N-(5-Amino-1H-tetra­zol-1-yl)formamide

He, C.-L.; Du, Z.-M.; Tang, Z.-Q.; Cong, X.-M.; Meng, L.-Q.

doi:10.1107/S1600536809044833

organic compounds

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Volume 65| Part 11| November 2009| Page o2901

https://doi.org/10.1107/S1600536809044833

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N-(5-Amino-1H-tetrazol-1-yl)formamide

Chun-Lin He,^a Zhi-Ming Du,^a ^* Zheng-Qiang Tang,^a Xiao-Min Cong ^a and Ling-Qiao Meng ^a

^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

(Received 12 October 2009; accepted 23 October 2009; online 28 October 2009)

In the title compound, C₂H₄N₆O, the planar [maximum deviation = 0.006 (2) Å] aminotetrazole group makes a dihedral angle of 83.65 (8)° with the formamide unit. In the crystal structure, intermolecular N—H⋯N, N—H⋯O and C—H⋯N hydrogen bonds are responsible for the formation of a three-dimensional network.

Related literature

For energetic nitrogen-rich derivatives of 1,5-diaminotetrazole, see: Joo et al. (2008 ). For nitrogen-rich metastable green chemistry compounds, see: Steinhauser et al. (2008 ). For 1,5-diamino-1H-tetrazole derivatives, see: Galvez-Ruiz et al. (2005 ). For the structure of N-(1-diacetylamino-1H-tetrazol-5-yl)-acetamide, see: He et al. (2009 ).

Experimental

Crystal data

C₂H₄N₆O
M_r = 128.11
Orthorhombic, P n n 2
a = 10.232 (10) Å
b = 12.054 (12) Å
c = 4.208 (4) Å
V = 519.1 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 93 K
0.47 × 0.27 × 0.07 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.940, T_max = 0.991
3464 measured reflections
659 independent reflections
545 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.089
S = 1.00
659 reflections
94 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯N1ⁱ	0.84 (3)	2.02 (3)	2.851 (4)	168 (3)
N6—H6A⋯O1ⁱⁱ	0.87 (3)	2.54 (3)	2.981 (4)	113 (2)
N6—H6A⋯N3ⁱⁱⁱ	0.87 (3)	2.35 (3)	3.164 (4)	156 (3)
N6—H6B⋯O1^iv	0.91 (3)	2.12 (3)	3.006 (4)	167 (2)
C2—H2⋯N2^v	0.95	2.53	3.404 (5)	152
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x, y, z+1; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809044833/si2213sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044833/si2213Isup2.hkl

checkCIF report

Comment top

Nitrogen-containing compounds have received an increasing interest during the last years, these compounds exhibit potential application in gas generator, "green" pyrotechnics and high density energetic materials (Galvez-Ruiz et al., 2005; Steinhauser & Klapötke, 2008; Joo et al., 2008). Rencently, we synthesized a new nitrogen-containing compound, N-(5-amino-1H-tetrazol-1-yl)formamide, which has a nitrogen content of 65.62%. Herein, we report the crystal structure of the title compound.

The molecular structure of the title compound is presented in Fig. 1. The aminotetrazole group is essentially planar and makes a dihedral angle of 83.65 (8)° with the formamide unit. The bond distances and bond angels in the title compound are similar to the corresponding distances and angles reported by He et al. (2009). In the crystal structure, the molecules are linked to each other via intermolecular N—H···N, N—H···O and C—H···N hydrogen bonds (Table 1), forming a three-dimensional network structure.

Related literature top

For energetic nitrogen-rich derivatives of 1,5-diaminotetrazole, see: Joo et al. (2008). For nitrogen-rich metastable green chemistry compounds, see: Steinhauser et al. (2008). For 1,5-diamino-1H-tetrazole derivatives, see: Galvez-Ruiz et al. (2005). For the structure of N-(1-diacetylamino-1H-tetrazole-5-yl)-acetamide, see: He et al. (2009).

Experimental top

Diamino-tetrazole (10 mmol) was dissolved in 10 ml formic acid, 0.3 g sodium formate was added to the above mixture and reacted under refluxing, use TLC to control the reaction process. After cooling, the crude product precipitated and was filtered. The purity of the compound was checked by its melting point. ¹H-NMR (DMSO—d₆, 400 MHz): 11.71(1H,s), 8.34(1H,s), 7.02(2H, s); MS (EI,70 eV) m/z:128(M⁺). 70 mg of the obtained product was dissolved in the mixture solution of methanol (20 ml) and acetone (10 ml) and the solution was kept at room temperature to give suitable crystals for X-ray structure determination.

Structure description top

For energetic nitrogen-rich derivatives of 1,5-diaminotetrazole, see: Joo et al. (2008). For nitrogen-rich metastable green chemistry compounds, see: Steinhauser et al. (2008). For 1,5-diamino-1H-tetrazole derivatives, see: Galvez-Ruiz et al. (2005). For the structure of N-(1-diacetylamino-1H-tetrazole-5-yl)-acetamide, see: He et al. (2009).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: 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).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

N-(5-Amino-1H-tetrazol-1-yl)formamide top

Crystal data top

C₂H₄N₆O	F(000) = 264
M_r = 128.11	D_x = 1.639 Mg m⁻³
Orthorhombic, Pnn2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 -2n	Cell parameters from 1548 reflections
a = 10.232 (10) Å	θ = 3.4–27.2°
b = 12.054 (12) Å	µ = 0.14 mm⁻¹
c = 4.208 (4) Å	T = 93 K
V = 519.1 (9) Å³	Platelet, colorless
Z = 4	0.47 × 0.27 × 0.07 mm

Data collection top

Rigaku Saturn724+ diffractometer	659 independent reflections
Radiation source: Rotating Anode	545 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.3°, θ_min = 3.4°
multi–scan	h = −13→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→14
T_min = 0.940, T_max = 0.991	l = −5→5
3464 measured reflections

Refinement top

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) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0522P)²] where P = (F_o² + 2F_c²)/3
659 reflections	(Δ/σ)_max < 0.001
94 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂H₄N₆O	V = 519.1 (9) Å³
M_r = 128.11	Z = 4
Orthorhombic, Pnn2	Mo Kα radiation
a = 10.232 (10) Å	µ = 0.14 mm⁻¹
b = 12.054 (12) Å	T = 93 K
c = 4.208 (4) Å	0.47 × 0.27 × 0.07 mm

Data collection top

Rigaku Saturn724+ diffractometer	659 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	545 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.991	R_int = 0.051
3464 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.22 e Å⁻³
659 reflections	Δρ_min = −0.19 e Å⁻³
94 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

	x	y	z	U_iso*/U_eq
O1	0.32520 (17)	0.52017 (15)	0.4700 (5)	0.0250 (5)
N1	0.53348 (19)	0.80213 (18)	0.7377 (6)	0.0200 (5)
N2	0.4393 (2)	0.85281 (17)	0.5557 (6)	0.0219 (5)
N3	0.3276 (2)	0.80311 (18)	0.5797 (6)	0.0213 (5)
N4	0.34795 (18)	0.71697 (17)	0.7884 (6)	0.0177 (5)
N5	0.2526 (2)	0.6400 (2)	0.8533 (6)	0.0189 (5)
N6	0.5250 (2)	0.64294 (19)	1.0818 (6)	0.0210 (5)
C1	0.4751 (2)	0.7167 (2)	0.8815 (6)	0.0178 (6)
C2	0.2470 (2)	0.5459 (2)	0.6773 (7)	0.0203 (6)
H2	0.1769	0.4961	0.7180	0.024*
H5N	0.196 (3)	0.661 (2)	0.986 (9)	0.028 (8)*
H6A	0.607 (3)	0.645 (2)	1.134 (8)	0.043 (10)*
H6B	0.473 (3)	0.596 (2)	1.192 (8)	0.028 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0209 (11)	0.0284 (10)	0.0259 (11)	−0.0004 (8)	0.0050 (9)	−0.0016 (9)
N1	0.0113 (10)	0.0261 (12)	0.0226 (13)	0.0013 (8)	0.0011 (10)	0.0021 (11)
N2	0.0133 (10)	0.0263 (12)	0.0262 (14)	0.0021 (9)	0.0010 (11)	0.0016 (11)
N3	0.0137 (11)	0.0257 (11)	0.0247 (13)	0.0006 (8)	0.0006 (10)	0.0051 (11)
N4	0.0093 (10)	0.0220 (11)	0.0216 (12)	−0.0009 (8)	0.0009 (10)	0.0012 (10)
N5	0.0090 (10)	0.0269 (12)	0.0209 (13)	−0.0011 (8)	0.0050 (9)	0.0021 (10)
N6	0.0116 (10)	0.0265 (12)	0.0250 (14)	−0.0001 (9)	−0.0023 (10)	0.0025 (11)
C1	0.0107 (11)	0.0229 (13)	0.0198 (15)	0.0027 (9)	0.0004 (11)	−0.0028 (11)
C2	0.0143 (12)	0.0233 (15)	0.0232 (13)	−0.0014 (10)	−0.0013 (11)	0.0058 (13)

Geometric parameters (Å, º) top

O1—C2	1.224 (3)	N5—C2	1.356 (4)
N1—C1	1.335 (3)	N5—H5N	0.84 (4)
N1—N2	1.374 (3)	N6—C1	1.328 (4)
N2—N3	1.294 (3)	N6—H6A	0.87 (4)
N3—N4	1.376 (3)	N6—H6B	0.90 (3)
N4—C1	1.359 (3)	C2—H2	0.9500
N4—N5	1.374 (3)

C1—N1—N2	106.4 (2)	C1—N6—H6A	121 (2)
N3—N2—N1	111.7 (2)	C1—N6—H6B	121 (2)
N2—N3—N4	105.4 (2)	H6A—N6—H6B	117 (3)
C1—N4—N5	128.4 (2)	N6—C1—N1	129.2 (2)
C1—N4—N3	109.3 (2)	N6—C1—N4	123.6 (2)
N5—N4—N3	122.0 (2)	N1—C1—N4	107.2 (2)
C2—N5—N4	119.1 (2)	O1—C2—N5	125.0 (2)
C2—N5—H5N	126.0 (19)	O1—C2—H2	117.5
N4—N5—H5N	114.4 (19)	N5—C2—H2	117.5

C1—N1—N2—N3	−0.2 (3)	N2—N1—C1—N4	−0.4 (3)
N1—N2—N3—N4	0.7 (3)	N5—N4—C1—N6	−6.3 (4)
N2—N3—N4—C1	−1.0 (3)	N3—N4—C1—N6	−179.7 (2)
N2—N3—N4—N5	−174.8 (2)	N5—N4—C1—N1	174.2 (3)
C1—N4—N5—C2	−81.1 (3)	N3—N4—C1—N1	0.9 (3)
N3—N4—N5—C2	91.4 (3)	N4—N5—C2—O1	3.8 (4)
N2—N1—C1—N6	−179.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···N1ⁱ	0.84 (3)	2.02 (3)	2.851 (4)	168 (3)
N6—H6A···O1ⁱⁱ	0.87 (3)	2.54 (3)	2.981 (4)	113 (2)
N6—H6A···N3ⁱⁱⁱ	0.87 (3)	2.35 (3)	3.164 (4)	156 (3)
N6—H6B···O1^iv	0.91 (3)	2.12 (3)	3.006 (4)	167 (2)
C2—H2···N2^v	0.95	2.53	3.404 (5)	152

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, z+1; (iii) x+1/2, −y+3/2, z+1/2; (iv) x, y, z+1; (v) −x+1/2, y−1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂H₄N₆O
M_r	128.11
Crystal system, space group	Orthorhombic, Pnn2
Temperature (K)	93
a, b, c (Å)	10.232 (10), 12.054 (12), 4.208 (4)
V (Å³)	519.1 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.47 × 0.27 × 0.07

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.940, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	3464, 659, 545
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.646

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.089, 1.00
No. of reflections	659
No. of parameters	94
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···N1ⁱ	0.84 (3)	2.02 (3)	2.851 (4)	168 (3)
N6—H6A···O1ⁱⁱ	0.87 (3)	2.54 (3)	2.981 (4)	113 (2)
N6—H6A···N3ⁱⁱⁱ	0.87 (3)	2.35 (3)	3.164 (4)	156 (3)
N6—H6B···O1^iv	0.91 (3)	2.12 (3)	3.006 (4)	167 (2)
C2—H2···N2^v	0.9500	2.5300	3.404 (5)	152.00

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+1, z+1; (iii) x+1/2, −y+3/2, z+1/2; (iv) x, y, z+1; (v) −x+1/2, y−1/2, z+1/2.

Acknowledgements

This work was supported financially by the State Key Laboratory of Explosion Science and Technology of Beijing Institute of Technology, China (No. ZDKT08–01).

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