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access(5Z,7Z)-6,8-Dimethyl-9H-tetrazolo[1,5-b][1,2,4]triazepine
aState Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, People's Republic of China
*Correspondence e-mail: duzhiming430@sohu.com
The molecule of the title compound, C6H8N6, is approximately planar, with a maximum deviation from planarity of 0.099 (1) Å. In the crystal, molecules are linked to each other via pairs of N—H⋯N hydrogen bonding, forming inversion dimers. The is further stabilized by π–π stacking interactions, with a centroid–centroid distance of 3.419 (1) Å.
Related literature
For the preparation of the title compound, see: Gaponnik & Karavai (1984![[Gaponnik, P. N. & Karavai, V. P. (1984). Khim. Geterotsikl. Soedin. 12, 1683-1686.]](../../../../../../logos/arrows/e_arr.gif "Gaponnik, P. N. & Karavai, V. P. (1984). Khim. Geterotsikl. Soedin. 12, 1683-1686.")
). For applications of fused tetrazole ring compounds, see: Taha 2007; Zbigniew et al. (2007); Galvez-Ruiz et al. (2005); Klapötke & Sabaté (2008). For related structures, see: Taha (2005); He et al. (2009a,b).
![[Scheme 1]](wn2354scheme1.gif)
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear; data reduction: CrystalClear ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S160053680904392X/wn2354sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680904392X/wn2354Isup2.hkl
The title compound was obtained according to the literature method (Gaponnik & Karavai, 1984). The purity of the compound was checked by determining its melting point, 477–479 K. Single crystals suitable for X-ray determination were obtained by slow evaporation of an acetone solution at room temperature over two days.
The H atom directly attached to the triazepine ring and that bonded to N were located in difference Fourier maps and refined freely. Methyl H atoms were placed in calculated positions, with C—H = 0.98 Å and refined as riding; Uiso(H) = 1.2Ueq(C).
Compounds based on the tetrazole ring have generated much interest (Taha 2005). On the one hand, fused tetrazole derivatives play an important role in many biological activities (Taha 2007; Zbigniew et al.,2007); on the other hand, nitrogen-rich compounds, in particular those containing the tetrazole ring, have great potential for energetic applications (Klapötke & Sabaté 2008); Galvez-Ruiz et al.2005). The title compound was first prepared by Gaponnik & Karavai (1984), but its has hitherto not been reported. Here, we present the of the title compound.
The molecular structure is shown in Fig.1. The molecule of the title compound assumes an approximately planar structure. The maximum deviation from planarity is 0.099 (1) Å for atom C3. Bond distances and angles are similar to the corresponding distances and angles reported for related compounds (He et al.2009a; He et al.2009b).
In the molecules are linked to each other via N—H···N hydrogen bonding (Table 1), forming a dimer structure. Intermolecular π-π interactions with a centroid···centroid distance of 3.419 (1) Å (Table 2), further help to stabilize the The crystal packing of the title compound is shown in Fig. 2, viewed down the a axis.
For the preparation of the title compound, see: Gaponnik & Karavai (1984). For applications of fused tetrazole ring compounds, see: Taha 2007; Zbigniew et al. (2007); Galvez-Ruiz et al. (2005); Klapötke & Sabaté (2008). For related structures, see: Taha (2005); He et al. (2009a,b).
Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./wn2354fig1thm.gif) | Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as spheres of arbitrary radius. |
![[Figure 2]](./wn2354fig2thm.gif) | Fig. 2. The packing of the title compound, viewed along the a-axis, showing the formation of dimers via N—H···N hydrogen bonds (dashed lines). |
| C6H8N6 | F(000) = 344 |
| Mr = 164.18 | Dx = 1.497 Mg m−3 |
| Monoclinic, P21/c | Melting point: 477 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 3.9184 (8) Å | Cell parameters from 2263 reflections |
| b = 13.584 (3) Å | θ = 3.3–27.5° |
| c = 13.767 (3) Å | µ = 0.11 mm−1 |
| β = 96.274 (3)° | T = 93 K |
| V = 728.4 (3) Å3 | Chunk, red |
| Z = 4 | 0.47 × 0.33 × 0.13 mm |
| Rigaku Saturn 724+ diffractometer | 1445 reflections with I > 2σ(I) |
| Radiation source: Rotating Anode | Rint = 0.019 |
| Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
| Detector resolution: 28.5714 pixels mm-1 | h = −4→5 |
| multi–scan | k = −17→17 |
| 5029 measured reflections | l = −11→17 |
| 1647 independent reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.031P)2 + 0.36P] where P = (Fo2 + 2Fc2)/3 |
| 1647 reflections | (Δ/σ)max < 0.001 |
| 119 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.22 e Å−3 |
| C6H8N6 | V = 728.4 (3) Å3 |
| Mr = 164.18 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 3.9184 (8) Å | µ = 0.11 mm−1 |
| b = 13.584 (3) Å | T = 93 K |
| c = 13.767 (3) Å | 0.47 × 0.33 × 0.13 mm |
| β = 96.274 (3)° |
| Rigaku Saturn 724+ diffractometer | 1445 reflections with I > 2σ(I) |
| 5029 measured reflections | Rint = 0.019 |
| 1647 independent reflections |
| R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
| wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | Δρmax = 0.26 e Å−3 |
| 1647 reflections | Δρmin = −0.22 e Å−3 |
| 119 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.4467 (3) | 0.24707 (7) | 0.45448 (7) | 0.0165 (2) | |
| N2 | 0.5870 (3) | 0.24983 (8) | 0.36816 (7) | 0.0208 (2) | |
| N3 | 0.6547 (3) | 0.16030 (8) | 0.34635 (8) | 0.0223 (3) | |
| N4 | 0.5650 (3) | 0.09674 (8) | 0.41698 (7) | 0.0195 (2) | |
| N5 | 0.3238 (3) | 0.11503 (8) | 0.56546 (8) | 0.0207 (3) | |
| N6 | 0.3868 (3) | 0.34046 (7) | 0.49433 (7) | 0.0176 (2) | |
| C1 | 0.4389 (3) | 0.15238 (9) | 0.48318 (8) | 0.0163 (3) | |
| C2 | 0.1660 (3) | 0.16746 (9) | 0.63408 (8) | 0.0165 (3) | |
| C3 | 0.1175 (3) | 0.26544 (9) | 0.63462 (9) | 0.0180 (3) | |
| C4 | 0.2395 (3) | 0.34313 (9) | 0.57359 (9) | 0.0165 (3) | |
| C5 | 0.0598 (3) | 0.10241 (9) | 0.71313 (9) | 0.0202 (3) | |
| H5A | 0.2595 | 0.0819 | 0.7548 | 0.024* | |
| H5B | −0.0569 | 0.0456 | 0.6844 | 0.024* | |
| H5C | −0.0914 | 0.1380 | 0.7509 | 0.024* | |
| C6 | 0.1945 (3) | 0.44529 (9) | 0.61191 (9) | 0.0206 (3) | |
| H6A | 0.2920 | 0.4920 | 0.5705 | 0.025* | |
| H6B | 0.3084 | 0.4503 | 0.6771 | 0.025* | |
| H6C | −0.0457 | 0.4588 | 0.6126 | 0.025* | |
| H3 | 0.006 (4) | 0.2905 (11) | 0.6876 (11) | 0.025 (4)* | |
| H5N | 0.342 (4) | 0.0478 (14) | 0.5724 (12) | 0.036 (5)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0214 (5) | 0.0138 (5) | 0.0148 (5) | 0.0006 (4) | 0.0043 (4) | 0.0002 (4) |
| N2 | 0.0285 (6) | 0.0182 (5) | 0.0167 (5) | 0.0010 (4) | 0.0074 (4) | 0.0004 (4) |
| N3 | 0.0309 (6) | 0.0180 (5) | 0.0191 (5) | 0.0013 (5) | 0.0078 (4) | 0.0014 (4) |
| N4 | 0.0261 (6) | 0.0167 (5) | 0.0166 (5) | 0.0007 (4) | 0.0062 (4) | 0.0005 (4) |
| N5 | 0.0315 (6) | 0.0130 (5) | 0.0193 (5) | 0.0016 (4) | 0.0106 (5) | 0.0019 (4) |
| N6 | 0.0230 (5) | 0.0110 (5) | 0.0189 (5) | 0.0009 (4) | 0.0030 (4) | −0.0018 (4) |
| C1 | 0.0177 (6) | 0.0151 (6) | 0.0161 (6) | 0.0000 (5) | 0.0013 (4) | 0.0005 (4) |
| C2 | 0.0174 (6) | 0.0168 (6) | 0.0153 (5) | −0.0009 (5) | 0.0021 (4) | −0.0007 (4) |
| C3 | 0.0196 (6) | 0.0181 (6) | 0.0168 (6) | 0.0000 (5) | 0.0050 (5) | −0.0007 (5) |
| C4 | 0.0163 (6) | 0.0147 (6) | 0.0181 (6) | 0.0004 (4) | −0.0002 (5) | −0.0002 (4) |
| C5 | 0.0240 (6) | 0.0174 (6) | 0.0202 (6) | −0.0003 (5) | 0.0072 (5) | 0.0024 (5) |
| C6 | 0.0246 (6) | 0.0155 (6) | 0.0224 (6) | 0.0011 (5) | 0.0055 (5) | −0.0020 (5) |
| N1—C1 | 1.3469 (15) | C2—C3 | 1.3446 (17) |
| N1—N2 | 1.3635 (14) | C2—C5 | 1.4958 (16) |
| N1—N6 | 1.4119 (14) | C3—C4 | 1.4615 (17) |
| N2—N3 | 1.2874 (15) | C3—H3 | 0.953 (15) |
| N3—N4 | 1.3745 (14) | C4—C6 | 1.5018 (16) |
| N4—C1 | 1.3207 (15) | C5—H5A | 0.9600 |
| N5—C1 | 1.3623 (15) | C5—H5B | 0.9600 |
| N5—C2 | 1.3820 (15) | C5—H5C | 0.9600 |
| N5—H5N | 0.920 (18) | C6—H6A | 0.9600 |
| N6—C4 | 1.2897 (16) | C6—H6B | 0.9600 |
| C1—N1—N2 | 107.83 (10) | C2—C3—H3 | 115.8 (9) |
| C1—N1—N6 | 137.23 (10) | C4—C3—H3 | 112.8 (9) |
| N2—N1—N6 | 114.45 (9) | N6—C4—C3 | 132.13 (11) |
| N3—N2—N1 | 106.88 (10) | N6—C4—C6 | 113.82 (10) |
| N2—N3—N4 | 110.69 (10) | C3—C4—C6 | 114.02 (11) |
| C1—N4—N3 | 105.82 (10) | C2—C5—H5A | 109.5 |
| C1—N5—C2 | 126.17 (11) | C2—C5—H5B | 109.5 |
| C1—N5—H5N | 115.3 (10) | H5A—C5—H5B | 109.5 |
| C2—N5—H5N | 118.4 (10) | C2—C5—H5C | 109.5 |
| C4—N6—N1 | 117.58 (10) | H5A—C5—H5C | 109.5 |
| N4—C1—N1 | 108.78 (10) | H5B—C5—H5C | 109.5 |
| N4—C1—N5 | 122.92 (11) | C4—C6—H6A | 109.5 |
| N1—C1—N5 | 128.29 (11) | C4—C6—H6B | 109.5 |
| C3—C2—N5 | 126.01 (11) | H6A—C6—H6B | 109.5 |
| C3—C2—C5 | 122.01 (11) | C4—C6—H6C | 109.5 |
| N5—C2—C5 | 111.95 (11) | H6A—C6—H6C | 109.5 |
| C2—C3—C4 | 131.03 (12) | H6B—C6—H6C | 109.5 |
| C1—N1—N2—N3 | 0.80 (13) | N6—N1—C1—N5 | 8.2 (2) |
| N6—N1—N2—N3 | 174.17 (10) | C2—N5—C1—N4 | −174.90 (12) |
| N1—N2—N3—N4 | −0.47 (14) | C2—N5—C1—N1 | 5.0 (2) |
| N2—N3—N4—C1 | −0.04 (14) | C1—N5—C2—C3 | −4.3 (2) |
| C1—N1—N6—C4 | −12.5 (2) | C1—N5—C2—C5 | 177.67 (12) |
| N2—N1—N6—C4 | 176.81 (10) | N5—C2—C3—C4 | −7.1 (2) |
| N3—N4—C1—N1 | 0.55 (13) | C5—C2—C3—C4 | 170.75 (12) |
| N3—N4—C1—N5 | −179.54 (11) | N1—N6—C4—C3 | 0.64 (19) |
| N2—N1—C1—N4 | −0.84 (14) | N1—N6—C4—C6 | 178.52 (10) |
| N6—N1—C1—N4 | −171.93 (13) | C2—C3—C4—N6 | 10.9 (2) |
| N2—N1—C1—N5 | 179.24 (12) | C2—C3—C4—C6 | −167.02 (13) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5N···N4i | 0.920 (19) | 1.999 (19) | 2.9156 (17) | 173.5 (15) |
| Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C6H8N6 |
| Mr | 164.18 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 93 |
| a, b, c (Å) | 3.9184 (8), 13.584 (3), 13.767 (3) |
| β (°) | 96.274 (3) |
| V (Å3) | 728.4 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.11 |
| Crystal size (mm) | 0.47 × 0.33 × 0.13 |
| Data collection | |
| Diffractometer | Rigaku Saturn 724+ |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5029, 1647, 1445 |
| Rint | 0.019 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.082, 1.00 |
| No. of reflections | 1647 |
| No. of parameters | 119 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.26, −0.22 |
Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5N···N4i | 0.920 (19) | 1.999 (19) | 2.9156 (17) | 173.5 (15) |
| Symmetry code: (i) −x+1, −y, −z+1. |
| Cgi | Cgj | Cgi···Cgj | α | Cgi_perp | Cgj_perp |
| Cg1 | Cg2i | 3.419 (1) | 2.83 | 3.384 | 3.390 |
| Symmetry code:(i)1+x, y, z; Cg1, Cg2 are the centroids of the five- and seven-membered rings, respectively. α is the dihedral angle between ring planes and Cgi_perp is the perpendicular distance of Cgi on ring j, Cgj_perp is the perpendicular distance of Cgj on ring i. |
Acknowledgements
This work was supported financially by the State Key Laboratory of Explosion Science and Technology of the Beijing Institute of Technology, China (No. ZDKT08–01).
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Compounds based on the tetrazole ring have generated much interest (Taha 2005). On the one hand, fused tetrazole derivatives play an important role in many biological activities (Taha 2007; Zbigniew et al.,2007); on the other hand, nitrogen-rich compounds, in particular those containing the tetrazole ring, have great potential for energetic applications (Klapötke & Sabaté 2008); Galvez-Ruiz et al.2005). The title compound was first prepared by Gaponnik & Karavai (1984), but its crystal structure has hitherto not been reported. Here, we present the crystal structure of the title compound.
The molecular structure is shown in Fig.1. The molecule of the title compound assumes an approximately planar structure. The maximum deviation from planarity is 0.099 (1) Å for atom C3. Bond distances and angles are similar to the corresponding distances and angles reported for related compounds (He et al.2009a; He et al.2009b).
In the crystal structure, molecules are linked to each other via N—H···N hydrogen bonding (Table 1), forming a dimer structure. Intermolecular π-π interactions with a centroid···centroid distance of 3.419 (1) Å (Table 2), further help to stabilize the crystal structure. The crystal packing of the title compound is shown in Fig. 2, viewed down the a axis.