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A novel type of 4,4′,5,5′-tetranitro-1H,1′H-(2,2′-biimidazole)-1,1′-diamine (DATNBI)/TNT energetic cocrystal (cocrystal-1) was prepared by the solvent evaporation method. The molar ratio of the cocrystal is 1:2 and the crystal density is 1.784 g cm−3 at 23°C. It belongs to the triclinic system with space group P1. The thermal stability, mechanical sensitivity and detonation performance of cocrystal-1 were studied. Compared with DATNBI, the mechanical sensitivity (H50 and FS, friction sensitivity) and thermal stability (Td, detonation temperature) of cocrystal-1 were significantly improved (H50, FS and Td of DATNBI and cocrystal-1 are, respectively, 27.8 cm, 160 N, 240°C and 65.6 cm, >360 N, 253°C). Combining these results with other characterizations, it was found that cocrystal-1 exhibited a polymorphic transformation, phase separation and melting of the two single components in succession. The ability to control the properties and understand the structural stability of this explosive cocrystal is of great value.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S160057672300729X/jo5082sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S160057672300729X/jo5082Isup2.hkl |
 | Portable Document Format (PDF) file https://doi.org/10.1107/S160057672300729X/jo5082sup3.pdf |
CCDC reference: 2097129
Computing details top
Cell refinement: SAINT v8.34A (Bruker, 2013); data reduction: SAINT v8.34A (Bruker, 2013); program(s) used to solve structure: ShelXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).
(I) top
Crystal data top
| 2(C7H5N3O6)·C6H4N10O8 | Z = 1 |
| Mr = 798.47 | F(000) = 406 |
| Triclinic, P1 | Dx = 1.758 Mg m−3 |
| a = 4.9325 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 6.8773 (16) Å | Cell parameters from 957 reflections |
| c = 22.462 (5) Å | θ = 2.7–22.8° |
| α = 84.728 (4)° | µ = 0.16 mm−1 |
| β = 84.780 (4)° | T = 296 K |
| γ = 86.014 (4)° | Block |
| V = 754.1 (3) Å3 | 0.08 × 0.07 × 0.05 mm |
Data collection top
| CCD area detector diffractometer | Rint = 0.027 |
| Graphite monochromator | θmax = 25.0°, θmin = 0.9° |
| phi and ω scans | h = −5→5 |
| 3708 measured reflections | k = −7→8 |
| 2584 independent reflections | l = −25→26 |
| 1421 reflections with I > 2σ(I) |
Refinement top
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.078 | H-atom parameters constrained |
| wR(F2) = 0.287 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.95 | (Δ/σ)max < 0.001 |
| 2584 reflections | Δρmax = 0.42 e Å−3 |
| 255 parameters | Δρmin = −0.55 e Å−3 |
| 0 restraints |
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 | ||
| O1 | 0.4867 (12) | 0.3804 (8) | 0.7184 (2) | 0.0880 (16) | |
| O2 | 0.8664 (10) | 0.2163 (7) | 0.70182 (19) | 0.0767 (14) | |
| O3 | 1.0615 (10) | −0.3814 (7) | 0.8234 (2) | 0.0757 (13) | |
| O4 | 0.7044 (11) | −0.5283 (7) | 0.8573 (3) | 0.0976 (18) | |
| O5 | −0.0737 (9) | −0.0016 (8) | 0.93521 (19) | 0.0743 (14) | |
| O6 | 0.1471 (10) | 0.2561 (7) | 0.9400 (2) | 0.0785 (15) | |
| N1 | 0.6507 (11) | 0.2451 (8) | 0.7302 (2) | 0.0583 (13) | |
| N2 | 0.8186 (11) | −0.3812 (7) | 0.8398 (2) | 0.0548 (13) | |
| N3 | 0.1171 (9) | 0.1013 (8) | 0.92007 (19) | 0.0516 (12) | |
| C1 | 0.5806 (11) | 0.1098 (8) | 0.7824 (2) | 0.0442 (13) | |
| C2 | 0.7260 (11) | −0.0683 (8) | 0.7878 (2) | 0.0450 (13) | |
| H2 | 0.8649 | −0.1024 | 0.7591 | 0.054* | |
| C3 | 0.6575 (11) | −0.1944 (7) | 0.8376 (2) | 0.0457 (13) | |
| C4 | 0.4605 (11) | −0.1510 (8) | 0.8839 (2) | 0.0444 (13) | |
| C5 | 0.3250 (10) | 0.0327 (7) | 0.8743 (2) | 0.0395 (12) | |
| C6 | 0.3765 (11) | 0.1629 (8) | 0.8248 (2) | 0.0443 (13) | |
| H6 | 0.2769 | 0.2824 | 0.8202 | 0.053* | |
| C7 | 0.4122 (14) | −0.2809 (9) | 0.9409 (3) | 0.0645 (17) | |
| H7B | 0.3574 | −0.2019 | 0.9735 | 0.097* | |
| H7C | 0.5772 | −0.3572 | 0.9490 | 0.097* | |
| H7A | 0.2710 | −0.3667 | 0.9365 | 0.097* | |
| O7 | −0.0013 (9) | 0.6714 (7) | 0.67500 (18) | 0.0662 (13) | |
| O8 | 0.3340 (9) | 0.8331 (7) | 0.69490 (19) | 0.0715 (14) | |
| O9 | 0.5305 (9) | 1.1062 (6) | 0.6074 (2) | 0.0714 (13) | |
| O10 | 0.9196 (9) | 1.0006 (6) | 0.5666 (2) | 0.0652 (12) | |
| N4 | 0.6441 (9) | 0.7203 (6) | 0.52182 (18) | 0.0438 (11) | |
| N5 | 0.6822 (10) | 0.9839 (7) | 0.58313 (19) | 0.0483 (11) | |
| N6 | 0.2219 (10) | 0.7383 (7) | 0.66226 (19) | 0.0487 (12) | |
| N7 | 0.3104 (8) | 0.5550 (6) | 0.57257 (17) | 0.0385 (10) | |
| N8 | 0.0949 (8) | 0.4306 (7) | 0.58389 (19) | 0.0471 (12) | |
| H8A | 0.1411 | 0.3212 | 0.5683 | 0.057* | |
| H8B | 0.0572 | 0.4061 | 0.6222 | 0.057* | |
| C8 | 0.3609 (10) | 0.7059 (7) | 0.6053 (2) | 0.0405 (12) | |
| C9 | 0.5637 (10) | 0.8037 (7) | 0.5724 (2) | 0.0386 (12) | |
| C10 | 0.4885 (10) | 0.5670 (8) | 0.5228 (2) | 0.0415 (12) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.104 (4) | 0.081 (3) | 0.068 (3) | 0.015 (3) | 0.013 (3) | 0.017 (3) |
| O2 | 0.072 (3) | 0.094 (4) | 0.058 (3) | −0.010 (3) | 0.023 (2) | 0.005 (2) |
| O3 | 0.065 (3) | 0.070 (3) | 0.088 (3) | 0.016 (2) | 0.002 (2) | −0.011 (2) |
| O4 | 0.084 (4) | 0.047 (3) | 0.164 (6) | −0.008 (3) | −0.018 (4) | −0.007 (3) |
| O5 | 0.049 (2) | 0.114 (4) | 0.062 (3) | −0.029 (3) | 0.013 (2) | −0.021 (2) |
| O6 | 0.091 (3) | 0.068 (3) | 0.074 (3) | −0.008 (3) | 0.027 (3) | −0.029 (2) |
| N1 | 0.065 (3) | 0.063 (3) | 0.043 (3) | −0.003 (3) | 0.011 (2) | 0.000 (2) |
| N2 | 0.054 (3) | 0.045 (3) | 0.067 (3) | 0.000 (2) | −0.010 (3) | −0.009 (2) |
| N3 | 0.043 (3) | 0.075 (3) | 0.036 (2) | −0.006 (2) | 0.008 (2) | −0.010 (2) |
| C1 | 0.046 (3) | 0.053 (3) | 0.034 (3) | −0.007 (2) | 0.001 (2) | −0.005 (2) |
| C2 | 0.046 (3) | 0.050 (3) | 0.040 (3) | −0.003 (2) | 0.001 (2) | −0.014 (2) |
| C3 | 0.048 (3) | 0.040 (3) | 0.051 (3) | −0.002 (2) | −0.008 (2) | −0.011 (2) |
| C4 | 0.043 (3) | 0.054 (3) | 0.038 (3) | −0.015 (2) | −0.002 (2) | −0.007 (2) |
| C5 | 0.034 (3) | 0.044 (3) | 0.041 (3) | −0.006 (2) | 0.004 (2) | −0.008 (2) |
| C6 | 0.043 (3) | 0.045 (3) | 0.044 (3) | −0.003 (2) | 0.003 (2) | −0.007 (2) |
| C7 | 0.077 (4) | 0.057 (4) | 0.058 (4) | −0.018 (3) | −0.007 (3) | 0.015 (3) |
| O7 | 0.059 (3) | 0.084 (3) | 0.056 (2) | −0.019 (2) | 0.023 (2) | −0.021 (2) |
| O8 | 0.069 (3) | 0.100 (4) | 0.051 (2) | −0.009 (3) | 0.000 (2) | −0.034 (2) |
| O9 | 0.069 (3) | 0.058 (3) | 0.092 (3) | 0.006 (2) | −0.014 (2) | −0.032 (2) |
| O10 | 0.055 (3) | 0.068 (3) | 0.074 (3) | −0.020 (2) | 0.008 (2) | −0.014 (2) |
| N4 | 0.043 (2) | 0.049 (3) | 0.040 (2) | −0.009 (2) | 0.0047 (19) | −0.0079 (19) |
| N5 | 0.055 (3) | 0.047 (3) | 0.043 (2) | −0.003 (2) | −0.005 (2) | −0.005 (2) |
| N6 | 0.048 (3) | 0.063 (3) | 0.035 (2) | 0.004 (2) | 0.005 (2) | −0.013 (2) |
| N7 | 0.037 (2) | 0.042 (2) | 0.035 (2) | −0.0032 (18) | 0.0062 (17) | −0.0023 (17) |
| N8 | 0.043 (3) | 0.052 (3) | 0.045 (3) | −0.011 (2) | 0.014 (2) | −0.010 (2) |
| C8 | 0.039 (3) | 0.049 (3) | 0.034 (3) | 0.002 (2) | 0.002 (2) | −0.014 (2) |
| C9 | 0.040 (3) | 0.035 (3) | 0.041 (3) | −0.003 (2) | 0.001 (2) | −0.008 (2) |
| C10 | 0.038 (3) | 0.049 (3) | 0.037 (3) | −0.005 (2) | 0.005 (2) | −0.006 (2) |
Geometric parameters (Å, º) top
| O1—N1 | 1.216 (7) | C7—H7B | 0.9600 |
| O2—N1 | 1.204 (6) | C7—H7C | 0.9600 |
| O3—N2 | 1.221 (6) | C7—H7A | 0.9600 |
| O4—N2 | 1.208 (6) | O7—N6 | 1.222 (6) |
| O5—N3 | 1.221 (5) | O8—N6 | 1.216 (6) |
| O6—N3 | 1.216 (6) | O9—N5 | 1.220 (6) |
| N1—C1 | 1.460 (7) | O10—N5 | 1.206 (6) |
| N2—C3 | 1.462 (7) | N4—C9 | 1.334 (6) |
| N3—C5 | 1.471 (6) | N4—C10 | 1.344 (6) |
| C1—C2 | 1.377 (8) | N5—C9 | 1.456 (6) |
| C1—C6 | 1.376 (7) | N6—C8 | 1.425 (6) |
| C2—H2 | 0.9300 | N7—N8 | 1.401 (5) |
| C2—C3 | 1.382 (8) | N7—C8 | 1.374 (6) |
| C3—C4 | 1.396 (7) | N7—C10 | 1.358 (6) |
| C4—C5 | 1.396 (8) | N8—H8A | 0.8664 |
| C4—C7 | 1.502 (8) | N8—H8B | 0.8666 |
| C5—C6 | 1.378 (7) | C8—C9 | 1.366 (6) |
| C6—H6 | 0.9300 | C10—C10i | 1.431 (10) |
| O1—N1—C1 | 117.6 (5) | C4—C7—H7C | 109.5 |
| O2—N1—O1 | 124.3 (5) | C4—C7—H7A | 109.5 |
| O2—N1—C1 | 118.2 (6) | H7B—C7—H7C | 109.5 |
| O3—N2—C3 | 118.4 (5) | H7B—C7—H7A | 109.5 |
| O4—N2—O3 | 123.1 (5) | H7C—C7—H7A | 109.5 |
| O4—N2—C3 | 118.4 (5) | C9—N4—C10 | 105.0 (4) |
| O5—N3—C5 | 117.5 (5) | O9—N5—C9 | 116.8 (5) |
| O6—N3—O5 | 124.8 (5) | O10—N5—O9 | 125.8 (5) |
| O6—N3—C5 | 117.8 (4) | O10—N5—C9 | 117.4 (5) |
| C2—C1—N1 | 118.1 (5) | O7—N6—C8 | 118.4 (4) |
| C6—C1—N1 | 119.9 (5) | O8—N6—O7 | 124.4 (4) |
| C6—C1—C2 | 121.9 (5) | O8—N6—C8 | 117.2 (4) |
| C1—C2—H2 | 121.3 | C8—N7—N8 | 126.9 (4) |
| C1—C2—C3 | 117.4 (5) | C10—N7—N8 | 126.4 (4) |
| C3—C2—H2 | 121.3 | C10—N7—C8 | 106.2 (4) |
| C2—C3—N2 | 114.2 (5) | N7—N8—H8A | 109.4 |
| C2—C3—C4 | 124.8 (5) | N7—N8—H8B | 110.5 |
| C4—C3—N2 | 121.0 (5) | H8A—N8—H8B | 108.6 |
| C3—C4—C5 | 113.4 (5) | N7—C8—N6 | 123.3 (4) |
| C3—C4—C7 | 123.8 (6) | C9—C8—N6 | 130.8 (4) |
| C5—C4—C7 | 122.7 (5) | C9—C8—N7 | 105.8 (4) |
| C4—C5—N3 | 119.6 (5) | N4—C9—N5 | 118.8 (4) |
| C6—C5—N3 | 115.5 (5) | N4—C9—C8 | 111.5 (4) |
| C6—C5—C4 | 124.8 (5) | C8—C9—N5 | 129.5 (4) |
| C1—C6—C5 | 117.6 (5) | N4—C10—N7 | 111.4 (4) |
| C1—C6—H6 | 121.2 | N4—C10—C10i | 123.9 (5) |
| C5—C6—H6 | 121.2 | N7—C10—C10i | 124.7 (5) |
| C4—C7—H7B | 109.5 |
| Symmetry code: (i) −x+1, −y+1, −z+1. |
