5-(4-Nitro­benz­yl)-1H-1,2,3,4-tetra­zole

Chen, J.M.; Zhao, H.

doi:10.1107/S1600536810043576

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2989

https://doi.org/10.1107/S1600536810043576

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5-(4-Nitrobenzyl)-1H-1,2,3,4-tetrazole

Jin Mei Chen ^a and Hong Zhao ^a ^*

^aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: zhaohong@seu.edu.cn

(Received 22 October 2010; accepted 26 October 2010; online 31 October 2010)

In the title compound, C₈H₇N₅O₂, the dihedral angle between the benzene and tetrazole rings is 63.13 (8)°. The crystal structure exhibits intermolecular N—H⋯N hydrogen bonds which lead to the formation of one-dimensional chains along the [010] direction.

Related literature

For the applications of tetrazoles, see: Demko & Sharpless (2001 ). For our previous work on this class of compounds, see: Zhao et al. (2008 ).

Experimental

Crystal data

C₈H₇N₅O₂
M_r = 205.19
Monoclinic, P 2₁ /c
a = 6.3393 (10) Å
b = 4.9381 (6) Å
c = 28.801 (4) Å
β = 101.905 (14)°
V = 882.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 295 K
0.50 × 0.42 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.982, T_max = 0.990
8583 measured reflections
2088 independent reflections
1823 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.128
S = 1.20
2088 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4ⁱ	0.87	1.94	2.803 (2)	176
Symmetry code: (i) x, y-1, z.

Data collection: CrystalClear (Rigaku, 2005); 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: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810043576/bx2321sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043576/bx2321Isup2.hkl

checkCIF report

Comment top

Tetrazole ligands have found a wide range of application in medicine chemistry, coordination chemistry and material chemistry (Demko & Sharpless, 2001). As part of an ongoing program in our laboratory to explore the structural characterization of the tetrazole-related compounds (Zhao et al., 2008), the crystal structure of the title compound is reported here.

In the molecule of the title compound (Fig. 1) bond lengths and angles have normal values. The dihedral angle between the benzene ring and tetrazole ring is 63.13 (8)°. The crystal structure exhibits intermolecular N—H···N hydrogen bonds which lead to the formation of one dimensional chains along the [010] direction. (Fig. 2; Table 1).

Related literature top

For the applications of tetrazoles, see: Demko & Sharpless (2001). For our previous work on this class of compounds, see: Zhao et al. (2008). [Please confirm amended text]

Experimental top

A mixture of 2-(4-nitrophenyl)acetonitrile (20 mmol), NaN₃ (22 mmol) and NH₄Cl (22 mmol) in DMF (15 ml) was heated at 120°C for 20 h then cooled and the solvent removed under vacuum. The residue was poured into water (20 ml) to give the crude title compound. Colourless prismatic crystals suitable for X-ray analysis were obtained by slow evaporation of a 95% ethanol/water solution.

Structure description top

For the applications of tetrazoles, see: Demko & Sharpless (2001). For our previous work on this class of compounds, see: Zhao et al. (2008). [Please confirm amended text]

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: SHELXS97 (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. The displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Diagram of the molecules linked into one-dimensional chain by a simple N—H···N interaction.

5-(4-Nitrobenzyl)-1H-1,2,3,4-tetrazole top

Crystal data top

C₈H₇N₅O₂	F(000) = 424
M_r = 205.19	D_x = 1.545 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2188 reflections
a = 6.3393 (10) Å	θ = 3.2–27.5°
b = 4.9381 (6) Å	µ = 0.12 mm⁻¹
c = 28.801 (4) Å	T = 295 K
β = 101.905 (14)°	Prism, pale yellow
V = 882.2 (2) Å³	0.50 × 0.42 × 0.28 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2088 independent reflections
Radiation source: fine-focus sealed tube	1823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.9°, θ_min = 2.9°
CCD_Profile_fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −6→6
T_min = 0.982, T_max = 0.990	l = −37→37
8583 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0293P)² + 0.5689P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max < 0.001
2088 reflections	Δρ_max = 0.27 e Å⁻³
138 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.037 (6)

Crystal data top

C₈H₇N₅O₂	V = 882.2 (2) Å³
M_r = 205.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.3393 (10) Å	µ = 0.12 mm⁻¹
b = 4.9381 (6) Å	T = 295 K
c = 28.801 (4) Å	0.50 × 0.42 × 0.28 mm
β = 101.905 (14)°

Data collection top

Rigaku SCXmini diffractometer	2088 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1823 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.990	R_int = 0.034
8583 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.20	Δρ_max = 0.27 e Å⁻³
2088 reflections	Δρ_min = −0.25 e Å⁻³
138 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	0.6521 (3)	−0.0440 (4)	0.23878 (6)	0.0537 (5)
O2	0.3476 (3)	0.0031 (4)	0.18977 (6)	0.0538 (5)
N1	0.7922 (3)	0.6457 (3)	0.02183 (6)	0.0340 (4)
H1	0.7833	0.4706	0.0214	0.051*
N2	0.7245 (3)	0.7302 (4)	−0.02353 (6)	0.0402 (4)
N3	0.7205 (3)	0.9910 (4)	−0.02326 (6)	0.0413 (5)
N4	0.7847 (3)	1.0783 (3)	0.02209 (6)	0.0358 (4)
N5	0.5369 (3)	0.0619 (4)	0.20421 (6)	0.0367 (4)
C1	0.8285 (3)	0.8620 (4)	0.04930 (7)	0.0297 (4)
C2	0.9119 (4)	0.8641 (4)	0.10150 (7)	0.0399 (5)
H2A	0.8881	1.0425	0.1135	0.048*
H2B	1.0664	0.8337	0.1076	0.048*
C3	0.8111 (3)	0.6555 (4)	0.12886 (7)	0.0327 (4)
C4	0.9324 (3)	0.5398 (4)	0.16973 (7)	0.0369 (5)
H4	1.0754	0.5918	0.1802	0.044*
C5	0.8439 (3)	0.3485 (4)	0.19519 (7)	0.0371 (5)
H5	0.9255	0.2715	0.2225	0.044*
C6	0.6314 (3)	0.2747 (4)	0.17898 (7)	0.0316 (4)
C7	0.5058 (3)	0.3865 (5)	0.13898 (7)	0.0382 (5)
H7	0.3629	0.3337	0.1288	0.046*
C8	0.5962 (3)	0.5790 (4)	0.11420 (7)	0.0386 (5)
H8	0.5124	0.6585	0.0874	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0614 (10)	0.0516 (10)	0.0475 (9)	−0.0025 (8)	0.0098 (8)	0.0188 (8)
O2	0.0503 (9)	0.0592 (11)	0.0516 (9)	−0.0227 (8)	0.0099 (8)	0.0033 (8)
N1	0.0432 (9)	0.0243 (8)	0.0348 (9)	−0.0038 (7)	0.0085 (7)	−0.0009 (7)
N2	0.0465 (10)	0.0401 (10)	0.0332 (9)	−0.0083 (8)	0.0064 (7)	0.0007 (8)
N3	0.0388 (9)	0.0413 (10)	0.0421 (10)	−0.0031 (8)	0.0041 (8)	0.0134 (8)
N4	0.0354 (9)	0.0301 (9)	0.0430 (9)	−0.0003 (7)	0.0104 (7)	0.0087 (7)
N5	0.0476 (10)	0.0317 (9)	0.0326 (9)	−0.0050 (8)	0.0127 (7)	−0.0009 (7)
C1	0.0318 (9)	0.0234 (9)	0.0352 (10)	−0.0035 (7)	0.0102 (7)	0.0009 (7)
C2	0.0530 (12)	0.0330 (11)	0.0332 (10)	−0.0122 (9)	0.0074 (9)	−0.0023 (9)
C3	0.0406 (10)	0.0278 (10)	0.0301 (9)	−0.0033 (8)	0.0083 (8)	−0.0022 (8)
C4	0.0354 (10)	0.0395 (11)	0.0336 (10)	−0.0073 (9)	0.0021 (8)	−0.0012 (9)
C5	0.0408 (11)	0.0385 (11)	0.0290 (9)	−0.0031 (9)	0.0006 (8)	0.0024 (8)
C6	0.0400 (10)	0.0268 (9)	0.0292 (9)	−0.0033 (8)	0.0102 (8)	−0.0006 (7)
C7	0.0333 (10)	0.0439 (12)	0.0365 (10)	−0.0045 (9)	0.0048 (8)	0.0031 (9)
C8	0.0389 (10)	0.0395 (12)	0.0350 (10)	−0.0010 (9)	0.0018 (8)	0.0090 (9)

Geometric parameters (Å, º) top

O1—N5	1.224 (2)	C2—H2B	0.9700
O2—N5	1.221 (2)	C3—C4	1.389 (3)
N1—C1	1.321 (2)	C3—C8	1.392 (3)
N1—N2	1.354 (2)	C4—C5	1.384 (3)
N1—H1	0.8666	C4—H4	0.9300
N2—N3	1.288 (3)	C5—C6	1.381 (3)
N3—N4	1.356 (3)	C5—H5	0.9300
N4—C1	1.320 (2)	C6—C7	1.374 (3)
N5—C6	1.473 (2)	C7—C8	1.382 (3)
C1—C2	1.487 (3)	C7—H7	0.9300
C2—C3	1.516 (3)	C8—H8	0.9300
C2—H2A	0.9700

C1—N1—N2	108.07 (16)	C4—C3—C8	118.78 (18)
C1—N1—H1	145.0	C4—C3—C2	120.03 (18)
N2—N1—H1	106.6	C8—C3—C2	121.18 (18)
N3—N2—N1	107.76 (17)	C5—C4—C3	121.02 (18)
N2—N3—N4	108.73 (16)	C5—C4—H4	119.5
C1—N4—N3	107.42 (16)	C3—C4—H4	119.5
O2—N5—O1	123.73 (18)	C6—C5—C4	118.38 (18)
O2—N5—C6	118.18 (17)	C6—C5—H5	120.8
O1—N5—C6	118.08 (17)	C4—C5—H5	120.8
N4—C1—N1	108.02 (17)	C7—C6—C5	122.25 (18)
N4—C1—C2	125.59 (18)	C7—C6—N5	118.43 (17)
N1—C1—C2	126.35 (17)	C5—C6—N5	119.28 (17)
C1—C2—C3	114.87 (16)	C6—C7—C8	118.63 (19)
C1—C2—H2A	108.6	C6—C7—H7	120.7
C3—C2—H2A	108.5	C8—C7—H7	120.7
C1—C2—H2B	108.6	C7—C8—C3	120.92 (18)
C3—C2—H2B	108.6	C7—C8—H8	119.5
H2A—C2—H2B	107.5	C3—C8—H8	119.5

C1—N1—N2—N3	0.1 (2)	C3—C4—C5—C6	0.0 (3)
N1—N2—N3—N4	−0.2 (2)	C4—C5—C6—C7	−0.7 (3)
N2—N3—N4—C1	0.2 (2)	C4—C5—C6—N5	177.08 (18)
N3—N4—C1—N1	−0.2 (2)	O2—N5—C6—C7	−3.4 (3)
N3—N4—C1—C2	177.72 (18)	O1—N5—C6—C7	177.28 (19)
N2—N1—C1—N4	0.1 (2)	O2—N5—C6—C5	178.74 (19)
N2—N1—C1—C2	−177.80 (18)	O1—N5—C6—C5	−0.5 (3)
N4—C1—C2—C3	138.7 (2)	C5—C6—C7—C8	0.1 (3)
N1—C1—C2—C3	−43.8 (3)	N5—C6—C7—C8	−177.64 (19)
C1—C2—C3—C4	147.51 (19)	C6—C7—C8—C3	1.1 (3)
C1—C2—C3—C8	−33.4 (3)	C4—C3—C8—C7	−1.7 (3)
C8—C3—C4—C5	1.1 (3)	C2—C3—C8—C7	179.3 (2)
C2—C3—C4—C5	−179.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.87	1.94	2.803 (2)	176

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₈H₇N₅O₂
M_r	205.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	6.3393 (10), 4.9381 (6), 28.801 (4)
β (°)	101.905 (14)
V (Å³)	882.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.50 × 0.42 × 0.28

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.982, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	8583, 2088, 1823
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.128, 1.20
No. of reflections	2088
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.87	1.94	2.803 (2)	176.0

Symmetry code: (i) x, y−1, z.

Acknowledgements

This work was financially supported by a Southeast University Grant for Young Researchers (grant No. 4007041027).

References

Demko, Z. P. & Sharpless, K. B. (2001). Org. Lett. 3, 4091–4094. Web of Science CrossRef PubMed CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, H., Qu, Z. R., Ye, H. Y. & Xiong, R. G. (2008). Chem. Soc. Rev. 37, 84–100. Web of Science CrossRef PubMed Google Scholar