Correlation between structure and energetic properties of three nitroaromatic compounds: Bis(2,4-dinitrophenyl) ether, bis(2,4,6-trinitrophenyl) ether, and bis(2,4,6-trinitrophenyl) thioether

Article abstract of DOI:10.1021/jacs.9b11086

Decades after the initial discovery of bis(2,4,6-trinitrophenyl) ether derivatives, the first single-crystal X-ray structures for three members of this compound class can finally be shown and the analytical data could be completed. This group of molecules is an interesting example that illustrates why older predictive models for the sensitivity values of energetic materials like bond dissociation enthalpy and electrostatic potential sometimes give results that deviate significantly from the experimentally determined values. By applying newer models like Hirshfeld surface analysis and fingerprint plot analysis that utilize the crystal structure of an energetic material, the experimentally found trend of sensitivities could be understood and the older models could be brought into a proper perspective. In the future, the prediction of structure-property relationships for energetic molecules starting from a crystal structure can be achieved and should be pursued.

Full text of DOI:10.1021/jacs.9b11086

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Article
The correlation between structure and energetic properties of
three nitroaromatic compounds: Bis(2,4-dinitrophenyl) ether,
Bis(2,4,6-trinitrophenyl) ether and Bis(2,4,6-trinitrophenyl) thioether
Marco Reichel, Dominik Dosch, Thomas Klapoetke, and Konstantin Karaghiosoff
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b11086 • Publication Date (Web): 20 Nov 2019
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Journal of the American Chemical Society
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The correlation between structure and energetic properties of three
nitroaromatic compounds: Bis(2,4-dinitrophenyl) ether, Bis(2,4,6-tri-
nitrophenyl) ether and Bis(2,4,6-trinitrophenyl) thioether
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Marco Reichel,†‡ Dominik Dosch,†‡ Thomas Klapötke,*† Konstantin Karaghiosoff†
†
Department of Chemistry, Ludwig Maximilian University of Munich, Butenandtstr. 5-13 (D), D-81377 Munich, Germany
Supporting Information Placeholder
many years of uncertainty, a deeper insight into the energetic be-
havior of the title compounds bis(2,4-dinitrophenyl) ether (1),
bis(2,4,6-trinitrophenyl) ether (2) and bis(2,4,6-trinitrophenyl) thi-
oether (3), could be gained. This was achieved by combining theo-
retical methods with structural investigations of the HEDMs to un-
derstand the trends that were found for the experimental sensitivity
values.
ABSTRACT: Decades after the initial discovery of bis(2,4,6-tri-
nitrophenyl) ether (TNB) ether derivatives, the first single-crystal
X-ray structures for three members of this compound class could
finally be shown and the analytical data could be completed. This
group of molecules is an interesting example that illustrates why
older predictive models for the sensitivity values of energetic ma-
terials like bond dissociation enthalpy and electrostatic potential
sometimes give results that deviate significantly from the experi-
mentally determined values. By applying newer models like
Hirshfeld surface analysis and fingerprint plot analysis that utilize
the crystal-structure of an energetic material, the experimentally
found trend of sensitivities could be understood and the older mod-
els could be brought into a proper perspective. In the future the pre-
diction of structure-property relationships for energetic molecules
starting from a crystal structure can be achieved and should be pur-
sued.
RESULTS AND DISCUSSION
Spectroscopic Characterization. All three compounds were
prepared according to modified and optimized methods (Scheme
1).[9]
INTRODUCTION
About 150 years ago, Alfred Nobel recognized, that the industri-
alization of “new” synthetic explosives must be accompanied by
their safe handling. The development of dynamite was the first step
in this direction.[1] Just a quarter of a century later, Dynamit Nobel
AG focused on TNT, which replaced its predecessors due to its ex-
cellent handling safety and brisance.[2] Although nitroaromatic
compounds are no longer the centerpiece of modern explosive in-
vestigations,[3] Alfred Nobel's fundamental aim of increased han-
dling safety that was implemented with this group of materials con-
tinues to exist.[4] The insensitivity to external stimuli is one of the
most important requirements for the synthesis of new HEDMs, next
to other characteristics such as higher environmental compatibility,
high density, high thermal stability and higher detonation veloc-
ity/pressure.[3b, 5] The desired high performance of HEDMs can be
achieved by using compounds with a high heat of formation, but
these candidates tend to be more sensitive towards external stim-
uli.[4a] The contrary behavior of the desired parameters for
HEDMs[4a, 6] leads to the conclusion, that not only the molecular
design, but also the crystallographic design has to be considered to
find a balance between performance and safety for new energetic
materials.[7] A better visualization and understanding of the sensi-
tizing properties can be achieved by combining older prediction
models - such as the calculation of h50 values, electrostatic surface
potential (ESP) or EES values[3b, 4a] - with newer methods like
Hirshfeld surface analysis and Fingerprint plot analysis.[8] After
Scheme 1. Reaction schemes for compounds (1) – (3).
Although some of these compounds have existed for almost a
century and show some importance today, various fundamental an-
alytical data such as NMR or vibrational spectroscopy are still
missing.[9a, 10] Therefore all three compounds were characterized
through multinuclear NMR-, infrared-, Raman spectroscopy, ele-
mental analysis, and single-crystal X-ray diffraction. The 1H NMR
chemical shifts of the proton in ortho position between the NO2
groups (1: 8.9, 2: 8.6; 3: 9.1), correspond well with those of 1-sub-
stituted trinitro derivatives such as TNT (8.8 ppm) or picric acid
(9.0 ppm).[11] In the 13C NMR spectra, the corresponding chemical
shifts are observed between 160 ppm and 120 ppm. In the 14N NMR
of 1, 2 and 3 the differently substituted NO2 groups are not distinct,
due to the signal width of 316 Hz, 280 Hz, and 520 Hz. Character-
istic infrared and Raman vibration modes could be assigned accord-
ing to the literature[12] and are listed in Table 1.
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The substitution of the sulfur in 3 by the more electronegative
3 < 2). Thus, these older prediction models are insufficient to ex-
plain the actual sensitivities values that were obtained in experi-
ments. In order to explain this, more modern methods that use the
crystal structure and packaging effects have to be applied to cor-
rectly asses the structure property relationships and therefore the
sensitivities of this group of nitroaromatic compounds.
Structure property relationship. In the crystal an external me-
chanical stimulus like impact or friction can cause a displacement
of the layers, which generates internal strains. If this strain energy
is below the lowest BDE, the molecular integrity is not destroyed.
If the strain energy is higher than the energy required to break the
weakest bond the material is destroyed.[8b] The strain caused by the
sliding of the layers depends strongly on the stacking of the layers
and other interactions in the crystal, such has hydrogen bridges.[15]
1
2
3
4
5
6
7
8
oxygen in 2 and 1 causes a shift to higher wavenumbers, which is
observed for the ν(C-N) vibration mode. This displacement can be
regarded as a measure of the corresponding bond strength. The
greater the shift to higher wavenumbers, the stronger the C-N bond.
Thus, the bond strength correlates proportionally with the bond dis-
sociation enthalpy (BDE), which – as many researchers have
shown – is associated with the sensitivity of energetic materials.[13]
According to this model 3 is expected to have the lowest BDE
whereby 2 and 1 should be in a similar range.
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Table 1. Characteristic vibration modes of 1, 2 and 3.
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1
2
3
IR
Raman
IR
Raman
IR
Raman
3090
1530
1342
913
3106
1543
1361
940
3103
1536
1339
913
3107
1543
1362
941
3093
1530
1332
911
3094
1545
1354
936
ν(C-H)
νas(NO2)
νs(NO2)
ν(C-N)
δ(NO2)
743
796
749
797
748
773
ν
as/s asymmetric/ symmetric vibration mode; δ: deformation vibration
In this work, the BDEs were calculated from their crystal structure
data using the B3LYP/6-311G+(d,p) method, the found values are
depicted in Figure 1.
Figure 1. Calculated BDE Values of the weakest Bond in the molecule 1, 2 and 3,
considering all X-C bonds (X: C, O, N, S)
Since the values of the BDEs for the three compounds all range
between RDX (161 kJ mol-1) and TATB (355 kJ mol-1), they can
be categorized as sensitive.[14] The calculated trend of decreasing
BDEs from 1 to 3 is consistent with the trend of experimental ob-
servation of the shift to higher wavenumbers of the ν(C-N) vibra-
tion mode. As numerous studies have shown, BDEs are considered
the most important factor in pyrogenic decomposition for the pos-
sible trigger binding that breaks first and can therefore be used to
assess the sensitivity of a material.[7] Besides the calculation of h50
values or the determination of volume-based sensitivities, the elec-
trostatic potential (ESP) is often used to understand changes of the
sensitivities and to visualize the bond strength variation.[3b]
Figure 3. Single-crystal X-ray structure of 1 (a), 2 (b), 3 (c) and the crystal packing of
1 (d), 2 (e), 3 (f).
It can be seen from the monomers a, b and c, that the phenyl resi-
dues in the molecules are twisted against each other to different
degrees (Figure 3). This results in a different packing behavior in
the crystal (d, e, f). The strain energy resulting from a mechanical
stimulus should be the greatest for 2, since the gearing of the indi-
vidual layers is the highest. The higher interlayer distance which is
present in 3 facilitates an easier moving of the layers against each
other. This effect can reduce the slip barrier to such an extent that
it becomes smaller than the BDE.[8b] In addition to the lower gear-
ing of 3 versus 2, this effect is another indication for the higher
sensitivity of compound 2 when compared with compound 3. In
addition to crystal packing, intermolecular interactions contribute
significantly to the height of the slide barrier and therefore to the
sensitivity to external mechanical stimuli. A feature exhibited by
insensitive molecules is, that the Hirshfeld surface on a plane has
the most red dots representing close contacts.[15] In the present case
all compounds (1, 2 and 3) have red dots which point out of a plane
(Figure 4). The close contacts are not arranged in a slideable plane,
which results in interlayer repulsion that can be significantly in-
creased by shifting the plane.
Figure 2. ESP of 1 (left), 2 (center) and 3 (right), calculated on the 0.02 electron
bohr-3 hypersurface.
The visualization of the ESP for compounds (1) – (3) is shown in
Figure 2. For all compounds, the positive range is larger than the
negative range. All positive values are significantly stronger than
the negative absolute values. In addition to the strongly positive
center of the respective molecules, this is a general indication of
their sensitive character.[3b-d] According to the BDEs and the ESP,
the sensitivity of the compounds should increase from 1 to 3. How-
ever, a different trend is present in experimental observations (1 <
The O∙∙∙O interaction is a very important close contact interaction.
In most cases a high frequency of O∙∙∙O contacts indicates a high
sensitivity, because more nitro groups are exposed on the molecular
surface and that increases the risk of explosion due to the exceeding
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repulsion via an interlayer sliding.[7, 8b, 14a, 15] Thus, graph d clearly
older literature values 1.70 (2) and 1.61 g cm-3 (3).[2]. To gain ac-
curate values for the heat of formation (HOF) it is important to use
high precision theoretical methods, as experimental values are of-
ten inaccurate.[7] Therefore, the heat of formation was computed by
ab initio calculations using the optimized geometry of molecules
starting from the X-ray diffraction experiment.
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shows that 2 is the most sensitive compound. With 37.9 % of O∙∙∙O
contacts, 2 has the most of those contacts compared to 3 with 33.5
% and 1 with 16.6 %. This distribution can be retrieved from the
2D plot because the marked O∙∙∙O interactions decrease from a via
c to b in area and color intensity. Furthermore, O∙∙∙H and N∙∙∙H con-
tacts, which generate an intermolecular 3D network, can make a
compound more sensitive, since an interlayer slide strongly alters
these stabilizing interactions. However, the replacement of hard
O∙∙∙O interactions with softer N∙∙∙H or O∙∙∙H interactions often leads
to a better absorption of mechanical stimuli in a material.[14a]
Table 2. Physical and Calculated detonation parameters of compound 1, 2 and 3 using
EXPLO5 computer code.
1
2
C12H4N6O13
440.19
9
3
C12H4N6O12
456.25
12.5
formula
C12H6N4O9
350.20
>40
S
9
Mr [g mol−1
IS[a] [J]
]
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FS[b] [N]
ESD [mJ]
N[c] [%]
>360
50
>360
50
19.09
66.34
-47.25
---
256
1.84
1.80
-132.9
>360
50
18.42
60.50
-56.11
253
310
1.85
1.81
-20.3
16.00
57.12
-82.24
246.32
336.73
1.73
N + O[d] [%]
ΩCO2[e] [%]
Tmelt[f] [°C]
[g]
Tdec [°C]
[h]
ρ143 K [g cm−3] (X−ray)
[i]
ρ298 K [g cm−3
]
]
1.68
-168.1
∆퐻푓°[j] [kJ mol−1
EXPLO5 V 6.03
∆푈푓°[k] [kJ kg−1
]
-3934
2958
16.7
6582
582.5
-4850
3695
24.9
7634
620.4
-4689
2740
15.9
6912
427.5
TC−J[l] [K]
PC−J[m] [GPa]
Vdet[n] [ms−1
]
Vo[o] [dm3 kg−1
]
[a] Impact sensitivity[14d] [b] friction sensitivity[14e] [c] nitrogen content [d] combined
nitrogen and oxygen content [e] absolute oxygen balance assuming the formation of
CO or CO2 [f] melting point from DTA [g] decomposition from DTA [h] density
determined by X−ray experiment at 143
K [i] ambient temperature density,
extrapolated from X-ray value [j] Heat of formation calculated at the CBS-4M level of
theory for FMN, experimental determined for MN [k] detonation energy [l] detonation
temperature [m] detonation pressure [n] detonation velocity [o] volume of detonation
gases at standard temperature and pressure conditions
According to Trouton´s Rule, the heat of formation (HOF) was cal-
culated by subtracting the enthalpy of sublimation from the HOF
of the corresponding gas-phase species.[16] The values for the HOF
of the gas phase species was obtained by subtraction of the atomi-
zation energies from the total enthalpy of the molecule.[17] Calcula-
tions were performed using the CBS-4M level of theory in combi-
nation with the crystal structures. By using the specific densities
and the EXPLO5 (V6.01) program, the detonation properties of 1,
2 and 3 could be estimated. They were calculated at the Chap-
man−Jouguet point (C-J point) with the help of the stationary det-
onation model using a modified Becker−Kistiakowski−Wilson
state equation for gaseous detonation products and the Murnaghan
equation of state for condensed products (compressible solids and
liquids). By using the first derivative of the Hugoniot curve of the
system the C-J point could be found.[18] Given a high density and
heat of formation, it is not surprising that compound 2 exhibits a
better performance than 1 and 3. Although 1 has a higher heat of
formation, the influence of the increased density of 2 predominates
so strongly that 2 has the best performance. As can be seen in Table
2, the oxygen balance for 1 is lowest due to the lower number of
NO2 groups. The substitution of the ether bridge in 2 by a sulfur
atom deteriorates the oxygen balance from 2 to 3 as expected. With
respect to the detonation velocity, the values of 2 and 3 exceed TNT
(6881 m s-1) were 1 falls below it.
Figure 4. Two dimensional fingerprint plot in crystal stacking as well as the corre-
sponding Hirshfeld surface (bottom right in 2D plot) of 1 (a), 2 (b) and 3 (c) (color
coding: white, distance d equals VDW distance; blue, d exceeds VDW distance, red,
d, smaller than VDW distance). Population of close contacts of 1, 2, and 3 in crystal
stacking (d).
Strong O∙∙∙H and N∙∙∙H interactions are often found in less sensitive
compounds, because the interlayers are more rigid and can absorb
energy better without a shifting of the planes, which would induce
a repulsion between the layers. [8b] The 2D fingerprint plot exhibits
two distinctive spikes for strong O∙∙∙H bonding.[15] With respect to
di + de (di: distance from the Hirshfeld surface to the nearest atom
interior; de: distance from the Hirshfeld surface to the nearest atom
exterior) we can ascertain that for 1 with a total of 44.3 % the most
and strongest hydrogen bonds are present. For 2 the 27.7 % of H-
bridges are the fewest and weakest. With a total of 30.1 %, mole-
cule 3 forms more H-bridges than compound 2 but less then mole-
cule 1 while showing similar strong H-bridges than compound 1.
The interlayer contacts of C∙∙∙O show weak interactions (distances
above 3.5 Å) and therefore can be neglected. This also applies for
the N∙∙∙H and N∙∙∙O contacts.[15] According to this newer model the
frequencies of O∙∙∙O contacts and the strength and frequency of H-
bridges are the most relevant indicator for the impact sensitivity of
an explosive material and therefore the order of decreasing sensi-
tivity for the discussed compounds should be 2 > 3 > 1.
Heat of formation and detonation parameters. Density plays
an important role for the performance of energetic materials and is
a direct result of the packing in the crystal. With respect to 1, 2 and
3, crystal densities are observed to be 1.73, 1.84 and 1.85 g cm-3 at
143 K and the extrapolated values at room temperature are 1.69,
1.80 and 1.81 g cm-3. These values deviate significantly from the
CONCLUSIONS
Bis(2,4-dinitrophenyl) ether, bis(2,4,6-trinitrophenyl) ether, and
bis(2,4,6-trinitrophenyl) thioether have been synthesized and char-
acterized. The structures of these three compounds were deter-
mined by single-crystal X-ray diffraction. The results of the older
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prediction models (BDE, ESP) for the sensitivities were compared
1
2
3
4
5
6
7
8
with results for newer prediction models based on the crystal struc-
ture (Hirshfeld Surface and Fingerprint Plot analysis). The inaccu-
rate trend for the sensitivities that was observed for the older mod-
els (3 > 2 > 1) could be corrected. The trend for the sensitivities
shown by the experimental values (decreasing 2 > 3 > 1), could be
verified by the newer predictive methods which are based on the
crystal structure. The application of this newer methods could lead
to a better understanding and assessment of sensitivity values with-
out the necessity to synthesize large amounts of new energetic ma-
terials, which leads to an increase in safety. The performance of the
compounds was calculated and it was found that it decreases from
2 to 3 to 1 with all three compounds showing similar values as TNT.
Bis(2,4,6-trinitrophenyl) ether. Diphenylether (1.00 g, 5.88 mmol)
was added at 0 °C successively to a mixed acid consisting of 22 mL
oleum (30 %) and white fuming nitric acid (4.4 mL, 106 mmol).
The mixture was stirred for 30 min. After being warmed to room
temperature, the solution was heated to 150 °C for 4 d. The ob-
tained white suspension was cooled to room temperature and
poured into 750 mL of ice water. The solid was filtered of and
washed with water (3 × 100 mL). The filter cake was recrystallized
from boiling chloroform and the colorless powder was dried under
1
ambient conditions (0.53 g, yield: 24%). H NMR (DMSO-d6,400
9
MHz): δ 8.60 (s, 4H) ppm. 13C NMR (DMSO-d6,100 MHz): δ
160.6, 141.8, 125.2, 124.6 ppm. 14N (DMSO-d6, 29 MHz): δ -11 (s,
NO2) ppm. FT-IR (ATR): ṽ 3103 (m), 1612 (m), 1601 (m), 1536
(s), 1455 (m), 1415 (m), 1339 (s), 1268 (s), 1212 (m), 1191 (m),
1085 (m), 944 (m), 927 (m), 913 (m), 832 (m), 795 (m), 749 (m),
733 (m), 717 (s) 523 (m). Raman (1064 nm, 1074 mW): ṽ 3107
(w), 1627 (m), 1559 (m), 1543 (m), 1362 (s), 1275 (w), 1214 (m),
1171 (w), 1083 (w), 941 (w), 829 (m), 797 (w), 329 (w), 270 (w),
202 (w). EA calcd (%) for C12H4N6O13: C 32.74, H 0.92, N 19.09;
found: C 32.71, H 1.01, N 18.88. DTA: 256 °C (dec) IS: 9.0 J. FS:
360 N. ESD: 50 mJ.
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EXPERIMENTAL SECTION
General Information. Diphenylether, nitric acid, oleum, picryl
chloride and sodium thiosulfate were commercially available. For
NMR spectroscopy the solvent DMSO-d6 was dried using 3 Å mole
sieve. Spectra were recorded on a Bruker Avance III spectrometer
operating at 400.1 MHz (1H), 100.6 MHz (13C) and 28.9 MHz
(14N). Chemical shifts are referred to TMS (1H, 13C) and MeNO2
(14N). Raman spectra were recorded with a Bruker MultiRam FT
Raman spectrometer using a neodymium-doped yttrium aluminum
garnet (Nd:YAG) laser (λ = 1064 nm) with 1074 mW. The samples
for Infrared spectroscopy were placed under ambient conditions
onto an ATR unit using a Perkin Elmer Spectrum BX II FT-IR Sys-
tem spectrometer. Melting and / or decomposition points were de-
tected with a OZM DTA 552-Ex instrument. The scanning temper-
ature range was set from 293 K to 673 K at a scanning rate of 5 K
min-1. Elemental analysis was done with a Vario EL instrument and
a Metrohm 888 Titrando device.
Bis(2,4,6-trinitrophenyl) thioether. Sodium thiosulfate (0.498 g,
3.15 mmol) was added successively to a reflux heated suspension
of picryl chloride (1.00 g, 4.04 mmol) and magnesium carbonate
(0.190 g, 2.26 mmol) in absolute ethanol (25 mL). The mixture was
heated for 1 h. The mixture turned into a yellow suspension. After
being cooled to room temperature the obtained suspension was fil-
tered of and the filter cake washed with ethanol (3 × 15 mL), 1.0 M
HCl (3 × 5 mL) and water (3 × 5 mL). The yellow powder was
dried under a nitrogen stream (1.1 g, yield: 60%). 1H NMR
(DMSO-d6,400 MHz): δ 9.17 (s, 4H) ppm. 13C NMR (DMSO-
d6,100 MHz): δ 151.6, 147.8, 125.6, 124.4 ppm. 14N (DMSO-d6, 29
MHz): δ -19 (s, NO2) ppm. FT-IR (ATR): ṽ 3093 (m), 2917 (w),
2850 (w), 1598 (m), 1530 (s), 1392 (w), 1332 (s), 1169 (w), 1112
(w), 1047 (m), 931 (m), 911 (s), 822 (m), 748 (m), 726 (s), 718 (s),
687 (m). Raman (1064 nm, 1074 mW): ṽ 3094 (w), 1601 (m), 1545
(m), 1354 (s), 1301 (w), 1180 (m), 1059 (m), 936 (m), 825 (w), 773
(m), 433 (w), 370 (w), 331 (w), 287 (w). EA calcd (%) for
C12H4N6O12S: C 31.59, H 0.88, N 18.42, S 7.03; found: C 31.48, H
0.94, N 18.34, S 7.17. DTA: 253 °C (mp), 310 °C (dec) IS: 12.5 J.
FS: 360 N. ESD: 50 mJ.
Caution! All investigated compounds are explosives, which show
partly increased sensitivities toward various stimuli (e.g. higher
temperatures, impact, friction or electrostatic discharge). There-
fore, proper safety precautions (safety glass, Kevlar gloves and
earplugs) have to be applied while synthesizing and handling the
described compounds.
Bis(2,4-dinitrophenyl) ether. Diphenylether (2.15 g, 12.65 mmol)
was added at 0 °C to a mixed acid consisting of 1.15 mL sulfuric
acid, 2.74 mL Oleum (65%) and white fuming nitric acid (2.7 mL,
63.26 mmol). The mixture was stirred for 45 min. After being
warmed to room temperature, the solution was heated to 125 °C for
19 hours. The obtained reddish suspension was cooled to room tem-
perature and poured into 750 mL of ice water. The solid was filtered
of and washed with water (3 × 100 mL). The filter cake was recrys-
tallized from boiling ethyl acetate and the beige-red powder was
dried under ambient conditions (1.4 g, yield: 32%).
X-Ray Measurements. Bis(2,4,6-trinitrophenyl) ether and
bis(2,4-dinitrophenyl) ether were solved in ethylacetate and
single crystals have been received after slow solvent
evaporation. Single crystals of bis(2,4,6-trinitrophenyl)
thioether have been received of the decomposition of
fluoromethyl-(2,4,6)-trinitrobenzene
sulfonate
with
1H NMR (DMSO-d6,400 MHz): δ 7.67 (d, 2H, J = 2.8 Hz), 8.60
(dd, 2H, J = 9.1, 2.8 Hz), 8.98 (s, 2H, J = 9.1 Hz) ppm. 13C NMR
(DMSO-d6,100 MHz): δ 151.7, 143.8, 140.3, 130.2, 122.4, 122.3
ppm. 14N (DMSO-d6, 29 MHz): δ -20 (s, NO2) ppm. FT-IR (ATR):
ṽ 3365 (w), 3090 (w), 3076 (w), 2879 (w), 1592 (m), 1530 (s), 1483
(m), 1472 (m), 1422 (w), 1342 (s), 1265 (s), 1155 (w), 1136 (w),
1122 (w), 1067 (s), 972 (w), 928 (m), 913 (s), 867 (s), 834 (s), 787
(w), 762 (w), 743 (s), 721 (s), 687 (w), 661 (m), 639 (m), 603 (w),
521 (w), 499 (w), 458 (w), 435 (w). Raman (1064 nm, 300 mW): ṽ
3076 (w), 2263 (w), 2217 (w), 2202 (w), 2157 (w), 2137 (w), 2062
(w), 1951 (w), 1611 (m), 1597 (w), 1547 (w), 1352 (s), 1270 (w),
1213 (w), 1156 (w), 1137 (w), 1066 (w), 838 (m), 641 (w). EA
calcd (%) for C12H6N4O9: C 41.16, H 1.73, N 16.00; found: C
41.09, H 1.82, N 15.82. DTA: 246 °C (melting), 336 °C (dec) IS:
>40.0 J. FS: >360 N. ESD: 50 mJ.
triphenylphosphine sulfid in DCM after slow solvent
evaporation. Data collection was performed with an Oxford
Xcalibur3 diffractometer with a CCD area detector, equipped
with a multilayer monochromator, a Photon 2 detector and a
rotating-anode generator were employed for data collection
using Mo-Kα radiation (λ= 0.7107 Å). Data collection and
reduction were carried out using the Crysalispro software.[19]
The structures were solved by direct methods (SIR-2014)[20] and
refined (SHELXLE)[21] by full-matrix least-squares on F2
(ShelxL)([22][23]) and finally checked using the platon
software[24] integrated in the WinGX software suite.[25] The
non-hydrogen atoms were refined anisotropically and the
hydrogen atoms were located and freely refined. All Diamond
3 plots are shown with thermal ellipsoids at the 50% probability
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[4]
a) Zhi, C.-Y.; Cheng, X.-L.; Zhao, F. The Correlation
between Electric Spark Sensitivity of Polynitroaromatic
Compounds and Their Molecular Electronic Properties.
Propellants, Explos., Pyrotech. 2010, 35, 555-560; b)
Zeman, S.; Krupka, M. New aspects of impact reactivity
of polynitro compounds, part III. Impact sensitivity as a
function of the intermolecular interactions. Propellants,
Explos., Pyrotech. 2003, 28, 301-307; c) Tan, B.; Li, H.;
Huang, H.; Han, Y.; Li, J.; Li, M.; Long, X. Large π-π
separation energies of some energetic compounds. Chem.
Phys. 2019, 520, 81-87.
Gao, H.; Shreeve, J. Azole-Based Energetic Salts. Chem.
Rev. (Washington, DC, U. S.) 2011, 111, 7377-7436.
Thottempudi, V.; Gao, H.; Shreeve, J. Trinitromethyl-
substituted 5-nitro- or 3-azo-1,2,4-triazoles: synthesis,
characterization, and energetic properties. J. Am. Chem.
Soc. 2011, 133, 6464-6471.
Zhang, J.; Zhang, Q.; Vo, T. T.; Parrish, D. A.; Shreeve,
J. Energetic Salts with π-Stacking and Hydrogen-
Bonding Interactions Lead the Way to Future Energetic
Materials. Journal of the American Chemical Society
2015, 137, 1697–1704.
a) Spackman, M. A.; Jayatilaka, D. Hirshfeld surface
analysis. CrystEngComm 2009, 11, 19-32; b) Ma, Y.;
Zhang, A.; Xue, X.; Jiang, D.; Zhu, Y.; Zhang, C. Crystal
Packing of Impact-Sensitive High-Energy Explosives.
Cryst. Growth Des. 2014, 14, 6101-6114.
level and hydrogen atoms are shown as small spheres of
arbitrary radius.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS
Publication website.
1H, 13C, 14N NMR spectra; Detonation parameter calculations (out-
put files) (PDF)
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X-ray data for bis(2,4-dinitrophenyl) ether (CIF)
CCDC: 1959182
X-ray data for bis(2,4,6-trinitrophenyl) ether (CIF)
CCDC: 1959183
X-ray data for bis(2,4,6-trinitrophenyl) thioether (CIF)
CCDC: 1959184
[7]
[8]
AUTHOR INFORMATION
Corresponding Author
* tmk@cup.uni-muenchen.de
ORCID
Konstantin Karaghiosoff: 0000-0002-8855-730X
Thomas Klapötke: 0000-0003-3276-1157
Marco Reichel: 0000-0003-0137-4816
Dominik Dosch: 0000-0003-4804-6473
[9]
a) Rath, C.; Rost, A.; Rittler, K. W. Hexanitrodiphenyl
ether. Chemische Fabrik von Heyden A.-G. . 1936; b)
Sprengstoff-A.-G. Carbonit . 1912.
Author Contributions
[10]
a) Isanbor, C.; Emokpae, T. A. Anilinolysis of nitro-
substituted diphenyl ethers in acetonitrile: The effect of
some ortho-substituents on the mechanism of SNAr
reactions. Int. J. Chem. Kinet. 2009, 42, 37-49; b)
Davydov, D. V.; Mikaya, A. I.; Zaikin, V. G. Mass-
spectrometric study of substituted trinitrobenzenes. Zh.
Obshch. Khim. 1983, 53, 455-462; c) Desvergnes, L.
Some physical properties of nitro derivatives. Monit. Sci.
Doct. Quesneville 1926, 16, 201-208; d) Zhou, J.; Zhang,
C.; Wang, Y.; Zhang, M.; Li, Y.; Huang, F.; Hu, L.; Xi,
W.; Wang, Q. 2,2',4,4',6,6'-hexanitrodiphenyl sulfide
refining method. Modern Chemistry Research Institute,
Peop. Rep. China . 2015, p. 6pp.
a) Hussain, I.; Tariq, M. I.; Siddiqui, H. L. Structure
elucidation of chromogen resulting from Jaffe's reaction.
J. Chem. Soc. Pak. 2009, 31, 937-948; b) Soojhawon, I.;
Lokhande, P. D.; Kodam, K. M.; Gawai, K. R.
Biotransformation of nitroaromatics and their effects on
mixed function oxidase system. Enzyme Microb.
Technol. 2005, 37, 527-533.
‡ Marco Reichel and Dominik Dosch contributed equally to this
work.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
For financial support of this work by Ludwig−Maximilian Univer-
sity (LMU), the Office of Naval Research (ONR) under grant no.
ONR.N00014-16-1-2062 and the Strategic Environmental Re-
search and Development Program (SERDP) under contract no.
WP19-1287 are gratefully acknowledged. The authors also thank
Ms. Teresa Küblböck for help with the graphics and F−Select
GmbH for the generous donation of fluoro-chemicals.
[11]
REFERENCES
[12]
[13]
Lewis, I. R.; Daniel, N. W.; Griffiths, P. R. Interpretation
of Raman spectra of nitro-containing explosive
materials. Part I: Group frequency and structural class
membership. Appl. Spectrosc. 1997, 51, 1854-1867.
a) Li, J. Relationships for the Impact Sensitivities of
Energetic C-Nitro Compounds Based on Bond
Dissociation Energy. J. Phys. Chem. B 2010, 114, 2198-
2202; b) Li, J. A quantitative relationship for the shock
sensitivities of energetic compounds based on X-NO2 (X
= C, N, O) bond dissociation energy. J. Hazard. Mater.
2010, 180, 768-772.
a) Tang, Y.; Zhang, J.; Mitchell, L. A.; Parrish, D. A.;
Shreeve, J. Taming of 3,4-Di(nitramino)furazan. J. Am.
Chem. Soc. 2015, 137, 15984–15987; b) Test methods
according to the UN Manual of Tests and Criteria,
Recommendations on the Transport of Dangerous
Goods, N. Y. United Nations Publication, Geneva, 4th
[1]
[2]
Nobel, A. Dynamit. United Kingdom, 1867.
a) Köhler, J.; Meyer, R.; Homburg, A. Explosivstoffe,
Wiley-VCH, 2008, Weinheim; b) Klapötke, T. M.
Energetic Materials Encyclopedia, De Gruyter, 1st edn.,
2018, Boston/Berlin.
[3]
a) Giles, J. Green explosives: collateral damage. Nature
2004, 427, 580-581; b) Klapötke, T. M. Chemistry of
High-Energy Materials, De Gruyter, 5th edn., 2019,
Boston/Berlin c) Reichel, M.; Krumm, B.; Vishnevskiy,
Y.; Blomeyer, S.; Schwabedissen, J.; Stammler, H.-G.;
Karaghiosoff, K.; Mitzel, N. W. Angew. Chem. Int. Ed.
2019, in Press (DOI: 10.1002/anie.201911300); d)
Reichel, M.; Krumm, B.; Karaghiosoff, K. Synthesis and
investigation of highly energetic and shock-sensitive
fluoromethyl perchlorate. J. Fluorine Chem. 2019, 226,
109351.
[14]
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 7
revised ed., 2003: Impact: insensitive >40 J, less
yl) nitramine, a new sensitive explosive combining a ni-
trate ester with a nitramine. Z. Anorg. Allg. Chem. 2010,
636, 2343-2346.
CrysAlisPRO (Version 171.33.41), 2009, Oxford Dif-
fraction Ltd.
1
2
3
4
5
6
7
sensitive ≥35 J, sensitive ≥4 J, very sensitive ≤3 J;
friction: insensitive >360 N, less sensitive: 360 N,
sensitive <360 N and >80 N, very sensitive ≤ 80 N,
extremely sensitive ≤ 10 N; c) www.reichel-partner.com;
d) NATO, Standardization Agreement 4489 (STANAG
4489), Explosives, Impact Sensitivity Tests. Brussels,
Belgium 1999; e) NATO, Standardization Agreement
4487 (STANAG 4487), Explosives, Friction Sensitivity
Tests. Brussels, Belgium 2002.
Zhang, C.; Xue, X.; Cao, Y.; Zhou, Y.; Li, H.; Zhou, J.;
Gao, T. Intermolecular friction symbol derived from
crystal information. CrystEngComm 2013, 15, 6837-
6844.
[19]
[20]
Burla, M. C.; Caliandro, R.; Carrozzini, B.; Cascarano,
G. L.; Cuocci, C.; Giacovazzo, C.; Mallamo, M.; Maz-
zone, A.; Polidori, G., Crystal structure determination
and refinement via SIR2014. J. Appl. Crystallogr. 2015,
48, 306.
8
9
[15]
[21]
[22]
Hübschle, C.B., Sheldrick, G.M., Dittrich B. ShelXle: a
Qt graphical user interface for SHELXL. J. Appl. Cryst.
2011, 44, 1281.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Sheldrick, G. M., SHELXL-97, Program for the Refine-
ment of Crystal Structures., 1997 University of Göttin-
gen, Germany.
[16]
[17]
Klapötke, T. M. Chemie der hochenergetischen
Materialien, De Gruyter, 2009, Boston/Berlin.
a) Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.;
Pople, J. A. Assessment of Gaussian-2 and density
functional theories for the computation of enthalpies of
formation. J. Chem. Phys. 1997, 106, 1063–1079; b)
Byrd, E.; Rice, B. M. Improved Prediction of Heats of
Formation of Energetic Materials Using Quantum
Mechanical Calculations. J. Phys. Chem. A 2006, 110,
1005–1013.
[23]
[24]
[25]
Sheldrick, M. A short history of SHELX. Acta Crystal-
logr. Sect. A 2008, 112.
Spek, A. L., PLATON, A Multipurpose Crystallographic
Tool., 1991, Utrecht University, The Netherlands.
Farrugia, L. J., WinGX and ORTEP for Windows: an up-
date. J. Appl. Cryst. 2012, 849.
[18]
a) Suceska, M. EXPLO5 6.01 2013, Brodarski Institute:
Zagreb, Croatia; b) Klapoetke, T. M.; Krumm, B.;
Steemann, F. X.; Umland, K.-D. Bis(1,3-dinitratoprop-2-
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