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In the title compound, CH4N6, the tetrazole ring is planar to within 0.001 (1) Å. The 5-amino group is conjugated with the π-system of the tetrazole ring. In contrast, the N atom of the 1-­amino group is sp3 hybridized and is not conjugated with the π system of the tetrazole ring. All H atoms are localized at the exocyclic N atoms. The mol­ecules are connected by N—H...N hydrogen bonds, forming an infinite three-dimensional framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010001622X/av1058sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010001622X/av1058Isup2.hkl
Contains datablock I

CCDC reference: 159997

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

H atom positions were found from the ΔF map and all associated parameters were refined freely.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atom-numbering scheme (non-H atom displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram of (I).
1,5-diaminotetrazole top
Crystal data top
CH4N6F(000) = 208
Mr = 100.10Dx = 1.571 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 6.780 (1) ÅCell parameters from 25 reflections
b = 6.112 (1) Åθ = 21.0–23.7°
c = 10.694 (2) ŵ = 0.12 mm1
β = 107.25 (1)°T = 293 K
V = 423.2 (1) Å3Prism, colourless
Z = 40.56 × 0.48 × 0.26 mm
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.020
Radiation source: fine-focus sealed tubeθmax = 30.1°, θmin = 3.2°
Graphite monochromatorh = 09
ω/2θ scansk = 08
1378 measured reflectionsl = 1514
1239 independent reflections3 standard reflections every 100 reflections
1069 reflections with I > 2σ(I) intensity decay: 3.5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: difference Fourier map
wR(F2) = 0.132All 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 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
CH4N6V = 423.2 (1) Å3
Mr = 100.10Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.780 (1) ŵ = 0.12 mm1
b = 6.112 (1) ÅT = 293 K
c = 10.694 (2) Å0.56 × 0.48 × 0.26 mm
β = 107.25 (1)°
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.020
1378 measured reflections3 standard reflections every 100 reflections
1239 independent reflections intensity decay: 3.5%
1069 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.132All H-atom parameters refined
S = 1.08Δρmax = 0.26 e Å3
1239 reflectionsΔρmin = 0.35 e Å3
80 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.70568 (13)0.18350 (14)0.43618 (7)0.0308 (2)
N20.69412 (15)0.40275 (16)0.41203 (9)0.0394 (3)
N30.77516 (15)0.49478 (15)0.52286 (9)0.0418 (3)
N40.84106 (15)0.34528 (14)0.62148 (8)0.0361 (3)
C50.79648 (14)0.15085 (16)0.56482 (8)0.0285 (2)
N50.63818 (17)0.02231 (16)0.34251 (8)0.0399 (3)
N60.82467 (16)0.04594 (16)0.62126 (9)0.0417 (3)
H5A0.501 (3)0.040 (3)0.3075 (16)0.052 (4)*
H5B0.697 (2)0.052 (3)0.2778 (16)0.057 (4)*
H6A0.912 (3)0.057 (3)0.7081 (18)0.063 (5)*
H6B0.804 (2)0.162 (3)0.5706 (16)0.048 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0385 (4)0.0283 (4)0.0209 (4)0.0004 (3)0.0016 (3)0.0001 (3)
N20.0522 (5)0.0296 (5)0.0299 (4)0.0007 (4)0.0025 (4)0.0046 (3)
N30.0583 (6)0.0282 (5)0.0332 (5)0.0005 (4)0.0049 (4)0.0011 (3)
N40.0500 (5)0.0274 (4)0.0257 (4)0.0021 (3)0.0034 (4)0.0027 (3)
C50.0334 (4)0.0277 (5)0.0209 (4)0.0005 (3)0.0025 (3)0.0008 (3)
N50.0516 (6)0.0377 (5)0.0244 (4)0.0069 (4)0.0020 (4)0.0072 (3)
N60.0613 (6)0.0272 (5)0.0267 (4)0.0019 (4)0.0022 (4)0.0020 (3)
Geometric parameters (Å, º) top
N1—C51.345 (1)C5—N61.334 (1)
N1—N21.363 (1)N5—H5A0.90 (2)
N1—N51.383 (1)N5—H5B0.91 (2)
N2—N31.279 (1)N6—H6A0.94 (2)
N3—N41.367 (1)N6—H6B0.88 (2)
N4—C51.327 (1)
C5—N1—N2108.84 (8)N6—C5—N1123.87 (9)
C5—N1—N5126.02 (9)N1—N5—H5A107 (1)
N2—N1—N5125.13 (8)N1—N5—H5B107 (1)
N3—N2—N1105.79 (8)H5A—N5—H5B107 (1)
N2—N3—N4111.92 (9)C5—N6—H6A118 (1)
C5—N4—N3105.56 (8)C5—N6—H6B118 (1)
N4—C5—N6128.17 (8)H6A—N6—H6B119 (1)
N4—C5—N1107.90 (8)
C5—N1—N2—N30.09 (12)N3—N4—C5—N10.28 (12)
N5—N1—N2—N3178.95 (10)N2—N1—C5—N40.24 (12)
N1—N2—N3—N40.09 (12)N5—N1—C5—N4179.08 (9)
N2—N3—N4—C50.24 (12)N2—N1—C5—N6177.59 (10)
N3—N4—C5—N6177.49 (10)N5—N1—C5—N63.56 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···N2i0.90 (2)2.48 (2)3.063 (1)123 (1)
N5—H5A···N6ii0.90 (2)2.54 (1)3.277 (2)139 (1)
N5—H5B···N4iii0.91 (2)2.26 (2)3.172 (2)175 (1)
N6—H6A···N4iv0.94 (2)2.16 (2)3.074 (1)162 (1)
N6—H6B···N3v0.88 (2)2.15 (2)2.982 (2)157 (2)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y, z+1; (iii) x, y+1/2, z1/2; (iv) x+2, y1/2, z+3/2; (v) x, y1, z.

Experimental details

Crystal data
Chemical formulaCH4N6
Mr100.10
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)6.780 (1), 6.112 (1), 10.694 (2)
β (°) 107.25 (1)
V3)423.2 (1)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.56 × 0.48 × 0.26
Data collection
DiffractometerNicolet R3m four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1378, 1239, 1069
Rint0.020
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.132, 1.08
No. of reflections1239
No. of parameters80
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
N1—C51.345 (1)N3—N41.367 (1)
N1—N21.363 (1)N4—C51.327 (1)
N1—N51.383 (1)C5—N61.334 (1)
N2—N31.279 (1)
C5—N1—N2108.84 (8)N6—C5—N1123.87 (9)
C5—N1—N5126.02 (9)N1—N5—H5A107 (1)
N2—N1—N5125.13 (8)N1—N5—H5B107 (1)
N3—N2—N1105.79 (8)H5A—N5—H5B107 (1)
N2—N3—N4111.92 (9)C5—N6—H6A118 (1)
C5—N4—N3105.56 (8)C5—N6—H6B118 (1)
N4—C5—N6128.17 (8)H6A—N6—H6B119 (1)
N4—C5—N1107.90 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···N2i0.90 (2)2.48 (2)3.063 (1)123 (1)
N5—H5A···N6ii0.90 (2)2.54 (1)3.277 (2)139 (1)
N5—H5B···N4iii0.91 (2)2.26 (2)3.172 (2)175 (1)
N6—H6A···N4iv0.94 (2)2.16 (2)3.074 (1)162 (1)
N6—H6B···N3v0.88 (2)2.15 (2)2.982 (2)157 (2)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y, z+1; (iii) x, y+1/2, z1/2; (iv) x+2, y1/2, z+3/2; (v) x, y1, z.
 

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