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Science in China Ser. B Chemistry 2004 Vol.47 No.5 414 419

Theoretical studies on the possible conformers and properties of tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW)

WU Yukai1, OU Yuxiang1, LIU Zhiguo1, 2, LIU Jinquan1, MENG Zheng1 & CHEN Boren1
1. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China; 2. School of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, China Correspondence should be addressed to Ou Yuxiang (email: bjwujing@hotmail.com)

Received June 2, 2004

Tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW) is a novel polyazapolycyclic caged polyazidonitramine explosive first synthesized in our laboratory. All of the possible conformers of TNDAIW are optimized using both the AM1 and PM3 methods. TNDAIW is predicted to have more polymorphs than hexanitrohexaazoisowurtzitane (CL-20). The HF/6-31G(d) level of theory is used to investigate the lowest energy structures of D-TNDAIW for both AM1 and PM3. The possible conformers of TNDAIW are predicted to be more stable than epsilon-CL-20 based on the N-NO2 bond lengths. The impact and shock sensitivities of both the possible DA- and DP-TNDAIW are lower than the corresponding ones of epsilon-CL-20. TNDAIW with the possible conformers is estimated to be a promising novel high energy density explosive.

Keywords: tetranitrodiazidoacetylhexaazaisowurtzitane, molecular modeling, impact and shock sensitivities. DOI: 10.1360/04yb0046

All the spatial orientation of the nitro groups with respect to the five-membered rings and six-membered ring in the cage, the differences in crystal lattice packing, and the number of molecules per unit cell define the polymorphs of CL-20. So far, there exist four stable (alpha-, beta-, gamma- and epsilon-) polymorphs
Copyright by Science in China Press 2004

In this paper, all of the possible conformers of

Tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW), a novel polyazapolycyclic caged polyazidonitramine, possesses a similar structure to hexanitrohexaazoisowurtzitane (CL-20) which is the most powerful explosive ever tested[1 4]. TNDAIW has been synthesized via a six-step reaction in our laboratory[5]. The difference between CL-20 and TNDAIW is the substituents on the six-membered ring. In CL-20, the substituents are two nitro groups; whereas in TNDAIW, they are two azidoacetyl groups.

for CL-20 under ambient conditions[6]. Although one single crystal of TNDAIW was gained, and its structure has been established by X-ray diffraction[5], we are very interested in its other polymorphs and their performances, especially their stability, impact and shock sensitivities. Computational chemistry is an accessible approach in modeling the possible conformers of organic molecules. Ab initio methods are accurate in predicting many properties of molecules, and have been used in molding organic compounds[7 10]. Semiempirical methods of quantum chemistry, however, are the much more useful approaches in comprehensively exploring the possible conformers of relative large molecules, like TNDAIW. The AM1[11] and PM3[12,13] methods are currently extremely popular levels[14,15].

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Theoretical studies on the possible conformers and properties of tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW)

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Computational methods

The Gaussian program package[16] was used to perform the electronic structure calculation. For the starting structures the spatial orientations of the nitro groups of TNDAIW are based on the polymorphs of CL-20. The different spatial orientations of the oxygen atom and the azido group of each azidoacetyl group construct the starting structures of TNDAIW. Although the advantages of symmetry are primarily associated with computational efficiency, we did not employ symmetry in our study. Minima on a reduced-dimensionality potential energy surface (PES) may not be minima on the full PES[14]. The starting structures were fully optimized using both the AM1 and PM3 methods. The full optimizations of the selected geometries were then conducted at the Hartree-Fock level of theory with the 6-31G(d) standard basis. Vibrational frequency was computed to confirm the optimized geometry at the local minimum points on the potential energy surface. For the semi-empirical methods the cutoff values of maximum force, root-

Some starting structures of A-, C- and D-forms cannot obtain the corresponding optimized geometries with the local minimum energies. A few of the starting structures result in nearly the same optimized geometry by PM3 method, but not by AM1 method. The results using the AM1 and PM3 levels of theory are different in both the conformers and orders of energies for the optimized geometries. Table 1 lists the five lowest energies of different forms by both AM1 and PM3 methods. Azidoacetyl group has more atoms than nitro group, so the spatial orientations of the azidoacetyl groups in TNDAIW are more complicate than those of nitro groups in CL-20. TNDAIW has many local minimum points, and the five lowest energies of the optimized geometries for each form are
Energies

Table 1 The lowest energies of full optimized geometries of TNDAIW (Unit in hartree)

1 A-TNDAIW AM1 PM3 B-TNDAIW AM1 PM3 C-TNDAIW AM1 PM3 D-TNDAIW AM1 PM3 0.507828 0.254776 0.501146 0.251755 0.507656 0.255833 0.506527 0.256012

2 0.507853 0.256197 0.501554 0.252282 0.507828 0.256197 0.506628 0.257187

3 0.508006 0.256346 0.501896 0.252346 0.507853 0.256346 0.506795 0.257676

4 0.508177 0.257322 0.502139 0.252389 0.508006 0.257322 0.506971 0.258419

5 0.508398 0.259023 0.502186 0.253347 0.508177 0.258836 0.507205 0.258961

TNDAIW are comprehensively explored using both AM1 and PM3 methods. The ab initio method, the HF/6-31G(d) level of theory, is then used to study the lowest energy structures of the interested conformers for AM1 and PM3. The important parameters of the optimized geometries are presented. The corresponding results of epsilon-CL-20 are also given for comparison. Furthermore, the impact and shock sensitivities of TNDAIW and CL-20 are compared with each other.

mean-square (RMS) force, maximum displacement and RMS displacement used to determine convergence are 1.5105, 1.0105, 6.0105 and 4.0105, respectively. For the HF/6-31G(d) level the default options are used. 2 2.1 Results and discussion Possible conformers

Based on the four polymorphs of CL-20[17 21], we define the different spatial orientations of the nitro groups as the A-, B-, C- and D-forms of TNDAIW corresponding to the alpha-, beta-, gamma- and epsilon-CL-20. After considering the symmetry of the molecules, there are 36 possible starting structures for each A-and C-form, and 27 possible ones for each Band D-form.

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very close. So we predict that TNDAIW has more possible polymorphs than CL-20. It is well known that only epsilon-CL-20 has been studied in application. The other polymorphs must be changed to epsilon-form before use[3]. The energy difference between B- and D-TNDAIW by PM3 is 11.18 kJ/mol, slightly smaller than the corresponding values of CL-20 of 11.66 kJ/mol. The conformer of D-TNDAIW is significantly interesting for us to explore the parameters of geometry and their performance. The lowest energy structures of D-form for AM1 and PM3 are optimized at the HF/6-31G(d) level to obtain the conformer of DA- and DPTNDAIW (shown in fig. 1) with the total energies of 2003.545597 and 2003.542406 hartree, and the dipole moments of 5.092 and 7.619 debye, respectively. The corresponding values are 2003.541969 hartree and 0.6519 debye for the optimized experimental structure at the same level. The energy differences are only 9.52 kJ/mol for DA-TNDAIW, and 1.15 kJ/mol for DP-TNDAIW. So TNDAIW is predicted to exist in the structure of D-form. 2.2 Important bond lengths

The N-N bond with respect to the NO2 group is very important in nitramines. It is thought to be the first breaking bond during decomposition. In addition,

the N-N bonds of the adizoacetyl groups are also regarded to be unstable. Table 2 summarizes the N-N bond lengths of the optimized geometries of DA- and DP-TNDAIW at the HF/6-31G(d) level. The corresponding values of epsilon-CL-20 are also given for comparison. All of the lengths of the N-N bonds with respect to the NO2 groups for TNDAIW are shorter than the corresponding ones of CL-20. So the azidoacetyl groups seem to have the ability of stabilizing the N-N bond with respect to the nitro groups. The N-N bond lengths for the azidoacetyl groups are shorter than those connected to the nitro groups for both forms. They are predicted to be stronger than the N-NO2 bonds. Hence TNDAIW is estimated to be more stable than CL-20. The C-C bond is also important one. Table 2 presents all of the C-C bond lengths of DA-TNDAIW, DP-TNDAIW and epsilon-CL-20. The C-C bonds in the azidoacetyl groups are stronger than the ones in the cage, because they are extremely smaller in length than those in the cage. The lengths of the C(3)-C(11) and C(5)-C(9) bonds of TNDAIW seem to be slightly shorter than the corresponding ones of CL-20. But the differences are insignificant. So the azidoacetyl groups have slight effect on the C-C bonds in the polycyclic caged structure.

Fig. 1. The optimized geometries at the HF/6-31G(d) level.

Theoretical studies on the possible conformers and properties of tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW)

Table 2 The lengths of the important bonds of TNDAIW and CL-20 at the HF/6-31G(d) level (Unit in nm) Bond N(2)-N(16) N(6)-N(15) N(8)-N(14) N(12)-N(13) N(21)-N(22) N(24)-N(25) N(22)-N(23) N(25)-N(26) DA-TNDAIW 0.1344 0.1374 0.1364 0.1348 0.1240 0.1239 0.1097 0.1097 DP-TNDAIW 0.1345 0.1374 0.1374 0.1346 0.1241 0.1242 0.1096 0.1096 Epsilon-CL-20 0.1353 0.1380 0.1381 0.1353 0.1367a) 0.1367 a) Bond C(1)-C(7) C(3)-C(11) C(5)-C(9) C(17)-C(19) C(18)-C(20) C-N b) C(17)-N(4) C(18)-N(10) C(19)-N(21) C(20)-N(24) DA-TNDAIW 0.1582 0.1569 0.1570 0.1525 0.1524 0.1449 0.1383 0.1382 0.1467 0.1468 DP-TNDAIW 0.1579 0.1572 0.1568 0.1523 0.1528 0.1449 0.1383 0.1387 0.1470 0.1448 0.1449

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Epsilon-CL-20 0.1582 0.1578 0.1575

a) The lengths of the N-N bonds with respect to the N(4) and N(10) atoms for CL-20; b) the length with respect to the cage is average.

The C-N bond is another important bond in both TNDAIW and CL-20. The lengths of the C(17)-N(4) and C(18)-N(10) bond are smaller than the others. This indicates that they are stronger than the others. The lengths of the C(19)-N(21) and C(20)-N(24) bonds are nearly equal to the values of the C(5)-N(6) and C(9)-N(8) bonds. All of them are the greatest in length among all the C-N bonds (shown in table 3). The C(5)-N(6), C(9)-N(8), C(19)-N(21) and C(20)N(24) bonds are estimated to be more unstable than the other C-N bonds. In addition, the C-N bonds in the cage are almost the same for both TNDAIW and CL-20. Therefore, the azidoacetyl groups have little affect on the C-N bonds in the caged structure. 2.3 Impact and shock sensitivities The sensitivity of an energetic material to external stimuli is a key property in determining its potential applications and handling safety. Impact and shock sensitivities are the most widely used indicator. So we have much concern about the impact and shock sensi
Table 3 The important N-N bonding Mulliken populations at the HF/6-31G(d) level (Unit in a.u.) Bond DA-TNDAIW N(12)-N(13) N(21)-N(22) DP-TNDAIW N(12)-N(13) N(21)-N(22) Epsilon-CL-20 N(2)/N(12)-N N(4)/N(10)-N Population 0.2285 0.2215 0.2301 0.2445 0.2239 0.2193

tivities of TNDAIW. The thermal decomposition mechanisms are related to its sensitivities. The breaking of N-N bond is considered a key step in this process, and related to sensitivity. The smallest N-N bonding Mulliken population is used to forecast impact sensitivity[22]. Our studies indicated that the calculated N-N bonding Mulliken population by AM1 method is fit for the forecast of impact sensitivity of nitramines[23,24]. The smallest N-N bonding Mulliken population is on the N(21)-N(22) bond for DA-TNDAIW, and on the N(12)-N(13) bond for DP-TNAIW. Both of them are larger than that of epsilon-CL-20. The smallest N-N bonding Mulliken population is on the N(4)/N(10)-N bonds for epsilon-CL-20. Table 3 gives the important N-N bonding Mulliken population at the HF/6-31G(d) level. The N(12)-N(13) bonding Mulliken population of DA- and DP-TNDAIW, the smallest one among all the N-NO2 bonds, are greater than the corresponding value of epsilon-CL-20. Therefore, the impact sensitivities of the possible DA- and DP-TNDAIW are predicted to be lower than that of epsilon-CL-20. A good correlation of nitramine shock sensitivity with all N-N bond lengths and overall molecule size is presented in a straightforward manner as follows[25,26]: Sensitivity ~ nRa/M, where n is the number of N-NO2 linkages in the molecule, Ra is the average length of all N-NO2 bonds, and M is the molecule weight which

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2. Nielsen, A. T., US Patent 5 693 794, 1997-12-02. 3. Ren, W., Wang, Z., Theory and Practice of Propellants and Explosives (in Chinese), Beijing: China North Chemical Industries Corp., 2001, 240 4. Simpson, R. L., Urtiew, P. A., Ornellas, D. L. et al., CL-20 performance exceeds that of HMX and its sensitivity is moderate, Propellants, Explos., Pyrotech., 1997, 22: 249 retical study of 5. Wu, Y., Ou, Y., Liu, Z. et al., Synthesis, crystal structure and theotetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW), Propellants, Explos., Pyrotech. (in press). 6. Foltz, M. F., Coon, C. L., Garcia, F. et al., The thermal stability of the polymorphs of hexanitrohexaazaisowurtzitane, Part I, Propellants, Explos., Pyrotech., 1994, 19: 19 7. Xiao, H., Chen, L., Ju, X. et al., A theoretical study on nitration mechanism of benzene and solvent effects, Science in China, Se8. Xiao, H., Zhang, J., Theoretical prediction on heats of formation for polyisocyanocubanes 21 density material (HEDM), Science in China, Series B, 2002, 45(1): 9. Li, M., Tian, A., Quantum chemical study on asymmetric catalysis reduction of imine, Science in China, Series B, 2003, 46(2): 10. Li, J., Xie, D., Yan, G., Theoretical study of the intermolecular hydrogen bond interaction for furan-HCl and furan-CHCl3 complexes, Science in China, Series B, 2003, 46(2): 113118. 11. Dewar, M. J. S., Zoebisch, E. G., Healy, E. F. et al., AM1: A new general purpose quantum mechanical molecular model, J. Amer. Chem. Soc., 1985, 107(13): 3902 12. Stewart, J. J. P., Optimization of parameters for semiempirical methods I. Method, J. Comp. Chem., 1989, 10(2): 209 methods 264. 13. Stewart, J. J. P., Optimization of parameters for semiempirical . Applications, J. Comp. Chem., 1989, 109(2): 221 [ ] [PDF] 124131. [ ] [PDF] ries B, 2003, 46(5): 453

25.

3 Conclusions Both the AM1 and PM3 methods are used to optimize all of the possible structures of TNDAIW based on the polymorphs of CL-20. TNDAIW is probable to have more polymorphs than CL-20. We predict that it has at least one of A-, B-, C- and D-form conformers. D-TNDAIW is like epslion-CL-20 in the spatial orientations of the N-NO2 groups with respect to the five-membered rings. The HF/6-31G(d) level of theory is then used to perform the further investigation on the lowest energy D-forms of TNDAIW for AM1 and PM3. The ab initio study indicates that the azidoacetyl groups can stabilize the N-NO2 bonds in the polycyclic caged structure. So D-form TNDAIW of interest is predicted to be more stable than epsilon-CL-20 based on the N-N bond lengths. In addition, the azidoacetyl groups slightly shorten the C-C bonds, but have little effect on the C-N bonds in the cage. The impact and shock sensitivities of both the possible DA- and DP-TNDAIW are predicted to be lower than the corresponding ones of epsilon-CL-20. Therefore, TNDAIW with the possible conformers is estimated to be a promising high energy density explosive.

looking for typical high energetic

14. Cramer, C. J., Essentials of Computational Chemistry: Theories and Methods, England: John Wiley & Sons, Ltd., 2002, Chapter 6. 15. Yong, D. C., Computational Chemistry: A Practical Guide for Applying Techniques to Real-Word Problems. USA: John Wiley & Sons, Inc., 2001, Chapter 3. 16. Frisch, M. J., Trucks, G. W., Schlegel, H. B. et al., Gaussian 98, Revision A.7, Pittsburgh PA: Gaussian, Inc., 1998.

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is taken as a measure of molecule size. This relationship suggests that all N-NO2 bonds, taken in conjunction with the overall size of the molecule, help to determine the shock sensitivities of nitramines. The values of nRa/M are 1.056103 for DA-TNDAIW, 1.058103 for DP-TNDAIW, and 1.872103 for epsilon-CL-20, respectively. If the N(21)-N(22) and N(24)-N(25) bonds are considered, because their lengths are longer than the others in the azidoacetyl groups, the corresponding values are 1.538103 for DA-TNDAIW, and 1.541103 for DP-TNDAIW. All of the values of nRa/M of TNDAIW are much smaller than those of epsilon-CL-20. So the shock sensitivities of the possible forms of TNDAIW are predicted to be lower than that of epsilon-CL-20.

References
1. Nielsen, A. T., Nissan, R. A., Polynitropolyaza Caged Explosives Part 5, Naval Weapon Centre Technical Publication 6692, 1986.

251.

255.

Theoretical studies on the possible conformers and properties of tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW)

17. Ou, Y., Chen, B., Jia, H. et al., Identification of hexanitrohexaazaisowurtzitane, Energetic Materials (in Chinese), 1995, 3(3): 1 18. Ou, Y., Jia, H., Chen, B. et al., Crystal structure of four polymorphs of hexanitrohexaazaisowurtzitane, Huozhayao Xuebao (in Chinese), 1998, (4): 41 19. Ou, Y., Jia, H., Chen, B. et al., Crystal structure of -hexanitrohexaazaisowurtzitane, Journal of Beijing Institute of Technology (in Chinese), 1999, 19(5): 631636. 20. Ou, Y. Jia, H., Xu, Y. et al., Synthesis and crystal structure of -hexanitrohexaazaisowurtzitane, Science in China, Series B, 1999, 42(2): 217 21. Ou, Y., Jia, H., Chen, B. et al., Crystal structure of -hexanitrohexaazaisowurtzitane, Acta Chimica Sinica (in Chinese), 1999, 57: 431 22. Xiao, H., The Molecular Orbital Theory of Nitro Compounds (in

419

Chinese), Beijing: National Defence Industry Press, 1993, Chapter 5. 23. Wu, Y., Ou, Y., Liu, Z. et al., Theoretical studies on PNMFIW by AM1 and PM3 methods, Propellants, Explos., Pyrotech., 2003, 28: 281 24. Wu, Y., Ou, Y., Liu, Z. et al., Theoretical studies on pentanitromonoacetylhexaazaisowurtzitane (PNMAIW) by AM1 and PM3 methods, J. Energ. Mat., 2003, 21(4): 261273. 25. Murray, J. S., Politzer, P., Computational studies of energetic nitramines, Chemistry and Physics of Energetic Materials (ed. Bulusu, S. N.), Netherlands: Kluwer Academic Publisher, 1990, 175 26. Murray, J. S., Politzer, P., Structure-sensitivity relationships in energetic compounds, Chemistry and Physics of Energetic Materials (ed. Bulusu, S. N.), Netherlands: Kluwer Academic Publisher, 1990, 157173.

43.

224.

193.

436.

7.

286.[DOI]