (56.27); found: C (19.95), H (2.76), N (55.36).
-amino-4H-1,2,4-triazole-3-carbohydrazide 4,4’,5,5’-
tetranitro-bis-imidazolate (10). Yellow solid. Yield: 1.922 g, 84.3 %.
has poor solubility in most of solvents except DMF and DMSO.
12 20 )
H N O12 (398.26 : C
Chem. A, 2015,
and J. M. Shreeve, J. Mater. Chem. A, 2015,
3, 2658–2668; (f) P. Yin, J. Zhang, D. A. Parrish
3, 8606–8612; (g)
5
Q. Ma, Y. Chen, L. Liao, H. Lu, G. Fan and J. Huang, Dalton
Trans., 2017, 46, 7467–7479.
1
0
4
5
(a) J. Wang, J. Zhang, X. Yin, M. Sun, and T. Zhang, Z. Anorg.
Allg. Chem., 2013, 639, 2354–2358; (b) Y. Zhang, D. A. Parrish
and J. M. Shreeve, J. Mater. Chem.,2012, 22, 12659–12665; (c)
H. Xue, B. Twamley and J. M. Shreeve, J. Mater. Chem., 2005,
15, 3459–3465.
Light-yellow solid and is also partially soluble in anhydrous
(onset): 204 C. 1H (DMSO-d
o
methanol. Light-yellow solid.
δ=9.71 (br, s, 2H), 8.28 (s, 2H) ppm; 13C (DMSO-d
50.76, 141.36, 139.57 ppm; IR (KBr pellet): 3744 (w), 3366 (m), 3307
T
d
6
):
6
): δ=158.94, 157.17,
1
(a) Y. Tang, C. He, G. H. Imler, D. A. Parrish and J. M. Shreeve,
(
(
(
(
(
(
w), 2973 (w), 2929 (w), 2725 (w), 2390 (w), 2304 (w), 1693 (s), 1486
s), 1378 (s), 1302 (m), 1207 (m), 1108 (w), 1058 (w), 1019 (w), 984
w), 857 (m), 810 (s), 747 (w), 700 (m), 665 (w), 618 (w), 517 (w), 464
J. Mater. Chem. A, 2017,
Klapötke and C. M. Sabaté, Chem. Eur. J., 2008, 14, 5756–5771;
c) J. T. Wu, J. G. Zhang, X. Yin and K. Wu, Chem. Asian J., 2015,
5, 6100-6105; (b) C. Darwich, T. M.
(
-1
w), 426 (w) cm . Elemental analysis calcd (%) for C
8
H
12
N
14
O
3
10, 1239–1244; (d) H. Huang, Y. Shi, Y. Liu and J. Yang, Dalton
Trans., 2016, 45, 15382–15389.
(a) Z. Xu, G. Cheng, S. Zhu, Q. Lin and H. Yang, J. Mater. Chem.
456.25): C (23.69), H (1.77), N (42.98); found: C (22.86), H (2.21), N
43.36).
6
7
8
A, 2018, 6, 2239–2248; (b) J. Tian, H. Xiong, Q. Lin, G. Cheng
5
-amino-4H-1,2,4-triazole-3-carbohydrazide
(E)-1,2-bis(4-
and H. Yang, New J. Chem., 2017, 41, 1918–1924; (c) P. He, L.
Wu, J. Wu, Q. Wang, Z. Li, M. Gozin and J. Zhang, Chem. Eur.
J., 2017, 23, 11159–11168; (d) Q. Yu, G. Cheng, X. Ju, C. Lu, Q.
Lin and H. Yang, Dalton Trans., 2017, 46, 14301–14309.
(nitroamino)-1,2,5-oxadiazol-3-yl) diazene 1-oxide (11). Yellow
solid. Yield: 1.867 g, 84.1 %. 11 has poor solubility in most of
solvents except DMF and DMSO. Light-yellow solid and is also
(a) A. A. Dippold and T. M. Klapotke, Chem. Asian J., 2013,
1
8,
463-1471; (b) A. A. Abd-Elhafez, H. M. Mohamed, H. Y.
partially soluble in anhydrous methanol. Light-yellow solid. T
d
o
1
(
onset): 161 C. H (DMSO-d
13C (DMSO-d
): δ=157.43, 155.53, 155.45, 154.21, 153.00, 151.47,
47.62 ppm; IR (KBr pellet): 3520 (w), 3462 (w), 3324 (w), 3173 (m),
6
): δ=11.58 (br, s, 2H), 8.53 (br, s, 2H) ppm;
Hassan, G. S. El-Karamany, N. A. El-Koussi, A. F. Youssef,
Bulletin of Pharmaceutical Sciences, 1997, 20, 47-61; (c) G. E.
Cipens, V. Grinsteins, Latvijas PSR Zinatnu Akademijas Vestis,
Kimijas Serija, 1965.
(a) T. W. Myers, J. A. Bjorgaard, K. E. Brown, D. E. Chavez, S. K.
Hanson, R. J. Scharff, S. Tretiak and J. M. Veauthier, J. Am.
Chem. Soc., 2016, 138, 4685–4692; (b) T. W. Myers, K. E.
Brown, D. E. Chavez, R. J. Scharff and J. M. Veauthier, Inorg.
Chem., 2017, 56, 2297–2303; (c) W. Tong, J. Liu, Q. Wang, L.
Yang and T. Zhang, Z. Anorg. Allg. Chem., 2014, 640, 2991–
6
1
1
1
9
7
698 (s), 1607 (w), 1555 (s), 1517 (w), 1478 (m), 1394 (m), 1271 (m),
219 (w), 1179 (w), 1076 (w), 1047 (s), 1039 (s), 1017 (m), 982 (m),
55 (m), 940 (w), 901 (w), 890 (w), 872 (w), 855 (w), 833 (w),824 (m),
74 (m), 756 (w), 739 (w), 721 (m), 666 (w), 594 (m), 566 (m), 535
-1
(
w), 502 (w), 481 (w), 472 (w), 460 (w), 405 (w) cm . Elemental
analysis calcd (%) for C12 (444.25): C (18.93), H (1.82), N
50.45); found: C (17.57), H (1.80), N (48.00).
12 18 8
H N O
2
2
997; (d) W. Tong, R. Zhang, T. Zhang and L. Yang, RSC Adv.,
015, , 22031–22037.
(
5
9
1
(a) Y. Ma, A. Zhang, X. Xue, D. Jiang, Y. Zhu and C. Zhang, Cryst.
Growth Des., 2014, 14, 6101–6114; (b) J. Zhang, L. A. Mitchell,
Acknowledgements
D. A. Parrish and J. M. Shreeve, J. Am. Chem. Soc., 2015, 137
0532–10535; (c) J. Zhang, Q. Zhang, T. T. Vo, D. A. Parrish and
J. M. Shreeve, J. Am. Chem. Soc., 2015, 137, 1697–1704.
0 (a) Q. Sun, C. Shen, X. Li, Q. Lin and M. Lu, Cryst. Growth Des.,
017, 17, 6105–6110; (b) C. J. Snyder, D. E. Chavez, G. H. Imler,
E. F. C. Byrd, P. W. Leonard and D. A. Parrish, Chem. Eur. J.,
017, 23, 16466–16471.
,
1
We thank the Science Challenge Project (TZ2018004), the NSAF
Foundation of National Natural Science Foundation of China
and China Academy of Engineering Physics (Grant No.
U1530262), the National Natural Science Foundation of China
2
2
(Grant No. 11402237 and 11302200) and the Science and
1
1
1 R. Wang, H. Xu, Y. Guo, R. Sa, and J. M. Shreeve, J. Am. Chem.
Soc.,2010, 132, 11904-11905.
2 (a) G. M. Sheldrick, SHELXS-97, Program for solution of crystal
structures, University of Gottingen, Germany, 1997; (b) G. M.
Sheldrick, SHELXL-97, Program for refinement of crystal
structures, University of Gottingen, Germany, 1997.
3 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci,
G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian,
Technology Development Foundation of China Academy of
Engineering Physics (Grant No. 2015B0302055) for financial
support. We also appreciate Prof. Qinghua Zhang and Dr.
Shiliang Huang for their generous assistence in testing
experimental densities and the structure refinement of single-
crystal X-ray diffraction.
1
1
0 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 11 of 12
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn sa rgins
Journal Name
ARTICLE
A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada,
M. Ehara, K. Toyota, J. H. R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. T. Vreven, J. A.
Montgomery Jr, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd,
E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R.
Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C.
Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam,
M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J.
Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin,
R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K.
Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J.
Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B.
Foresman, J. C. J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian
View Article Online
DOI: 10.1039/C8DT01760C
0
9 D.01, Gaussian, Inc., Wallingford CT (USA), 2010.
4 (a) J. Zhang and J. M. Shreeve, J. Am. Chem. Soc., 2014, 136
437–4445; (b) J. Zhang, S. Dharavath, L. A. Mitchell, D. A.
Parrish and J. M. Shreeve, J. Am. Chem. Soc., 2016, 138, 7500–
1
1
,
4
7
5
503; (c) C. He and J. M. Shreeve, Angew. Chem. Int. Ed., 2015,
, 6260–6264; (c) Y. Tang, H. Gao, L. A. Mitchell, D. A. Parrish
4
and J. M. Shreeve, Angew. Chem. Int. Ed., 2016, 128, 1159–
162.
5 (a) O. M. Suleimenov and T. K. Ha, Chem. Phys. Lett., 1998,
90, 451–457; (b) Y. Guo, G. H. Tao, Z. Zeng, H. Gao, D. A.
Parrish and J. M. Shreeve, Chem. Eur. J., 2010, 16, 3753–3762;
c) Q. Wu, W. Zhu and H. Xiao, J. Mater. Chem. A, 2014,
3006–13015; (d) W. J. Hehre, R. Ditchfield, L. Radom and J. A.
1
2
(
2,
1
Pople, J. Am. Chem. Soc., 1970, 92, 4796–4801; (e) X. X. Zhao,
S. H. Li, Y. Wang, Y. C. Li, F. Q. Zhao and S. P. Pang, J. Mater.
Chem. A, 2016,
Li, H. Gao, W. Fu and Z. Zhou, Dalton Trans., 2016, 45, 17956–
7965.
6 H. D. B. Jenkins, D. Tudela and L. Glasser, Inorg. Chem., 2002,
, 2364–2367.
4, 5495–5504; (f) C. Li, M. Zh ang, Q. Chen, Y.
1
1
4
1
1
1
7 M. Sućeska, EXPLO5, version 6.02, 2013.
8 (a) J. Zhang and J. M. Shreeve, J. Am. Chem. Soc., 2014, 136
4
,
437-4445;(b) T. M. Klapötke, A. Preimesser and J. Stierstorfer,
Z. Anorg. Allg. Chem., 2012, 638, 1278–1286; (c) T. S. Hermann,
K. Karaghiosoff, T. M. Klapötke and J. Stierstorfer, Chem. Eur.
J., 2017, 23, 12087–12091; (d) W. Zhang, J. Zhang, M. Deng, X.
Qi, F. Nie and Q. Zhang, Nat. Commun., 2017, 8, 181.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 11
Please do not adjust margins

Dalton Transactions
Page 12 of 12
View Article Online
DOI: 10.1039/C8DT01760C
A new strategy for constructing nitrogen-rich cation through energetic moieties (energetic “gene”)
combination was presented and their derivatives based on this new cation were successfully
synthesized and investigated.