Crystal structure, thermal properties and detonation characterization of bis­(5-amino-1,2,4-triazol-4-ium-3-yl)methane dinitrate

Bis(5-amino-1,2,4-triazol-4-ium-3-yl)methane dinitrate, BATZM·(NO₃)₂ or C₅H₁₀N₈²⁺·2NO₃⁻, was synthesized and its crystal structure determined by single-crystal X-ray diffraction. It crystallizes in the space group Pbcn (ortho­rhom­bic) with Z = 4. BATZM·(NO₃)₂ is a V-shaped mol­ecule where hydrogen bonds form a two-dimensional corrugated sheet with reasonable chemical geom­etry and no disorder. The specific molar heat capacity (C_p,m) of BATZM·(NO₃)₂ was determined using the continuous C_p mode of a micro­calorimeter and theoretical calculations, and the C_p,m value is 366.14 J K⁻¹ mol⁻¹ at 298.15 K. The relative deviations between the theoretical and experimental values of C_p,m, H_T – H_298.15K and S_T – S_298.15K of BATZM·(NO₃)₂ are almost equivalent at each temperature. The detonation velocity (D) and detonation pressure (P) were estimated using the nitro­gen equivalent equation according to the experimental density; BATZM·(NO₃)₂ has a higher detonation velocity (7927.47 ± 3.63 m s⁻¹) and detonation pressure (27.50 ± 0.03 GPa) than 2,4,6-tri­nitro­toluene (TNT). The above results for BATZM·(NO₃)₂ are com­pared with those of bis­(5-amino-1,2,4-triazol-3-yl)methane (BATZM) and bis­(5-amino-1,2,4-triazol-4-ium-3-yl)methane di­hydro­chloride (BATZM·Cl₂), and the effect of nitrate formation is discussed.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Methylenebis(5-amino-1,2,4-triazol-4-ium) dinitrate

Crystal data

C5H10N8^2+·2NO3^−	Dx = 1.710 Mg m^−3
Mr = 306.23	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 2960 reflections
a = 7.7416 (16) Å	θ = 2.6–28.7°
b = 8.9487 (18) Å	µ = 0.15 mm^−1
c = 17.168 (3) Å	T = 296 K
V = 1189.3 (4) Å^3	Rodlike, colourless
Z = 4	0.37 × 0.32 × 0.27 mm
F(000) = 632

Data collection

Bruker APEXII CCD diffractometer	1240 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 28.9°, θmin = 3.5°
Tmin = 0.945, Tmax = 0.959	h = −9→9
6447 measured reflections	k = −11→12
1476 independent reflections	l = −11→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	All H-atom parameters refined
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0527P)^2 + 0.2645P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1476 reflections	Δρmax = 0.24 e Å^−3
117 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0093 (17)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N4	0.26604 (17)	1.09743 (15)	0.43580 (8)	0.0483 (3)
N3	0.09405 (13)	0.94979 (11)	0.34993 (6)	0.0336 (3)
N2	0.29749 (14)	0.83162 (13)	0.28447 (6)	0.0399 (3)
N1	0.36750 (14)	0.92772 (13)	0.33965 (6)	0.0403 (3)
N5	0.74687 (13)	0.12768 (14)	0.42174 (6)	0.0408 (3)
O3	0.89030 (13)	0.16661 (16)	0.44456 (8)	0.0718 (4)
O1	0.73330 (12)	0.02284 (12)	0.37331 (6)	0.0483 (3)
O2	0.61582 (13)	0.19240 (14)	0.44553 (7)	0.0629 (4)
C1	0.24492 (15)	0.99885 (14)	0.37944 (7)	0.0340 (3)
C2	0.13286 (15)	0.84798 (12)	0.29291 (6)	0.0316 (3)
C3	0.000000	0.75929 (19)	0.250000	0.0362 (4)
H3A	0.064 (2)	0.6949 (16)	0.2119 (8)	0.046 (4)*
H1	0.481 (2)	0.9381 (17)	0.3474 (9)	0.055 (5)*
H3	−0.009 (2)	0.9775 (17)	0.3636 (8)	0.047 (4)*
H4A	0.373 (2)	1.1206 (18)	0.4467 (9)	0.053 (5)*
H4B	0.170 (3)	1.136 (2)	0.4566 (11)	0.073 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N4	0.0406 (7)	0.0527 (7)	0.0515 (7)	−0.0065 (6)	−0.0070 (5)	−0.0093 (6)
N3	0.0237 (5)	0.0381 (5)	0.0389 (5)	0.0004 (4)	0.0012 (4)	−0.0021 (4)
N2	0.0304 (6)	0.0494 (6)	0.0400 (5)	0.0052 (5)	0.0019 (4)	0.0002 (4)
N1	0.0241 (5)	0.0505 (6)	0.0464 (6)	0.0001 (5)	−0.0017 (4)	0.0022 (5)
N5	0.0286 (6)	0.0491 (6)	0.0448 (6)	0.0042 (4)	−0.0017 (4)	−0.0078 (5)
O3	0.0269 (6)	0.0951 (9)	0.0935 (9)	0.0014 (5)	−0.0084 (5)	−0.0426 (7)
O1	0.0403 (6)	0.0526 (6)	0.0521 (6)	0.0050 (4)	−0.0031 (4)	−0.0163 (5)
O2	0.0295 (6)	0.0701 (7)	0.0890 (8)	0.0077 (5)	0.0034 (5)	−0.0324 (6)
C1	0.0289 (6)	0.0367 (6)	0.0363 (6)	−0.0020 (5)	−0.0019 (4)	0.0060 (5)
C2	0.0288 (6)	0.0351 (6)	0.0310 (5)	0.0036 (5)	−0.0001 (4)	0.0037 (4)
C3	0.0357 (9)	0.0359 (8)	0.0370 (8)	0.000	−0.0021 (6)	0.000

Geometric parameters (Å, º)

N4—C1	1.3195 (18)	N1—C1	1.3313 (17)
N4—H4A	0.874 (18)	N1—H1	0.897 (18)
N4—H4B	0.89 (2)	N5—O3	1.2279 (14)
N3—C1	1.3467 (15)	N5—O2	1.2375 (14)
N3—C2	1.3706 (15)	N5—O1	1.2580 (15)
N3—H3	0.866 (17)	C2—C3	1.4935 (14)
N2—C2	1.2911 (16)	C3—H3A	1.003 (14)
N2—N1	1.3896 (15)	C3—H3A^i	1.003 (14)
C1—N4—H4A	115.6 (11)	N4—C1—N1	127.42 (12)
C1—N4—H4B	116.7 (13)	N4—C1—N3	126.96 (12)
H4A—N4—H4B	127.6 (18)	N1—C1—N3	105.62 (11)
C1—N3—C2	107.17 (10)	N2—C2—N3	111.84 (10)
C1—N3—H3	127.0 (10)	N2—C2—C3	124.35 (10)
C2—N3—H3	125.8 (10)	N3—C2—C3	123.68 (10)
C2—N2—N1	103.79 (10)	C2^i—C3—C2	115.80 (14)
C1—N1—N2	111.57 (10)	C2^i—C3—H3A	108.9 (8)
C1—N1—H1	125.1 (10)	C2—C3—H3A	106.7 (8)
N2—N1—H1	123.3 (10)	C2^i—C3—H3A^i	106.7 (8)
O3—N5—O2	120.22 (12)	C2—C3—H3A^i	108.9 (8)
O3—N5—O1	119.86 (11)	H3A—C3—H3A^i	109.8 (16)
O2—N5—O1	119.91 (11)
C2—N2—N1—C1	−0.06 (13)	N1—N2—C2—C3	−175.48 (10)
N2—N1—C1—N4	179.97 (12)	C1—N3—C2—N2	−0.66 (13)
N2—N1—C1—N3	−0.33 (14)	C1—N3—C2—C3	175.29 (10)
C2—N3—C1—N4	−179.72 (12)	N2—C2—C3—C2^i	−126.21 (12)
C2—N3—C1—N1	0.58 (13)	N3—C2—C3—C2^i	58.34 (9)
N1—N2—C2—N3	0.44 (13)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^ii	0.897 (18)	2.138 (18)	3.0129 (15)	164.6 (14)
N4—H4A···O2^ii	0.874 (18)	1.986 (18)	2.8430 (17)	166.3 (15)
N3—H3···O1^iii	0.866 (17)	2.044 (17)	2.8962 (15)	167.6 (14)
N3—H3···O3^iii	0.866 (17)	2.325 (16)	2.9819 (16)	132.7 (13)
N4—H4B···O3^iii	0.89 (2)	2.20 (2)	2.9777 (18)	146.2 (17)
N4—H4B···O2^iv	0.89 (2)	2.32 (2)	3.0068 (18)	134.3 (17)

Symmetry codes: (ii) x, y+1, z; (iii) x−1, y+1, z; (iv) x−1/2, −y+3/2, −z+1.