Supporting information (SI)

New Pyrazole energetic materials: Combining the Dinitromethyl group with Nitropyrazole

Caijin Leia, Hongwei Yanga and Guangbin Chenga

School of Chemical Engineering, Nanjing University of Science and Technology, Xiaolingwei 200,

Nanjing, Jiangsu, China. Fax: (+) 86 25 8430 3286

E-mail: gcheng@mail.njust.edu.cn

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2020

Table of Contents

Table of Contents.....................................................................................2

1．The crystallographic data ....................................................................2

2. Computational Details ........................................................................7

3．1H and 13C NMR spectra of compounds...............................................8

1．The crystallographic dataTable S1 Crystallographic Data for 5 and 6

5 6

Empirical formula C4H2N5O6K C4H2N5O6Na

Formula weight 255.21 239.10

Temperature/K 100.0 100.0

Crystal system monoclinic orthorhombic

Space group P21/c Pbca

a/Å 7.8439(5) 7.1249(14)

b/Å 7.8757(5) 14.795(3)

c/Å 13.5483(9) 15.912(3)

α/° 90 90

β/° 96.881(2) 90

γ/° 90 90

Volume/Å3 830.93(9) 1677.4(6)

Z 4 8

ρcalc g/cm3 2.040 1.894

μ/mm-1 0.669 0.218

F(000) 512.0 960.0

Crystal size/mm3 0.12×0.08×0.05 0.12 × 0.08 × 0.04

Radiation MoKα (λ=0.71073) MoKα (λ = 0.71073)

2Θ range for data collection/° 5.232 to 55.024 5.12 to 54.964

Index ranges -10≤h≤10, -10≤k≤10, -16≤l≤ 17 -7 ≤ h ≤ 9, -19 ≤ k ≤ 19, -15 ≤ l ≤ 20

Reflections collected 9948 9927

Independent reflections 1904 [Rint = 0.0413, Rsigma = 0.0299] 1906 [Rint = 0.0744, Rsigma = 0.0559]

Data/restraints/parameters 1904/128/1449 1906/0/145

Goodness-of-fit on F2 0.950 1.116

Final R indexes [I>=2σ (I)] R1 = 0.0274, wR2 = 0.0631 R1 = 0.0592, wR2 =0.1583

Final R indexes [all data] R1 = 0.0350, wR2 = 0.0684 R1 = 0.0942, wR2 = 0.1803

Largest diff. peak/hole / e Å-3 0.39/-0.30 0.71/-0.52

CCDC 1948361 1948364

Table S2 Crystallographic Data for 7 and 7a

7 7a

Empirical formula C4H3N5O6 C4H6N6O6

Formula weight 217.11 234.15

Temperature/K 100.0 100.0

Crystal system triclinic orthorhombic

Space group P-1 Pbca

a/Å 12.035(2) 7.1753(3)

b/Å 14.4979(19) 14.9458(6)

c/Å 30.215(5) 15.9277(6)

α/° 93.041(4) 90

β/° 96.612(5) 90

γ/° 113.699(4) 90

Volume/Å3 4766.5(13) 1708.10(12)

Z 24 8

ρcalc g/cm3 1.815 1.821

μ/mm-1 0.172 0.170

F(000) 2640.0 960.0

Crystal size/mm3 0.08 × 0.05 × 0.02 0.08 × 0.05 × 0.04

Radiation MoKα (λ = 0.71073) MoKα (λ=0.71073)

2Θ range for data collection/° 4.5 to 50.054 5.116 to 55.05

Index ranges -14≤h≤14, -17≤k≤17, -35≤l≤35 -9≤ h≤ 9, -19≤ k≤19, -20≤l≤20

Reflections collected 50372 16479

Independent reflections 16803 [Rint=0.1161,Rsigma= 0.1427] 1959 [Rint=0.0789, Rsigma=0.0446]

Data/restraints/parameters 16803/0/1621 1959/0/165

Goodness-of-fit on F2 1.044 1.100

Final R indexes [I>=2σ (I)] R1 = 0.0944, wR2 =0.2140 R1 = 0.0461, wR2 =0.0902

Final R indexes [all data] R1 = 0.1760, wR2 = 0.2600 R1 = 0.0692, wR2 = 0.0998

Largest diff. peak/hole / e Å-3 0.82/-0.61 0.35/-0.30

CCDC 1948363 1948362

Table S3 Bond distances of compound 7

parameter Å parameter Å

O1 -N4

O2-N4

O3-N5

O4-N5

O5-N1

O6-N1

C1-C2

C2-C3

C2-C4

1.211(10)

1.215(9)

1.232(10)

1.186(9)

1.229(8)

1.217(8)

1.478(10)

1.402(9)

1.368(10)

N1-C3

N2-N3

N2-C3

N3-C4

N4-C1

N5-C1

C1-H1

C4-H4

N3-H3

1.443(9)

1.356(8)

1.321(9)

1.343(9)

1.516(9)

1.501(11)

1.0000

0.9500

0.8800

Table S4 Bond angles of compound 7

parameter o parameter o

O5-N1-O6

O5-N1-C3

O6-N1-C3

N3-N2-C3

N2-N3-C4

O1-N4-O2

124.7(6)

116.2(6)

119.1(6)

102.5(5)

113.3(6)

126.7(7)

N4-C1-N5

N4 -C1-C2

N5-C1-C2

C3-C2-C4

C1-C2-C4

C1-C2-C3

106.2(6)

111.6(6)

113.5(5)

103.5(6)

130.6(6)

125.9(6)

O1-N4-C1

O2-N4-C1

O3-N5-O4

O3 -N5-C1

O4-N5-C1

N2-N3-H3

C4-N3-H3

N3-C4-H4

118.7(6)

114.6(6)

123.3(8)

116.5(6)

120.2(7)

123.00

123.00

126.00

N1-C3-N2

N1-C3-C2

N2-C3-C2

N3-C4-C2

C2-C1 -H1

N4-C1-H1

N5-C1-H1

C2-C4-H4

118.2(6)

128.1(6)

113.7(6)

107.0(6)

108.00

109.00

108.00

127.00

Table S5 Torsion angles of compound 7

parameter o parameter o

O5-N1-C3-N2

O5-N1-C3-C2

O6-N1-C3-N2

O6-N1-C3-C2

C3-N2-N3-C4

N3-N2-C3-N1

N3-N2-C3-C2

N2-N3-C4-C2

O1-N4-C1-N5

O1-N4-C1-C2

O2-N4-C1-N5

O2-N4-C1-C2

O3-N5-C1-N4

169.6(6)

-8.5(10)

-9.8(9)

172.1(6)

-0.4(7)

-177.6(6)

0.7(7)

-0.1(8)

17.4(9)

-106.8(8)

-163.8(6)

72.1(8)

74.2(8)

N4-C1-C2-C4

N5-C1-C2-C4

N5-C1-C2-C3

N4-C1-C2-C3

C4-C2-C3-N2

C1 -C2-C3 -N1

C3 -C2-C4 -N3

C4-C2-C3-N1

C1-C2-C3-N2

C1-C2-C4-N3

O3-N5-C1-C2

O4-N5-C1-N4

O4-N5-C1-C2

22.8(10)

-97.1(8)

84.1(8)

-156.0(6)

-0.8(8)

-3.6(11)

0.6(7)

177.3(6)

178.2(6)

-178.5(6)

-162.9(7)

-106.7(8)

16.2(10)

Table S6 Hydrogen bonds of compound 7

D-H···A d(D-H)/Å d(H···A)/ Å d(D···A)/ Å <(DHA)/ °

N3-H3···O17

N3-H3···N6

N36-H36···O6

N36-H36···N2

C1-H···O5

C1-H1···O65

C4-H4···O19

C20-H20A···O5

0.8800

0.8800

0.8800

0.8800

1.0000

1.0000

0.9500

0.9500

2.5600

2.2300

2.2900

2.1500

2.3900

2.5600

2.3900

2.5100

3.304(8)

3.304(8)

2.905(8)

2.967(8)

2.843(8)

3.242(9)

3.272(8)

3.415(9)

142.00

150.00

127.00

154.00

107.00

125.00

154.00

160.00

Table S7 Bond distances of compound 7a

parameter Å parameter Å

O1-N1

O2-N1

O3-N2

O4-N2

O5-N3

1.263(2)

1.249(2)

1.256(2)

1.248(2)

1.230(2)

N3-C3

N4-N5

N4-C3

N5-C4

C1-C2

1.441(3)

1.334(2)

1.323(2)

1.343(3)

1.454(3)

O6-N3

N1-C1

N2-C1

1.226(2)

1.383(3)

1.385(3)

C2-C4

C2-C3

1.383(3)

1.414(3)

TableS6 Bond angles of compound 7a

parameter o parameter o

O1-N1-O2

O1-N1-C1

O2-N1-C1

O3-N2-O4

O3-N2-C1

O4-N2 -C1

O5-N3-O6

O5-N3-C3

O6-N3-C3

N5 -N4-C3

N4-N5 -C4

119.83(15)

116.46(16)

123.71(16)

119.88(16)

123.37(16)

116.74(17)

123.80(16)

117.76(16)

118.35(16)

103.89(16)

113.00(17)

N1-C1-C2

N1-C1-N2

N2-C1-C2

C1-C2-C4

C1-C2 -C3

C3-C2-C4

N3-C3-N4

N3-C3-C2

N4-C3-C2

N5-C4-C2

119.99(17)

120.60(17)

119.32(17)

127.10(18)

130.70(18)

102.19(17)

116.56(17)

130.09(17)

113.22(17)

107.70(17)

TableS9 Torsion angles of compound 7a

parameter o parameter o

O1-N1-C1-N2

O1-N1-C1-C2

O2-N1-C1 -N2

O2-N1-C1-C2

O3-N2-C1-N1

O3-N2-C1 -C2

O4-N2-C1-N1

O4-N2-C1-C2

O5-N3-C3-N4

O5-N3-C3-C2

O6-N3-C3-N4

O6-N3-C3-C2

C3-N4-N5-C4

-177.59(16)

-1.1(3)

2.7(3)

179.19(18)

-6.9(3)

176.60(17)

174.63(17)

-1.9(3)

172.12(16)

-3.3(3)

-4.6(3)

-180.0(2)

-0.2(2)

N5-N4-C3 -N3

N5-N4-C3 -C2

N4-N5-C4-C2

N1-C1-C2-C3

N1-C1-C2-C4

N2-C1-C2-C3

N2-C1-C2-C4

C1-C2-C3-N3

C1-C2-C3-N4

C4-C2-C3-N3

C4-C2-C3-N4

C1-C2-C4-N5

C3-C2-C4-N5

-175.71(16)

0.5(2)

-0.2(2)

130.9(2)

-47.7(3)

-52.6(3)

128.8(2)

-3.9(4)

-179.5(2)

175.0(2)

-0.6(2)

179.4(2)

0.4(2)

Table S10 Hydrogen bonds of the compound 7a

D-H···A d(D-H)/Å d(H···A)/ Å d(D···A)/ Å <(DHA)/ °

N5-H5···O2

N5-H5···O3

N6-H6A···O3

N6-H6A···O4

N6-H6A···N2

N6-H6B···O4

N6-H6B···O5

0.83(3)

0.83(3)

0.86(3)

0.86(3)

0.86(3)

0.88(3)

0.88(3)

2.26(3)

2.09(3)

2.26(3)

2.53(3)

2.60(3)

2.39(3)

2.35(3)

2.947(2)

2.785(2)

2.902(2)

3.077(3)

3.154(3)

2.731(2)

2.989(3)

141(2)

141(3)

133(2)

123(2)

123(2)

104(2)

130(2)

N6-H6B···O2

N6-H6C···N4

N6-H6D···O1

C4-H4···O6

0.88(3)

0.85(3)

0.94(3)

0.9500

2.59(3)

2.03(3)

1.96(3)

2.4200

3.117(2)

2.876(3)

2.878(2)

3.359(2)

120(2)

172(2)

168(2)

172.00

2. Computational Details The calculation was performed by using the Gaussian 09 program package1. The geometric

optimization of all the structures and frequency analyses for calculation of heats of formation was carried out by

using B3-LYP functional2 with 6-311+G** basis set3,4 . All of the optimized structures were characterized to be local

energy minima on the potential surface without any imaginary frequencies. The heats of formation (HOF) of these

compounds were computed through appropriate isodesmic reactions (Scheme S1). Atomization energies were

calculated by the CBS-4M5. Total energy and heat of formation for the reference compounds are summarized in

Table S11. All the optimized structures were characterized to be true local energy minima on the potential-energy

surface without imaginary frequencies.

N

HNO2N

O2N

NO2

+ 3CH4 N

HN

+ CH3NO2 + CH3CH3 + O2N NO2

7

N

HNO2N

O2N

NO2

+ 3CH4 N

HN

+ CH3NO2 + CH3CH3 + O2N NO2

7

Scheme S1 Isodesmic and tautomeric reactions to compute the HOF.

Table S11 Total energy and heat of formation for the reference compounds

E0a/a.u. ZPE b / kJ·mol-1 ΔHT

c / kJ mol-1 HOF d / kJ mol-1

7

7

-879.223

-878.71

269.58

236.17

36.58

34.33

205.60

-59.30

CH4

CH3NO2

CH3CH3

CH2(NO2)

CH(NO2)-

Pyrazole

-40.53

-245.09

-79.86

-449.61

-449.03

-226.26

112.26

124.93

187.31

132.90

100.12

179.20

10.04

11.60

11.79

14.71

18.42

12.57

-74.60

-80.80

-84.00

-25.61

-295.70

177.40

a E0 in a.u. ZPE (vibrational zero-point energy)，ΔHT (thermal correction to enthalpy) and HOF are in kJ mol-1. bData are from Ref. [D. R.

Lide, ed., CRC Handbook of Chemistry and Physics, 88th Edition (Internet Version 2008), CRC Press/Taylor and Francis, Boca Raton, FL.]. cData obtained from CBS-4M calculation in combination with the atomization reaction of the corresponding compound. dData from Ref.

[N. Fischer, T. M. Klapötke and J. Stierstorfer, Z. Anorg. Allg. Chem., 2009, 635, 271.]

References

1. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A.

Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain,

O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski,

G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman,

J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts,

R. L. Martin, D. J. Fox, T. Keith, M. A. Laham, C. Y. Peng, A. Nanayakkara, C,Gonzalez, M. Challacombe, P. M.

W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle and J. A.

Pople. Gaussian 09, revision A. 01; Gaussian, Inc.: Wallingford, CT, 2009.

2. A. D. Becke, J. Phys. Chem. 1993, 98, 5648.

3. P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11623.

4. P. C. Hariharan, J. A. Pople. Theoretica Chimica Acta. 1973, 28, 213.

5. J. W. Ochterski, G. A. Petersson, J. A. Montgomery, J. Chem. Phys. 1996, 104, 2598.

3．1H and 13C NMR spectra of new compounds

Figure S121H NMR spectra (300 MHz) of 2 in [D6] DMSO at 25 oC.

Figure S13 13C NMR spectra (125 MHz) of 2 in [D6] DMSO at 25 oC.

Figure S141H NMR spectra (300 MHz) of 3 in [D6] DMSO at 25 oC.

Figure S15 13C NMR spectra (125 MHz) of 3 in [D6] DMSO at 25 oC.

Figure S16 1H NMR spectra (300 MHz) of 5 in [D6] DMSO at 25 oC.

Figure S17 13C NMR spectra (125 MHz) of 5 in [D6] DMSO at 25 oC.

Figure S18 1H NMR spectra (300 MHz) of 6 in [D6] DMSO at 25 oC.

Figure S19 13C NMR spectra (125 MHz) of 5 in [D6] DMSO at 25 oC.

Figure S20 1H NMR spectra (300 MHz) of 7 in [D6] DMSO at 25 oC.

Figure S2113C NMR spectra (125 MHz) of 7 in [D6] DMSO at 25oC.

Figur

e S22 1H NMR spectra (300 MHz) of 7a in [D6] DMSO at 25 oC.

Figure S2313C NMR spectra (125 MHz) of 7a in [D6] DMSO at 25 oC.

Figure S24 1H NMR spectra (300 MHz) of 7b in [D6] DMSO at 25 oC.

Figure S25 13C NMR spectra (125 MHz) of 7b in [D6] DMSO at 25 oC.

Figure S26 1H NMR spectra (300 MHz) of 7c in [D6] DMSO at 25 oC.

Figure S2713C NMR spectra (125 MHz) of 7c in [D6] DMSO at 25 oC.

Figure S28 1H NMR spectra (300 MHz) of 7d in [D6] DMSO at 25 oC.

Figure S29 13C NMR spectra (125 MHz) of 7d in [D6] DMSO at 25 oC.