Thermal stability improved by π-π stacking interactions: Synthesis, crystal structure and thermal decomposition of sodium nitroformate

Abstract

An energetic salt, sodium nitroformate (NaNF), was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was first determined by single crystal X-ray diffraction. The structure exhibits two types of π-π stacking interactions between the nitroformate anions, i e, the parallel-displaced and T-shaped configurations. Furthermore, the thermal decomposition mechanism was investigated by DSC, TG-DTG and FTIR techniques. The kinetic parameters of the thermal decomposition were also calculated by using Kissinger’s and Ozawa-Doyle’s methods. The results show that NaNF has a good thermal stability, which is attributed to the π-π stacking interactions.

Keywords

energetic material / nitroform / π-π stacking interaction / crystal structure / thermal stability

References

[1] Vallee R, Damman P, Dosiere M, . Nonlinear Optical Properties and Crystalline Orientation of 2-Methyl-4-nitroaniline Layers Grown on Nanostructured Poly(tetrafluoroethylene) Substrates[J]. J. Am. Chem. Soc., 2000, 122(28): 6 701-6 709.

[2] Nibedita S, Paul M L Hydrogen-bond-assisted, Crossed Dipole π-Stacking in 1,4-Bis(phenylethynyl)benzene[J]. Cryst. Growth Des., 2006, 6(6): 1 253-1 255.

[3] Hutchison G R, Ratner M A, Marks T J Intermolecular Charge Transfer between Heterocyclic Oligomers: Effects of Heteroatom and Molecular Packing on Hopping Transport in Organic Semiconductors[J]. J. Am. Chem. Soc., 2005, 127(48): 16 866-16 881.

[4] Yang X, Wang L, Wang C, . Influences of Crystal Structures and Molecular Sizes on the Charge Mobility of Organic Semiconductors: Oligothiophenes[J]. Chem. Mater., 2008, 20(9): 3 205-3 211.

[5] Raymo F M, Houk K N, Stoddart J F Origins of Selectivity in Molecular and Supramolecular Entities: Solvent and Electrostatic Control of the Translational Isomerism in [2]Catenanes[J]. J. Org. Chem., 1998, 63(19): 6 523-6 528.

[6] Lee E C, Kim D, Jurecka P, . Understanding of Assembly Phenomena by Aromatic-aromatic Interactions: Benzene Dimer and the Substituted Systems[J]. J. Phys. Chem. A, 2007, 111(18): 3 446-3 457.

[7] Zhang C, Wang X, Huang H π-Stacked Interactions in Explosive Crystals: Buffers against External Mechanical Stimuli[J]. J. Am. Chem. Soc., 2008, 130(26): 8 359-8 365.

[8] Song B, Wei H, Wang Z, . Supramolecular Nanoribers by Self-organization of Bola-amphiphiles through a Combination of Hydrogen Bonding and π-π Stacking Interactions[J]. Adv. Mater., 2007, 19(3): 416-420.

[9] Lovett J R, Edison N J Nitroform Salt of Certain Metals[P], 1971

[10] Zhang J, Zhang T, Zhang J, . Synthesis, Crystal Structure and Thermal Decomposition Character of [Zn(CHZ)₃][C(NO₂)₃]₂·(H₂O)₂ (CHZ = Carbohydrazide)[J]. Struct. Chem., 2008, 19(2): 321-328.

[11] Zhang J, Zhang T, Yang L, . Synthesis, Thermal Decomposition, and Properties of [Mn(CHZ)₃][C(NO₂)₃]₂[J]. Propellants Explos. Pyrotech., 2009, 34(1): 24-31.

[12] Yang L, Zhang J, Zhang T, . Crystal Structures, Thermal Decompositions and Sensitivity Properties of [Cu(ethylenediamine)₂(n itroformate)₂] and [Cd(ethylenediamine)₃](nitroformate)₂[J]. J. Hazard. Mater., 2009, 164(2–3): 962-967.

[13] Sheldrick G M SADABS: Program for Empirical Absorption Corrector Data[CP], 1996 Germany University of Göttingen

[14] Sheldrick G M SHELXTL-97: Structure Determination Software Programs[CP], 1997 Madison, WI, USA Bruker Analytical of X-ray System, Inc.

[15] Göbel M, Klapötke T M, Mayer P, . Crystal Structures of the Potassium and Silver Salts of Nitroform[J]. Z. Anorg. Allg. Chem., 2006, 632(6): 1 043-1 050.

[16] Huang H, Zhang S, Zhang T, . Comparative Theoretical Study of the Geometric and Electronic Structures of Potassium and Silver Salts of Nitroform[J]. Comput. Theor. Chem., 2013, 1004(1–3): 1-4.

[17] Xia S, Bobev S Cation-anion Interactions as Structure Directing Factors: Structure and Bonding of Ca₂CdSb₂ and Yb₂CdSb₂[J]. J. Am. Chem. Soc., 2007, 129(13): 4 049-4 057.

[18] Kumar R, Bhakuni V Comparative Analysis of Malate Synthase G from Mycobacterium Tuberculosis and E. Coli: Role of Ionic Interaction in Modulation of Structural and Functional Properties[J]. Int. J. Biol. Macromol., 2011, 49(5): 917-922.

[19] Endo T, Morita T, Nishikawa K Crystal Polymorphism of a Room-temperature Ionic Liquid, 1,3-Dimethylimidazolium Hexafluorophosphate: Calorimetric and Structural Studies of Two Crystal Phases Having Melting Points of ∼ 50 K Difference[J]. Chem. Phys. Lett., 2011, 517(4–6): 162-165.

[20] Kissinger H E Reaction Kinetics in Differential Thermal Analysis[J]. Anal. Chem., 1957, 29(11): 1 702-1 706.

[21] Ozawa T A New Method of Analyzing Thermogravimetric Data[J]. Bull. Chem. Soc. Jpn., 1965, 38(11): 1 881-1 886.

[22] Doyle C D Kinetic Analysis of Thermogravimetric Data[J]. J. Appl. Polym. Sci., 1961, 5(15): 285-292.

[23] Hu R Z, Yang A Q, Ling Y J The Determination of the Most Probable Mechanism Function and 3 Kinetic-parameters of Exothermic Decomposition Reaction of Energetic Materials by a Single Nonisothermal DSC Curve[J]. Thermochim. Acta, 1988, 123(1): 135-151.