Supporting Information for Journal of Materials Science:

PromisingHydrazinium 3-Nitro-1, 2, 4-triazol-5-one and Its Analogues

Man Zhang1, Chuan Li1, Huiqi Gao1, Wei Fu1, Yingying Li1, Liwei Tang1,and Zhiming Zhou1,2*

1 School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing, 100081, R. P. China

2State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, R. P. China

E-mail:

Table of contents

1 Theoretical study

2 X-ray crystallography

Table 1 Band lengths (Å) for the structure of 10.

Table 2 Band lengths (Å) for the structure of 11.

3IR spectra

4Refernces

1 Theoretical study

Calculations were performed using the Gaussian 03 (Revision E.01) suite of programs[S1]. The geometric optimization of the structures and frequency analyses were conducted using the B3LYP functional with the 6–31+G** basis set[S2],and single-point energies were calculated at the MP2(full)/6–311++G** level. All of the optimized structures were characterized to be true local energy minima on the potential-energy surface without imaginary frequencies.

Based on the Born-Haber energy cycle (FigureS1), the heat of formation of a salt can be simplified according to Equation. (1),where ΔHL is the lattice energy of the salt.

ΔHfo(ionicsalt, 298K)=ΔHfo(cation, 298K)+ΔHfo(anion,298K)-ΔHL (1)

The ΔHL value could be predicted by the formula suggested by Jenkins et al. [Eq. 2] [S2],in which UPOT is the lattice potential energy and nM and nX depend on the nature of the ions Mp+ and Xq-, respectively, and are equal to three for monatomic ions, five for linear polyatomic ions, and six for nonlinear polyatomic ions.

ΔHL= UPOT + [p(nM/2－2) + q(nX/2－2)]RT (2)

The equation for the lattice potential energy, UPOT, takes the form of Equation (3), where ρm is the density (g cm-3), Mm is the chemical formula mass of the ionic material (g), and the coefficients γ (kJ mol-1 cm) and δ (kJ mol-1) are assigned literature values[S3].

UPOT (kJ mol-1) = γ (ρm/Mm)1/3 + δ (3)

Figure S1. Born-Haber cycle for the formation for energetic salts.

2 X-ray crystallography

Crystals of 10 and 11 was removed from the flask and covered with a layer of hydrocarbon oil. A suitable crystal was then selected, attached to a glass fiber, and placed in the low-temperature nitrogen stream.Data for salt 10 was collected at 102.8 K while for 11 was collected at 293.1 K, using a Rigaku Saturn724 CCD (AFC10/Saturn724+ for 7) diffractometer equipped with a graphite-monochromatized MoKα radiation (λ = 0.71073 Å) using omega scans. Data collection and reduction were performed and the unit cell was initially refined by using CrystalClear -SM Expert 2.0 r2 software[S4]. The reflection data were also corrected for Lp factors. The structure was solved by direct methods and refined by the least squares method on F2 using the SHELXTL-97 system of programs[S5]. Structure were solved in the space group P21/n for 10, Pī for 11, by analysis of systematic absences. In this all-light-atom structure the value of the Flack parameter did not allow the direction of polaraxisto be determined and Friedelreflections were then mergedforthe final refinement. Bond lengths are given in Table S1, S2.

Table S1Bond lengths (Å) for the structure of 10

compound 10
O1—N1 / 1.277 (2) / N5—C4 / 1.324 (2)
O2—N4 / 1.2340 (19) / N5—N6 / 1.4043 (17)
N4—O3 / 1.2271 (18) / C4—N7 / 1.357 (2)
N4—C2 / 1.447 (2 / N7—C3 / 1.381 (2)
N3—C2 / 1.340 (2) / N7—N8 / 1.3999(19)
N3—C1 / 1.354 (2) / C1—N1 / 1.364 (2)
N10—C4 / 1.316 (2) / C3—N6 / 1.306 (2)
N2—C2 / 1.308 (2) / C3—N6 / 1.359 (2)
N2—N1 / 1.370 (2)

Table S2Bond lengths (Å) for the structure of 11

compound 11
O1—C2 / 1.268(3) / N6—C3 / 1.386(3)
O2—N4 / 1.222(3) / N6—C4 / 1.373(3)
O3—N4 / 1.221(3) / N7—N8 / 1.403(3)
O4—C3 / 1.335(3) / N7—C3 / 1.327(3)
N1—N2 / 1.373(3) / N8—C4 / 1.352(3)
N1—C2 / 1.365(3) / N8—C5 / 1.348(3)
N2—C1 / 1.301(3) / N9—C5 / 1.327(3)
N3—C1 / 1.342(3) / N10—N11 / 1.400(3)
N3—C2 / 1.357(3) / N10—C5 / 1.338(3)
N4—C1 / 1.447(3) / N11—C4 / 1.301(3)
N5—N6 / 1.394(3)

3 IR spectra

IR-NTO

IR-salt 1

IR-salt 2

IR-salt 3

IR-salt 4

IR-salt 5

IR-salt 6

IR-salt 7

IR-salt 8

IR-salt 9

IR-salt 10

IR-salt 11

IR-salt 12

4 References

[S1] Gaussian 03, Revision E.01, M. J.Frisch, G. W.Trucks, H. B.Schlegel, G. E.Scuseria, M. A.Robb, J. R.Cheeseman, J. A.Montgomery, J. T.Vreven, K. N.Kudin, J. C.Burant, J. M.Millam, S. S.Iyengar, J.Tomasi, V.Barone, B.Mennucci, M.Cossi, G.Scalmani, N.Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul,S. Clifford, J. Cioslowski, B. B. Stefanov, G.Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.

[S2] R. G. Parr,W. Yang, Density Functional Theory of Atoms and Molecules,

OxfordUniversity Press, New York, 1989.

[S3] H. D. B. Jenkins, D. Tudeal, L. Glasser, Inorg. Chem. 2002, 41, 2364–2367.

[S4] CrystalClear: SM Expert 2.0 r2, An Integrated Program for the Collection and

Processing of AreaDetector Data, Rigaku Corporation, 2009.

[S5]G. M. Sheldrick, SHELXTL-97, Structure Determination Software Suite. Bruker

AXS, Madison WI,2008.

SI-1