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 (Cp,m) of BATZM·(NO3)2 was determined using the continuous Cp mode of a microcalorimeter and theoretical calculations, and the Cp,m value is 366.14 J K−1 mol−1 at 298.15 K. The relative deviations between the theoretical and experimental values of Cp,m, HT – H298.15K and ST – S298.15K 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.
Supporting information
CCDC reference: 1060498
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
top
Crystal data top
C5H10N82+·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) Å3 | Rodlike, colourless |
Z = 4 | 0.37 × 0.32 × 0.27 mm |
F(000) = 632 | |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | All H-atom parameters refined |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.2645P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0093 (17) |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—H3Ai | 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) | C2i—C3—C2 | 115.80 (14) |
C1—N1—N2 | 111.57 (10) | C2i—C3—H3A | 108.9 (8) |
C1—N1—H1 | 125.1 (10) | C2—C3—H3A | 106.7 (8) |
N2—N1—H1 | 123.3 (10) | C2i—C3—H3Ai | 106.7 (8) |
O3—N5—O2 | 120.22 (12) | C2—C3—H3Ai | 108.9 (8) |
O3—N5—O1 | 119.86 (11) | H3A—C3—H3Ai | 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—C2i | −126.21 (12) |
C2—N3—C1—N1 | 0.58 (13) | N3—C2—C3—C2i | 58.34 (9) |
N1—N2—C2—N3 | 0.44 (13) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1ii | 0.897 (18) | 2.138 (18) | 3.0129 (15) | 164.6 (14) |
N4—H4A···O2ii | 0.874 (18) | 1.986 (18) | 2.8430 (17) | 166.3 (15) |
N3—H3···O1iii | 0.866 (17) | 2.044 (17) | 2.8962 (15) | 167.6 (14) |
N3—H3···O3iii | 0.866 (17) | 2.325 (16) | 2.9819 (16) | 132.7 (13) |
N4—H4B···O3iii | 0.89 (2) | 2.20 (2) | 2.9777 (18) | 146.2 (17) |
N4—H4B···O2iv | 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. |
Thermodynamic properties of BATZM·(NO3)2 at a pressure of 101.3 kPa topT (K) | Cp,m (J K-1 mol-1) | | RD | HT–H298.15K (kJ mol-1) | | RD | ST–S298.15K (J K-1 mol-1) | | RD |
| Exp | Calc | | Exp | Calc | | Exp | Calc | |
288.15 | 354.99 | 310.74 | 12.47 | -3.61 | -3.15 | 12.76 | -12.31 | -10.74 | 12.72 |
293.15 | 360.87 | 314.80 | 12.77 | -1.82 | -1.58 | 12.87 | -6.15 | -5.36 | 12.83 |
298.15 | 366.14 | 318.84 | 12.92 | – | – | – | – | – | – |
303.15 | 370.93 | 322.86 | 12.96 | 1.84 | 1.60 | 12.97 | 6.13 | 5.34 | 12.92 |
308.15 | 375.34 | 326.85 | 12.92 | 3.71 | 3.23 | 12.97 | 12.23 | 10.65 | 12.93 |
313.15 | 379.49 | 330.82 | 12.83 | 5.60 | 4.87 | 12.94 | 18.31 | 15.95 | 12.91 |
318.15 | 383.50 | 334.76 | 12.71 | 7.50 | 6.54 | 12.90 | 24.35 | 21.22 | 12.87 |
323.15 | 387.46 | 338.68 | 12.59 | 9.43 | 8.22 | 12.84 | 30.36 | 26.47 | 12.83 |
328.15 | 391.51 | 342.58 | 12.50 | 11.38 | 9.92 | 12.78 | 36.34 | 31.69 | 12.79 |
333.15 | 395.75 | 346.45 | 12.46 | 13.35 | 11.65 | 12.72 | 42.30 | 36.90 | 12.76 |
338.15 | 400.29 | 350.30 | 12.49 | 15.34 | 13.39 | 12.67 | 48.22 | 42.08 | 12.74 |
343.15 | 405.26 | 354.12 | 12.62 | 17.35 | 15.16 | 12.64 | 54.14 | 47.24 | 12.73 |
348.15 | 410.75 | 357.93 | 12.86 | 19.39 | 16.94 | 12.62 | 60.04 | 52.38 | 12.75 |
Notes: `Exp' is the result of an experimental determination; `Calc' is the
result of a theoretical calculation; RD = 102(XExp –
XCalc)/XExp; HT–H298.15K is the enthalpy
change of taking 298.15 K as the benchmark; ST–S298.15K is
the entropy change of taking 298.15 K as the benchmark. |
Nitrogen equivalents of different detonation products topDetonation product | C | H2 | N2 | CO | CO2 |
Nitrogen equivalent index | 0.15 | 0.29 | 1 | 0.78 | 1.35 |