Energetic Materials: The Preparation and Structural Characterization of Three Biguanidinium Dinitramides

Abstract

Three biguanidinium salts of the energetic dinitramide anion have been prepared and structurally characterized from room-temperature X-ray diffraction data. Biguanidinium mono-dinitramide, (BIGH)(DN), triclinic, Pi, a = 4.3686(4), b = 9.404(2), c = 10.742(1)A,, c~= 83.54(1), ,;3 = 80.386(9), 7 = 79.93(1) ° , V = 426.8 (1)A, 3, Z = 2, Dx = 1.62 gcm -3. Biguanidinium bis-dinitramide, (BIGH2)(DN)2, monoclinic, C2/c, a= 11.892(2), b = 8.131(1), c = 13.038(2)A,, [2 = 115.79(1) ° , V = 1135.1(3)A, 3, Z = 4, Dx = 1.84 gcm -3. Biguanidinium bis-dinitramide monohydrate, (BIGH2)(DN)2.H20, orthorhombic, P212121, a= 6.4201 (6), b = 13.408(1), c = 14.584 (2) A,, V= 1255.4(4) A, 3, Z = 4, Dx = 1.76 gcm -3. All three structures are characterized by extensive hydrogen bonding. Both the mono-and diprotontated cations consist of two planar halves twisted with respect to each other. The dinitramide anion has a surprisingly variable and asymmetric structure. The two halves of the anion are twisted with respect to each other; however, the twist varies from 5.1 to 28.9 ° . In addition, the two ends of the anion have significantly different geometries, e.g. the 'equivalent' N--N bond lengths differ by up to 0.045/~,.

Synthesis and Structures of Triorganochalcogenium (Te, Se, S) Dinitramides

“…The reaction of trimethyloxonium tetrafluoroborate with silver dinitramide was also performed, but no evidence for the formation of the desired trimethyloxonium dinitramide was found. According to the 14 4 ] with silver dinitramide, but likely can exclude the formation of the protonated species HN(NO 2 ) 2 , as it was found with HN 3 for the corresponding reaction with silver azide.…”

“…Compounds 5 and 6 are less stable relative to the corresponding organotelluronium and organoselenonium salts and decompose slowly at ambient temperature. However, both compounds can be stored at temperatures below -32°C for several weeks without decomposition according to 14 N NMR spectroscopy.…”

“…The dinitramide anion was first discovered by Russian chemists in 1971, [1] but was kept secret until it was independently rediscovered in the late 1980s in the USA. [2] Afterwards, the Russian work was summarized in a series of publications, [1,[3][4][5][6][7][8][9][10] new aspects were added by different groups, [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] and also theoretical aspects of the dinitramide anion have been reported. [26][27][28] An overview of structural trends and variations in dinitramide salts has been given, [10,29,30] and potential applications for various dinitramide salts have been discussed.…”

1,2,4‐Triazolium‐Cation‐Based Energetic Salts

“…The overall geometry of the anion is similar to that observed in comparable dinitramide salts. [60][61][62] The two NÀN bond lengths are approximately symmetric ( % 1.38 ) and shorter than a normal NÀN single bond (1.454 ), though longer than a N=N double bond (1.245 ). [47] The N-N-N angle is 115.1(2)8 as expected.…”

Solanaceae — a model for linking genomics with biodiversity

“…It has a melting point of 92 °C and a density of ρ =1.82 g cm −3 . It is more stable or less sensitive compared with alkyl dinitramides 71,72 and the stability is attributed to the delocalized negative charge that stabilizes NNO 2 bonds to become susceptible to rupture 73…”