One Step Closer to an Ideal Insensitive Energetic Molecule: 3,5-Diamino-6-hydroxy-2-oxide-4-nitropyrimidone and its Derivatives

Diamino-6-hydroxy-2-oxide-4-nitropyrimidone and its Derivatives

Article

One Step Closer to an Ideal Insensitive Energetic Molecule: 3,5-

Jichuan Zhang, Yongan Feng, Yiyang Bo, Richard J. Staples, Jiaheng Zhang,* and Jean ’ne M. Shreeve *

Cite This: https://doi.org/10.1021/jacs.1c05292

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ABSTRACT: Reaching the goal of developing an insensitive high-energy molecule

IHEM) is a major challenge. In this study, 3,5-diamino-6-hydroxy-2-oxide-4-nitro-

pyrimidone (IHEM-1) was synthesized in one step from 2,4,6-triamino-5-nitropyrimidine-

(

−

,3-dioxide hydrate (ICM-102 hydrate). The density of compound IHEM-1 is 1.95 g cm

with a decomposition temperature of 271 °C. Its detonation velocity and pressure are 8660

−

m s and 33.64 GPa, respectively, which are far superior to the detonation performance of

,3,5-triamino-2,4,6-trinitrobenzene (TATB), while its sensitivity is identical with that of

TATB. In addition, four derivatives (1a, chloride; 1b, nitrate; 1c, perchlorate; and 1d,

dinitramide) were prepared on the basis of the weak base site (N−O group) and show

excellent energetic properties. By combining a series of advantages, including simple

preparation, high yield, high density, very low solubility in aqueous solution, high

thermostability, insensitivity, and excellent detonation performance, IHEM-1 approaches

an ideal insensitive high-energy molecule. Compounds 1b−1d are also competitive as new

high-energy-density materials.

INTRODUCTION

Energetic compounds have played an essential role in defense

and civilian industries since the time of Alfred Nobel. Many

compounds with excellent detonation performance have been

explored for more than a hundred years. However, owing to

the competing properties of high energy and high safety,

accidents have occurred occasionally during the preparation,

transportation, and application of high-energy-density materi-

pressure increases with the square of the density. The

preparations of TADNPyO and DADNP both involve tedious

steps and even harsh reaction conditions, which increase the

■

cost. The removal of H O from ICM-102 crystals involves

temperatures as high as 178 °C or large quantities of organic

solvents at 130 °C. This process often causes the collapse of

crystals, which interferes with highly dense packing, and gives

rise to a low-energy density. NTO is strongly acidic (pK

3.67), which results in good solubility in aqueous solutions

als because of their high sensitivities. The development of

−

insensitive high-energy molecules (IHEM) has become

(160 g L ) and can corrode metallic equipment during long-

extremely important. In particular, in the ﬁelds of nuclear

term storage. Therefore, in conclusion, an ideal insensitive

weapons and space exploration, insensitive high-energy

compounds are essential due to the special applied environ-

ments. However, their evolution is slow. To date, the most

commonly utilized insensitive energetic molecule is 2,4,6-

triamino-1,3,5-trinitrobenzene (TATB), which was invented in

high-energy molecule (IHEM) with promising applications

should have not only a high density but also some notable

drawbacks, such as complicated synthetic steps, strong acidity

of resulting compounds, and the invariable presence of

hydrates must be absent. Clearly, this is a huge challenge for

molecular design and organic synthesis.

888. Its detonation energy is only 65% of that of

cyclotetramethylenetetranitramine (HMX), and therefore, it

does not meet the requirements of a modern day insensitive

energetic compound.

New IHEMs, such as 2,4,6-triamino-3,5-dinitropyridine-1-

Planar molecular conﬁgurations accompanying layer-by-layer

compact stacking (planar layered and wavelike layered, Scheme

−10

a) are less sensitive than other stacking modes because they

can transform the mechanical energy acting on bulk material

into relative motion between layers when they are subjected to

1,12

oxide (TADNPyO),

the 3,9-diamino-4,8-dinitro-pyrazolo-

triazine (DADNPT)₇, 2,4,6-triamino-5-nitropyrimidine-1,3-

dioxide (ICM-102), 3-nitro-1,2,4-triazol-5-one (NTO),

Received: May 22, 2021

etc., have been explored over the past decades. However,

their further applications have been hindered for diﬀerent

reasons. TADNPyO has an oxygen balance similar to TATB

(

−55.6% vs −55.8%) but a lower density at room temperature

−3 −3

than TATB (1.876 g cm vs 1.937 g cm ). Density is directly

propotional to detonation velocity, and the detonation

XXXX American Chemical Society

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Article

Scheme 1. (a) Variation Trend of Sensitivities for

reaction between 2,4,6-triamino-5-nitropyrimidine-1,3-dioxide

Compounds with Diﬀerent Packings, (b) Variation of

Densities in Several Compounds upon the Introduction of

the Carbonyl Group, and (c) Title Compound in This Work

monohydrate and dilute HNO (1 M). IHEM-1 is only very

slightly soluble in water and has an experimental density of

−

1.95 g cm at ambient temperature. Since its safety and

synthetic feasibility are comparable to those of TATB, while

displaying a higher energy density, IHEM-1 is a potential

substitute for TATB. Four energetic salts (1a, chloride; 1b,

nitrate; 1c, perchlorate; and 1d, dinitramide) with excellent

energetic properties were also obtained with compound

IHEM-1 as the precursor.

RESULTS AND DISCUSSION

Synthesis and Single-Crystal Structure. 2,4,6-Triamino-

-nitropyrimidine-1,3-dioxide monohydrate (ICM-102 hy-

■

drate) was synthesized simply in two steps in high yield

from the commercial starting material, 2,4,6-triamino-pyrimi-

dine. ICM-102 nitrate was prepared by reaction of ICM-102

hydrate with 60% HNO at room temperature. However,

when dilute HNO (1 M) was utilized at 90 °C, a yellow

precipitate (Figure S1 ) was formed after 2 h. The mixture was

cooled to room temperature and the yellow precipitate was

ﬁltered and dried. Since the yellow precipitate is nearly

insoluble in such solvents as H O, DMSO, and other organic

solvents, H and C NMR spectra were not obtained, and a

suitably sized crystal was not available for X-ray single-crystal

diﬀraction. This made the conﬁrmation of the molecular

structure for the yellow precipitate diﬃcult. However, its gas

chromatography−mass spectrometry (GC−MS) spectrum

shows that there is a main peak at 202 (Figure S2 ), and

compared to its precursor in the infrared spectrum, it has a

very strong characteristic peak assigned to CO at 1738

(

Figure S3 ). These two clues combined with the element

analysis (Figure S4 ) show that the molecular formula is

C H N O , and its molecular structure is most likely one

7−21

intense mechanical stimuli.

Additionally, the strong

intermolecular hydrogen bonds formed with neighboring

molecules and the close π−π packing not only enhance the

density of the resulting compound but also cause this kind of

compound to be nearly insoluble in water, which decreases

acidity and avoids hydrate formation. Examples of these

species are TATB, 2,6-diamino-3,5-dinitropyridine-1-oxide

selected from IHEM-1 to IHEM-3 (Scheme 1).

These three possible structures contain an N−O group, and

NBO analysis shows that the charge values of the O atom

(belonging to the N−O group) from IHEM-1 to IHEM-3 are

−0.605, −0.660, and −0.578, respectively (Figures S5 −S8),

which are close to that of its precursor (ICM-102, − 0.651),

thus the N−O sites in these three structures are the weak base

sites. Here, in order to conﬁrm its molecular structure,

hydrochloric, nitric, and perchloric acids were used to react

with the yellow precipitate, and compounds 1a, 1b, and 1c

(Scheme 2) were obtained directly from reactions between

IHEM-1 and the strong acids, respectively. The single-crystal

structures (Figure 1) of 1a and 1b were obtained through slow

evaporation from the corresponding reaction solutions,

respectively. Clearly, from the crystal structures of 1a and

1b, the molecular structure of yellow precipitate was conﬁrmed

to be IHEM-1. In addition, compound 1d was formed from a

metathesis reaction between compound 1a and silver

dinitramide in dimethyl sulfoxide (DMSO). However, the

neutral multinitro N-heterocyclic compounds, such as 3,4,5-

trinitro-1H-pyrazole, 4-amino-3,5-dinitro-1H-pyrazole, or their

silver salts, do not give the corresponding salts through

reactions with IHEM-1 (or 1a). This is the case because these

N-heterocyclic compounds are weaker acids than hydrochloric,

(

ANPyO), 1,1-diamino-2,2-dinitroethene (FOX-7), and

,15

TADNPyO.

Generally speaking, NO , NO, and

NHNO are the traditional groups that result in high density

in the resulting compounds;

22−24

unfortunately, these groups

increase the sensitivity of the resulting compounds concom-

itantly. However, the carbonyl group also increases density

signiﬁcantly without a concomitant increase in sensitivity of

5,26

the resulting compounds.

For example, the introduction of

the CO group into 3-nitro-1,2,4-triazole (NT), 3-

dinitromethanide-1,2,4-triazole (DNMT), and cyclotrime-

thylenetrinitramine (RDX) results in marked increases in

density of the resulting compounds NTO, DNMTO, and K-

,30,31

from 1.72, 1.75, and 1.81 to 1.92, 1.91, and 1.93 g

−

cm , respectively (Scheme 1b). The impact sensitivities (IS)

are >60, 22, and 7.5 J, respectively, which are equal to or even

less sensitive than their precursors. Surprisingly, the CO

group has not received much attention, although the insertion

of a CO group is more easily realized than more energetic

2,33

groups.

nitric, and perchloric acids and neutral dinitramide.

In view of the above, a new insensitive high-energy molecule,

,5-diamino-6-hydroxy-2-oxide-4-nitropyrimidone (IHEM-1,

Scheme 1c), which is planar and has layer-by-layer close

stacking and a carbonyl group, was synthesized by a simple

Compound 1a crystallized (colorless plates) from a

concentrated HCl solution in the orthorhombic (Pbca)

group with a calculated density of 1.919 g cm at 173 K.

Each unit cell contains one 3,5-diamino-6-hydroxy-4-nitro-

−

J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

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Article

Scheme 2. Synthesis of IHEM-1: 1a−1d

eight cations and eight nitrate anions. Just as the cation in

compound 1a, the cation is nearly planar, and the lengths of

the four additional intramolecular H bonds are 2.193, 2.005,

1.971, and 2.156 Å. Each cation is surrounded by four nitrate

anions and four cations through 11 H bonds (with lengths

from 1.654 to 2.588 Å, Figure 1c and Figure S10 ), and each

nitrate anion is surrounded by three cations through ﬁve H

bonds. The H bond (1.654 Å) between NO and OH is one of

31,36

the shortest H bonds found in energetic compounds,

since

IHEM-1 is less basic than ICM-102 (the length of the H bond

in the same position in ICM-102 nitrate is 1.772 Å). Finally,

the structure is connected by these intermolecular H bonds to

form a face-to-face double-layered 2D network structure

(

Figure 1d).

A suitably sized crystal of IHEM-1 was not available for X-

ray single-crystal diﬀraction, even though its aqueous solution

was cooled. Nevertheless, its powder X-ray diﬀraction (PXRD,

Figure S11 ) and its images obtained via scanning electron

microscopy (SEM, Figure S12 ) show it has good crystallinity.

The crystal structure of IHEM-1 was resolved in an ab initio

manner from powder diﬀraction data. To solve this problem,

we used a C H N O molecular formula as an independent

motif in a simulated annealing approach. An initial structure

was obtained, then corrected by density functional theory

pyrimidone-2-oxide cation and one chloride anion, and each

cation is surrounded by four chloride anions and four

additional 3,5-diamino-6-hydroxy-4-nitropyrimidone-2-oxide

cations through 6 H bonds (bond lengths between 2.158

and 2.423 Å, Figure 1 a). The cation is nearly planar (except for

the H atoms; Figure S9), and the four intramolecular hydrogen

bonds have bond lengths of 2.151, 2.025, 2.036, and 2.146 Å.

The crystal is connected by six intermolecular H bonds,

forming a 2D wave-like network (Figure 1b).

(

DFT) geometry optimization, and ﬁnally reﬁned via the

37,38

Rietveld method.

As shown in Figure 2a, the ﬁnal structure

obtained after reﬁnement produced a good ﬁt to the diﬀraction

pattern, with R = 9.77% and Rwp = 13.82%. The compound

crystallizes in a centrosymmetric orthorhombic system (space

group Pcab), with lattice constants of a = 14.6278(9) Å, b =

13.8636(11) Å, c = 6.8291(3) Å, and V = 1384.90(15) Å . Its

−

Compound 1b crystallized (colorless plate-needles) in the

orthorhombic (Pbca) group with a calculated density of 1.959

calculated density is an astonishing 1.949 g cm at room

temperature (Table S1). Similar to its precursor (ICM-102), it

is a planar molecule, with ﬁve intramolecular hydrogen bonds

−

g cm at 173 K from a 70% HNO solution. Each unit cell has

Figure 1. (a and b) Arrangement and packing mode of compound 1a. (c and d) Arrangement and packing mode of 1b (atom color: C, black gray;

H, gray; N, blue; O, red; Cl, green; H-bonds, blue-gray dashed line).

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Figure 2. (a) PXRD (powder X-ray diﬀraction) pattern and Rietveld reﬁnement of IHEM-1 structure. (b) Single-molecular structure. (c) Single-

layer arrangement of IHEM-1. (d) Layer-by layer packing of IHEM-1 (atom color: C, black gray; H, gray; N, blue; O, red; H bonds are blue-gray

dashed lines).

with lengths of 1.772, 1.821, 1.903, 1.989, and 2.199 Å (Figure

b). Compound IHEM-1 has a wavelike two-dimensional

Scheme 3. Proposed Reaction Mechanism of IHEM-1

layer-by-layer stacking with a distance of 3.15 Å (Figure S13 ),

and in each layer, each molecule is bonded with six

surrounding molecules through six intermolecular H bonds

(Figure 2c, three coupled H bonds at 2.114, 2.263, and 2.485

Å). The two-dimensional layers are connected by intermo-

lecular hydrogen bonds, thus forming a 3D network (Figure

d).

It was worthwhile to investigate the mechanism of the

formation of IHEM-1. Since ICM-102 is a weak base, it forms

salts with strong acids (HNO , HClO , etc.) and it forms a

34,36

cocrystal with HIO , a moderately strong acid.

Given that

ICM-102 forms a monocation with an excess of strong acids,

2,33,39,40

on the basis of the literature,

the reaction mechanism

is believed to be the hydrolysis reaction catalyzed by HNO₃,

and the supposed reaction steps may be as shown in Scheme

Thermostability and Sensitivity. The thermostabilities

of IHEM-1 and 1a−1d were determined by using diﬀerential

−1

a. When ICM-102 interacts with a strong acid, the basic site

scanning calorimetry (DSC) at 5 °C min in a nitrogen

atmosphere, and the onset decomposition temperatures of

these ﬁve compounds are 271, 270, 175, 142, and 152 °C

(Table 1, Figures S14 −S19 ), respectively. Among them, the

decomposition temperature of IHEM-1 is not only higher than

(O atom of the N−O group) is protonated to form a cation

(step 1) (Scheme 3). Under the conditions of excess acid and a

high temperature, the proton is transferred from the ring to the

NH moiety, forming an NH₃group (step 2). Subsequently,

in the presence of H O, the intermediate species formed in

that of the precursor, ICM-102, but also notably higher than

step 2 is changed to the unstable species in step 3. Then, NH₃

is lost to give IHEM-1. Believing this mechanism, other strong

acids (HClO , H SO , HCl) were tried, and IHEM-1 was

invariably obtained in similar yields (68%−75%). Iodic, oxalic,

and acetic acids also reacted with ICM-102 to give IHEM-1 at

those of the carbonyl-containing compounds vide

,15,25,26,30

supra

and is comparable to that of HMX, Since

IHEM-1 exhibits excellent thermal stability, Kissinger and

Ozawa methods were employed to investigate its thermody-

namic properties and compare them with those of traditional

heat-resistant energetic compounds. The diﬀerential scanning

∼90 °C.

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is shown in Figure 3 . The apparent activation energies (E )

Article

Table 1. Physical Properties of IHEM-1 and its Derivatives, TATB, NTO, RDX, and HMX

(g cm⁻³

Δ H° (kJ mol⁻¹)

D_v(m s⁻¹

compound

T_d(°C)

)

P (GPa)

IS (J)

FS (N)

OB (%)

IHEM-1

271

270

175

142

152

315

237

205

270

1.95

1.88

1.92

2.01

1.93

1.94

1.92

1.81

−204.5

−262.9

−343.1

−302.0

+139.4

−139.5

8660

7774

8698

8841

9337

8114

8446

8795

9144

33.64

25.52

35.72

36.98

40.51

32.4

32.90

34.90

39.20

>60

7.5

>360

240

160

240

>360

120

−43.35

−40.07

−18.03

−10.54

−10.32

−55.81

−24.62

−21.61

TATB

NTO

RDX

HMX

+80.0

+74.8

1.91

120

−1

Decomposition temperature (onset). Experimental density at room temperature. Enthalpy of formation (kJ mol ). Detonation velocity (m

−

s ). Detonation pressure (GPa). Impact sensitivity (J). Friction sensitivity (N). Oxygen balance calculated using OB = (O-2C-1 − 2H)1600/

M}. Refs 7 and 41. Refs 42 and 43. Refs 31, 44, and 45.

calorimetry (DSC) proﬁle of IHEM-1 at diﬀerent heating rates

Table 2. Molecular Simulations of IHEM-1 and Typical

Insensitive Molecules

compound

IHEM-1

TATB

290.46

ICM-102

NTO

BDE of C−NO (kJ mol⁻¹)

290.49

455.31

0.903

321.92

474.44

0.897

274.72

BDE of N−O (kJ mol⁻

bond order of C−NO₂

bond order of N−O

)

0.898

0.786

1.141

1.127

eﬀect in the molecule and to stabilize the system.

Comprehensively, a high BDE and short intramolecular

hydrogen bonds give rise to high thermostability and heat

resistance for IHEM-1. Therefore, IHEM-1 is an excellent

candidate as a heat-resistant energetic molecule.

Sensitivities toward impact and friction, determined using

BAM (Bundesanstalt fur Materialforschung and -Prufung)

̈ ̈

standards, show that IHEM-1 has a very low sensitivity to

impact and friction stimulation with values similar to those of

TATB (impact sensitivity, IS > 60 J, and friction sensitivity, FS

,15

360 N).

Compound 1a is also insensitive to impact and

friction at higher than 60 J and 360 N, respectively. The impact

and friction sensitivities of compounds 1b−1d were

determined to be 10, 6, and 7 J, and 240, 160, and 240 N,

respectively. The extremely low sensitivity of IHEM-1 is

Figure 3. DSC curves of IHEM-1 at diﬀerent heating rates.

obtained by the two methods agree well with each other at

−

20.3 and 219.0 kJ mol , respectively. The correlation

further explained from both molecular and crystal levels. At the

49,50

coeﬃcients (r ) of these two methods are 0.9965 and

.9968, respectively, very close to 1, which indicates that the

molecular level, it is known that higher bond orders,

negative ESP, and an average deviation of ESP approaching

0.25 result in low sensitivity of an energetic molecule.

Compared with those of TATB, ICM-102, and NTO, the bond

results are reliable. The activation energies of IHEM-1

obtained using these methods are higher than that of TATB

−

(

211 kJ mol ), thus showing that IHEM-1 has a better heat

orders of C−NO and N−O in IHEM-1 are 0.903 and 1.141,

resistance than TATB. Excellent thermostability and heat

resistance depend mainly on intramolecular factors, such as

respectively (Table 2 and Tables S2 −S5). The C−NO bond

order in IHEM-1 is not only higher than that of its precursor

(ICM-102, 0.897) but also higher than those in TATB (0.896,

and NTO (0.786). The N−O bond order of IHEM-1 is higher

than that in ICM-102 (1.127). The most negative ESP in

IHEM-1 is −56.05, clearly lower than those in TATB, ICM-

102, and NTO. Meanwhile, the average deviation of ESP in

IHEM-1 is 0.249 (Figure 4a, Table 2, and Figures S20 −S23),

which is very close to 0.25, and higher than those of three

insensitive molecules. Additionally, from the view of crystal

structure and compared to its precursor ICM-102 and to

TATB, the planar IHEM-1 molecule is trapped by

intermolecular hydrogen bonds not only from the same layer

but also from neighboring layers. The distance between layers

is 3.15 Å (Figure S13), shorter than that in ICM-102 (3.19 Å,

Table S6) and only slightly longer than that in TATB (3.14 Å),

which shows that the π−π interactions between layers in

bond dissociation energies (BDEs) and intramolecular

7,48

hydrogen bonds.

The C−NO , and N−O bonds, which

possibly lead to the initial decomposition of IHEM-1, have

been investigated by BDE calculations, and the results show

that the BDEs of C−NO in IHEM-1, TATB, ICM-102, and

−

NTO are 290.49, 290.46, 321.92, and 274.72 kJ mol ,

respectively (Table 2), and the BDEs of N−O in IHEM-1 and

−

ICM-102 are 455.31 and 474.44 kJ mol , respectively. The

BDE of C−NO in IHEM-1 is higher than those in TATB and

NTO, although the BDEs of C−NO and N−O in IHEM-1

are lower than those in ICM-102; the average intramolecular

hydrogen bond length in IHEM-1 is 1.937 Å (Table S6),

which is shorter than that in ICM-102 (2.168 Å) but longer

than that in TATB (1.810 Å). Because the intramolecular

hydrogen bond is another factor to enhance the conjugation

Journal of the American Chemical Society

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Figure 4. (a) Calculations of ESP for IHEM-1, TATB, ICM-102, and NTO. (b and c) Noncovalent interaction (NCI) plots of IHEM-1(b) and

ICM-102 (c). The surfaces are colored on a blue−green−red scale indicating strong attractive interactions, weak attractive, and strong nonbonded

overlap, respectively (upper, layer−layer viewpoint, down, layer−layer overlap viewpoint).

IHEM-1 are stronger than that of ICM-102. This is supported

low solubility may arise from the abundance of short

intermolecular H-bonds. The same is true for compound 1b.

The solubility of compound 1b was found to be 23 mg in 100

mL of water at room temperature. The low solubilities of

IHEM-1 and 1b support their further applications because

problems caused by hygroscopicity and moisture are avoided.

Additionally, the low solubility causes the molecules to be

friendly to biological systems and the environment, since they

will not poison or pollute through being dissolved in aqueous

solutions.

by NCI calculations (Figure 4b,c and Figure S24), where the

31,53

green areas in IHEM-1 are larger than that in ICM-102.

Notably, the close layer-by-layer stacking of IHEM-1 could

consume mechanical energy acting on the bulk material,

,54

leading to the formation of local hot spots.

A high BDE,

short intramolecular hydrogen bonds, high bond orders, low

negative ESP, and a close to 0.25 of the average deviation of

ESP, layer−layer structure, strong π−π interactions, and

compact packing through multihydrogen bonds are positive

factors that contribute markedly to the excellent thermal

stability and insensitivity of IHEM-1 to heat, impact, and

friction, respectively, which ensures its high potential as a new

insensitive high-energy molecule.

NBO analysis gives a charge value of the H bonded to the

N−OH group at 0.550, which suggests a strongly acidic

behavior for IHEM-1. However, the pH of IHEM-1 in a

saturated solution was determined to be 5.33, which is similar

Solubility, Acidity, and Density. The solubility of

IHEM-1 in water is limited and it is even lower in organic

solvents, such as DMSO, MeOH, EtOH, acetonitrile (MeCN),

dimethylformamide (DMF), and ethyl acetate (EA). Its

solubility was determined to be 6.75 mg in 100 mL of water

to that of normal rain (5.0−5.5), and its pK was determined

to be 6.17, thus it is a very weak acid. The pH of NTO in a

saturated solution was determined to be 2.33, and its pK is

3.67, which is notably higher than that of IHEM-1. The weak

acidity of IHEM-1 is due to the poor solubility and the strong

intramolecular H bonds (measuring 1.821 Å), which limit

dissociation. Properties such as low solubility and very weak

acidity do make IHEM-1 noncorrosive to the metallic parts of

equipment and devices.

at room temperature (25 °C), and even at 100 °C, its

solubility is only 28.1 mg in 100 mL, which is signiﬁcantly

lower than those of ICM-102 and NTO (220 and 1600 mg in

,16

00 mL of water at room temperature, respectively),

This

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Figure 5 and Table S8 ), which is not only higher than those of

Article

The densities of IHEM-1 and 1a−1d were determined using

CONCLUSION

■

−

a gas pycnometer to be 1.95, 1.87, 1.92, 2.01, and 1.93 g cm ,

A new insensitive high-energy compound, 3,5-diamino-6-

hydroxy-2-oxide-4-nitropyrimidone (IHEM-1), with high

density, high thermal stability, extremely low mechanical

sensitivity, and excellent detonation performance was synthe-

sized easily through the acidic hydrolysis of 2,4,6-triamino-5-

nitropyrimidine-1,3-dioxide (ICM-102). Its wavelike two-

dimensional layer-by-layer stacking pattern was conﬁrmed by

employing PXRD analysis. Coupled with its other two

advantages of low solubility and weak acidity, IHEM-1 is

very close to being an ideal, promising insensitive high-energy

compound needed to replace TATB. Additionally, four

derivatives with high densities and good detonation perform-

ance were also synthesized and are attractive as new high-

energy-density materials.

respectively. The density of IHEM-1 is not only much higher

−

than that of its precursor (anhydrous ICM-102, 1.85 g cm at

98 K, Table S7) but also higher than those of TATB and

NTO. The calculation of the packing index values shows that

the packing index of IHEM-1 is 79.1% at room temperature

EXPERIMENTAL SECTION

■

Safety Precautions. Although none of the energetic MOFs

described herein exploded or detonated in the course of this research,

these materials should be handled with extreme care using the best

safety practices.

General Methods. All reagents were purchased from AKSci or

Alfa Aesar in analytical grade and were used as supplied. H NMR and

C NMR spectra were recorded on a 300 MHz (Bruker AVANCE

00) nuclear magnetic resonance spectrometer. Chemical shifts for

Figure 5. Packing indices, detonation performance, and densities of

several energetic compounds.

H NMR and C NMR spectra are given with respect to (CH ) Si

(

H and C). DMSO-d₆was used as a locking solvent unless

otherwise stated. IR spectra were recorded using KBr pellets with a

FT-IR spectrometer (Thermo Nicolet AVATAR 370). Density was

determined at room temperature by employing a Micromeritics

AccuPyc II 1340 gas pycnometer. Decomposition temperature

(onset) was recorded using dry nitrogen gas at a heating rate of 5

°C min and diﬀerent rates (5, 10, 15, and 20 °C min ,

respectively) on a diﬀerential scanning calorimeter (DSC, TA

Instruments Q2000). Thermal behavior was also recorded by

thermogravimetric analysis (TGA, TA Q50). Elemental analyses (C,

H, N) were performed with a Vario Micro cube Elementar Analyzer.

Impact and friction sensitivity measurements were carried out using a

standard BAM Fallhammer and a BAM friction tester.

TATB (78.5%) and NTO (76.0%) but also higher than the

majority of 380 randomly collected energetic molecules at

room temperature (Figure S25 ). Among these energetic

molecules, only two compounds (dihydroxylammonium 5,50-

−

−1

bistetrazole-1,10-diolate and 4,8-dihydrodifurazano[3,4-b,e]-

pyrazine ) with packing indices of 79.6% and 79.3%,

respectively, were higher. Although the packing index of

compound 1b (76.9%) is lower than that of ICM-102 nitrate

Computational Methods. The gas phase enthalpies of formation

were calculated on the basis of the G2 method. The solid-state heat of

formation of IHEM-1 was calculated on the basis of Trouton’s rule

according to eq 1 (T represents either the melting point or the

decomposition temperature when no melting occurs prior to

(

78.0%), it has a better oxygen content, leading to a good

−

density (1.922 g cm at 298 K),₋which is comparable to that

of ICM-102 nitrate (1.919 g cm at 298 K).

Detonation Properties. Detonation performance was

evaluated by calculating the detonation velocity (D ) and

decomposition).

ΔH_s_u_b= 188 J mol K × T

For energetic salts (1a−1d), the solid-phase enthalpies of

detonation pressure (P) using the experimental density and the

calculated heat of formation. The heats of formation of IHEM-

−

1 −1

(1)

1,34

and 1a−1d were calculated, according to the literature,

63,64

−

formation were obtained using a Born−Haber energy cycle.

to be −204.5, −262.9, −343.1, −302.0, and +139.4 kJ mol

Table 1 and Tables S7 and S9), respectively. With

Crystal Structure Analysis. The molecular structure (IHEM-1)

was deduced by the single-crystal structure of its nitrate salt (1b), and

then, the pure IHEM-1 was conﬁrmed by its elemental analysis. When

the pure IHEM-1 was scanned by X-ray powder diﬀraction, the crystal

structure of IHEM-1 was resolved in an ab initio manner from

powder diﬀraction data. The indexing of the diﬀraction pattern was

(

experimental densities in hand, the detonation performance

of IHEM-1 and 1a−1d was achieved using EXPLO 5 software

(

6.01 version). As shown in Table 1, the detonation velocity

−

and detonation pressure of IHEM-1 are 8660 m s and 33.64

GPa, respectively. Although the insertion of the carbonyl group

leads to a lower heat of formation than that of its precusor, its

higher oxygen balance and higher density result in the

detonation performance for IHEM-1, which is superior to

those of ICM-102, NTO, and TATB and comparable to that of

RDX. Compounds 1b−1d also exhibit excellent detonation

performance. Their detonation velocities and pressures are

calculated to be 7774, 8698, 8841, and 9337 m s⁻and 25.52,

readily realized using the DICVOL91 program. The program

suggested orthorhombic lattices for the title compound, with lattice

constants of a = 14.6278(9) Å, b = 13.8636(11) Å, c = 6.8291(3) Å,

and V = 1384.90(15) Å . The examination of diﬀraction extinctions

reveals that the unit cells are primitive, and the extinction conditions

corresponding to three glide planes of c, a, and b can be conﬁrmed,

suggesting that the space groups should be Pcab. To solve the crystal

structure, we used C H N O molecules as independent motifs in a

simulated annealing approach. An initial structure is successfully

obtained on the basis of the Powder Solve module implemented in

software Reﬂex. Then, this initial crystal structure is corrected by

density functional theory (DFT) geometry optimization and ﬁnally

5.72, 36.98, and 40.51 GPa, respectively. It is noteworthy that

the detonation properties of 1d are higher than those of HMX.

J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society

https://pubs.acs.org/doi/10.1021/jacs.1c05292.

Article

7,38

reﬁned via the Rietveld method.

As shown in Figure 2b, the ﬁnal

ASSOCIATED CONTENT

sı Supporting Information

The Supporting Information is available free of charge at

■

structure obtained after reﬁnement produced a good ﬁt to the

diﬀraction pattern, with R_p= 9.77% and R_w_p= 13.82%. The

compound crystallizes in a centrosymmetric orthorhombic system

(

space group Pcab), with eight C H N O molecules located in the

4 5 5 5

general positions. The detailed crystallographic information is listed in

Table S1.

Figures of yellow powder precipitate image, GC−MS

spectrum, IR spectrum, elemental analysis, NBO

distributions, single-crystal and packing modes, XRD

pattern, SEM images, TGA curves, DSC curves, ESP

calculations, NCI π−π interactions, and statistics of

packing index vs density, tables of crystallographic data

and structure reﬁnement parameters, bond orders,

hydrogen bond lengths and layer distance, physical

properties, packing index and densities, statistics of

packing index vs density, and enthalpies of the species,

and scheme of isodesmic reactions, (PDF)

A colorless plate-shaped crystal of 1a with dimensions 0.25 × 0.13

0.07 mm was mounted on a nylon loop with Paratone oil. Data

were collected using a Bruker APEX-II CCD diﬀractometer equipped

with an Oxford Cryosystems low-temperature device, operating at T =

73(2) K. Data were measured using ε of −0.50° per frame for 100.83

s using Mo Kα radiation (sealed tube, 50 kV, 40 mA). The total

number of runs and images was based on the strategy calculation from

the program COSMO (BRUKER, V1.61, 2009). The achieved

resolution was Θ = 26.025. A colorless plate-needle-shaped crystal of

b with dimensions 0.24 × 0.08 × 0.04 mm was mounted on a nylon

loop with Paratone oil. Data were collected using a Bruker APEX-II

CCD diﬀractometer equipped with an Oxford Cryosystems low-

temperature device, operating at T = 173(2) K. Data were measured

using ε of −0.50° per frame for 200.83 s using Mo Kα radiation

Accession Codes

CCDC 2008342 −2008343 and 2062676 contain the supple-

mentary crystallographic data for this paper. These data can be

obtained free of charge via www.ccdc.cam.ac.uk/data_request/

cif , or by emailing data_request@ccdc.cam.ac.uk , or by

contacting The Cambridge Crystallographic Data Centre, 12

Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

(

sealed tube, 50 kV, 40 mA). The total number of runs and images

was based on the strategy calculation from the program COSMO

(

BRUKER, V1.61, 2009). The achieved resolution was Θ = 26.064.

Synthesis of Compound IHEM-1. Hydrated ICM-102

C H N O ·H O) was synthesized in two steps in high yield based

(

on the literature. The hydrated ICM-102 (0.44 g, 2 mmol) was

AUTHOR INFORMATION

Corresponding Authors

added to water (60 mL), which was heated to 90 °C, and then, HNO

■

−

(

3 mL, 1 mmol mL , 1 M) was added to the mixture, which was

stirred at this temperature for 2 h. A yellow precipitate formed, and

the mixture was cooled to room temperature, ﬁltered, and dried; 0.31

g (76.4% yield) of the resulting compound, IHEM-1, was obtained.

IR (KBr): ν 3372, 3266, 1738, 1627, 1516, 1392, 1291, 1207, 1101,

Jiaheng Zhang − Sauvage Laboratory for Smart Materials,

Harbin Institute of Technology, Shenzhen 518055, China;

orcid.org/0000-0002-2377-9796; Email: zhangjiaheng@

hit.edu.cn

Jean’ne M. Shreeve − Department of Chemistry, University of

Idaho, Moscow, Idaho 83844-2343, United States;

orcid.org/0000-0001-8622-4897; Email: jshreeve@

uidaho.edu

−

49, 757, 634 cm . C H N O (203.11): calcd, C 23.65, H 2.48, N

4 5 5 5

4.48%; found, C 23.63, H 2.59, N 34.80%.

General Method for Preparing 1a−1c. Compound IHEM-1

(

0.406 g, 2 mmol) was added to concentrated HCl (15 mL), 70%

HNO (15 mL), or 70% HClO (10 mL), respectively. After stirring

for 30 min, the solution was ﬁltered and put in a quiet place for slow

evaporation (about 1−2 days). Crystal samples of 1a−1c were

collected and washed with a small amount of water (5 mL). Finally,

Authors

Jichuan Zhang − Department of Chemistry, University of

Idaho, Moscow, Idaho 83844-2343, United States; Shenzhen

Institute of Advanced Technology, Chinese Academy of

Sciences, Shenzhen 518055, China

Yongan Feng − School of Environmental and Safety

Engineering, North University of China, Taiyuan 030051,

China; orcid.org/0000-0001-8456-5065

Yiyang Bo − Sauvage Laboratory for Smart Materials, Harbin

Institute of Technology, Shenzhen 518055, China

Richard J. Staples − Department of Chemistry, Michigan State

University, East Lansing, Michigan 48824, United States;

orcid.org/0000-0003-2760-769X

1a (0.35g, 73% yield), 1b (0.43 g, 81% yield), and 1c (0.39 g, 64%

yield) were obtained, as well as the crystals of 1a and 1b suitable for

X-ray single-crystal diﬀraction analysis.

Compound 1a. Colorless crystal. H NMR (DMSO-d ): δ 9.83

(

s, 4H). ¹³C NMR (DMSO-d ): δ 152.0, 143.3, 103.5 ppm. IR (KBr):

ν 3369, 3238, 2915, 1767, 1634, 1526, 1412, 1298, 1203, 1104, 977,

−

03, 648 cm . C H ClN O (239.57): calcd, C 20.05, H 2.52, N

4 6 5 5

9.23%; found, C 19.76, H 2.57, N 29.20%.

Compound 1b. Colorless crystal. H NMR (DMSO-d ): δ 9.88

_s_,₄_H₎_.₁3C NMR (DMSO-d ): δ 152.0, 143.5, 103.6 ppm. IR (KBr):

(

ν 3388, 3277, 1769, 1661, 1528, 1431, 1381, 1298, 1209, 1104, 1038,

−

75, 828, 765, 705, 628 cm . C H N O (266.13): calcd, C 18.05, H

4 6 6 8

.27, N 31.58%; found, C 17.60, H 2.40, N 31.51%.

Complete contact information is available at:

https://pubs.acs.org/10.1021/jacs.1c05292

Compound 1c. Colorless crystal. H NMR (DMSO-d ): δ 9.86

_s_,₄_H₎_.1 C NMR (DMSO-d ): δ 152.00, 143.5, 103.7 ppm. IR

(

KBr): ν 3373, 3261, 1776, 1757, 1655, 1526, 1380, 1305, 1248,

221, 1199, 1102, 980, 768, 697, 626 cm . C H ClN O (303.57):

−

Notes

The authors declare no competing ﬁnancial interest.

calcd, C 15.83, H 1.99, N 23.07%; found, C 15.68, H 2.06, N 23.06%.

Synthesis of Compound 1d. Compound 1a (0.24g, 1 mmol)

was dissolved in DMSO (10 mL), and AgN(NO ) (0.22g, 1 mmol)

ACKNOWLEDGMENTS

The Rigaku Synergy S Diﬀractometer was purchased with

support from the National Science Foundation MRI program

■

was dissolved in DMSO (5 mL). After both were dissolved

completely, the solutions were combined. The precipitate was ﬁltered,

and water (40 mL) was added to the ﬁltrate. A white precipitate

(

1919565). This work was supported by the National Natural

formed and was ﬁltered and dried to give 0.19 g (62% yield) of 1d. H

Science Foundation of China (21905069), the Shenzhen

Science and Technology Innovation Committee

(JCYJ20180507183907224, KQTD20170809110344233),

Economic, Trade and Information Commission of Shenzhen

Municipality through the Graphene Manufacture Innovation

NMR (DMSO-d ): δ 9.89 (s, 4H). C NMR (DMSO-d ): δ 152.0,

43.5, 103.7 ppm. IR (KBr): ν 3371, 3238, 2920, 1768, 1663, 1633,

525, 1419, 1380, 1298, 1202, 1104, 1028, 977, 767, 702, 643 cm .

−

C H N O (310.14): calcd, C 15.49, H 1.95, N 36.13%; found, C

5.91, H 2.19, N 35.22%.

J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society

fused-ring energetic materials with high energy and good stability.

Article

Center (201901161514), and Guangdong Province Covid-19

Pandemic Control Research Fund 2020KZDZX1220.

Engineering 2020, 6, 1006−1012.

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