Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010001622X/av1058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010001622X/av1058Isup2.hkl |
CCDC reference: 159997
For related literature, see: Bryden (1955); Colapietro et al. (1982); Desenko et al. (1990); Foces-Foces, Cano, Claramunt, Sanz, Catalan, Fabero, Fruchier & Elguero (1990); Gao et al. (1991); Gaponik & Karavai (1984); International (1992); Krutikov et al. (1991); Levchik et al. (1993); Ohno et al. (1998); Sinditskii & Fogelzang (1997); Willer & Henry (1988).
The title compound was prepared by a previously described method (Gaponik & Karavai, 1984). Trimethylsilyl azide was used as the azidation agent instead of a mixture of sodium azide and ammonium chloride. This increases the yield of (I) from 60 to 80%. Single crystals were grown by slow crystallization from aqueous solution.
H atom positions were found from the ΔF map and all associated parameters were refined freely.
Data collection: Nicolet R3m Software (Nicolet, 1980); cell refinement: Nicolet R3m Software; data reduction: Nicolet R3m Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III for Windows (Farrugia, 1997); software used to prepare material for publication: SHELX97.
Fig. 1. The molecular structure of (I) with the atom-numbering scheme (non-H atom displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. Packing diagram of (I). |
CH4N6 | F(000) = 208 |
Mr = 100.10 | Dx = 1.571 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 6.780 (1) Å | Cell parameters from 25 reflections |
b = 6.112 (1) Å | θ = 21.0–23.7° |
c = 10.694 (2) Å | µ = 0.12 mm−1 |
β = 107.25 (1)° | T = 293 K |
V = 423.2 (1) Å3 | Prism, colourless |
Z = 4 | 0.56 × 0.48 × 0.26 mm |
Nicolet R3m four-circle diffractometer | Rint = 0.020 |
Radiation source: fine-focus sealed tube | θmax = 30.1°, θmin = 3.2° |
Graphite monochromator | h = 0→9 |
ω/2θ scans | k = 0→8 |
1378 measured reflections | l = −15→14 |
1239 independent reflections | 3 standard reflections every 100 reflections |
1069 reflections with I > 2σ(I) | intensity decay: 3.5% |
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)] = 0.041 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.132 | All H-atom parameters refined |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0884P)2 + 0.0322P] where P = (Fo2 + 2Fc2)/3 |
1239 reflections | (Δ/σ)max = 0.001 |
80 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
CH4N6 | V = 423.2 (1) Å3 |
Mr = 100.10 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.780 (1) Å | µ = 0.12 mm−1 |
b = 6.112 (1) Å | T = 293 K |
c = 10.694 (2) Å | 0.56 × 0.48 × 0.26 mm |
β = 107.25 (1)° |
Nicolet R3m four-circle diffractometer | Rint = 0.020 |
1378 measured reflections | 3 standard reflections every 100 reflections |
1239 independent reflections | intensity decay: 3.5% |
1069 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.132 | All H-atom parameters refined |
S = 1.08 | Δρmax = 0.26 e Å−3 |
1239 reflections | Δρmin = −0.35 e Å−3 |
80 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 | 0.70568 (13) | 0.18350 (14) | 0.43618 (7) | 0.0308 (2) | |
N2 | 0.69412 (15) | 0.40275 (16) | 0.41203 (9) | 0.0394 (3) | |
N3 | 0.77516 (15) | 0.49478 (15) | 0.52286 (9) | 0.0418 (3) | |
N4 | 0.84106 (15) | 0.34528 (14) | 0.62148 (8) | 0.0361 (3) | |
C5 | 0.79648 (14) | 0.15085 (16) | 0.56482 (8) | 0.0285 (2) | |
N5 | 0.63818 (17) | 0.02231 (16) | 0.34251 (8) | 0.0399 (3) | |
N6 | 0.82467 (16) | −0.04594 (16) | 0.62126 (9) | 0.0417 (3) | |
H5A | 0.501 (3) | 0.040 (3) | 0.3075 (16) | 0.052 (4)* | |
H5B | 0.697 (2) | 0.052 (3) | 0.2778 (16) | 0.057 (4)* | |
H6A | 0.912 (3) | −0.057 (3) | 0.7081 (18) | 0.063 (5)* | |
H6B | 0.804 (2) | −0.162 (3) | 0.5706 (16) | 0.048 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0385 (4) | 0.0283 (4) | 0.0209 (4) | −0.0004 (3) | 0.0016 (3) | −0.0001 (3) |
N2 | 0.0522 (5) | 0.0296 (5) | 0.0299 (4) | 0.0007 (4) | 0.0025 (4) | 0.0046 (3) |
N3 | 0.0583 (6) | 0.0282 (5) | 0.0332 (5) | −0.0005 (4) | 0.0049 (4) | 0.0011 (3) |
N4 | 0.0500 (5) | 0.0274 (4) | 0.0257 (4) | −0.0021 (3) | 0.0034 (4) | −0.0027 (3) |
C5 | 0.0334 (4) | 0.0277 (5) | 0.0209 (4) | 0.0005 (3) | 0.0025 (3) | −0.0008 (3) |
N5 | 0.0516 (6) | 0.0377 (5) | 0.0244 (4) | −0.0069 (4) | 0.0020 (4) | −0.0072 (3) |
N6 | 0.0613 (6) | 0.0272 (5) | 0.0267 (4) | 0.0019 (4) | −0.0022 (4) | 0.0020 (3) |
N1—C5 | 1.345 (1) | C5—N6 | 1.334 (1) |
N1—N2 | 1.363 (1) | N5—H5A | 0.90 (2) |
N1—N5 | 1.383 (1) | N5—H5B | 0.91 (2) |
N2—N3 | 1.279 (1) | N6—H6A | 0.94 (2) |
N3—N4 | 1.367 (1) | N6—H6B | 0.88 (2) |
N4—C5 | 1.327 (1) | ||
C5—N1—N2 | 108.84 (8) | N6—C5—N1 | 123.87 (9) |
C5—N1—N5 | 126.02 (9) | N1—N5—H5A | 107 (1) |
N2—N1—N5 | 125.13 (8) | N1—N5—H5B | 107 (1) |
N3—N2—N1 | 105.79 (8) | H5A—N5—H5B | 107 (1) |
N2—N3—N4 | 111.92 (9) | C5—N6—H6A | 118 (1) |
C5—N4—N3 | 105.56 (8) | C5—N6—H6B | 118 (1) |
N4—C5—N6 | 128.17 (8) | H6A—N6—H6B | 119 (1) |
N4—C5—N1 | 107.90 (8) | ||
C5—N1—N2—N3 | −0.09 (12) | N3—N4—C5—N1 | −0.28 (12) |
N5—N1—N2—N3 | −178.95 (10) | N2—N1—C5—N4 | 0.24 (12) |
N1—N2—N3—N4 | −0.09 (12) | N5—N1—C5—N4 | 179.08 (9) |
N2—N3—N4—C5 | 0.24 (12) | N2—N1—C5—N6 | 177.59 (10) |
N3—N4—C5—N6 | −177.49 (10) | N5—N1—C5—N6 | −3.56 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N2i | 0.90 (2) | 2.48 (2) | 3.063 (1) | 123 (1) |
N5—H5A···N6ii | 0.90 (2) | 2.54 (1) | 3.277 (2) | 139 (1) |
N5—H5B···N4iii | 0.91 (2) | 2.26 (2) | 3.172 (2) | 175 (1) |
N6—H6A···N4iv | 0.94 (2) | 2.16 (2) | 3.074 (1) | 162 (1) |
N6—H6B···N3v | 0.88 (2) | 2.15 (2) | 2.982 (2) | 157 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y, −z+1; (iii) x, −y+1/2, z−1/2; (iv) −x+2, y−1/2, −z+3/2; (v) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | CH4N6 |
Mr | 100.10 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.780 (1), 6.112 (1), 10.694 (2) |
β (°) | 107.25 (1) |
V (Å3) | 423.2 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.56 × 0.48 × 0.26 |
Data collection | |
Diffractometer | Nicolet R3m four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1378, 1239, 1069 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.132, 1.08 |
No. of reflections | 1239 |
No. of parameters | 80 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.35 |
Computer programs: Nicolet R3m Software (Nicolet, 1980), Nicolet R3m Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-III for Windows (Farrugia, 1997), SHELX97.
N1—C5 | 1.345 (1) | N3—N4 | 1.367 (1) |
N1—N2 | 1.363 (1) | N4—C5 | 1.327 (1) |
N1—N5 | 1.383 (1) | C5—N6 | 1.334 (1) |
N2—N3 | 1.279 (1) | ||
C5—N1—N2 | 108.84 (8) | N6—C5—N1 | 123.87 (9) |
C5—N1—N5 | 126.02 (9) | N1—N5—H5A | 107 (1) |
N2—N1—N5 | 125.13 (8) | N1—N5—H5B | 107 (1) |
N3—N2—N1 | 105.79 (8) | H5A—N5—H5B | 107 (1) |
N2—N3—N4 | 111.92 (9) | C5—N6—H6A | 118 (1) |
C5—N4—N3 | 105.56 (8) | C5—N6—H6B | 118 (1) |
N4—C5—N6 | 128.17 (8) | H6A—N6—H6B | 119 (1) |
N4—C5—N1 | 107.90 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N2i | 0.90 (2) | 2.48 (2) | 3.063 (1) | 123 (1) |
N5—H5A···N6ii | 0.90 (2) | 2.54 (1) | 3.277 (2) | 139 (1) |
N5—H5B···N4iii | 0.91 (2) | 2.26 (2) | 3.172 (2) | 175 (1) |
N6—H6A···N4iv | 0.94 (2) | 2.16 (2) | 3.074 (1) | 162 (1) |
N6—H6B···N3v | 0.88 (2) | 2.15 (2) | 2.982 (2) | 157 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y, −z+1; (iii) x, −y+1/2, z−1/2; (iv) −x+2, y−1/2, −z+3/2; (v) x, y−1, z. |
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1,5-Diaminotetrazole, (I), being a simple bifunctional tetrazole derivative with high nitrogen content (84%), is attractive as a gas-generating agent (Gao et al., 1991; Levchik at al., 1993) and a valuable intermediate in the preparation of high energetic materials (Willer & Henry, 1988; Sinditskii & Fogelzang, 1997) and other useful tetrazole-containing compounds (Gaponik & Karavai, 1984; Desenko et al., 1990; Krutikov et al., 1991). However, the structure of (I) has not been investigated. Only a hypothesis about preferable tautomeric form of (I) (amino-imino tautomerism), based on IR spectroscopy data, has been made (Gaponik & Karavai, 1984; Levchik et al., 1993). \sch
Our X-ray investigation shows that the tetrazole ring of (I) is planar to within 0.001 (1) Å. All the formal single endocyclic bonds are considerably shorter than those usually found for normal single bonds, but some formal double bonds are longer than the normal double bonds (International Tables for Crystallography, 1992). This indicates that the tetrazole ring of (I) reveals a conjugated system of bonds similar to that found in other tetrazole derivatives. On the other hand, significant differences of endocyclic bond lengths show considerable localization of charge within the ring. In general, the angles and bond distances in the heteroring of (I) are consistent with those observed previously for 1-mono- and 1,5-disubstituted tetrazoles.
The exocyclic C5—N6 bond of 1.334 (1) Å is shorter than that of 1.47 Å in ethylenediamine (Ohno et al., 1998), but longer than that of 1.29 Å in 1,3-dimethyl-5-iminotetrazoline hydrochloride (Bryden, 1955) and close to one in p-nitroaniline (1.355 Å) (Colapietro et al., 1982). The difference between the C5—N1 and C5—N4 bond lengths is rather small. It should be noted that the 5-amino group lies in the tetrazole ring plane - the deviation of the N6 atom from the least-squares tetrazole ring is 0.045 (2) Å. The angles around N6 atom are close to 120° and take on the values 118 (1)° for two C5—N6—H angles and 119 (1)° for the H—N6—H angle. These data indicate a conjugation between the π-systems of the tetrazole ring and the 5-amino group. The obtained results confirm an assumption about preference of 5-aminotetrazole form (I) rather than iminotetrazoline one in solid (Gaponik & Karavai, 1984).
Similar to the N6 atom, the atom N5 also lies in the tetrazole ring plane. The N1—N5 bond length of 1.383 (1) Å is shorter than that of 1.42 Å in tetramethylhydrazine (Ohno et al., 1998) and similar to one in 2-aminobenzotriazole (1.386 Å) (Foces-Foces et al., 1990). The lone electron pair of N5 atom is not conjugated with π system of heteroring. This conclusion follows from the hydrogen atoms position of this amino group. The three bond angles around the N5 atom are equal to 107 (1)°. This value being close to one of tetrahedral angle indicates that the N6 atom has sp3 hybridization. It should be noted that the hydrogen atoms of 1-amino group are located on different sides of the tetrazole plane (Fig. 1) and consequently the N5 lone pair must lie in this plane. These data confirm the conclusions of theoretical study concerned with the hybridization and conformation of the amino group in N-aminoazoles (Foces-Foces et al., 1990), where sp3 hybridization of amino groups was found to be favoured over sp2 and amino lone pair eclipses the ring for monocyclic N-aminoazoles, including 1-aminotetrazole.
Inspection of the packing of the molecules (Fig. 2) reveals that the individual molecules are linked by N—H···N hydrogen bonds forming infinite three-dimensional framework.