Energetic propane-1,3-diaminium and butane-1,4-diaminium salts of N,N′-dinitroethylenediazanide: syntheses, crystal structures and thermal properties

Article abstract of DOI:10.1107/S2053229618017588

The acidity of the amine H atoms and the consequent salt formation ability of ethylenedinitramine (EDNA) were analyzed in an attempt to improve the thermal stability of EDNA. Two short-chain alkanediamine bases, namely propane-1,3-diamine and butane-1,4-diamine, were chosen for this purpose. The resulting salts, namely propane-1,3-diaminium N,N′-dinitroethylenediazanide, C₃H₁₂N₂²⁺·C₂H₄N₄O₄^2?, and butane-1,4-diaminium N,N′-dinitroethylenediazanide, C₄H₁₄N₂²⁺·C₂H₄N₄O₄^2?, crystallize in the orthorhombic space group Pbca and the monoclinic space group P2₁/n, respectively. The resulting salts display extensive hydrogen-bonding networks because of the presence of ammonium and diazenide ions in the crystal lattice. This results in an enhanced thermal stability and raises the thermal decomposition temperatures to 202 and 221 °C compared to 180 °C for EDNA. The extensive hydrogen bonding present also plays a crucial role in lowering the sensitivity to impact of these energetic salts.

Full text of DOI:10.1107/S2053229618017588

research papers
Energetic propane-1,3-diaminium and butane-1,4-
0
diaminium salts of N,N -dinitroethylenediazanide:
syntheses, crystal structures and thermal properties
ISSN 2053-2296
a
a
b
Gerhard T. Roodt, Bhawna Uprety, Demetrius C. Levendis and Charmaine
a
Arderne *
Received 5 December 2018
Accepted 12 December 2018
a
b
Chemistry, University of Johannesburg, 524 Johannesburg, Gauteng 2006, South Africa, and Molecular Science
Institute, School of Chemistry, University of Witwatersrand, Johannesburg, Gauteng 2050, South Africa. *Correspondence
e-mail: carderne@uj.ac.za
Edited by J. White, The University of Melbourne,
Australia
The acidity of the amine H atoms and the consequent salt formation ability of
ethylenedinitramine (EDNA) were analyzed in an attempt to improve the
thermal stability of EDNA. Two short-chain alkanediamine bases, namely
propane-1,3-diamine and butane-1,4-diamine, were chosen for this purpose. The
Keywords: energetic salts; explosive parameters;
detonation velocity; detonation pressure; crystal
structure; EDNA; butane-1,4-diamine; propane-
1,3-diamine; ethylenedinitramine.
0
resulting salts, namely propane-1,3-diaminium N,N -dinitroethylenediazanide,
2ꢁ
2
2
+
0
C H N ꢀC H N O , and butane-1,4-diaminium N,N -dinitroethylenediaza-
3
12
2
4
+
4
4
CCDC references: 1884498; 1884497
2
2ꢁ
4
nide, C H N ꢀC H N O , crystallize in the orthorhombic space group Pbca
4
14
2
2
4
4
and the monoclinic space group P2 /n, respectively. The resulting salts display
1
Supporting information: this article has
supporting information at journals.iucr.org/c
extensive hydrogen-bonding networks because of the presence of ammonium
and diazenide ions in the crystal lattice. This results in an enhanced thermal
ꢂ
stability and raises the thermal decomposition temperatures to 202 and 221 C
ꢂ
compared to 180 C for EDNA. The extensive hydrogen bonding present also
plays a crucial role in lowering the sensitivity to impact of these energetic salts.
1
. Introduction
Energetic materials are important chemical compounds that
are chiefly used in industries such as armaments, mining,
fireworks and space exploration (Aaker o¨ y et al., 2015). They
play an important role in the military, as well as in the civil
sector, having applications in construction, demolition
requirements, metal workings and even the production of
synthetic diamonds (Pagoria et al., 2002; Elbeih et al., 2013).
However, their large-scale production and use is often limited
due to the tedious synthetic methods and/or difficult storage
and handling conditions required. Overcoming these chal-
lenges and allowing a facile usage of energetic materials with
existing and/or new energetic materials has been the focus of
intense research among scientists working on energetic
materials worldwide. Some of the earlier accounts describe the
use of polymorphism, although with mixed success. More
recently, cocrystallization, as well as salt formation, as a crystal
engineering tool has emerged as a promising technique in
overcoming the shortcomings commonly found with energetic
materials (Xue et al., 2004). The extensive hydrogen-bonding
networks in these compounds are known to increase the
thermal and mechanical stability of the crystal as a result of
the possibility of extensive charge-assisted hydrogen bonding
being present (Gomathi & Theivarasu, 2017).
0
Ethylenedinitramine (EDNA; systematic name: N,N -di-
nitroethylenediamine) is a secondary explosive that was
initially developed at the Picatinny Arsenal in 1935 (Hale,
1935) as a potential substitute for the then most commonly
#
2019 International Union of Crystallography
Acta Cryst. (2019). C75
https://doi.org/10.1107/S2053229618017588 1 of 7

research papers
Table 1
Experimental details.
I
II
Crystal data
Chemical formula
2
2
+
42ꢁ
2+
42ꢁ
O
C
224.24
3
H
12
N
ꢀC
H N
2 4 4
O
C
4
H
14
238.26
N
2
ꢀC
2
H N
4 4
M
r
Crystal system, space group
Temperature (K)
Orthorhombic, Pbca
100
12.3448 (14), 9.9435 (13), 16.9904 (19)
90, 90, 90
2085.6 (4)
8
Mo Kꢀ
0.12
1
Monoclinic, P2 /n
100
5.408 (3), 7.203 (4), 14.288 (8)
90, 98.03 (3), 90
551.0 (5)
2
Mo Kꢀ
0.12
0.44 ꢄ 0.41 ꢄ 0.26
˚
a, b, c (A)
ꢂ
ꢀ
, ꢁ, ꢂ ( )
˚
3
V (A )
Z
Radiation type
ꢁ
1
ꢃ (mm
Crystal size (mm)
)
0.26 ꢄ 0.17 ꢄ 0.08
Data collection
Diffractometer
Absorption correction
Bruker APEXII CCD
Multi-scan (SADABS; Bruker, 2016)
0.656, 0.746
Bruker APEXII CCD
Multi-scan (SADABS; Bruker, 2016)
0.697, 0.746
Tmin, Tmax
No. of measured, independent and observed
I > 2ꢄ(I)] reflections
18809, 2591, 1827
11975, 1371, 1258
[
R
int
0.077
0.668
0.044
0.668
˚
ꢁ1
)
(sin ꢅ/ꢆ)max (A
Refinement
2
2
2
R[F > 2ꢄ(F )], wR(F ), S
No. of reflections
0.046, 0.115, 1.02
2591
0.031, 0.086, 1.07
1371
No. of parameters
No. of restraints
H-atom treatment
160
6
85
3
H atoms treated by a mixture of independent
and constrained refinement
0.24, ꢁ0.25
H atoms treated by a mixture of independent
and constrained refinement
0.42, ꢁ0.22
˚
ꢁ3
)
Áꢇmax, Áꢇmin (e A
Computer programs: APEX2 (Bruker, 2015), SAINT (Bruker, 2015), SHELXT2014 (Sheldrick, 2015a), SHELXL2018 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009).
used explosive RDX. Its complete crystallographic analyses
were reported in 1948 (Llewellyn & Whitmore, 1948).
However, its crystal structure was not reported in the
Cambridge Structural Database (CSD; Groom et al., 2016)
until 1968 (as DNEDAM; Turley, 1968), and that is the only
entry to date for EDNA in the CSD. It possesses several
desirable properties, such as high brisance, low impact sensi-
tivity and high heat sensitivity. Despite its early discovery, the
synthetic protocol for EDNA was optimized only in 1959 by
the Dow Chemical Company (Levine, 1959). Currently,
EDNA finds applications as an explosive booster, a secondary
explosive and in the preparation of castable explosives like
Ednatol (Aaker o¨ y et al., 2015).
have been crystallized and published so far in the CSD, i.e.
disodium ethanebis(nitramine) (CSD refcode NAETNA;
Allentoff & Wright, 1953) and bis(hydrozinium) N,N -di-
0
nitroethylenediaminate (TEGXUY; Bircher et al., 1996).
Studies using EDNA salts with organic bases are quite scarce
in the literature. Recently EDNA cocrystals with heterocyclic
aromatic diamine bases have been reported (Aaker o¨ y et al.,
2015). However, not much data is available concerning linear
alkanediamine bases and EDNA.
Therefore, the present study reports the syntheses, com-
plete structural characterization and analyses of the thermal
behaviour of two new EDNA salts with linear alkanediamines.
The diamines chosen for this purpose were propane-1,3-di-
amine and butane-1,4-diamine. Some explosive parameters,
such as detonation velocity and pressure, were also calculated
theoretically, and the results are compared with existing data
in the literature for similar compounds.
2
. Experimental
2
.1. General
The explosive properties of these EDNA salts depend
greatly on the stabilizing counter-ion; thus, the properties can
be fine-tuned simply by changing the cationic part of the
energetic salt. A variety of inorganic EDNA salt derivatives
EDNA was prepared from a modified military method
(Department of the Army Technical Manual, 1984). All the
starting materials were commercially available and were used
without further purification. Differential scanning calorimetry
(DSC) experiments were performed using a Mettler Toledo
882e Differential Scanning Calorimeter under a nitrogen
+
+
+
+
+
2+
2+
+
(Li , Na , K , NH , Ag , Mg , Hg and H N ) (Cherskaya
et al., 1985; Lamberton & Yusuf, 1969; Shlyapochnikov et al.,
4 5 2
2002) have been reported in the literature. However, only two
ꢃ
2
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ꢁ
1
atmosphere at a flow rate of 25 ml min . The heating rate was
ꢁ1
3. Results and discussion
.1. Crystal structure analysis
ꢂ
ꢂ
5 C min from ambient temperature to 500 C. The ther-
mogravimetric analysis (TGA) was performed on a TA
3
0
Propane-1,3-diaminium N,N -dinitroethylenediazanide, I
(Fig. 1), crystallizes in the orthorhombic space group Pbca.
ꢂ
ꢁ1
Instruments SDT-Q600 at a heating rate of 5 C min , from
ꢂ
room temperature to 500 C. The FT–IR analysis was per-
formed on a PerkinElmer FT–IR Spectrum BX spectrometer
The unit cell contains both the diaminium cation and the
2ꢁ
3
EDNA anion. Atoms N5 and N6 of the cation are sp -
ꢁ
1
in the region 4000–600 cm .
hybridized. The HN—NO groups of EDNA are deprotonated
2
and have an anionic character. This is reflected in the shorter
2
.2. Synthesis and crystallization
˚
N1—N2 [1.272 (2) A] and N3—N4 [1.269 (2) A] bond lengths
˚
2ꢁ
Caution: EDNA (secondary explosive) and EDNA-derived
in the EDNA anion compared to those in free EDNA
˚
DNEDAM: 1.301 A). However, the bonds are slightly longer
salts are potentially explosive and should be handled only in
small amounts using proper safety equipment, including
gloves, safety glasses, lab coat and nonstatic generating
clothes.
The synthesis of EDNA was carried out using the following
modified method. A solution of 2-imidazolidone (2 g,
23.23 mmol) in the minimum amount of ice-cold 95% sulfuric
acid was added dropwise to a solution of sulfuric acid (15.8%),
nitric acid (66.7%) and water (17.5%) in an ice bath at 0 C.
The resulting mixture was stirred in the ice bath for 10 min and
(
than typical double bonds, indicating the delocalization of the
negative charge as a result of resonance stabilization.
A Mogul Geometry Check within Mercury (Macrae et al.,
2ꢁ
2008) reveals that the two N—N—C angles on the EDNA
anion are unusual; the C1—N2—N1 and C2—N3—N4 angles
ꢂ
are 113.65 (13) and 114.95 (13) , respectively. They deviate
significantly from that in free EDNA, which has a value of
ꢂ
ꢂ
1
22.87 . This narrowing in the C—N—N angle can also be
ascribed to the above-stated resonance of delocalized charge/
anion resulting in steric hindrance. This observed narrowing
has only been observed in two other structures found in the
ꢂ
then on an oil bath (at 45 C) for another 25 min. Addition of
ice-cold water to the reaction mixture resulted in precipitation
of the nitro intermediate 1,3-dinitro-2-imidazolidone. Hy-
drolysis of the intermediate with boiling water resulted in the
formation of EDNA as a white crystalline powder (yield:
ꢂ
CSD, namely 1-amino-2-nitraminoethane (TIJKEC; 112.560 )
ꢂ
and disodium ethane-1,2-bisnitramine (NAETNA; 113.421 ).
No unusual bond angles or torsion angles are observed in
the propane-1,3-diaminium cation. However, the anion of I
exhibits several deviations with respect to its torsion angles.
The N—N—C—C torsion angle changes to ꢁ176.08 (N1—
3.03 g, 87%).
The two title salts, i.e. propane-1,3-diaminium N,N -di-
0
0
nitroethylenediazanide (I) and butane-1,4-diaminium N,N -
dinitroethylenediazanide (II), were synthesized by the addi-
tion of an aqueous solution of EDNA (0.100 g, 0.667 mmol) to
the corresponding aqueous solution of the diamine, i.e.
propane-1,3-diamine (0.049 g, 0.667 mmol) and butane-1,4-
diamine (0.058 g, 0.667 mmol), at room temperature. The
reaction mixture was allowed to crystallize by slow evapora-
tion, resulting in crystals of the EDNA–organic salts.
ꢂ
N2—C1—C2) and 177.19 (N4—N3—C2—C1) compared to
free EDNA.
Data for I: sheet-like crystals; yield (after drying samples in
a vacuum desiccator for 24 h): 0.177 g, >100%. FT–IR (ATR;
s = symmetric and as = asymmetric): ꢆ
3164, 3074, 2916
max
+
(
NH ), 2713, 2540, 1605, 1569, 1520, 1414 (NNO ) , 1293, 1253
3 2 s
ꢁ1
(
NNO ) , 1109, 1052, 966, 752, 723 cm .
2
as
Data for II: block-like crystals; yield (after drying samples
in a vacuum desiccator for 24 h): 0.171 g, >100%. FT–IR
+
3
(
ATR): ꢆmax 3164, 3063, 2916 (NH ), 2547, 1608, 1569, 1522,
1
405 (NNO ) , 1340, 1295, 1255 (NNO ) , 1222, 1105, 1055,
2 s 2 as
ꢁ
1
964, 751, 723 cm .
2.3. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. H atoms were located from
difference Fourier maps. All carbon-bound H atoms were
placed in calculated positions and refined using a riding-model
˚
approximation, with C—H = 0.95–1.00 A and U (H) =
iso
1.2U (C) for other H atoms. H atoms linked to N atoms were
located from difference Fourier electron-density maps and
eq
Figure 1
The molecular structures of (a) I and (b) II, with displacement ellipsoids
drawn at the 50% probability level. [Symmetry codes: (i) ꢁx, ꢁy + 1,
ꢁz + 2; (ii) ꢁx + 1, ꢁy + 2, ꢁz + 2.]
refined with restraints of the N—H bonds to distances of 0.89–
˚
0.91A and with U (H) = 1.2U (N).
iso eq
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4
Table 2
Hydrogen-bond geometry (A, ) for I.
and R (30). The crystal packing of I (Fig. 3) utilizes the
4
˚
ꢂ
presence of the ammonium and nitramine functional groups
(N—Hꢀ ꢀ ꢀO) as building blocks for the observed infinite
hydrogen-bonding network. All the relevant hydrogen-
bonding data is presented in Table 2. The packing type
observed can be described as a combination of mixing-type
and crossing-type stacking based on the descriptions as
proposed by Ma and co-workers (Ma, Zhang, Zhang et al.,
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
i
N5—H5Bꢀ ꢀ ꢀO3
N5—H5Cꢀ ꢀ ꢀO4
N6—H6Bꢀ ꢀ ꢀO1
N6—H6Cꢀ ꢀ ꢀO3
0.89 (1)
0.90 (1)
0.89 (1)
0.89 (1)
2.02 (1)
1.84 (1)
1.87 (1)
1.99 (1)
2.8421 (18)
2.725 (2)
2.761 (2)
153 (2)
170 (2)
177 (2)
171 (2)
ii
iii
2.8687 (18)
3
2
1
2
3
2
Symmetry codes: (i) ꢁx þ 1; ꢁy; ꢁz þ 1; (ii) ꢁx þ ; ꢁy þ 1; z ꢁ ; (iii) ꢁx þ ; ꢁy,
1
z ꢁ .
2
2014).
0
Butane-1,4-diaminium N,N -dinitroethylenediazanide, II
(Fig. 1), crystallizes in the monoclinic space group P2 /n. The
Table 3
Hydrogen-bond geometry (A, ) for II.
˚
ꢂ
1
asymmetric unit consists of half of the cation and half of the
anion, with the remainder of the fragments being generated by
the symmetry operations (ꢁx, ꢁy + 1, ꢁz + 2) and (ꢁx + 1,
ꢁy + 2, ꢁz + 2). As seen with compound I, the diaminium
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Aꢀ ꢀ ꢀO2
0.93 (1)
0.93 (1)
0.92 (1)
1.92 (1)
1.96 (1)
1.96 (1)
2.8422 (15)
2.8927 (15)
2.8723 (16)
170 (1)
179 (1)
171 (1)
i
N1—H1Bꢀ ꢀ ꢀN2
ii
N1—H1Cꢀ ꢀ ꢀO1
3
cation in II undergoes sp -hybridization, as well from the
1
1
1
2
Symmetry codes: (i) x ꢁ 1; y; z; (ii) ꢁx þ ; y ꢁ ; ꢁz þ .
2
2
neutralization reaction between EDNA and butane-1,4-di-
amine. Also, as in compound I, partial double-bond character
The graph-set analyses reveal a variety of direct, chain and
4
is observed in the HN—NO fragment of the EDNA dianion
2
due to the delocalization of the anionic charge. The presence
ring motifs, the most obviously visible being R (12) (Fig. 2)
4
Figure 2
Graph sets of compounds (a) I and (b) II, showing R (12) and R (18) ring motifs. The bonds denoted by a, b and c refer to the specific hydrogen-bonding
4
4
2
4
contacts involving the N—Hꢀ ꢀ ꢀO interactions.
Figure 3
Packing diagram of I, viewed down the a (left) and b (right) axes.
ꢃ
4
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Table 4
Thermal properties of I and II.
hydrogen bonding in energetic materials is mostly associated
with reduced sensitivity (Ma, Zhang, Zhang et al., 2014; Zhang
et al., 2013). Therefore, although sensitivity studies were not
performed on these compounds, it can be postulated that
compounds I and II would possess reduced sensitivity to shock
and friction from the number of hydrogen bonds present.
The calculated densities for compounds I and II, i.e. 1.428
ꢂ
ꢁ1
)
Compound
Melting point ( C)
Energy released (kJ mol
EDNA
I
II
174.5
198.1
217.4
208.97
252.90
207.29
ꢁ3
and 1.436 Mg m , are both lower than the calculated density
ꢁ3
of the anionic moiety contributes to the sharpening of the
ꢂ
for EDNA (DNEDAM: 1.709 Mg m ). This observed
decrease in calculated density can be attributed to the low
densities of propane-1,3-diamine and butane-1,4-diamine
C3—N2—N3 angle [114.41 (8) ] compared with the value of
ꢂ
122.87 (C—N—N) in EDNA (DNEDAM).
ꢁ3
As observed in compound I, compound II exhibits no
deviating bond angles or torsion angles with respect to the
butane-1,4-diaminium fragment. The N3—N2—C3—C3
group of the anion undergoes a slight but significant distortion
(0.880 and 0.877 Mg m , respectively), highlighting the role
of the densities of both precursors in salt formation.
A search of the CSD for compounds containing the ethyl-
i
2
ꢁ
enebis(nitraminate) fragment, C H N O , gave no hits,
2 4 4 4
ꢂ
in its torsion angle, i.e. ꢅ81.03 , as compared with the value of
showing that deprotonated EDNA has not been investigated
crystallographically in its use as an energetic anion. However,
ꢂ
ꢂ
ꢅ83.81 in EDNA (DNEDAM). A torsion angle of ꢁ180 is
ꢁ
observed for compound I [II?] in the N—C—C—N backbone;
ꢂ
the CH N O fragment, containing the nitramine functional
2
2
2
for EDNA (DNEDAM), this torsion angle is 180 .
The crystal packing arrangement of compound II (Fig. 4)
contains two types of hydrogen-bonding moieties, namely
group, gave a total of 167 hits, with a series of energetic
materials being synthesized, such as DEJDEE, DEJDII,
DEJDOO, DEJDUU and DEJFAC (Wang et al., 2017),
MEDDEH and MEDDIL (Tang et al., 2017), YEHXOB
(Astakhov et al., 2017) and CAZCUD (Dippold et al., 2012). A
total of 377 compounds contained the propane-1,3-diaminium
(
ammonium)N—Hꢀ ꢀ ꢀO(nitramine) and (ammonium)N—
Hꢀ ꢀ ꢀN(nitramine), which result in the observed hydrogen-
bonding network. The packing types observed can be
described as being a combination of mixing-type and crossing-
type stacking for I, and wave-like (a axis), face-to-face-type (b
axis) and a crossing-type (c axis) stacking for II. Such packing
types have been described in the literature (Ma, Zhang, Zhang
2
+
(C H N ) cation, with 284 compounds containing the
3
12
2
2+
butane-1,4-diaminium (C H N ) cation, which were not
4
14
2
related to energetic materials.
et al., 2014). A graph-set analysis of compound II reveals a
2
3.2. Thermal behaviour and thermal stability
variety of direct, chain and ring motifs, with R (18) (Fig. 2) and
4
6
6
R (48) being the most obviously visible. Table 3 lists the
hydrogen-bond geometry observed for compound II.
The DSC and TGA curves of I and II are shown in Fig. 5
and the data are compiled in Table 4. The thermograms of
both salts showed similar trends: there was an observed loss of
The friction and heat sensitivity of the energetic cocrystals
and salts can be tuned by selectively choosing suitable co-
formers. Compounds exhibiting strong Oꢀ ꢀ ꢀO interactions are
associated with shock- and friction-sensitive materials (Ma,
Zhang, Xue et al., 2014; Manner et al., 2014). The presence of
ꢂ
unbound water (A) at around 80–100 C. The melting points
(B) of the two energetic salts were found to be 198.1 (for I)
ꢂ
and 217.4 C (for II). Compound I began to decompose (C) at
ꢁ1
ꢂ
228.3 C, with an associated energy release of 1127.8 J g
Figure 4
Packing diagram of II, viewed down the a (left) and c (right) axes.
ꢃ
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Table 5
Nitrogen equivalent indices for some detonation products.
represents the detonation velocity of the explosive, ꢇ denotes
0
ꢁ3
the density of an explosive (Mg m ) and P indicates the
detonation pressure. The Kamlet–Jacob method was used to
determine which detonation products would be formed
Detonation product
N
2
2
H O
CO
CO
2
C
H
2
Nitrogen equivalent index
1
0.54
0.78
1.35
0.15
0.29
(Kamlet & Jacobs, 1968), which is given below.
ꢁ
1
252.90 kJ mol ). The melting of II had an onset temperature
(
of 210.5 C, with decomposition (C) occurring at 220.9 C and
I C H N O ꢀC H N = 4H O + 4H + 5C + 3N
2
2
4
4
4
3
12
2
2
2
2
ꢂ
ꢂ
II C H N O ꢀC H N = 4H O + 5H + 6C + 3N
2
4
4
4
4
14
2
2
2
ꢁ
1
ꢁ1
an associated energy release of 870.0 J g (207.29 kJ mol ).
These associated exothermic releases for I and II are
comparable with those of the polymer-bonded explosives
The nitrogen-equivalent indices of the determined detona-
tion products are listed in Table 5. The calculated ÆN, V and
P values for I, II and EDNA are given in Table 6. The influ-
ence of additional carbon content dilutes the detonation
velocity and the detonation pressure such that these nitrogen-
D
ꢁ
1
BCHMX–Formex (1273.0 J g )
1
691.0 J g ), respectively (Yan, Zeman et al., 2013).
and
HMX-Formex
ꢁ
(
3.3. Detonation characterization
rich compounds will have good V and P values.
D
The oxygen balance (which is the ability to convert all the
compound’s available carbon and hydrogen into CO and H O
The detonation velocity and detonation pressure (Meyer et
al., 2007) are important indicators, gauging the strength of
energetic materials. This can be predicted with the nitrogen
equivalent equation (Guo & Zhang, 1983) using the formulae
below for the two synthesized energetic salts (Yan, Zhao et al.,
2
2
from its oxygen reserves) of these compounds was calculated
by the following mathematical equation (Thottempudi &
Shreeve, 2011), where C H O N ;
a
b
c
d
2013; Chen et al., 2010):
OB% = 1600 [c – 2a – b/2]/Mr
(
(
(
1) ÆN = 100Æꢈ N /M
i i
2) V = (690 + 1160ꢇ )ÆN
The calculated energetic properties are listed in Table 6. A
higher carbon content in the molecule usually serves to
suppress the energetic properties by decreasing the oxygen
balance of the molecule. This trend can be clearly seen in
D
0
2
3) P = 1.092(ꢇ ÆN) – 0.574
0
where ÆN represents the nitrogen equivalent of the detona-
tion products, ꢈ is the mole number of a specific detonation
0
Table 4. The corresponding results for bis(hydrazinium) N,N -
i
product which is produced by a mole of explosive, N is the
i
dinitroethylenediaminate (TEGXUY) are also included in the
table to allow a better comparison of the results in relation to
carbon chain length. TEGXUY is claimed to be extremely
nitrogen equivalent index of the specific detonation product
and M signifies the molecular weight of the explosive. VD
Table 6
Detonation properties of organic salts as compared to EDNA.
ꢁ3 a
)
ꢁ1
Compound
ÆN
Density (Mg m
Velocity of detonation (m s
)
Detonation pressure (GPa)
Oxygen balance (%)
EDNA
TEGXUY
I
3.01
3.42
3.15
2.65
1.767
1.59
1.428
1.436
8250
8667
7398
6239
30.34
32.71
21.56
15.22
ꢁ31.98
ꢁ52.29
ꢁ99.89
ꢁ114.16
II
Note: (a) low-temperature densities were calculated by SC-XRD.
Figure 5
TGA and DSC curves for (a) I and (b) II.
ꢃ
6
of 7 Roodt et al. Propane-1,3-diaminium and butane-1,4-diaminium salts
Acta Cryst. (2019). C75

research papers
insensitive and fairly insensitive to impact and friction,
respectively (Bircher et al., 1996).
Dippold, A. A., Klap o¨ tke, T. M., Martin, F. A. & Wiedbrauk, S.
(2012). Eur. J. Inorg. Chem. pp. 2429–2443.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. &
Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
Elbeih, A., Zeman, S., Jungov a´ , M. & V a´ vra, P. (2013). Propellants
Explos. Pyrotech. 38, 379–385.
Gomathi, V. & Theivarasu, C. (2017). Acta Cryst. C73, 97–103.
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta
Cryst. B72, 171–179.
4
. Summary
Two new alkanediaminium salts of EDNA were synthesized
and characterized by single-crystal XRD. They crystallize in
the orthorhombic space group Pbca (for I) and the monoclinic
space group P2 /n (for II). The intermolecular charge-assisted
1
Guo, Y. X. & Zhang, H. S. (1983). Explos. Shock Waves, 3, 56–66.
Hale, G. C. (1935). Explosive. US Patent No. 2011578.
Kamlet, M. J. & Jacobs, S. J. (1968). J. Chem. Phys. 48, 23–35.
Lamberton, A. H. & Yusuf, H. M. (1969). J. Chem. Soc. C, pp. 397–400.
Levine, L. (1959). Preparation of Ethylene Urea. US Patent No.
hydrogen-bonding interactions in both salts show that the
EDNA N—C—C—N backbone has a large ability to twist,
thereby enhancing the packing, resulting in two new, and
possibly insensitive, energetic salts. These features increase
the overall thermal stability of the salts compared with pure
EDNA. Upon thermal decomposition, energy releases of
2
892843.
Llewellyn, F. J. & Whitmore, F. E. (1948). J. Chem. Soc. pp. 1316–
323.
1
ꢁ
1
Ma, Y., Zhang, A., Xue, X., Jiang, D., Zhu, Y. & Zhang, C. (2014).
Cryst. Growth Des. 14, 6101–6114.
Ma, Y., Zhang, A., Zhang, C., Jiang, D., Zhu, Y. & Zhang, C. (2014).
Cryst. Growth Des. 14, 4703–4713.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe,
P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. &
Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.
Manner, V. W., Tappan, B. C., Scott, B. L., Preston, D. N. & Brown, G.
W. (2014). Cryst. Growth Des. 14, 6154–6160.
Meyer, R., Kohler, J. & Homburg, A. (2007). In Explosives.
Weinheim: Wiley.
Pagoria, P. F., Lee, G. S., Mitchell, A. R. & Schmidt, R. D. (2002).
Thermochim. Acta, 384, 187–204.
1127.8 (for I) and 870.0 J g (for II) are observed. The
theoretical detonation velocity and detonation pressure have
ꢁ
1
been calculated to be 7398 m s and 21.56 GPa for I, and
ꢁ1
6
238 m s and 15.22 GPa for II.
Funding information
Funding for this research was provided by: National Research
Foundation South Africa (bursary No. SFH160708176662, to
GTR).
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
Shlyapochnikov, V. A., Cherskaya, N. O., Ivshin, V. P., Levchenkov,
D. V. & Kharitonkin, A. B. (2002). Russ. Chem. Bull. Int. Ed. 51,
1071–1074.
References
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ꢃ
Acta Cryst. (2019). C75
Roodt et al.
Propane-1,3-diaminium and butane-1,4-diaminium salts 7 of 7

supporting information
supporting information
Acta Cryst. (2019). C75 [https://doi.org/10.1107/S2053229618017588]
Energetic propane-1,3-diaminium and butane-1,4-diaminium salts of N,N′-di-
nitroethylenediazanide: syntheses, crystal structures and thermal properties
Gerhard T. Roodt, Bhawna Uprety, Demetrius C. Levendis and Charmaine Arderne
Computing details
Data collection: APEX2 (Bruker, 2016) for mo_17ca_grcc5a_0ma; APEX2 (Bruker, 2015) for mo_17ca_grcc6_0m. Cell
refinement: SAINT (Bruker, 2016) for mo_17ca_grcc5a_0ma; SAINT (Bruker, 2015) for mo_17ca_grcc6_0m. Data
reduction: SAINT (Bruker, 2016) for mo_17ca_grcc5a_0ma; SAINT (Bruker, 2015) for mo_17ca_grcc6_0m. For both
structures, program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure:
SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare
material for publication: OLEX2 (Dolomanov et al., 2009).
Propane-1,3-diaminium (ethane-1,2-diyl)bis(nitroazanide) (mo_17ca_grcc5a_0ma)
Crystal data
2+
2−
−3
C
H N
3 12 2
·C
H N O
2 4 4 4
x
D = 1.428 Mg m
M
r
= 224.24
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2241 reflections
θ = 2.4–24.2°
µ = 0.12 mm
T = 100 K
Orthorhombic, Pbca
a = 12.3448 (14) Å
b = 9.9435 (13) Å
c = 16.9904 (19) Å
V = 2085.6 (4) Å
Z = 8
−1
3
Block, clear colourless
0.26 × 0.17 × 0.08 mm
F(000) = 960
Data collection
Bruker APEXII CCD
diffractometer
2591 independent reflections
1827 reflections with I > 2σ(I)
φ and ω scans
R
int = 0.077
Absorption correction: multi-scan
θmax = 28.3°, θmin = 2.4°
(
SADABS; Bruker, 2016)
h = −16→16
k = −9→13
l = −22→22
T
1
min = 0.656, Tmax = 0.746
8809 measured reflections
Refinement
2
Refinement on F
Hydrogen site location: mixed
Least-squares matrix: full
H atoms treated by a mixture of independent
and constrained refinement
2
2
R[F > 2σ(F )] = 0.046
2
2
2
2
wR(F ) = 0.115
w = 1/[σ (F
o
) + (0.0437P) + 0.6333P]
2
2
S = 1.02
where P = (F
o
+ 2F )/3
c
2
1
6
591 reflections
60 parameters
restraints
(Δ/σ)max < 0.001
Δρmax = 0.24 e Å
Δρmin = −0.25 e Å
−
3
−
3
Primary atom site location: dual
Acta Cryst. (2019). C75
sup-1

supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
O1
O2
O3
O4
N1
N2
N3
N4
0.52445 (10)
0.62676 (11)
0.56105 (9)
0.67822 (10)
0.56838 (11)
0.55013 (11)
0.64024 (11)
0.62552 (11)
0.64848 (11)
0.7032 (13)
0.5844 (12)
0.6522 (16)
0.89704 (11)
0.9411 (15)
0.9196 (16)
0.9024 (16)
0.60335 (14)
0.682372
0.574704
0.58044 (13)
0.604022
0.501852
0.65865 (12)
0.607638
0.638830
0.77355 (12)
0.790641
0.825733
0.78367 (13)
0.757743
0.84025 (13)
0.85073 (13)
0.18981 (13)
0.19857 (13)
0.78109 (16)
0.65589 (15)
0.38529 (15)
0.25971 (15)
−0.07170 (16)
−0.111 (2)
−0.1040 (19)
0.0172 (14)
−0.10009 (17)
−0.149 (2)
−0.0147 (14)
−0.129 (2)
0.59631 (18)
0.612859
0.636047
0.44706 (18)
0.408707
0.430337
−0.09557 (18)
−0.036108
−0.189875
−0.06866 (18)
0.028115
−0.120459
0.72260 (7)
0.61563 (7)
0.55971 (6)
0.46112 (7)
0.66152 (8)
0.65373 (8)
0.52363 (7)
0.51576 (7)
0.44556 (8)
0.4714 (10)
0.4607 (10)
0.4549 (11)
0.21727 (8)
0.2470 (11)
0.2187 (11)
0.1678 (8)
0.58573 (9)
0.587960
0.536522
0.58800 (9)
0.638970
0.581751
0.35959 (9)
0.331128
0.347697
0.33093 (9)
0.336666
0.363156
0.24521 (9)
0.238837
0.0297 (3)
0.0370 (4)
0.0261 (3)
0.0297 (3)
0.0256 (3)
0.0239 (3)
0.0230 (3)
0.0232 (3)
0.0218 (3)
0.035 (5)*
0.031 (5)*
0.035 (6)*
0.0224 (3)
0.041 (6)*
0.035 (6)*
0.035 (5)*
0.0232 (4)
0.028*
0.028*
0.0242 (4)
0.029*
0.029*
0.0223 (4)
0.027*
0.027*
0.0215 (4)
0.026*
0.026*
0.0246 (4)
0.030*
N5
H5A
H5B
H5C
N6
H6A
H6B
H6C
C1
H1A
H1B
C2
H2A
H2B
C3
H3A
H3B
C4
H4A
H4B
C5
−0.10960 (19)
−0.203187
−0.050622
H5D
H5E
0.737193
0.212600
0.030*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
O1
O2
O3
O4
0.0322 (7)
0.0510 (8)
0.0217 (6)
0.0286 (7)
0.0338 (8)
0.0317 (8)
0.0323 (8)
0.0291 (7)
0.0232 (6)
0.0002 (6)
−0.0132 (6)
−0.0079 (5)
0.0004 (5)
0.0068 (5)
0.0154 (6)
0.0001 (5)
0.0067 (5)
0.0004 (5)
0.0016 (5)
0.0081 (5)
0.0016 (5)
0.0282 (7)
0.0243 (6)
0.0315 (6)
Acta Cryst. (2019). C75
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supporting information
N1
N2
N3
N4
N5
N6
C1
C2
C3
C4
C5
0.0232 (7)
0.0204 (7)
0.0209 (7)
0.0182 (7)
0.0163 (7)
0.0192 (7)
0.0209 (8)
0.0215 (8)
0.0172 (8)
0.0170 (8)
0.0186 (8)
0.0334 (9)
0.0291 (9)
0.0270 (8)
0.0298 (9)
0.0264 (9)
0.0305 (9)
0.0309 (10)
0.0322 (10)
0.0285 (10)
0.0293 (10)
0.0317 (10)
0.0202 (7)
0.0223 (7)
0.0211 (7)
0.0217 (7)
0.0225 (7)
0.0175 (6)
0.0179 (7)
0.0189 (7)
0.0213 (7)
0.0183 (7)
0.0236 (8)
−0.0021 (6)
−0.0039 (6)
−0.0052 (6)
−0.0040 (6)
0.0010 (6)
0.0000 (5)
−0.0004 (5)
−0.0002 (5)
−0.0017 (5)
0.0019 (5)
0.0006 (6)
−0.0015 (6)
−0.0007 (6)
0.0004 (6)
−0.0006 (6)
0.0001 (6)
0.0041 (6)
0.0028 (6)
0.0013 (6)
0.0050 (6)
0.0036 (6)
0.0028 (6)
0.0028 (7)
0.0010 (7)
−0.0027 (7)
0.0023 (6)
−0.0030 (7)
0.0014 (6)
−0.0047 (7)
−0.0074 (7)
−0.0013 (7)
−0.0019 (7)
−0.0022 (7)
Geometric parameters (Å, º)
O1—N1
O2—N1
O3—N4
O4—N4
N1—N2
N2—C1
N3—N4
N3—C2
N5—H5A
N5—H5B
N5—H5C
N5—C3
N6—H6A
N6—H6B
N6—H6C
1.3103 (18)
N6—C5
1.481 (2)
1.2676 (18)
1.2939 (17)
1.2863 (18)
1.272 (2)
1.455 (2)
1.269 (2)
C1—H1A
C1—H1B
C1—C2
C2—H2A
C2—H2B
C3—H3A
C3—H3B
C3—C4
C4—H4A
C4—H4B
C4—C5
C5—H5D
C5—H5E
0.9900
0.9900
1.511 (2)
0.9900
0.9900
0.9900
0.9900
1.523 (2)
0.9900
0.9900
1.517 (2)
0.9900
0.9900
1.455 (2)
0.894 (13)
0.892 (12)
0.899 (13)
1.485 (2)
0.887 (13)
0.894 (13)
0.889 (12)
O2—N1—O1
O2—N1—N2
N2—N1—O1
N1—N2—C1
N4—N3—C2
O4—N4—O3
N3—N4—O3
N3—N4—O4
H5A—N5—H5B
H5A—N5—H5C
H5B—N5—H5C
C3—N5—H5A
C3—N5—H5B
C3—N5—H5C
H6A—N6—H6B
H6A—N6—H6C
H6B—N6—H6C
C5—N6—H6A
118.50 (15)
124.85 (14)
116.64 (13)
113.65 (13)
114.95 (13)
118.28 (14)
123.77 (14)
117.95 (13)
111.8 (18)
107.6 (18)
110.4 (18)
110.4 (12)
107.5 (12)
109.1 (12)
108.2 (19)
108.6 (19)
107.8 (18)
111.2 (14)
C2—C1—H1B
N3—C2—C1
110.3
107.47 (13)
110.2
110.2
110.2
110.2
108.5
109.3
109.3
111.42 (13)
108.0
109.3
109.3
109.7
109.7
108.2
109.66 (13)
109.7
N3—C2—H2A
N3—C2—H2B
C1—C2—H2A
C1—C2—H2B
H2A—C2—H2B
N5—C3—H3A
N5—C3—H3B
N5—C3—C4
H3A—C3—H3B
C4—C3—H3A
C4—C3—H3B
C3—C4—H4A
C3—C4—H4B
H4A—C4—H4B
C5—C4—C3
C5—C4—H4A
Acta Cryst. (2019). C75
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supporting information
C5—N6—H6B
C5—N6—H6C
N2—C1—H1A
N2—C1—H1B
N2—C1—C2
110.3 (13)
110.7 (13)
110.3
110.3
107.16 (13)
108.5
C5—C4—H4B
N6—C5—C4
109.7
111.62 (13)
109.3
109.3
109.3
N6—C5—H5D
N6—C5—H5E
C4—C5—H5D
C4—C5—H5E
H5D—C5—H5E
H1A—C1—H1B
C2—C1—H1A
109.3
108.0
110.3
O1—N1—N2—C1
O2—N1—N2—C1
N1—N2—C1—C2
N2—C1—C2—N3
N4—N3—C2—C1
−178.69 (13)
0.1 (2)
176.08 (13)
−175.71 (12)
−177.19 (13)
N5—C3—C4—C5
C2—N3—N4—O3
C2—N3—N4—O4
C3—C4—C5—N6
173.46 (14)
1.4 (2)
−178.29 (13)
−173.42 (15)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
i
N5—H5B···O3
0.89 (1)
0.90 (1)
0.89 (1)
0.89 (1)
2.02 (1)
1.84 (1)
1.87 (1)
1.99 (1)
2.8421 (18)
2.725 (2)
2.761 (2)
153 (2)
170 (2)
177 (2)
171 (2)
N5—H5C···O4
ii
N6—H6B···O1
iii
N6—H6C···O3
2.8687 (18)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, −y+1, z−1/2; (iii) −x+3/2, −y, z−1/2.
Butane-1,4-diaminium (ethane-1,2-diyl)bis(nitroazanide) (mo_17ca_grcc6_0m)
Crystal data
2
+
2−
C
M
4
H
14
N
2
·C
H N O
2 4 4 4
F(000) = 256
= 1.436 Mg m
−3
r
= 238.26
D
x
Monoclinic, P2
a = 5.408 (3) Å
b = 7.203 (4) Å
c = 14.288 (8) Å
β = 98.03 (3)°
1
/n
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 6899 reflections
θ = 2.9–28.6°
µ = 0.12 mm
T = 100 K
−1
3
V = 551.0 (5) Å
Block, colourless
Z = 2
0.44 × 0.41 × 0.26 mm
Data collection
Bruker APEXII CCD
diffractometer
1371 independent reflections
1258 reflections with I > 2σ(I)
φ and ω scans
R
int = 0.044
Absorption correction: multi-scan
θmax = 28.3°, θmin = 2.9°
(
SADABS; Bruker, 2016)
h = −7→7
k = −9→9
l = −18→19
T
1
min = 0.697, Tmax = 0.746
1975 measured reflections
Refinement
2
Refinement on F
1371 reflections
Least-squares matrix: full
85 parameters
3 restraints
Primary atom site location: dual
Hydrogen site location: mixed
2
2
R[F > 2σ(F )] = 0.031
2
wR(F ) = 0.086
S = 1.07
Acta Cryst. (2019). C75
sup-4

supporting information
H atoms treated by a mixture of independent
and constrained refinement
(Δ/σ)max < 0.001
Δρmax = 0.42 e Å
Δρmin = −0.22 e Å
−
3
2
2
2
−3
w = 1/[σ (F
o
) + (0.0442P) + 0.1942P]
2
2
where P = (F
o
+ 2F )/3
c
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
O1
O2
N2
N3
0.57312 (12)
0.69613 (12)
0.98232 (14)
0.75026 (14)
1.03227 (16)
0.932325
1.210935
0.26171 (14)
0.406 (2)
0.174 (2)
0.164 (2)
0.32151 (18)
0.411205
0.164198
0.50962 (10)
0.32306 (10)
0.42748 (11)
0.42316 (10)
0.54830 (13)
0.663346
0.36574 (5)
0.25666 (5)
0.37090 (5)
0.33261 (5)
0.45476 (6)
0.443575
0.01429 (17)
0.01567 (18)
0.01234 (19)
0.01133 (18)
0.0120 (2)
0.014*
C3
H3A
H3B
N1
H1A
H1B
H1C
C1
H1D
H1E
C2
H2A
H2B
0.583655
0.464369
0.014*
0.13317 (11)
0.1838 (18)
0.2286 (17)
0.0814 (19)
−0.01024 (13)
−0.114988
−0.058994
0.07085 (12)
0.184428
0.29615 (5)
0.2778 (10)
0.3205 (9)
0.2444 (9)
0.37207 (6)
0.347103
0.390608
0.45915 (6)
0.479772
0.01154 (18)
0.023 (3)*
0.019 (3)*
0.026 (4)*
0.0145 (2)
0.017*
0.017*
0.0130 (2)
0.016*
0.48284 (17)
0.402580
0.648300
0.105825
0.442502
0.016*
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
O1
O2
N2
N3
C3
N1
C1
C2
0.0104 (3)
0.0150 (3)
0.0094 (3)
0.0108 (3)
0.0113 (4)
0.0111 (3)
0.0182 (4)
0.0148 (4)
0.0184 (4)
0.0199 (4)
0.0152 (4)
0.0123 (4)
0.0132 (4)
0.0123 (4)
0.0121 (4)
0.0121 (4)
0.0143 (3)
0.0033 (2)
−0.0031 (3)
−0.0003 (3)
−0.0008 (3)
−0.0021 (3)
0.0000 (3)
0.0024 (2)
−0.0001 (2)
−0.0003 (3)
0.0015 (3)
0.0011 (3)
−0.0004 (3)
−0.0032 (3)
−0.0015 (3)
0.0007 (2)
−0.0043 (3)
−0.0013 (3)
0.0012 (3)
−0.0015 (3)
0.0006 (3)
0.0017 (3)
0.0005 (3)
0.0115 (3)
0.0119 (4)
0.0109 (3)
0.0114 (4)
0.0107 (4)
0.0117 (4)
0.0111 (4)
−0.0011 (3)
−0.0009 (3)
Geometric parameters (Å, º)
O1—N3
O2—N3
N2—N3
1.2869 (11)
1.3017 (11)
1.2974 (12)
N1—H1C
N1—C1
C1—H1D
0.924 (11)
1.5000 (12)
0.9900
Acta Cryst. (2019). C75
sup-5

supporting information
N2—C3
C3—C3
C3—H3A
C3—H3B
N1—H1A
N1—H1B
1.4749 (12)
1.5503 (18)
0.9900
0.9900
0.931 (11)
0.931 (10)
C1—H1E
C1—C2
C2—C2
C2—H2A
C2—H2B
0.9900
i
1.5320 (13)
1.5420 (18)
0.9900
ii
0.9900
N3—N2—C3
O1—N3—O2
O1—N3—N2
N2—N3—O2
114.41 (8)
118.84 (8)
124.00 (8)
117.16 (8)
112.06 (10)
109.2
109.2
109.2
109.2
107.9
C1—N1—H1B
C1—N1—H1C
N1—C1—H1D
N1—C1—H1E
N1—C1—C2
107.9 (8)
110.0 (9)
109.3
109.3
111.44 (8)
108.0
109.3
109.3
110.92 (10)
109.5
109.5
i
N2—C3—C3
N2—C3—H3A
N2—C3—H3B
H1D—C1—H1E
C2—C1—H1D
C2—C1—H1E
i
C3 —C3—H3A
i
ii
C3 —C3—H3B
C1—C2—C2
H3A—C3—H3B
H1A—N1—H1B
H1A—N1—H1C
H1B—N1—H1C
C1—N1—H1A
C1—C2—H2A
C1—C2—H2B
108.0 (12)
109.8 (13)
109.5 (12)
111.6 (8)
ii
C2 —C2—H2A
109.5
109.5
108.0
ii
C2 —C2—H2B
H2A—C2—H2B
i
N3—N2—C3—C3
81.04 (11)
−2.72 (12)
C3—N2—N3—O2
N1—C1—C2—C2
178.03 (7)
173.34 (9)
ii
C3—N2—N3—O1
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1A···O2
N1—H1B···N2
N1—H1C···O1
0.93 (1)
0.93 (1)
0.92 (1)
1.92 (1)
1.96 (1)
1.96 (1)
2.8422 (15)
2.8927 (15)
2.8723 (16)
170 (1)
179 (1)
171 (1)
iii
iv
Symmetry codes: (iii) x−1, y, z; (iv) −x+1/2, y−1/2, −z+1/2.
Acta Cryst. (2019). C75
sup-6