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The energetic ionic salt bis(1-aminoguanidin-2-ium) 5,5′-[1,2,4,5-tetrazine-3,6-diylbis(azanediyl)]bis(1
H-1,2,3,4-tetrazol-1-ide) dihydrate, 2CH
7N
4+·C
4H
2N
142−·2H
2O, (I), with a high nitrogen content, has been synthesized and examined by elemental analysis, Fourier transform IR spectrometry,
1H NMR spectroscopy and single-crystal X-ray crystallography. Compound (I) crystallizes in the monoclinic space group
P2
1/
c with two water molecules. However, the water molecules are disordered about an inversion centre and were modelled as half-occupancy molecules in the structure. The crystal structure reveals a three-dimensional network of molecules linked through N—H
N, N—H
O, O—H
N and O—H
O hydrogen bonds. Thermal decomposition was investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The exothermic peak temperature is 509.72 K, which indicates that hydrated salt (I) exhibits good thermal stability. Non-isothermal reaction kinetic parameters were calculated
via both the Kissinger and the Ozawa methods to yield activation energies of
Ek = 239.07 kJ mol
−1, lg
Ak = 22.79 s
−1 and
EO = 235.38 kJ mol
−1 for (I). Additionally, the thermal safety was evaluated by calculating critical temperatures and thermodynamic values,
viz. TSADT,
TTIT,
Tb, Δ
S≠, Δ
H≠ and Δ
G≠. The results reveal that (I) exhibits good thermal safety compared to other ion salts of 3,6-bis[(1
H-1,2,3,4-tetrazol-5-yl)amino]-1,2,4,5-tetrazine (BTATz).
Supporting information
CCDC reference: 1513078
Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
Bis[amino(hydrazinyl)methylidene]azanium
5,5'-[1,2,4,5-tetrazine-3,6-diylbis(azanediyl)]bis(1
H-1,2,3,4-tetrazol-1-ide) dihydrate
top
Crystal data top
2CH7N4+·C4H2N142−·2H2O | F(000) = 452 |
Mr = 432.44 | Dx = 1.670 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.231 (6) Å | Cell parameters from 618 reflections |
b = 3.919 (2) Å | θ = 2.9–21.9° |
c = 17.968 (9) Å | µ = 0.13 mm−1 |
β = 92.949 (9)° | T = 296 K |
V = 860.1 (8) Å3 | Block, red |
Z = 2 | 0.37 × 0.22 × 0.11 mm |
Data collection top
Bruker APEXII CCD diffractometer | 1028 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.064 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | θmax = 25.4°, θmin = 2.3° |
Tmin = 0.617, Tmax = 0.745 | h = −14→11 |
4049 measured reflections | k = −4→4 |
1572 independent reflections | l = −21→21 |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.057 | w = 1/[σ2(Fo2) + (0.0994P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.182 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.31 e Å−3 |
1572 reflections | Δρmin = −0.36 e Å−3 |
171 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
12 restraints | Extinction coefficient: 0.042 (9) |
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 | Occ. (<1) |
N1 | 0.7274 (2) | 0.2551 (9) | 0.35909 (15) | 0.0469 (8) | |
N2 | 0.7851 (2) | 0.4089 (9) | 0.30677 (15) | 0.0525 (9) | |
N3 | 0.7236 (2) | 0.4566 (8) | 0.24691 (15) | 0.0479 (8) | |
N4 | 0.6225 (2) | 0.3367 (8) | 0.25700 (14) | 0.0438 (8) | |
N5 | 0.5399 (2) | 0.0592 (8) | 0.35698 (14) | 0.0412 (8) | |
H5 | 0.494 (3) | −0.039 (10) | 0.329 (2) | 0.049* | |
N6 | 0.5876 (2) | 0.1925 (7) | 0.48181 (13) | 0.0370 (7) | |
N7 | 0.5644 (2) | 0.1620 (7) | 0.55235 (13) | 0.0366 (7) | |
N8 | 0.2560 (3) | 0.3882 (9) | 0.38392 (18) | 0.0484 (9) | |
H8A | 0.269 (3) | 0.284 (10) | 0.340 (2) | 0.058* | |
H8B | 0.309 (3) | 0.539 (11) | 0.396 (2) | 0.058* | |
N9 | 0.1003 (3) | 0.0876 (9) | 0.40739 (18) | 0.0506 (9) | |
H9A | 0.089 (3) | 0.028 (12) | 0.366 (2) | 0.061* | |
H9B | 0.048 (3) | 0.034 (11) | 0.442 (2) | 0.061* | |
N10 | 0.1906 (2) | 0.3792 (8) | 0.50133 (15) | 0.0437 (8) | |
H10 | 0.237 (3) | 0.503 (11) | 0.519 (2) | 0.052* | |
N11 | 0.1146 (3) | 0.2539 (10) | 0.55001 (17) | 0.0475 (9) | |
H11A | 0.151 (3) | 0.104 (11) | 0.580 (2) | 0.057* | |
H11B | 0.094 (3) | 0.414 (12) | 0.572 (2) | 0.057* | |
C1 | 0.6288 (3) | 0.2167 (8) | 0.32612 (16) | 0.0334 (8) | |
C2 | 0.5225 (2) | 0.0304 (8) | 0.43043 (16) | 0.0321 (8) | |
C3 | 0.1833 (3) | 0.2839 (9) | 0.43030 (18) | 0.0388 (8) | |
O1 | 0.9873 (7) | 0.731 (5) | 0.2850 (5) | 0.120 (5) | 0.55 (2) |
H1A | 0.9692 | 0.5451 | 0.2650 | 0.180* | 0.55 (2) |
H1B | 0.9328 | 0.8245 | 0.3043 | 0.180* | 0.55 (2) |
O1A | 1.0062 (15) | 0.990 (10) | 0.2515 (16) | 0.199 (9) | 0.45 (2) |
H1AA | 1.0644 | 0.8801 | 0.2441 | 0.298* | 0.45 (2) |
H1AB | 0.9586 | 0.8563 | 0.2316 | 0.298* | 0.45 (2) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0468 (16) | 0.066 (2) | 0.0277 (14) | −0.0106 (15) | −0.0019 (12) | 0.0068 (14) |
N2 | 0.0576 (18) | 0.071 (2) | 0.0294 (15) | −0.0139 (17) | 0.0019 (14) | 0.0014 (15) |
N3 | 0.0583 (19) | 0.057 (2) | 0.0283 (15) | −0.0043 (16) | 0.0031 (13) | 0.0058 (14) |
N4 | 0.0492 (17) | 0.058 (2) | 0.0235 (14) | 0.0035 (14) | −0.0006 (12) | 0.0050 (13) |
N5 | 0.0461 (17) | 0.058 (2) | 0.0194 (13) | −0.0133 (14) | −0.0038 (12) | −0.0027 (13) |
N6 | 0.0421 (15) | 0.0468 (18) | 0.0217 (13) | −0.0022 (13) | −0.0008 (11) | −0.0016 (12) |
N7 | 0.0429 (15) | 0.0461 (19) | 0.0207 (13) | −0.0036 (13) | −0.0003 (11) | −0.0021 (11) |
N8 | 0.0533 (18) | 0.056 (2) | 0.0357 (17) | −0.0074 (16) | 0.0043 (14) | −0.0084 (15) |
N9 | 0.0551 (19) | 0.060 (2) | 0.0357 (17) | −0.0124 (16) | −0.0067 (15) | −0.0096 (16) |
N10 | 0.0461 (17) | 0.053 (2) | 0.0312 (15) | −0.0108 (14) | −0.0022 (13) | −0.0048 (14) |
N11 | 0.0535 (19) | 0.053 (2) | 0.0356 (18) | −0.0047 (16) | 0.0017 (14) | −0.0006 (15) |
C1 | 0.0431 (18) | 0.0356 (19) | 0.0214 (15) | 0.0042 (14) | −0.0006 (13) | −0.0009 (13) |
C2 | 0.0354 (16) | 0.037 (2) | 0.0234 (15) | 0.0030 (14) | −0.0036 (12) | −0.0008 (13) |
C3 | 0.0447 (19) | 0.037 (2) | 0.0338 (18) | 0.0068 (16) | −0.0047 (15) | 0.0007 (15) |
O1 | 0.111 (6) | 0.132 (9) | 0.115 (7) | 0.011 (5) | −0.013 (4) | −0.014 (6) |
O1A | 0.203 (11) | 0.196 (13) | 0.196 (12) | −0.005 (9) | −0.002 (8) | −0.015 (9) |
Geometric parameters (Å, º) top
N1—N2 | 1.347 (4) | N9—H9A | 0.79 (4) |
N1—C1 | 1.324 (4) | N9—H9B | 0.93 (4) |
N2—N3 | 1.294 (4) | N9—C3 | 1.322 (5) |
N3—N4 | 1.344 (4) | N10—H10 | 0.80 (4) |
N4—C1 | 1.326 (4) | N10—N11 | 1.399 (4) |
N5—H5 | 0.83 (4) | N10—C3 | 1.328 (4) |
N5—C1 | 1.390 (4) | N11—H11A | 0.90 (4) |
N5—C2 | 1.352 (4) | N11—H11B | 0.79 (4) |
N6—N7 | 1.318 (3) | C2—N7i | 1.352 (4) |
N6—C2 | 1.347 (4) | O1—H1A | 0.8352 |
N7—C2i | 1.352 (4) | O1—H1B | 0.8500 |
N8—H8A | 0.90 (4) | O1A—H1AA | 0.8493 |
N8—H8B | 0.90 (4) | O1A—H1AB | 0.8500 |
N8—C3 | 1.315 (5) | | |
| | | |
C1—N1—N2 | 103.6 (3) | C3—N10—H10 | 125 (3) |
N3—N2—N1 | 110.0 (3) | C3—N10—N11 | 119.2 (3) |
N2—N3—N4 | 109.7 (3) | N10—N11—H11A | 106 (2) |
C1—N4—N3 | 103.9 (3) | N10—N11—H11B | 106 (3) |
C1—N5—H5 | 119 (2) | H11A—N11—H11B | 112 (4) |
C2—N5—H5 | 115 (2) | N1—C1—N4 | 112.8 (3) |
C2—N5—C1 | 126.3 (3) | N1—C1—N5 | 125.8 (3) |
N7—N6—C2 | 117.9 (3) | N4—C1—N5 | 121.4 (3) |
N6—N7—C2i | 118.8 (2) | N6—C2—N5 | 120.8 (3) |
H8A—N8—H8B | 111 (4) | N6—C2—N7i | 123.4 (3) |
C3—N8—H8A | 124 (2) | N7i—C2—N5 | 115.8 (3) |
C3—N8—H8B | 123 (3) | N8—C3—N9 | 121.1 (3) |
H9A—N9—H9B | 118 (4) | N8—C3—N10 | 120.5 (3) |
C3—N9—H9A | 124 (3) | N9—C3—N10 | 118.4 (3) |
C3—N9—H9B | 118 (3) | H1A—O1—H1B | 110.9 |
N11—N10—H10 | 116 (3) | H1AA—O1A—H1AB | 100.4 |
| | | |
N1—N2—N3—N4 | 0.1 (4) | N11—N10—C3—N8 | −177.6 (3) |
N2—N1—C1—N4 | 0.1 (4) | N11—N10—C3—N9 | 3.6 (5) |
N2—N1—C1—N5 | 177.9 (3) | C1—N1—N2—N3 | −0.1 (4) |
N2—N3—N4—C1 | 0.0 (4) | C1—N5—C2—N6 | 7.5 (5) |
N3—N4—C1—N1 | 0.0 (4) | C1—N5—C2—N7i | −173.9 (3) |
N3—N4—C1—N5 | −178.0 (3) | C2—N5—C1—N1 | 26.0 (6) |
N7—N6—C2—N5 | 178.1 (3) | C2—N5—C1—N4 | −156.4 (3) |
N7—N6—C2—N7i | −0.4 (5) | C2—N6—N7—C2i | 0.4 (5) |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N4ii | 0.83 (4) | 2.10 (4) | 2.912 (4) | 165 (4) |
N8—H8A···N3ii | 0.90 (4) | 2.03 (4) | 2.917 (5) | 166 (4) |
N8—H8B···N6iii | 0.90 (4) | 2.69 (4) | 3.421 (4) | 140 (3) |
N8—H8B···N7iii | 0.90 (4) | 2.12 (4) | 2.997 (5) | 168 (4) |
N9—H9A···O1iv | 0.79 (4) | 2.20 (5) | 2.897 (13) | 148 (4) |
N9—H9A···O1Aiv | 0.79 (4) | 2.24 (5) | 3.00 (2) | 159 (4) |
N9—H9B···N11v | 0.93 (4) | 2.30 (4) | 3.080 (5) | 141 (3) |
N10—H10···N1iii | 0.80 (4) | 2.40 (4) | 3.015 (4) | 135 (3) |
N10—H10···N6iii | 0.80 (4) | 2.46 (4) | 3.191 (4) | 153 (4) |
N11—H11A···N1i | 0.90 (4) | 2.28 (4) | 3.171 (5) | 168 (3) |
N11—H11B···N2iii | 0.79 (4) | 2.66 (4) | 3.091 (4) | 116 (3) |
O1—H1A···O1vi | 0.84 | 1.63 | 2.357 (11) | 144 |
O1A—H1AA···N2vii | 0.85 | 2.10 | 2.83 (2) | 143 |
O1A—H1AA···N3vii | 0.85 | 2.61 | 3.305 (19) | 140 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x−1, y−1, z; (v) −x, −y, −z+1; (vi) −x+2, y−1/2, −z+1/2; (vii) −x+2, y+1/2, −z+1/2. |
Kinetic parameters for the main exothermic decomposition process for
hydrated salt (I) top | Ek (kJ mol-1) | lgAk (s-1) | rk | EO (kJ mol-1) | rO | EeO (kJ mol-1) | Te0 (K) | Tp0 (K) |
(I) | 239.07 | 22.79 | 0.995519 | 235.38 | 0.995809 | 202.84 | 488.76 | 494.22 |
Thermal parameters of hydrated salt (I), GBT, BTATz and three ion salts of
BTATz top | TSADT (K) | TTIT (K) | Tb (K) | ΔS≠ (J mol-1 K-1) | ΔH≠ (kJ mol-1) | ΔG≠ (kJ mol-1) |
(I) | 488.76 | 531.74 | 503.17 | 178.85 | 234.96 | 146.57 |
GBTa | 531.61 | 540.41 | 542.62 | 228.19 | 279.37 | 157.56 |
DMABb | 576.87 | 589.49 | 601.93 | 111.54 | 241.12 | 175.36 |
PDABc | 511.90 | 522.92 | 524.66 | 65.61 | 186.15 | 152.52 |
BDABd | 521.55 | 531.62 | 536.73 | 62.36 | 189.05 | 156.36 |
BTATz | 559.28 | 572.76 | 585.30 | 131.83 | 244.24 | 167.57 |
Notes: BTATz as the (a) guanidinium salt;
(b) dimethylaminium salt;
(c) propane-1,3-diaminium salt;
(d) butane-1,4-diaminium salt. |
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