5-(4-Methyl-3-nitro­phen­yl)-1H-tetra­zole

Dai, W.; Fu, D.-W.

doi:10.1107/S1600536808018825

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1445

doi:10.1107/S1600536808018825

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5-(4-Methyl-3-nitrophenyl)-1H-tetrazole

Wei Dai ^a and Da-Wei Fu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 20 June 2008; accepted 21 June 2008; online 9 July 2008)

In the title compound, C₈H₇N₅O₂, the benzene ring makes a dihedral angle of 38.27 (11)° with the tetrazole ring. The crystal structure is stabilized by N—H⋯N hydrogen bonds, forming an infinite one-dimensional chain parallel to the a axis.

Related literature

For the use of tetrazole derivatives in coordination chemisty, see: Arp et al. (2000 ); Hu et al. (2007 ); Wang et al. (2005 ); Xiong et al. (2002 ).

Experimental

Crystal data

C₈H₇N₅O₂
M_r = 205.19
Monoclinic, P 2₁ /c
a = 4.9642 (10) Å
b = 16.982 (3) Å
c = 10.804 (2) Å
β = 100.71 (3)°
V = 894.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 (2) K
0.25 × 0.18 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.971, T_max = 0.977
7013 measured reflections
2039 independent reflections
1330 reflections with I > 2σ(I)
R_int = 0.093

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.190
S = 1.08
2039 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N4ⁱ	0.86	2.01	2.832 (3)	160
Symmetry code: (i) x-1, y, 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 (Sheldrick, 2008) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018825/dn2361sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018825/dn2361Isup2.hkl

checkCIF report

Comment top

In the past five years, our work have been focused on the chemistry of tetrazole derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Wang et al., 2005; Xiong et al., 2002). We report here the crystal structure of the title compound, 5-(4-methyl-3-nitrophenyl)-2H-tetrazole, (Fig.1).

The benzene ring makes a dihedral angle of 38.27 (0.11) ° with the tetrazole ring owing to the C–C bond bridge which force the two rings to be twisted from each other. The bond distances and bond angles of the tetrazole rings are in the usual ranges (Wang et al., 2005; Arp et al. , 2000; Hu et al., 2007). The crystal packing is stabilized by N—H···N hydrogen bonds to form an infinite one-dimensional chain parallel to the a axis. (Table 1, Fig. 2).

Related literature top

For the use of tetrazole derivatives in coordination chemisty, see: Arp et al. (2000); Hu et al. (2007); Wang et al. (2005); Xiong et al. (2002).

Experimental top

5-(4-methyl-3-nitrophenyl)-2H-tetrazole (3 mmol) was dissolved in ethanol (20 ml) and evaporated in the air affording colorless block crystals of this compound suitable for X-ray analysis were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing of the title compound showing the one dimensionnal hydrogen bondings network. Hydrogen atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity. [Symmetry code : (i) x-1, y, z]

5-(4-Methyl-3-nitrophenyl)-1H-tetrazole top

Crystal data top

C₈H₇N₅O₂	F(000) = 424
M_r = 205.19	D_x = 1.523 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2043 reflections
a = 4.9642 (10) Å	θ = 3.1–27.5°
b = 16.982 (3) Å	µ = 0.12 mm⁻¹
c = 10.804 (2) Å	T = 298 K
β = 100.71 (3)°	Block, colorless
V = 894.9 (3) Å³	0.25 × 0.18 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2039 independent reflections
Radiation source: fine-focus sealed tube	1330 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.093
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −22→21
T_min = 0.971, T_max = 0.977	l = −13→14
7013 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)] = 0.075	H-atom parameters constrained
wR(F²) = 0.190	w = 1/[σ²(F_o²) + (0.0844P)² + 0.0553P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2039 reflections	Δρ_max = 0.32 e Å⁻³
137 parameters	Δρ_min = −0.26 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 (7)

Crystal data top

C₈H₇N₅O₂	V = 894.9 (3) Å³
M_r = 205.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.9642 (10) Å	µ = 0.12 mm⁻¹
b = 16.982 (3) Å	T = 298 K
c = 10.804 (2) Å	0.25 × 0.18 × 0.15 mm
β = 100.71 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2039 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1330 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.977	R_int = 0.093
7013 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.190	H-atom parameters constrained
S = 1.08	Δρ_max = 0.32 e Å⁻³
2039 reflections	Δρ_min = −0.26 e Å⁻³
137 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
N1	0.0809 (4)	0.47072 (13)	0.8636 (2)	0.0355 (6)
H1A	−0.0824	0.4579	0.8719	0.043*
N4	0.5077 (4)	0.46190 (13)	0.8535 (2)	0.0375 (6)
C1	0.2914 (5)	0.42106 (15)	0.8715 (2)	0.0300 (6)
C2	0.2791 (5)	0.33663 (15)	0.8959 (2)	0.0316 (6)
N2	0.1626 (5)	0.54380 (12)	0.8406 (2)	0.0429 (6)
N3	0.4204 (5)	0.53814 (13)	0.8340 (2)	0.0445 (6)
C3	0.1202 (5)	0.30784 (15)	0.9784 (2)	0.0346 (6)
H3A	0.0240	0.3423	1.0211	0.041*
C4	0.1057 (5)	0.22713 (16)	0.9969 (2)	0.0360 (7)
C7	0.4202 (6)	0.28333 (16)	0.8331 (3)	0.0380 (6)
H7A	0.5288	0.3016	0.7777	0.046*
C6	0.3991 (6)	0.20365 (16)	0.8530 (3)	0.0448 (7)
H6A	0.4927	0.1694	0.8089	0.054*
C5	0.2449 (6)	0.17202 (15)	0.9358 (3)	0.0423 (7)
O1	−0.1907 (5)	0.25440 (14)	1.1326 (2)	0.0687 (8)
O2	−0.0896 (5)	0.13387 (15)	1.1108 (2)	0.0781 (9)
N5	−0.0701 (5)	0.20355 (16)	1.0866 (2)	0.0468 (7)
C8	0.2416 (8)	0.08409 (18)	0.9527 (4)	0.0681 (10)
H8A	0.3551	0.0599	0.9006	0.102*
H8B	0.0571	0.0650	0.9289	0.102*
H8C	0.3103	0.0713	1.0393	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0248 (12)	0.0353 (12)	0.0489 (14)	−0.0016 (9)	0.0130 (9)	0.0005 (9)
N4	0.0280 (12)	0.0381 (13)	0.0489 (15)	−0.0015 (9)	0.0138 (9)	0.0055 (10)
C1	0.0237 (13)	0.0375 (14)	0.0308 (13)	−0.0009 (10)	0.0101 (9)	−0.0005 (10)
C2	0.0231 (13)	0.0376 (14)	0.0350 (15)	0.0014 (10)	0.0076 (10)	−0.0001 (10)
N2	0.0352 (13)	0.0384 (14)	0.0569 (16)	−0.0006 (10)	0.0135 (11)	0.0049 (11)
N3	0.0366 (14)	0.0415 (14)	0.0587 (16)	−0.0041 (10)	0.0172 (11)	0.0038 (11)
C3	0.0295 (15)	0.0390 (15)	0.0374 (16)	0.0000 (11)	0.0120 (11)	−0.0006 (11)
C4	0.0320 (15)	0.0399 (15)	0.0363 (15)	−0.0035 (11)	0.0065 (11)	0.0057 (11)
C7	0.0349 (15)	0.0411 (15)	0.0406 (16)	0.0059 (11)	0.0141 (12)	−0.0002 (12)
C6	0.0464 (18)	0.0422 (17)	0.0466 (18)	0.0123 (13)	0.0106 (13)	−0.0044 (12)
C5	0.0426 (17)	0.0371 (16)	0.0442 (17)	0.0017 (12)	0.0005 (13)	0.0024 (12)
O1	0.0701 (17)	0.0762 (17)	0.0721 (17)	−0.0033 (13)	0.0451 (13)	0.0098 (13)
O2	0.096 (2)	0.0572 (16)	0.087 (2)	−0.0154 (12)	0.0304 (16)	0.0263 (13)
N5	0.0377 (15)	0.0574 (17)	0.0444 (15)	−0.0108 (11)	0.0053 (11)	0.0132 (12)
C8	0.091 (3)	0.0377 (18)	0.074 (3)	−0.0006 (17)	0.011 (2)	0.0031 (16)

Geometric parameters (Å, º) top

N1—C1	1.333 (3)	C4—N5	1.475 (3)
N1—N2	1.343 (3)	C7—C6	1.377 (4)
N1—H1A	0.8600	C7—H7A	0.9300
N4—C1	1.323 (3)	C6—C5	1.388 (4)
N4—N3	1.369 (3)	C6—H6A	0.9300
C1—C2	1.461 (3)	C5—C8	1.505 (4)
C2—C3	1.385 (3)	O1—N5	1.209 (3)
C2—C7	1.395 (3)	O2—N5	1.220 (3)
N2—N3	1.299 (3)	C8—H8A	0.9600
C3—C4	1.389 (4)	C8—H8B	0.9600
C3—H3A	0.9300	C8—H8C	0.9600
C4—C5	1.400 (4)

C1—N1—N2	109.7 (2)	C6—C7—C2	120.1 (2)
C1—N1—H1A	125.2	C6—C7—H7A	119.9
N2—N1—H1A	125.2	C2—C7—H7A	119.9
C1—N4—N3	106.0 (2)	C7—C6—C5	123.2 (3)
N4—C1—N1	107.9 (2)	C7—C6—H6A	118.4
N4—C1—C2	127.1 (2)	C5—C6—H6A	118.4
N1—C1—C2	125.0 (2)	C6—C5—C4	115.1 (2)
C3—C2—C7	118.8 (2)	C6—C5—C8	118.8 (3)
C3—C2—C1	120.7 (2)	C4—C5—C8	126.0 (3)
C7—C2—C1	120.5 (2)	O1—N5—O2	122.7 (3)
N3—N2—N1	106.0 (2)	O1—N5—C4	118.4 (2)
N2—N3—N4	110.4 (2)	O2—N5—C4	119.0 (3)
C2—C3—C4	119.5 (2)	C5—C8—H8A	109.5
C2—C3—H3A	120.3	C5—C8—H8B	109.5
C4—C3—H3A	120.3	H8A—C8—H8B	109.5
C5—C4—C3	123.3 (2)	C5—C8—H8C	109.5
C5—C4—N5	122.2 (3)	H8A—C8—H8C	109.5
C3—C4—N5	114.5 (2)	H8B—C8—H8C	109.5

N3—N4—C1—N1	−0.1 (3)	C2—C3—C4—N5	−179.9 (2)
N3—N4—C1—C2	179.8 (2)	C3—C2—C7—C6	0.4 (4)
N2—N1—C1—N4	−0.2 (3)	C1—C2—C7—C6	−177.5 (2)
N2—N1—C1—C2	179.9 (2)	C2—C7—C6—C5	−1.1 (4)
N4—C1—C2—C3	142.9 (3)	C7—C6—C5—C4	1.2 (4)
N1—C1—C2—C3	−37.2 (4)	C7—C6—C5—C8	−178.5 (3)
N4—C1—C2—C7	−39.2 (4)	C3—C4—C5—C6	−0.6 (4)
N1—C1—C2—C7	140.7 (3)	N5—C4—C5—C6	179.2 (2)
C1—N1—N2—N3	0.4 (3)	C3—C4—C5—C8	179.1 (3)
N1—N2—N3—N4	−0.5 (3)	N5—C4—C5—C8	−1.1 (4)
C1—N4—N3—N2	0.4 (3)	C5—C4—N5—O1	−177.7 (3)
C7—C2—C3—C4	0.1 (4)	C3—C4—N5—O1	2.2 (4)
C1—C2—C3—C4	178.1 (2)	C5—C4—N5—O2	1.9 (4)
C2—C3—C4—C5	0.0 (4)	C3—C4—N5—O2	−178.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.86	2.01	2.832 (3)	160

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₇N₅O₂
M_r	205.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.9642 (10), 16.982 (3), 10.804 (2)
β (°)	100.71 (3)
V (Å³)	894.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.971, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	7013, 2039, 1330
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.190, 1.08
No. of reflections	2039
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.26

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4ⁱ	0.86	2.01	2.832 (3)	159.8

Symmetry code: (i) x−1, y, z.

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.

References

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