12
Z. Tang et al. / Journal of Molecular Structure 1004 (2011) 8–12
III followed by splitting out of the nitrogen molecule. The IR spec-
trum of solid residue at 290 °C shows that there is a absorption at
2061 cmꢀ1, which indicates that the azido-bridged structure of the
complex still exists. Taking into account of above facts, this stage
can be predicted as the breaking-up of the coordinated DAT li-
gands, and the gaseous products are 2N2, HN3, NH3 (calc. 29.27%)
with some volatile condensed products formed.
The second stage with mass loss 17.39% starts at 290 °C, ends at
400 °C, and reaches the largest rate at 330 °C. In the IR spectrum of
the solid residue at 400 °C, the absorption at 2003 cmꢀ1 indicates
that the azido ligands still exist. The volatile condensed products
are formed during the first stage decompose during this tempera-
ture range, and this step can be assigned to the evolution of N2,
NH3 and HCN [24,25] (calc. 18.17%).
The third mass loss stage starts at 400 °C, ends at 530 °C, and
reaches the largest rate at 500 °C with mass loss 21.06%. This stage
roughly coincides with the value of 21.19%, calculated for the loss
of three nitrogen molecules, and the final solid residues are Cd
(calc. 28.34%) and few condensed products (found 31.11%). The
IR spectrum of the final solid residue shows that all azido ligands
have decomposed.
In conclusion, on the basis of the DSC, TG-DTG and FT-IR analy-
ses, the thermal decomposition processes of [Cd(DAT)2(N3)2]n can
be predicted as follows:
environmentally friendly gases. It may be further studied in the
fields of energetic materials.
Acknowledgments
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (NSAF: 10776002,
NSFC: 20911120033), the project of State Key Laboratory of
Explosives Science and Technology (Beijing Institute ofTechnology)
(No. ZDKT10-01b, YBKT10-03), and the Program for New Century
Excellent Talents in University (NCET-09-0051).
References
[1] G.X. Ma, T.L. Zhang, J.G. Zhang, K.B. Yu, Thermochim. Acta 423 (2004) 137.
[2] O.A. Ivashkevich, V.A. Krasitsky, A.I. Lesnikovich, V.M. Astashinsky, E.A.
Kostyukevich, B.M. Khusid, V.A. Mansurov, Combust. Flame 110 (1997) 113.
[3] J. Neutz, O. Grosshardt, S. Schäufele, H. Schuppler, W. Schweikert, Propellants,
Explos., Pyrotech. 28 (2003) 181.
[4] H. Xue, S.W. Arritt, B. Twamley, J.N.M. Shreeve, Inorg. Chem. 43 (2004) 7972.
[5] T.M. Klapötke, P. Mayer, A. Schulz, J.J. Weigand, J. Am. Chem. Soc. 127 (2005)
2032.
[6] P.N. Gaponik, S.V. Voitekhovich, A.S. Lyakhov, V.E. Matulis, O.A. Ivashkevich, M.
Quesada, J. Reedijk, Inorg. Chim. Acta 358 (2005) 2549.
[7] J.C. Gálvez-Ruiz, G. Holl, K. Karaghiosoff, T.M. Klapötke, K. Löhnwitz, P. Mayer,
H. Nöth, K. Polborn, C.J. Rohbogner, M. Suter, J.J. Weigand, Inorg. Chem. 44
(2005) 4237.
[8] G. Fischer, G. Holl, T.M. Klapötke, J.J. Weigand, Thermochim. Acta 437 (2005)
168.
[9] V.E. Matulis, A.S. Lyakhov, P.N. Gaponik, S.V. Voitekhovich, O.A. Ivashkevich, J.
Mol. Struct. 649 (2003) 309.
[10] K.C. Patil, C. Nesamani, V.R.P. Verneker, Synth. React. Inorg. Met. -Org. Chem.
12 (1982) 383.
[11] V.P. Sinditskii, T.Y. Vernidub, A.E. Fogelzang, Zh. Neorg. Khim. 35 (1990) 685.
[12] M.H.V. Huynh, M.A. Hiskey, T.J. Meyer, M. Wetzler, Proc. Natl. Acad. Sci. USA
103 (2006) 5409.
½CdðDATÞ ðN3Þ ꢄ ðsÞ 50ꢀ208 deg C
!
½CdðDATÞ2ðN3Þ2ꢄnðlÞ
2
2
n
C
208ꢀ290ꢅ
ꢃ ꢀ2N
!
C
½CdðN3Þ2ꢄnðsÞ þ volatile condensed productsðsÞ
2;ꢀHN3;ꢀNH3ꢀNH3
290ꢀ400ꢅ
ꢃ ꢀN
!
ꢅ
½CdðN3Þ2ꢄnðsÞ þ condensed productsðsÞ
2ꢀHCN;ꢀNH3
ꢃ 400ꢀ530
!
C CdðsÞ þ condensed productsðsÞ
[13] M.H.V. Huynh, M.D. Coburn, T.J. Meyer, M. Wetzler, Proc. Natl. Acad. Sci. USA
103 (2006) 10322.
ꢀ3N2
[14] M.B. Talawar, A.P. Agrawal, J.S. Chhabra, S.N. Asthana, J. Hazard. Mater. A113
(2004) 57.
[15] G.M. Sheldrick. SADABS: Program for Empirical Absorption Correction of Area
Detector Data, University of Göttingen, Germany, 1996.
[16] G.M. Sheldrick. SHELXS-97, Program for the Solution of Crystal Structures,
University of Göttingen, Germany, 1997.
[17] G.M. Sheldrick. SHELXL-97, Program for the Refinement of Crystal Structures,
University of Göttingen, Germany, 1997.
[18] Z.H. Liu, T.L. Zhang, J.G. Zhang, S.Z. Wang, J. Hazard. Mater. 154 (2008) 832.
[19] H.J. Chen, X.M. Chen, Inorg. Chim. Acta 329 (2002) 13.
[20] M.A.S. Goher, A.K. Hafez, M.A.M. Abu-Youssef, A.M.A. Badr, C. Gspan, F.A.
Mautner, Polyhedron 23 (2004) 2349.
[21] E.Q. Gao, Z.M. Wang, C.H. Yan, Chem. Commun. 3 (2003) 1748.
[22] A. Escuer, R. Vicente, M.A.S. Goher, F.A. Mautner, Inorg. Chem. 34 (1995) 5707.
[23] M.A.M. Abu-Youssef, F.A. Mautner, R. Vicente, Inorg. Chem. 46 (2007) 4654.
[24] A.I. Lesnikovich, O.A. Ivashkevich, S.V. Levchik, A.I. Balabanovich, P.N. Gaponik,
A.A. Kulak, Thermochim. Acta 388 (2002) 233.
4. Conclusion
polymeric
[Cd(DAT)2(N3)2]n, where DAT = 1,5-diaminotetrazole, has been
synthesized and characterized. Each center Cd (II) atom is six-coor-
A
nitrogen-rich
cadmium
(II)
complex:
dinated with two trans DAT ligands and four trans
l-1,3 azido
bridged ligands. The two zigzag chains linked by azido ligands
are vertical to each other, and a novel two-dimensional rectangu-
lar-grid-like layer parallel to the ab-plane of unit cell is formed.
The thermal analysis shows that under nitrogen atmosphere with
a heating rate of 10 °C/min, the thermal decomposition of the title
compound starts just after the melting and yielding mainly
[25] T.M. Klapötke, C.M. Sabaté, M. Rusan, Z. Anorg. Allg. Chem. 634 (2008) 688.